Sample records for crystal size needed
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Advances and new directions in crystallization control.
Nagy, Zoltan K; Braatz, Richard D
2012-01-01
The academic literature on and industrial practice of control of solution crystallization processes have seen major advances in the past 15 years that have been enabled by progress in in-situ real-time sensor technologies and driven primarily by needs in the pharmaceutical industry for improved and more consistent quality of drug crystals. These advances include the accurate measurement of solution concentrations and crystal characteristics as well as the first-principles modeling and robust model-based and model-free feedback control of crystal size and polymorphic identity. Research opportunities are described in model-free controller design, new crystallizer designs with enhanced control of crystal size distribution, strategies for the robust control of crystal shape, and interconnected crystallization systems for multicomponent crystallization.
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Understanding Crystal Populations; Looking Towards 3D Quantitative Analysis
NASA Astrophysics Data System (ADS)
Jerram, D. A.; Morgan, D. J.
2010-12-01
In order to understand volcanic systems, the potential record held within crystal populations needs to be revealed. It is becoming increasingly clear, however, that the crystal populations that arrive at the surface in volcanic eruptions are commonly mixtures of crystals, which may be representative of simple crystallization, recycling of crystals and incorporation of alien crystals. If we can quantify the true 3D population within a sample then we will be able to separate crystals with different histories and begin to interrogate the true and complex plumbing within the volcanic system. Modeling crystal populations is one area where we can investigate the best methodologies to use when dealing with sections through 3D populations. By producing known 3D shapes and sizes with virtual textures and looking at the statistics of shape and size when such populations are sectioned, we are able to gain confidence about what our 2D information is telling us about the population. We can also use this approach to test the size of population we need to analyze. 3D imaging through serial sectioning or x-ray CT, provides a complete 3D quantification of a rocks texture. Individual phases can be identified and in principle the true 3D statistics of the population can be interrogated. In practice we need to develop strategies (as with 2D-3D transformations), that enable a true characterization of the 3D data, and an understanding of the errors and pitfalls that exist. Ultimately, the reproduction of true 3D textures and the wealth of information they hold, is now within our reach.
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Automated protein crystal growth facility
NASA Astrophysics Data System (ADS)
Donald, Stacey
A customer for the protein crystal growth facility fills the specially designed chamber with the correct solutions, fills the syringes with their quenching solutions, and submits the data needed for the proper growth of their crystal. To make sure that the chambers and syringes are filled correctly, a NASA representative may assist the customer. The data needed is the approximate growth time, the growth temperature, and the desired crystal size, but this data can be changed anytime from the ground, if needed. The chambers are gathered and placed into numbered slots in special drawers. Then, data is entered into a computer for each of the chambers. Technicians map out when each chamber's growth should be activated so that all of the chambers have enough time to grow. All of this data is up-linked to the space station when the previous growth session is over. Anti-vibrational containers need to be constructed for the high forces encountered during the lift off and the landing of the space shuttle, and though our team has not designed these containers, we do not feel that there is any reason why a suitable one could not be made. When the shuttle reaches the space station, an astronaut removes a drawer of quenched chambers from the growth facility and inserts a drawer of new chambers. All twelve of the drawers can be replaced in this fashion. The optical disks can also be removed this way. The old drawers are stored for the trip back to earth. Once inside the growth facility, a chamber is removed by the robot and placed in one of 144 active sites at a time previously picked by a technician. Growth begins when the chamber is inserted into an active site. Then, the sensing system starts to determine the size of the protein crystal. All during the crystal's growth, the customer can view the crystal and read all of the crystal's data, such as growth rate and crystal size. When the sensing system determines that the crystal has reached the predetermined size, the robot is told to pick up a syringe filled with the correct quenchant solution and inject it into the chamber to stop the crystal growth. The chamber is then removed from the active site and placed into its original storage slot.
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Automated protein crystal growth facility
NASA Technical Reports Server (NTRS)
Donald, Stacey
1994-01-01
A customer for the protein crystal growth facility fills the specially designed chamber with the correct solutions, fills the syringes with their quenching solutions, and submits the data needed for the proper growth of their crystal. To make sure that the chambers and syringes are filled correctly, a NASA representative may assist the customer. The data needed is the approximate growth time, the growth temperature, and the desired crystal size, but this data can be changed anytime from the ground, if needed. The chambers are gathered and placed into numbered slots in special drawers. Then, data is entered into a computer for each of the chambers. Technicians map out when each chamber's growth should be activated so that all of the chambers have enough time to grow. All of this data is up-linked to the space station when the previous growth session is over. Anti-vibrational containers need to be constructed for the high forces encountered during the lift off and the landing of the space shuttle, and though our team has not designed these containers, we do not feel that there is any reason why a suitable one could not be made. When the shuttle reaches the space station, an astronaut removes a drawer of quenched chambers from the growth facility and inserts a drawer of new chambers. All twelve of the drawers can be replaced in this fashion. The optical disks can also be removed this way. The old drawers are stored for the trip back to earth. Once inside the growth facility, a chamber is removed by the robot and placed in one of 144 active sites at a time previously picked by a technician. Growth begins when the chamber is inserted into an active site. Then, the sensing system starts to determine the size of the protein crystal. All during the crystal's growth, the customer can view the crystal and read all of the crystal's data, such as growth rate and crystal size. When the sensing system determines that the crystal has reached the predetermined size, the robot is told to pick up a syringe filled with the correct quenchant solution and inject it into the chamber to stop the crystal growth. The chamber is then removed from the active site and placed into its original storage slot. Another chamber is then placed into the active site and the process is repeated in all of the active sites until all of the chambers have complted their growth. After ninety days (the scheduled time between shuttle visits), the crystal growth is completed, and the old drawers are replaced with new ones. Once the customer extracts the crystals, the chambers are retrieved for future customers.
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2017-01-01
Crystal size and shape can be manipulated to enhance the qualities of the final product. In this work the steady-state shape and size of succinic acid crystals, with and without a polymeric additive (Pluronic P123) at 350 mL, scale is reported. The effect of the amplitude of cycles as well as the heating/cooling rates is described, and convergent cycling (direct nucleation control) is compared to static cycling. The results show that the shape of succinic acid crystals changes from plate- to diamond-like after multiple cycling steps, and that the time required for this morphology change to occur is strongly related to the type of cycling. Addition of the polymer is shown to affect both the final shape of the crystals and the time needed to reach size and shape steady-state conditions. It is shown how this phenomenon can be used to improve the design of the crystallization step in order to achieve more efficient downstream operations and, in general, to help optimize the whole manufacturing process. PMID:28867966
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Microfluidic sorting of protein nanocrystals by size for X-ray free-electron laser diffraction
Abdallah, Bahige G.; Zatsepin, Nadia A.; Roy-Chowdhury, Shatabdi; Coe, Jesse; Conrad, Chelsie E.; Dörner, Katerina; Sierra, Raymond G.; Stevenson, Hilary P.; Camacho-Alanis, Fernanda; Grant, Thomas D.; Nelson, Garrett; James, Daniel; Calero, Guillermo; Wachter, Rebekka M.; Spence, John C. H.; Weierstall, Uwe; Fromme, Petra; Ros, Alexandra
2015-01-01
The advent and application of the X-ray free-electron laser (XFEL) has uncovered the structures of proteins that could not previously be solved using traditional crystallography. While this new technology is powerful, optimization of the process is still needed to improve data quality and analysis efficiency. One area is sample heterogeneity, where variations in crystal size (among other factors) lead to the requirement of large data sets (and thus 10–100 mg of protein) for determining accurate structure factors. To decrease sample dispersity, we developed a high-throughput microfluidic sorter operating on the principle of dielectrophoresis, whereby polydisperse particles can be transported into various fluid streams for size fractionation. Using this microsorter, we isolated several milliliters of photosystem I nanocrystal fractions ranging from 200 to 600 nm in size as characterized by dynamic light scattering, nanoparticle tracking, and electron microscopy. Sorted nanocrystals were delivered in a liquid jet via the gas dynamic virtual nozzle into the path of the XFEL at the Linac Coherent Light Source. We obtained diffraction to ∼4 Å resolution, indicating that the small crystals were not damaged by the sorting process. We also observed the shape transforms of photosystem I nanocrystals, demonstrating that our device can optimize data collection for the shape transform-based phasing method. Using simulations, we show that narrow crystal size distributions can significantly improve merged data quality in serial crystallography. From this proof-of-concept work, we expect that the automated size-sorting of protein crystals will become an important step for sample production by reducing the amount of protein needed for a high quality final structure and the development of novel phasing methods that exploit inter-Bragg reflection intensities or use variations in beam intensity for radiation damage-induced phasing. This method will also permit an analysis of the dependence of crystal quality on crystal size. PMID:26798818
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Microfluidic sorting of protein nanocrystals by size for X-ray free-electron laser diffraction
Abdallah, Bahige G.; Zatsepin, Nadia A.; Roy-Chowdhury, Shatabdi; ...
2015-08-19
We report that the advent and application of the X-ray free-electron laser (XFEL) has uncovered the structures of proteins that could not previously be solved using traditional crystallography. While this new technology is powerful, optimization of the process is still needed to improve data quality and analysis efficiency. One area is sample heterogeneity, where variations in crystal size (among other factors) lead to the requirement of large data sets (and thus 10–100 mg of protein) for determining accurate structure factors. To decrease sample dispersity, we developed a high-throughput microfluidic sorter operating on the principle of dielectrophoresis, whereby polydisperse particles canmore » be transported into various fluid streams for size fractionation. Using this microsorter, we isolated several milliliters of photosystem I nanocrystal fractions ranging from 200 to 600 nm in size as characterized by dynamic light scattering, nanoparticle tracking, and electron microscopy. Sorted nanocrystals were delivered in a liquid jet via the gas dynamic virtual nozzle into the path of the XFEL at the Linac Coherent Light Source. We obtained diffraction to ~4 Å resolution, indicating that the small crystals were not damaged by the sorting process. We also observed the shape transforms of photosystem I nanocrystals, demonstrating that our device can optimize data collection for the shape transform-based phasing method. Using simulations, we show that narrow crystal size distributions can significantly improve merged data quality in serial crystallography. From this proof-of-concept work, we expect that the automated size-sorting of protein crystals will become an important step for sample production by reducing the amount of protein needed for a high quality final structure and the development of novel phasing methods that exploit inter-Bragg reflection intensities or use variations in beam intensity for radiation damage-induced phasing. Ultimately, this method will also permit an analysis of the dependence of crystal quality on crystal size.« less
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Torad, Nagy L; Naito, Masanobu; Tatami, Junichi; Endo, Akira; Leo, Sin-Yen; Ishihara, Shinsuke; Wu, Kevin C-W; Wakihara, Toru; Yamauchi, Yusuke
2014-03-01
Nanometer-sized zeolite A with a large cesium (Cs) uptake capability is prepared through a simple post-milling recrystallization method. This method is suitable for producing nanometer-sized zeolite in large scale, as additional organic compounds are not needed to control zeolite nucleation and crystal growth. Herein, we perform a quartz crystal microbalance (QCM) study to evaluate the uptake ability of Cs ions by zeolite, to the best of our knowledge, for the first time. In comparison to micrometer-sized zeolite A, nanometer-sized zeolite A can rapidly accommodate a larger amount of Cs ions into the zeolite crystal structure, owing to its high external surface area. Nanometer-sized zeolite is a promising candidate for the removal of radioactive Cs ions from polluted water. Our QCM study on Cs adsorption uptake behavior provides the information of adsorption kinetics (e.g., adsorption amounts and rates). This technique is applicable to other zeolites, which will be highly valuable for further consideration of radioactive Cs removal in the future. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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NASA Technical Reports Server (NTRS)
Vekilov, Peter G.
2003-01-01
Insight into the crystallization processes of biological macromolecules into crystals or aggregates can provide valuable guidelines in many fundamental and applied fields. Such insight will prompt new means to regulate protein phase transitions in-vivo, e.g., polymerization of hemoglobin S in the red cells, crystallization of crystallins in the eye lens, etc. Understanding of protein crystal nucleation will help achieve narrow crystallite size distributions, needed for sustained release of pharmaceutical protein preparations such as insulin or interferon. Traditionally, protein crystallization studies have been related to the pursuit of crystal perfection needed to improve the structure details provided by x-ray, electron or neutron diffraction methods. Crystallization trials for the purposes of structural biology carried out in space have posed an intriguing question related to the inconsistency of the effects of the microgravity growth on the quality of the crystals.
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Large scale crystallization of protein pharmaceuticals in microgravity via temperature change
NASA Technical Reports Server (NTRS)
Long, Marianna M.
1992-01-01
The major objective of this research effort is the temperature driven growth of protein crystals in large batches in the microgravity environment of space. Pharmaceutical houses are developing protein products for patient care, for example, human insulin, human growth hormone, interferons, and tissue plasminogen activator or TPA, the clot buster for heart attack victims. Except for insulin, these are very high value products; they are extremely potent in small quantities and have a great value per gram of material. It is feasible that microgravity crystallization can be a cost recoverable, economically sound final processing step in their manufacture. Large scale protein crystal growth in microgravity has significant advantages from the basic science and the applied science standpoints. Crystal growth can proceed unhindered due to lack of surface effects. Dynamic control is possible and relatively easy. The method has the potential to yield large quantities of pure crystalline product. Crystallization is a time honored procedure for purifying organic materials and microgravity crystallization could be the final step to remove trace impurities from high value protein pharmaceuticals. In addition, microgravity grown crystals could be the final formulation for those medicines that need to be administered in a timed release fashion. Long lasting insulin, insulin lente, is such a product. Also crystalline protein pharmaceuticals are more stable for long-term storage. Temperature, as the initiation step, has certain advantages. Again, dynamic control of the crystallization process is possible and easy. A temperature step is non-invasive and is the most subtle way to control protein solubility and therefore crystallization. Seeding is not necessary. Changes in protein and precipitant concentrations and pH are not necessary. Finally, this method represents a new way to crystallize proteins in space that takes advantage of the unique microgravity environment. The results from two flights showed that the hardware performed perfectly, many crystals were produced, and they were much larger than their ground grown controls. Morphometric analysis was done on over 4,000 crystals to establish crystal size, size distribution, and relative size. Space grown crystals were remarkably larger than their earth grown counterparts and crystal size was a function of PCF volume. That size distribution for the space grown crystals was a function of PCF volume may indicate that ultimate size was a function of temperature gradient. Since the insulin protein concentration was very low, 0.4 mg/ml, the size distribution could also be following the total amount of protein in each of the PCF's. X-ray analysis showed that the bigger space grown insulin crystals diffracted to higher resolution than their ground grown controls. When the data were normalized for size, they still indicated that the space crystals were better than the ground crystals.
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NASA Astrophysics Data System (ADS)
Foster, J. L.; Chang, A. T. C.; Hall, D. K.; Wergin, W. P.; Erbe, E. F.; Barton, J.
1998-11-01
On Earth, the temperature regime is such that water is generally fairly close to its freezing point, and thus relatively small differences in climate affect how much snow and ice are present and whether or not the snow covering will be seasonal or last from one year to the next. On Mars, as on Earth, the presence of ice also plays a role in large-scale climate processes and it is important in controlling the abundance of atmospheric carbon dioxide (CO2) and water vapor. Passive microwave radiometry has been used to derive snow extent and snow depth on Earth, where scattering by snow (H2O) crystals is the dominant effect on the microwave radiation emanating from the ground and emerging from the snowpack. Microwave remote sensing may also prove to be useful for assessing the coverage and thickness of the frozen H2O and CO2 on Mars, but more exact information is needed on how both H2O crystals and frozen CO2 crystals scatter and absorb passive microwave radiation. In this study, CO2 crystals have been produced in a laboratory cold chamber with temperature conditions similar to those found on the polar caps of Mars, and detailed three-dimensional images of their size and shape have been made with a low-temperature scanning electron microscope. Unlike the much larger H2O snow crystals found on Earth, which typically range in size between 0.1 mm and 1.0 mm (radius), CO2 crystals are differently shaped and considerably smaller. Bipyramid crystals (base to base four-sided pyramids) are commonly observed, some as small as 1.0 μm. A discrete dipole model was employed to calculate the passive microwave radiation scattered and absorbed by crystals of various sizes and shapes. Modeling results indicate that the shape of the crystal, whether for frozen CO2 or H2O, is of little consequence in affecting extinction efficiency. However, owing to their smaller size, frozen CO2 crystals are more emissive than the H2O crystals in the 37 GHz region of the microwave spectrum. For the larger sizes of the modeled crystals, scattering dominates over absorption since the particles approach the size of the wavelength. The scattering values are 2 orders of magnitude larger than absorption for the 900 μm size snow particles. For CO2 crystals of 3.0 μm in size, absorption is 7 orders of magnitude greater than scattering.
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Can Supersaturation Affect Protein Crystal Quality?
NASA Technical Reports Server (NTRS)
Gorti, Sridhar
2013-01-01
In quiescent environments (microgravity, capillary tubes, gels) formation of a depletion zone is to be expected, due either to limited sedimentation, density driven convection or a combination of both. The formation of a depletion zone can: Modify solution supersaturation near crystal; Give rise to impurity partitioning. It is conjectured that both supersaturation and impurity partitioning affect protein crystal quality and size. Further detailed investigations on various proteins are needed to assess above hypothesis.
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Controlling Vapor Pressure In Hanging-Drop Crystallization
NASA Technical Reports Server (NTRS)
Carter, Daniel C.; Smith, Robbie
1988-01-01
Rate of evaporation adjusted to produce larger crystals. Device helps to control vapor pressure of water and other solvents in vicinity of hanging drop of solution containing dissolved enzyme protein. Well of porous frit (sintered glass) holds solution in proximity to drop of solution containing protein or enzyme. Vapor from solution in frit controls evaporation of solvent from drop to control precipitation of protein or enzyme. With device, rate of nucleation limited to decrease number and increase size (and perhaps quality) of crystals - large crystals of higher quality needed for x-ray diffraction studies of macromolecules.
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NASA Astrophysics Data System (ADS)
Rezaei, M.; Kermanpur, A.; Sadeghi, F.
2018-03-01
Fabrication of single crystal (SC) Ni-based gas turbine blades with a minimum crystal misorientation has always been a challenge in gas turbine industry, due to its significant influence on high temperature mechanical properties. This paper reports an experimental investigation and numerical simulation of the SC solidification process of a Ni-based superalloy to study effects of withdrawal rate and starter block size on crystal orientation. The results show that the crystal misorientation of the sample with 40 mm starter block height is decreased with increasing withdrawal rate up to about 9 mm/min, beyond which the amount of misorientation is increased. It was found that the withdrawal rate, height of the starter block and temperature gradient are completely inter-dependent and indeed achieving a SC specimen with a minimum misorientation needs careful optimization of these process parameters. The height of starter block was found to have higher impact on crystal orientation compared to the withdrawal rate. A suitable withdrawal rate regime along with a sufficient starter block height was proposed to produce SC parts with the lowest misorientation.
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NASA Technical Reports Server (NTRS)
Mitchell, David L.; Arnott, W. Patrick
1994-01-01
This study builds upon the microphysical modeling described in Part 1 by deriving formulations for the extinction and absorption coefficients in terms of the size distribution parameters predicted from the micro-physical model. The optical depth and single scatter albedo of a cirrus cloud can then be determined, which, along with the asymmetry parameter, are the input parameters needed by cloud radiation models. Through the use of anomalous diffraction theory, analytical expressions were developed describing the absorption and extinction coefficients and the single scatter albedo as functions of size distribution parameters, ice crystal shapes (or habits), wavelength, and refractive index. The extinction coefficient was formulated in terms of the projected area of the size distribution, while the absorption coefficient was formulated in terms of both the projected area and mass of the size distribution. These properties were formulated as explicit functions of ice crystal geometry and were not based on an 'effective radius.' Based on simulations of the second cirrus case study described in Part 1, absorption coefficients predicted in the near infrared for hexagonal columns and rosettes were up to 47% and 71% lower, respectively, than absorption coefficients predicted by using equivalent area spheres. This resulted in single scatter albedos in the near-infrared that were considerably greater than those predicted by the equivalent area sphere method. Reflectances in this region should therefore be underestimated using the equivalent area sphere approach. Cloud optical depth was found to depend on ice crystal habit. When the simulated cirrus cloud contained only bullet rosettes, the optical depth was 142% greater than when the cloud contained only hexagonal columns. This increase produced a doubling in cloud albedo. In the near-infrared (IR), the single scatter albedo also exhibited a significant dependence on ice crystal habit. More research is needed on the geometrical properties of ice crystals before the influence of ice crystal shape on cirrus radiative properties can be adequately understood. This study provides a way of coupling the radiative properties of absorption, extinction, and single scatter albedo to the microphysical properties of cirrus clouds. The dependence of extinction and absorption on ice crystal shape was not just due to geometrical differences between crystal types, but was also due to the effect these differences had on the evolution of ice particle size spectra. The ice particle growth model in Part 1 and the radiative properties treated here are based on analytical formulations, and thus represent a computationally efficient means of modeling the microphysical and radiative properties of cirrus clouds.
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Equilibrium shape of 4He crystal under zero gravity below 200 mK
Takahashi, Takuya; Ohuchi, Haruka; Nomura, Ryuji; Okuda, Yuichi
2015-01-01
Equilibrium crystal shape is the lowest energy crystal shape that is hardly realized in ordinary crystals because of their slow relaxation. 4He quantum crystals in a superfluid have been expected as unique exceptions that grow extremely fast at very low temperatures. However, on the ground, gravity considerably deforms the crystals and conceals the equilibrium crystal shape, and thus, gravity-free environment is needed to observe the equilibrium shape of 4He. We report the relaxation processes of macroscopic 4He crystals in a superfluid below 200 mK under zero gravity using a parabolic flight of a jet plane. When gravity was removed from a gravity-flattened 4He crystal, the crystal rapidly transformed into a shape with flat surfaces. Although the relaxation processes were highly dependent on the initial condition, the crystals relaxed to a nearly homothetic shape in the end, indicating that they were truly in an equilibrium shape minimizing the interfacial free energy. Thanks to the equilibrium shape, we were able to determine the Wulff’s origin and the size of the c-facet together with the vicinal surface profile next to the c-facet. The c-facet size was extremely small in the quantum crystals, and the facet-like flat surfaces were found to be the vicinal surfaces. At the same time, the interfacial free energy of the a-facet and s-facet was also obtained. PMID:26601315
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Equilibrium shape of (4)He crystal under zero gravity below 200 mK.
Takahashi, Takuya; Ohuchi, Haruka; Nomura, Ryuji; Okuda, Yuichi
2015-10-01
Equilibrium crystal shape is the lowest energy crystal shape that is hardly realized in ordinary crystals because of their slow relaxation. (4)He quantum crystals in a superfluid have been expected as unique exceptions that grow extremely fast at very low temperatures. However, on the ground, gravity considerably deforms the crystals and conceals the equilibrium crystal shape, and thus, gravity-free environment is needed to observe the equilibrium shape of (4)He. We report the relaxation processes of macroscopic (4)He crystals in a superfluid below 200 mK under zero gravity using a parabolic flight of a jet plane. When gravity was removed from a gravity-flattened (4)He crystal, the crystal rapidly transformed into a shape with flat surfaces. Although the relaxation processes were highly dependent on the initial condition, the crystals relaxed to a nearly homothetic shape in the end, indicating that they were truly in an equilibrium shape minimizing the interfacial free energy. Thanks to the equilibrium shape, we were able to determine the Wulff's origin and the size of the c-facet together with the vicinal surface profile next to the c-facet. The c-facet size was extremely small in the quantum crystals, and the facet-like flat surfaces were found to be the vicinal surfaces. At the same time, the interfacial free energy of the a-facet and s-facet was also obtained.
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In situ encapsulation of liquids by means of crystallization
NASA Astrophysics Data System (ADS)
Hartwig, Anne; Ulrich, Joachim
2017-07-01
The in situ encapsulation process is due to its few process steps an innovative and cost effective alternative to common encapsulation techniques. It combines the well-known processes of pastillation and crystallization. This concept is proven with case studies of three xylitol capsules which vary in composition and size. It could be shown that the knowledge concerning the solubility of the components is essential to determine the suitable production conditions. The application of seed crystals and the temperatures during the process have major effects on the capsules quality. A fast crystallization of the capsules results in an instable shell. However, with increasing layer thickness of the shell, the crushing force that needs to be applied to break the capsules is increasing as well. But the stability which is related to the capsules size is decreasing with increasing diameter, even though layer thickness and crushing force are increasing, too.
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Kile, D.E.; Eberl, D.D.
2003-01-01
Crystal growth experiments were conducted using potassium alum and calcite crystals in aqueous solution under both non-stirred and stirred conditions to elucidate the mechanism for size-dependent (proportionate) and size-independent (constant) crystal growth. Growth by these two laws can be distinguished from each other because the relative size difference among crystals is maintained during proportionate growth, leading to a constant crystal size variance (??2) for a crystal size distribution (CSD) as the mean size increases. The absolute size difference among crystals is maintained during constant growth, resulting in a decrease in size variance. Results of these experiments show that for centimeter-sized alum crystals, proportionate growth occurs in stirred systems, whereas constant growth occurs in non-stirred systems. Accordingly, the mechanism for proportionate growth is hypothesized to be related to the supply of reactants to the crystal surface by advection, whereas constant growth is related to supply by diffusion. Paradoxically, micrometer-sized calcite crystals showed proportionate growth both in stirred and in non-stirred systems. Such growth presumably results from the effects of convection and Brownian motion, which promote an advective environment and hence proportionate growth for minute crystals in non-stirred systems, thereby indicating the importance of solution velocity relative to crystal size. Calcite crystals grown in gels, where fluid motion was minimized, showed evidence for constant, diffusion-controlled growth. Additional investigations of CSDs of naturally occurring crystals indicate that proportionate growth is by far the most common growth law, thereby suggesting that advection, rather than diffusion, is the dominant process for supplying reactants to crystal surfaces.
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Structure of initial crystals formed during human amelogenesis
NASA Astrophysics Data System (ADS)
Cuisinier, F. J. G.; Voegel, J. C.; Yacaman, J.; Frank, R. M.
1992-02-01
X-ray diffraction analysis revealed only the existence of carbonated hydroxyapatite (c.HA) during amelogenesis, whereas conventional transmission electron microscopy investigations showed that developing enamel crystals have a ribbon-like habit. The described compositional changes could be an indication for the presence of minerals different from c.HA. However, the absence of identification of such a mineral shows the need of studies by high resolution electron microscopy (HREM) of initial formed human enamel crystals. We demonstrate the existence of two crystal families involved in the early stages of biomineralization: (a) nanometer-size particles which appeared as a precursor phase; (b) ribbon-like crystals, with a structure closely related to c.HA, which by a progressive thickening process tend to attain the mature enamel crystal habit.
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NASA Astrophysics Data System (ADS)
Zahari, Zakirah Mohd; Zubaidah Adnan, Siti; Kanthasamy, Ramesh; Saleh, Suriyati; Samad, Noor Asma Fazli Abdul
2018-03-01
The specification of the crystal product is usually given in terms of crystal size distribution (CSD). To this end, optimal cooling strategy is necessary to achieve the CSD. The direct design control involving analytical CSD estimator is one of the approaches that can be used to generate the set-point. However, the effects of temperature on the crystal growth rate are neglected in the estimator. Thus, the temperature dependence on the crystal growth rate needs to be considered in order to provide an accurate set-point. The objective of this work is to extend the analytical CSD estimator where Arrhenius expression is employed to cover the effects of temperature on the growth rate. The application of this work is demonstrated through a potassium sulphate crystallisation process. Based on specified target CSD, the extended estimator is capable of generating the required set-point where a proposed controller successfully maintained the operation at the set-point to achieve the target CSD. Comparison with other cooling strategies shows a reduction up to 18.2% of the total number of undesirable crystals generated from secondary nucleation using linear cooling strategy is achieved.
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Sponge-like nanoporous single crystals of gold
Khristosov, Maria Koifman; Bloch, Leonid; Burghammer, Manfred; Kauffmann, Yaron; Katsman, Alex; Pokroy, Boaz
2015-01-01
Single crystals in nature often demonstrate fascinating intricate porous morphologies rather than classical faceted surfaces. We attempt to grow such crystals, drawing inspiration from biogenic porous single crystals. Here we show that nanoporous single crystals of gold can be grown with no need for any elaborate fabrication steps. These crystals are found to grow following solidification of a eutectic composition melt that forms as a result of the dewetting of nanometric thin films. We also present a kinetic model that shows how this nano-porous single-crystalline structure can be obtained, and which allows the potential size of the porous single crystal to be predicted. Retaining their single-crystalline nature is due to the fact that the full crystallization process is faster than the average period between two subsequent nucleation events. Our findings clearly demonstrate that it is possible to form single-crystalline nano porous metal crystals in a controlled manner. PMID:26554856
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NASA Astrophysics Data System (ADS)
Walcher, H.; Diehl, R.; Baars, J.
The technical importance of the mixed-crystal system Hg(1-x)Cd(x)Te (MCT) is related to a growing interest in detector devices for the infrared spectral ranges of the two atmospheric 'windows'. Applications are not restricted to the military sector, but are also related to astronomy, archeology, medicine, construction engineering, fire fighting, and the determination of pollutants in the atmosphere. It is found that MCT is uniquely qualified for the considered applications, because no other material combines, in the same way, all the required characteristics. However, problems arise in connection with the need for pure, homogeneous, single crystals of adequate size, which are free of any defects. The best results in attempts to grow such crystals have been obtained in experiments utilizing the traveling heater method (THM). Remaining difficulties are caused by effects of gravity. It is, therefore, expected that the crystals needed can be produced under conditions of microgravity. Suitable experiments for exploring this possibility are discussed.
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In cellulo serial crystallography of alcohol oxidase crystals inside yeast cells
Jakobi, Arjen J.; Passon, Daniel M.; Knoops, Kevin; ...
2016-03-01
The possibility of using femtosecond pulses from an X-ray free-electron laser to collect diffraction data from protein crystals formed in their native cellular organelle has been explored. X-ray diffraction of submicrometre-sized alcohol oxidase crystals formed in peroxisomes within cells of genetically modified variants of the methylotrophic yeast Hansenula polymorpha is reported and characterized. Furthermore, the observations are supported by synchrotron radiation-based powder diffraction data and electron microscopy. Based on these findings, the concept of in cellulo serial crystallography on protein targets imported into yeast peroxisomes without the need for protein purification as a requirement for subsequent crystallization is outlined.
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In cellulo serial crystallography of alcohol oxidase crystals inside yeast cells
DOE Office of Scientific and Technical Information (OSTI.GOV)
Jakobi, Arjen J.; Passon, Daniel M.; Knoops, Kevin
The possibility of using femtosecond pulses from an X-ray free-electron laser to collect diffraction data from protein crystals formed in their native cellular organelle has been explored. X-ray diffraction of submicrometre-sized alcohol oxidase crystals formed in peroxisomes within cells of genetically modified variants of the methylotrophic yeast Hansenula polymorpha is reported and characterized. Furthermore, the observations are supported by synchrotron radiation-based powder diffraction data and electron microscopy. Based on these findings, the concept of in cellulo serial crystallography on protein targets imported into yeast peroxisomes without the need for protein purification as a requirement for subsequent crystallization is outlined.
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In cellulo serial crystallography of alcohol oxidase crystals inside yeast cells
Jakobi, Arjen J.; Passon, Daniel M.; Knoops, Kèvin; Stellato, Francesco; Liang, Mengning; White, Thomas A.; Seine, Thomas; Messerschmidt, Marc; Chapman, Henry N.; Wilmanns, Matthias
2016-01-01
The possibility of using femtosecond pulses from an X-ray free-electron laser to collect diffraction data from protein crystals formed in their native cellular organelle has been explored. X-ray diffraction of submicrometre-sized alcohol oxidase crystals formed in peroxisomes within cells of genetically modified variants of the methylotrophic yeast Hansenula polymorpha is reported and characterized. The observations are supported by synchrotron radiation-based powder diffraction data and electron microscopy. Based on these findings, the concept of in cellulo serial crystallography on protein targets imported into yeast peroxisomes without the need for protein purification as a requirement for subsequent crystallization is outlined. PMID:27006771
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Formation of curved micrometer-sized single crystals.
Koifman Khristosov, Maria; Kabalah-Amitai, Lee; Burghammer, Manfred; Katsman, Alex; Pokroy, Boaz
2014-05-27
Crystals in nature often demonstrate curved morphologies rather than classical faceted surfaces. Inspired by biogenic curved single crystals, we demonstrate that gold single crystals exhibiting curved surfaces can be grown with no need of any fabrication steps. These single crystals grow from the confined volume of a droplet of a eutectic composition melt that forms via the dewetting of nanometric thin films. We can control their curvature by controlling the environment in which the process is carried out, including several parameters, such as the contact angle and the curvature of the drops, by changing the surface tension of the liquid drop during crystal growth. Here we present an energetic model that explains this phenomenon and predicts why and under what conditions crystals will be forced to grow with the curvature of the microdroplet even though the energetic state of a curved single crystal is very high.
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NASA Astrophysics Data System (ADS)
Fischetti, Massimo V.; Vandenberghe, William G.
2016-04-01
We show that the electron mobility in ideal, free-standing two-dimensional "buckled" crystals with broken horizontal mirror (σh) symmetry and Dirac-like dispersion (such as silicene and germanene) is dramatically affected by scattering with the acoustic flexural modes (ZA phonons). This is caused both by the broken σh symmetry and by the diverging number of long-wavelength ZA phonons, consistent with the Mermin-Wagner theorem. Non-σh-symmetric, "gapped" 2D crystals (such as semiconducting transition-metal dichalcogenides with a tetragonal crystal structure) are affected less severely by the broken σh symmetry, but equally seriously by the large population of the acoustic flexural modes. We speculate that reasonable long-wavelength cutoffs needed to stabilize the structure (finite sample size, grain size, wrinkles, defects) or the anharmonic coupling between flexural and in-plane acoustic modes (shown to be effective in mirror-symmetric crystals, like free-standing graphene) may not be sufficient to raise the electron mobility to satisfactory values. Additional effects (such as clamping and phonon stiffening by the substrate and/or gate insulator) may be required.
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Polymer-induced phase separation and crystallization in immunoglobulin G solutions.
Li, Jianguo; Rajagopalan, Raj; Jiang, Jianwen
2008-05-28
We study the effects of the size of polymer additives and ionic strength on the phase behavior of a nonglobular protein-immunoglobulin G (IgG)-by using a simple four-site model to mimic the shape of IgG. The interaction potential between the protein molecules consists of a Derjaguin-Landau-Verwey-Overbeek-type colloidal potential and an Asakura-Oosawa depletion potential arising from the addition of polymer. Liquid-liquid equilibria and fluid-solid equilibria are calculated by using the Gibbs ensemble Monte Carlo technique and the Gibbs-Duhem integration (GDI) method, respectively. Absolute Helmholtz energy is also calculated to get an initial coexisting point as required by GDI. The results reveal a nonmonotonic dependence of the critical polymer concentration rho(PEG) (*) (i.e., the minimum polymer concentration needed to induce liquid-liquid phase separation) on the polymer-to-protein size ratio q (equivalently, the range of the polymer-induced depletion interaction potential). We have developed a simple equation for estimating the minimum amount of polymer needed to induce the liquid-liquid phase separation and show that rho(PEG) (*) approximately [q(1+q)(3)]. The results also show that the liquid-liquid phase separation is metastable for low-molecular weight polymers (q=0.2) but stable at large molecular weights (q=1.0), thereby indicating that small sizes of polymer are required for protein crystallization. The simulation results provide practical guidelines for the selection of polymer size and ionic strength for protein phase separation and crystallization.
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NASA Technical Reports Server (NTRS)
Chernov, Alexander A.
2005-01-01
Nucleation, growth and perfection of protein crystals will be overviewed along with crystal mechanical properties. The knowledge is based on experiments using optical and force crystals behave similar to inorganic crystals, though with a difference in orders of magnitude in growing parameters. For example, the low incorporation rate of large biomolecules requires up to 100 times larger supersaturation to grow protein, rather than inorganic crystals. Nucleation is often poorly reproducible, partly because of turbulence accompanying the mixing of precipitant with protein solution. Light scattering reveals fluctuations of molecular cluster size, its growth, surface energies and increased clustering as protein ages. Growth most often occurs layer-by-layer resulting in faceted crystals. New molecular layer on crystal face is terminated by a step where molecular incorporation occurs. Quantitative data on the incorporation rate will be discussed. Rounded crystals with molecularly disordered interfaces will be explained. Defects in crystals compromise the x-ray diffraction resolution crucially needed to find the 3D atomic structure of biomolecules. The defects are immobile so that birth defects stay forever. All lattice defects known for inorganics are revealed in protein crystals. Contribution of molecular conformations to lattice disorder is important, but not studied. This contribution may be enhanced by stress field from other defects. Homologous impurities (e.g., dimers, acetylated molecules) are trapped more willingly by a growing crystal than foreign protein impurities. The trapped impurities induce internal stress eliminated in crystals exceeding a critical size (part of mni for ferritin, lysozyme). Lesser impurities are trapped from stagnant, as compared to the flowing, solution. Freezing may induce much more defects unless quickly amorphysizing intracrystalline water.
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Computationally-Guided Synthetic Control over Pore Size in Isostructural Porous Organic Cages
Slater, Anna G.; Reiss, Paul S.; Pulido, Angeles; ...
2017-06-20
The physical properties of 3-D porous solids are defined by their molecular geometry. Hence, precise control of pore size, pore shape, and pore connectivity are needed to tailor them for specific applications. However, for porous molecular crystals, the modification of pore size by adding pore-blocking groups can also affect crystal packing in an unpredictable way. This precludes strategies adopted for isoreticular metal-organic frameworks, where addition of a small group, such as a methyl group, does not affect the basic framework topology. Here, we narrow the pore size of a cage molecule, CC3, in a systematic way by introducing methyl groupsmore » into the cage windows. Computational crystal structure prediction was used to anticipate the packing preferences of two homochiral methylated cages, CC14-R and CC15-R, and to assess the structure-energy landscape of a CC15-R/CC3-S cocrystal, designed such that both component cages could be directed to pack with a 3-D, interconnected pore structure. The experimental gas sorption properties of these three cage systems agree well with physical properties predicted by computational energy-structure-function maps.« less
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Computationally-Guided Synthetic Control over Pore Size in Isostructural Porous Organic Cages
2017-01-01
The physical properties of 3-D porous solids are defined by their molecular geometry. Hence, precise control of pore size, pore shape, and pore connectivity are needed to tailor them for specific applications. However, for porous molecular crystals, the modification of pore size by adding pore-blocking groups can also affect crystal packing in an unpredictable way. This precludes strategies adopted for isoreticular metal–organic frameworks, where addition of a small group, such as a methyl group, does not affect the basic framework topology. Here, we narrow the pore size of a cage molecule, CC3, in a systematic way by introducing methyl groups into the cage windows. Computational crystal structure prediction was used to anticipate the packing preferences of two homochiral methylated cages, CC14-R and CC15-R, and to assess the structure–energy landscape of a CC15-R/CC3-S cocrystal, designed such that both component cages could be directed to pack with a 3-D, interconnected pore structure. The experimental gas sorption properties of these three cage systems agree well with physical properties predicted by computational energy–structure–function maps. PMID:28776015
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Computationally-Guided Synthetic Control over Pore Size in Isostructural Porous Organic Cages
DOE Office of Scientific and Technical Information (OSTI.GOV)
Slater, Anna G.; Reiss, Paul S.; Pulido, Angeles
The physical properties of 3-D porous solids are defined by their molecular geometry. Hence, precise control of pore size, pore shape, and pore connectivity are needed to tailor them for specific applications. However, for porous molecular crystals, the modification of pore size by adding pore-blocking groups can also affect crystal packing in an unpredictable way. This precludes strategies adopted for isoreticular metal-organic frameworks, where addition of a small group, such as a methyl group, does not affect the basic framework topology. Here, we narrow the pore size of a cage molecule, CC3, in a systematic way by introducing methyl groupsmore » into the cage windows. Computational crystal structure prediction was used to anticipate the packing preferences of two homochiral methylated cages, CC14-R and CC15-R, and to assess the structure-energy landscape of a CC15-R/CC3-S cocrystal, designed such that both component cages could be directed to pack with a 3-D, interconnected pore structure. The experimental gas sorption properties of these three cage systems agree well with physical properties predicted by computational energy-structure-function maps.« less
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Size-dependent cellular uptake mechanism and cytotoxicity toward calcium oxalate on Vero cells
NASA Astrophysics Data System (ADS)
Sun, Xin-Yuan; Gan, Qiong-Zhi; Ouyang, Jian-Ming
2017-02-01
Urinary crystals with various sizes are present in healthy individuals and patients with kidney stone; however, the cellular uptake mechanism of calcium oxalate of various sizes has not been elucidated. This study aims to compare the internalization of nano-/micron-sized (50 nm, 100 nm, and 1 μm) calcium oxalate monohydrate (COM) and dihydrate (COD) crystals in African green monkey renal epithelial (Vero) cells. The internalization and adhesion of COM and COD crystals to Vero cells were enhanced with decreasing crystal size. Cell death rate was positively related to the amount of adhered and internalized crystals and exhibited higher correlation with internalization than that with adhesion. Vero cells mainly internalized nano-sized COM and COD crystals through clathrin-mediated pathways as well as micron-sized crystals through macropinocytosis. The internalized COM and COD crystals were distributed in the lysosomes and destroyed lysosomal integrity to some extent. The results of this study indicated that the size of crystal affected cellular uptake mechanism, and may provide an enlightenment for finding potential inhibitors of crystal uptake, thereby decreasing cell injury and the occurrence of kidney stones.
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Development of an X-ray fluorescence holographic measurement system for protein crystals
NASA Astrophysics Data System (ADS)
Sato-Tomita, Ayana; Shibayama, Naoya; Happo, Naohisa; Kimura, Koji; Okabe, Takahiro; Matsushita, Tomohiro; Park, Sam-Yong; Sasaki, Yuji C.; Hayashi, Kouichi
2016-06-01
Experimental procedure and setup for obtaining X-ray fluorescence hologram of crystalline metalloprotein samples are described. Human hemoglobin, an α2β2 tetrameric metalloprotein containing the Fe(II) heme active-site in each chain, was chosen for this study because of its wealth of crystallographic data. A cold gas flow system was introduced to reduce X-ray radiation damage of protein crystals that are usually fragile and susceptible to damage. A χ-stage was installed to rotate the sample while avoiding intersection between the X-ray beam and the sample loop or holder, which is needed for supporting fragile protein crystals. Huge hemoglobin crystals (with a maximum size of 8 × 6 × 3 mm3) were prepared and used to keep the footprint of the incident X-ray beam smaller than the sample size during the entire course of the measurement with the incident angle of 0°-70°. Under these experimental and data acquisition conditions, we achieved the first observation of the X-ray fluorescence hologram pattern from the protein crystals with minimal radiation damage, opening up a new and potential method for investigating the stereochemistry of the metal active-sites in biomacromolecules.
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Stability relationship for water droplet crystallization with the NASA Lewis icing spray
NASA Technical Reports Server (NTRS)
Marek, C. John; Bartlett, C. Scott
1987-01-01
In order to produce small droplets for icing cloud simulation, high pressure air atomizing nozzles are used. For certain icing testing applications, median drop sizes as small as 5 mm are needed, which require air atomizing pressures greater than 3000 kPa. Isentropic expansion of the ambient temperature atomizing air to atmospheric pressure can result in air stream temperatures of -160 C which results in ice crystals forming in the cloud. To avoid such low temperatures, it is necessary to heat the air and water to high initial temperatures. An icing spray research program was conducted to map the temperatures below which ice crystals form. A soot slide technique was used to determine the presence of crystals in the spray.
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Large Area Microencapsulated Reflective Guest-Host Liquid Crystal Displays and Their Applications
NASA Astrophysics Data System (ADS)
Nakai, Yutaka; Tanaka, Masao; Enomoto, Shintaro; Iwanaga, Hiroki; Hotta, Aira; Kobayashi, Hitoshi; Oka, Toshiyuki; Kizaki, Yukio; Kidzu, Yuko; Naito, Katsuyuki
2002-07-01
We have developed reflective liquid crystal displays using microencapsulated guest-host liquid crystals, whose size was sufficiently large for viewing documents. A high-brightness image can be realized because there is no need for polarizers. Easy fabrication processes, consisting of screen-printing of microencapsulated liquid crystal and film adhesion, have enabled the realization of thinner and lighter cell structures. It has been confirmed that the display is tolerant of the pressures to which it would be subject in actual use. The optimization of fabrication processes has enabled the realization of reflectance uniformity in the display area and reduction of the driving voltage. Our developed display is suitable for portable information systems, such as electronic book applications.
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NASA Astrophysics Data System (ADS)
Wu, Yu-Chun; Tai, Yu-Chuen
2013-06-01
The effects of solvents on the anatase crystallite size prepared by sol-gel microwave-assisted solvothermal method were investigated in this study. Eight different alcohol solvents classified into two groups, i.e. primary and secondary/ternary alcohols, were used as reaction media and the effects of solvent properties, such as dielectric constant, boiling point, and internal pressure during the solvothermal process, on the crystallite size and shape were analyzed. According to the experimental results, selecting the solvent type allowed not only the alteration of the crystallite size but also the crystallite shape without the need of any additives. The boiling point of solvent was determined as the major factor influencing the crystallite size. Among the solvents with similar boiling points, the solvent with a higher carbon number produced the smaller crystallite size because of steric hindrance effect. In addition, the carboxyl groups dissociated from the alcohol solvent can play a role as a structural capping agent to retard the anatase crystal growth along the [001] direction and led to a rectangular crystallite shape with preferred development in {001} facets. On the other hand, the alcoholysis reaction was found easily occurred between the primary alcohol and isopropoxide that effectively limited the hydrolysis and condensation processes but also suppressed the structural capping effect. Therefore, the anatase crystals prepared in the primary alcohols became exceptionally small and showed spherical shape. Finally, the anatase crystals prepared using isopropanol demonstrated the highest photocatalytic activity due to its evident preferred crystallization in the {001} facets.
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Reduction of glycine particle size by impinging jet crystallization.
Tari, Tímea; Fekete, Zoltán; Szabó-Révész, Piroska; Aigner, Zoltán
2015-01-15
The parameters of crystallization processes determine the habit and particle size distribution of the products. A narrow particle size distribution and a small average particle size are crucial for the bioavailability of poorly water-soluble pharmacons. Thus, particle size reduction is often required during crystallization processes. Impinging jet crystallization is a method that results in a product with a reduced particle size due to the homogeneous and high degree of supersaturation at the impingement point. In this work, the applicability of the impinging jet technique as a new approach in crystallization was investigated for the antisolvent crystallization of glycine. A factorial design was applied to choose the relevant crystallization factors. The results were analysed by means of a statistical program. The particle size distribution of the crystallized products was investigated with a laser diffraction particle size analyser. The roundness and morphology were determined with the use of a light microscopic image analysis system and a scanning electron microscope. Polymorphism was characterized by differential scanning calorimetry and powder X-ray diffraction. Headspace gas chromatography was utilized to determine the residual solvent content. Impinging jet crystallization proved to reduce the particle size of glycine. The particle size distribution was appropriate, and the average particle size was an order of magnitude smaller (d(0.5)=8-35 μm) than that achieved with conventional crystallization (d(0.5)=82-680 μm). The polymorphic forms of the products were influenced by the solvent ratio. The quantity of residual solvent in the crystallized products was in compliance with the requirements of the International Conference on Harmonization. Copyright © 2014 Elsevier B.V. All rights reserved.
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NASA Astrophysics Data System (ADS)
Zhao, Yanlin; Yao, Jun; Wang, Mi
2016-07-01
On-line monitoring of crystal size in the crystallization process is crucial to many pharmaceutical and fine-chemical industrial applications. In this paper, a novel method is proposed for the on-line monitoring of the cooling crystallization process of L-glutamic acid (LGA) using electrical impedance spectroscopy (EIS). The EIS method can be used to monitor the growth of crystal particles relying on the presence of an electrical double layer on the charged particle surface and the polarization of double layer under the excitation of alternating electrical field. The electrical impedance spectra and crystal size were measured on-line simultaneously by an impedance analyzer and focused beam reflectance measurement (FBRM), respectively. The impedance spectra were analyzed using the equivalent circuit model and the equivalent circuit elements in the model can be obtained by fitting the experimental data. Two equivalent circuit elements, including capacitance (C 2) and resistance (R 2) from the dielectric polarization of the LGA solution and crystal particle/solution interface, are in relation with the crystal size. The mathematical relationship between the crystal size and the equivalent circuit elements can be obtained by a non-linear fitting method. The function can be used to predict the change of crystal size during the crystallization process.
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Epitaxially influenced boundary layer model for size effect in thin metallic films
NASA Astrophysics Data System (ADS)
Bažant, Zdeněk P.; Guo, Zaoyang; Espinosa, Horacio D.; Zhu, Yong; Peng, Bei
2005-04-01
It is shown that the size effect recently observed by Espinosa et al., [J. Mech. Phys. Solids51, 47 (2003)] in pure tension tests on free thin metallic films can be explained by the existence of a boundary layer of fixed thickness, located at the surface of the film that was attached onto the substrate during deposition. The boundary layer is influenced by the epitaxial effects of crystal growth on the dislocation density and texture (manifested by prevalent crystal plane orientations). This influence is assumed to cause significantly elevated yield strength. Furthermore, the observed gradual postpeak softening, along with its size independence, which is observed in short film strips subjected to pure tension, is explained by slip localization, originating at notch-like defects, and by damage, which can propagate in a stable manner when the film strip under pure tension is sufficiently thin and short. For general applications, the present epitaxially influenced boundary layer model may be combined with the classical strain-gradient plasticity proposed by Gao et al., [J. Mech. Phys. Solids 47, 1239 (1999)], and it is shown that this combination is necessary to fit the test data on both pure tension and bending of thin films by one and the same theory. To deal with films having different crystal grain sizes, the Hall-Petch relation for the yield strength dependence on the grain size needs to be incorporated into the combined theory. For very thin films, in which a flattened grain fills the whole film thickness, the Hall-Petch relation needs a cutoff, and the asymptotic increase of yield strength with diminishing film thickness is then described by the extension of Nix's model of misfit dislocations by Zhang and Zhou [J. Adv. Mater. 38, 51 (2002)]. The final result is a proposal of a general theory for strength, size effect, hardening, and softening of thin metallic films.
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Dependence of Raman Spectral Intensity on Crystal Size in Organic Nano Energetics.
Patel, Rajen B; Stepanov, Victor; Qiu, Hongwei
2016-08-01
Raman spectra for various nitramine energetic compounds were investigated as a function of crystal size at the nanoscale regime. In the case of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20), there was a linear relationship between intensity of Raman spectra and crystal size. Notably, the Raman modes between 120 cm(-1) and 220 cm(-1) were especially affected, and at the smallest crystal size, were completely eliminated. The Raman spectral intensity of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), like that of CL-20's, depended linearly on crystal size. The Raman spectral intensity of 1,3,5-trinitroperhydro-1,3,5-triazine (RDX), however, was not observably changed by crystal size. A non-nitramine explosive compound, 2,4,6-triamino-1,3,5- trinitrobenzene (TATB), was also investigated. Its spectral intensity was also found to correlate linearly with crystal size, although substantially less so than that of HMX and CL-20. To explain the observed trends, it is hypothesized that disordered molecular arrangement, originating from the crystal surface, may be responsible. In particular, it appears that the thickness of the disordered surface layer is dependent on molecular characteristics, including size and conformational flexibility. Furthermore, as the mean crystal size decreases, the volume fraction of disordered molecules within a specimen increases, consequently, weakening the Raman intensity. These results could have practical benefit for allowing the facile monitoring of crystal size during manufacturing. Finally, these findings could lead to deep insights into the general structure of the surface of crystals. © The Author(s) 2016.
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Analysis of submicron-sized niflumic acid crystals prepared by electrospray crystallization.
Ambrus, Rita; Radacsi, Norbert; Szunyogh, Tímea; van der Heijden, Antoine E D M; Ter Horst, Joop H; Szabó-Révész, Piroska
2013-03-25
Interest in submicron-sized drug particles has emerged from both laboratory and industrial perspectives in the last decade. Production of crystals in the nano size scale offers a novel way to particles for drug formulation solving formulation problems of drugs with low solubility in class II of the Biopharmaceutical Classification System. In this work niflumic acid nanoparticles with a size range of 200-800nm were produced by the novel crystallization method, electrospray crystallization. Their properties were compared to those from evaporative and anti-solvent crystallizations, using the same organic solvent, acetone. There is a remarkable difference in the product crystal size depending on the applied methods. The size and morphology were analyzed by scanning electron microscopy and laser diffraction. The structure of the samples was investigated using differential scanning calorimetry, Fourier-transformed infrared spectroscopy and X-ray powder diffraction. The particles produced using electrospray crystallization process were probably changing from amorphous to crystalline state after the procedure. Copyright © 2012 Elsevier B.V. All rights reserved.
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Controllable Growth of Monolayer MoS2 and MoSe2 Crystals Using Three-temperature-zone Furnace
NASA Astrophysics Data System (ADS)
Zheng, Binjie; Chen, Yuanfu
2017-12-01
Monolayer molybdenum disulfide (MoS2) and molybdenum diselenide (MoSe2) have attracted a great attention for their exceptional electronic and optoelectronic properties among the two dimensional family. However, controllable synthesis of monolayer crystals with high quality needs to be improved urgently. Here we demonstrate a chemical vapor deposition (CVD) growth of monolayer MoS2 and MoSe2 crystals using three-temperature-zone furnace. Systematical study of the effects of growth pressure, temperature and time on the thickness, morphology and grain size of crystals shows the good controllability. The photoluminescence (PL) characterizations indicate that the as-grown monolayer MoS2 and MoSe2 crystals possess excellent optical qualities with very small full-width-half-maximum (FWHM) of 96 me V and 57 me V, respectively. It is comparable to that of exfoliated monolayers and reveals their high crystal quality. It is promising that our strategy should be applicable for the growth of other transition metal dichalcogenides (TMDs) monolayer crystals.
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Parsons, Matthew T; Riffell, Jenna L; Bertram, Allan K
2006-07-06
Using an electrodynamic balance, we determined the relative humidity (RH) at which aqueous inorganic-malonic acid particles crystallized, with ammonium sulfate ((NH(4))(2)SO(4)), letovicite ((NH(4))(3)H(SO(4))(2)), or ammonium bisulfate (NH(4)HSO(4)) as the inorganic component. The results for (NH(4))(2)SO(4)-malonic acid particles and (NH(4))(3)H(SO(4))(2)-malonic acid particles show that malonic acid decreases the crystallization RH of the inorganic particles by less than 7% RH when the dry malonic acid mole fraction is less than 0.25. At a dry malonic acid mole fraction of about 0.5, the presence of malonic acid can decrease the crystallization RH of the inorganic particles by up to 35% RH. For the NH(4)HSO(4)-malonic acid particles, the presence of malonic acid does not significantly modify the crystallization RH of the inorganic particles for the entire range of dry malonic acid mole fractions studied; in all cases, either the particles did not crystallize or the crystallization RH was close to 0% RH. Size dependent measurements show that the crystallization RH of aqueous (NH(4))(2)SO(4) particles is not a strong function of particle volume. However, for aqueous (NH(4))(2)SO(4)-malonic acid particles (with dry malonic acid mole fraction = 0.36), the crystallization RH is a stronger function of particle volume, with the crystallization RH decreasing by 6 +/- 3% RH when the particle volume decreases by an order of magnitude. To our knowledge, these are the first size dependent measurements of the crystallization RH of atmospherically relevant inorganic-organic particles. These results suggest that for certain organic mole fractions the particle size and observation time need to be considered when extrapolating laboratory crystallization results to atmospheric scenarios. For aqueous (NH(4))(2)SO(4) particles, the homogeneous nucleation rate data are a strong function of RH, but for aqueous (NH(4))(2)SO(4)-malonic acid particles (with dry organic mole fraction = 0.36), the rates are not as dependent on RH. The homogeneous nucleation rates for aqueous (NH(4))(2)SO(4) particles were parametrized using classical nucleation theory, and from this analysis we determined that the interfacial surface tension between the crystalline ammonium sulfate critical nucleus and an aqueous ammonium sulfate solution is between 0.053 and 0.070 J m(-2).
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Chou, I.-Ming; Rostam-Abadi, M.; Lytle, J.M.; Achorn, F.P.
1996-01-01
Costs for constructing and operating a conceptual plant based on a proposed process that converts flue gas desulfurization (FGD)-gypsum to ammonium sulfate fertilizer has been calculated and used to estimate a market price for the product. The average market price of granular ammonium sulfate ($138/ton) exceeds the rough estimated cost of ammonium sulfate from the proposed process ($111/ ton), by 25 percent, if granular size ammonium sulfate crystals of 1.2 to 3.3 millimeters in diameters can be produced by the proposed process. However, there was at least ??30% margin in the cost estimate calculations. The additional costs for compaction, if needed to create granules of the required size, would make the process uneconomical unless considerable efficiency gains are achieved to balance the additional costs. This study suggests the need both to refine the crystallization process and to find potential markets for the calcium carbonate produced by the process.
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Connection between the growth rate distribution and the size dependent crystal growth
NASA Astrophysics Data System (ADS)
Mitrović, M. M.; Žekić, A. A.; IIić, Z. Z.
2002-07-01
The results of investigations of the connection between the growth rate dispersions and the size dependent crystal growth of potassium dihydrogen phosphate (KDP), Rochelle salt (RS) and sodium chlorate (SC) are presented. A possible way out of the existing confusion in the size dependent crystal growth investigations is suggested. It is shown that the size independent growth exists if the crystals belonging to one growth rate distribution maximum are considered separately. The investigations suggest possible reason for the observed distribution maxima widths, and the high data scattering on the growth rate versus the crystal size dependence.
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NASA Technical Reports Server (NTRS)
Barlow, Douglas A.; Baird, James K.; Su, Ching-Hua
2003-01-01
More than 75 years ago, von Weimarn summarized his observations of the dependence of the average crystal size on the initial relative concentration supersaturation prevailing in a solution from which crystals were growing. Since then, his empirically derived rules have become part of the lore of crystal growth. The first of these rules asserts that the average crystal size measured at the end of a crystallization increases as the initial value of the relative supersaturation decreases. The second rule states that for a given crystallization time, the average crystal size passes through a maximum as a function of the initial relative supersaturation. Using a theory of nucleation and growth due to Buyevich and Mansurov, we calculate the average crystal size as a function of the initial relative supersaturation. We confirm the von Weimarn rules for the case where the nucleation rate is proportional to the third power or higher of the relative supersaturation.
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Colloidal crystals with diamond symmetry at optical lengthscales
NASA Astrophysics Data System (ADS)
Wang, Yifan; Jenkins, Ian C.; McGinley, James T.; Sinno, Talid; Crocker, John C.
2017-02-01
Future optical materials promise to do for photonics what semiconductors did for electronics, but the challenge has long been in creating the structure they require--a regular, three-dimensional array of transparent microspheres arranged like the atoms in a diamond crystal. Here we demonstrate a simple approach for spontaneously growing double-diamond (or B32) crystals that contain a suitable diamond structure, using DNA to direct the self-assembly process. While diamond symmetry crystals have been grown from much smaller nanoparticles, none of those previous methods suffice for the larger particles needed for photonic applications, whose size must be comparable to the wavelength of visible light. Intriguingly, the crystals we observe do not readily form in previously validated simulations; nor have they been predicted theoretically. This finding suggests that other unexpected microstructures may be accessible using this approach and bodes well for future efforts to inexpensively mass-produce metamaterials for an array of photonic applications.
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NASA Astrophysics Data System (ADS)
Lee, Sooyun; Lee, Choul-Ho; Kim, Woo-Sik
2017-07-01
The influence of the fluid dynamic motions of a periodic Taylor vortex and random turbulent eddy on the anti-solvent crystallization of L-threonine was investigated. The Taylor vortex flow and random turbulent eddy flow were generated by the inner cylinder rotation in a Couette-Taylor (CT) crystallizer and the impeller agitation in a mixed-suspension mixed product removal (MSMPR) crystallizer, respectively. Furthermore, the circumferentially sinusoidal fluctuation of a Taylor vortex was induced in an elliptical Couette-Taylor (ECT) crystallizer . The periodic Taylor vortex flows in the CT and ECT crystallizers resulted in a smaller crystal size and higher crystal recovery ratio of L-threonine than the random turbulent flow in the MSMPR crystallizer due to induction of a higher supersaturation, resulting in a higher nucleation in the CT and ECT crystallizers than in the MSMPR crystallizer. Thus, the crystal size was reduced and the crystal recovery ratio enhanced when increasing the rotation/agitation speed and feed flow rate in the CT, ECT, and MSMPR crystallizers. When increasing the temperature, the crystal size and crystal recovery ratio were both increased due an enhanced mass transfer for crystal growth. The crystal morphology changes according to the fluid dynamic motion with various crystallization conditions were well correlated in terms of the supersaturation.
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NASA Astrophysics Data System (ADS)
Zhang, Boyu; Wang, Jun; Yaer, Xinba; Huo, Zhenzhen; Wu, Yin; Li, Yan; Miao, Lei; Liu, Chengyan; Zou, Tao; Ma, Wen
2015-07-01
Effect of crystal size distribution on thermoelectric performance of Lanthanum-doped strontium titanate (La-SrTiO3) ceramics are investigated in this study. Thermoelectric performance measurement, coupled with microstructure studies, shows that the electrical conductivity strongly depends on the crystal size, potential barrier on the grain boundary and porosity. Meantime, because the average potential barriers height are increased along with the reduction of crystal size, the Seebeck coefficients are increased by energy filtering effect at the large number of grain boundaries. As a result, by controlling of crystal size distribution, ZT value of La-SrTiO3 is improved.
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On geological interpretations of crystal size distributions: Constant vs. proportionate growth
Eberl, D.D.; Kile, D.E.; Drits, V.A.
2002-01-01
Geological interpretations of crystal size distributions (CSDs) depend on understanding the crystal growth laws that generated the distributions. Most descriptions of crystal growth, including a population-balance modeling equation that is widely used in petrology, assume that crystal growth rates at any particular time are identical for all crystals, and, therefore, independent of crystal size. This type of growth under constant conditions can be modeled by adding a constant length to the diameter of each crystal for each time step. This growth equation is unlikely to be correct for most mineral systems because it neither generates nor maintains the shapes of lognormal CSDs, which are among the most common types of CSDs observed in rocks. In an alternative approach, size-dependent (proportionate) growth is modeled approximately by multiplying the size of each crystal by a factor, an operation that maintains CSD shape and variance, and which is in accord with calcite growth experiments. The latter growth law can be obtained during supply controlled growth using a modified version of the Law of Proportionate Effect (LPE), an equation that simulates the reaction path followed by a CSD shape as mean size increases.
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A simple apparatus for controlling nucleation and size in protein crystal growth
NASA Technical Reports Server (NTRS)
Gernert, Kim M.; Smith, Robert; Carter, Daniel C.
1988-01-01
A simple device is described for controlling vapor equilibrium in macromolecular crystallization as applied to the protein crystal growth technique commonly referred to as the 'hanging drop' method. Crystal growth experiments with hen egg white lysozyme have demonstrated control of the nucleation rate. Nucleation rate and final crystal size have been found to be highly dependent upon the rate at which critical supersaturation is approached. Slower approaches show a marked decrease in the nucleation rate and an increase in crystal size.
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Dislocation, crystallite size distribution and lattice strain of magnesium oxide nanoparticles
NASA Astrophysics Data System (ADS)
Sutapa, I. W.; Wahid Wahab, Abdul; Taba, P.; Nafie, N. L.
2018-03-01
The oxide of magnesium nanoparticles synthesized using sol-gel method and analysis of the structural properties was conducted. The functional groups of nanoparticles has been analysed by Fourier Transform Infrared Spectroscopy (FT-IR). Dislocations, average size of crystal, strain, stress, the energy density of crystal, crystallite size distribution and morphologies of the crystals were determined based on X-ray diffraction profile analysis. The morphological of the crystal was analysed based on the image resulted from SEM analysis. The crystallite size distribution was calculated with the contention that the particle size has a normal logarithmic form. The most orientations of crystal were determined based on the textural crystal from diffraction data of X-ray diffraction profile analysis. FT-IR results showed the stretching vibration mode of the Mg-O-Mg in the range of 400.11-525 cm-1 as a broad band. The average size crystal of nanoparticles resulted is 9.21 mm with dislocation value of crystal is 0.012 nm-2. The strains, stress, the energy density of crystal are 1.5 x 10-4 37.31 MPa; 0.72 MPa respectively. The highest texture coefficient value of the crystal is 0.98. This result is supported by morphological analysis using SEM which shows most of the regular cubic-shaped crystals. The synthesis method is suitable for simple and cost-effective synthesis model of MgO nanoparticles.
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Growth of high quality bulk size single crystals of inverted solubility lithium sulphate monohydrate
DOE Office of Scientific and Technical Information (OSTI.GOV)
Silambarasan, A.; Rajesh, P., E-mail: rajeshp@ssn.edu.in; Ramasamy, P.
2015-06-24
The paper summarizes the processes of growing large lithium sulfate monohydrate (LSMH) single crystals. We have established a procedure to grow high quality bulk size single crystals of inverted solubility LSMH by a newly developed unidirectional crystallization technique called the Sankeranarayenan - Ramasamy (SR) method. The convective flow of crystal growth processes from solution and the conditions of growing crystals of various aspects were discussed. Good quality LSMH single crystal is grown of the size 20 mmX80 mm without cracks, localized-defects and inclusions. The as-grown crystals are suitable for piezoelectric and nonlinear optical applications.
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Influences of powder granularity on crystallizing characteristics in mica-contained glass ceramic
NASA Astrophysics Data System (ADS)
Xu, L. N.; Kong, D. Y.; Tian, Q. B.; Lv, Z. J.
2017-09-01
A machinable mica-contained glass ceramic in the SiO2-Al2O3-MgO-F glassy system was prepared by ball milling and hot pressed sintering. Three kinds of powder sizes of base glass were chosen and the effects of the glass powder sizes on the crystallization were explored by x-ray diffraction and scanning electron microscopy techniques. The results indicate that mica crystal as a major phase and KFeSi2O6 and mullite as minor phases are crystallized. Applying pressure at 670°C has little influences on the types of crystal precipitated and the preferential growth of crystal. The powder sizes, however, have obvious effects on the morphology of precipitated mica crystals. In the glass sample with a powder size of d50=16.4 µm, the plate-shaped mica phase is precipitated. As the powder size decrease to 9.9 µm and 3.3 µm, however, the particle-shaped mica is formed instead of the plate-shaped crystals.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Sato-Tomita, Ayana, E-mail: ayana.sato@jichi.ac.jp, E-mail: shibayam@jichi.ac.jp, E-mail: hayashi.koichi@nitech.ac.jp; Shibayama, Naoya, E-mail: ayana.sato@jichi.ac.jp, E-mail: shibayam@jichi.ac.jp, E-mail: hayashi.koichi@nitech.ac.jp; Okabe, Takahiro
Experimental procedure and setup for obtaining X-ray fluorescence hologram of crystalline metalloprotein samples are described. Human hemoglobin, an α{sub 2}β{sub 2} tetrameric metalloprotein containing the Fe(II) heme active-site in each chain, was chosen for this study because of its wealth of crystallographic data. A cold gas flow system was introduced to reduce X-ray radiation damage of protein crystals that are usually fragile and susceptible to damage. A χ-stage was installed to rotate the sample while avoiding intersection between the X-ray beam and the sample loop or holder, which is needed for supporting fragile protein crystals. Huge hemoglobin crystals (with amore » maximum size of 8 × 6 × 3 mm{sup 3}) were prepared and used to keep the footprint of the incident X-ray beam smaller than the sample size during the entire course of the measurement with the incident angle of 0°-70°. Under these experimental and data acquisition conditions, we achieved the first observation of the X-ray fluorescence hologram pattern from the protein crystals with minimal radiation damage, opening up a new and potential method for investigating the stereochemistry of the metal active-sites in biomacromolecules.« less
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Kile, D.E.; Eberl, D.D.
1999-01-01
The Crystal Peak area of the Pikes Peak batholith, near Lake George in central Colorado, is world-renowned for its crystals of amazonite (the blue-green variety of microcline) and smoky quartz. Such crystals, collected from individual miarolitic pegmatites, have a remakably small variation in crystal size within each pegmatite, and the shapes of plots of their crystal size distributions (CSDs) are invariably lognormal or close to lognormal in all cases. These observations are explained by a crystal growth mechanism that was governed initially by surface-controlled kinetics, during which crystals tended to grow larger in proportion to their size, thereby establishing lognormal CSDs. Surface-controlled growth was followed by longer periods of supply controlled growth, during which growth rate was predominantly size-independent, consequently preserving the lognormal shapes of the CSDs and the small size variation. The change from surface- to supply controlled growth kinetics may have resulted from an increasing demand for nutrients that exceeded diffusion limitations of the system. The proposed model for crystal growth in this locality appears to be common in the geologic record, and can be used with other information, such as isotopic data, to deduce physico-chemical conditions during crystal formation.
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NASA Astrophysics Data System (ADS)
Mauge-Lewis, Kevin
In response to the growing need for new crystallization techniques that afford for rapid processing times along with control over crystal size and distribution, the Aslan Research Group has recently demonstrated the use of Metal-Assisted and Microwave-Accelerated Evaporative Crystallization MA-MAEC technique in conjunction with metal nanoparticles and nanostructures for the crystallization of amino acids and organic small molecules. In this study, we have employed the newly developed MA-MAEC technique to the accelerated crystallization of chicken egg-white lysozyme on circular crystallization platforms in order to demonstrate the proof-of-principle application of the method for protein crystallization. The circular crystallization platforms are constructed in-house from poly (methyl methacrylate) (PMMA) and silver nanoparticle films (SNFs), indium tin oxide (ITO) and iron nano-columns. In this study, we prove the MA-MAEC method to be a more effective technique in the rapid crystallization of macromolecules in comparison to other conventional methods. Furthermore, we demonstrate the use of the novel iCrystal system, which incorporates the use of continuous, low wattage heating to facilitate the rapid crystallization of the lysozyme while still retaining excellent crystal quality. With the incorporation of the iCrystal system, we observe crystallization times that are even shorter than those produced by the MA-MAEC technique using a conventional microwave oven in addition to significantly improved crystal quality.
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NASA Technical Reports Server (NTRS)
Aggarwal, Mohan D.; Kochary, F.; Penn, Benjamin G.; Miller, Jim
2007-01-01
There has been a growing interest in recent years in lead based perovskite ferroelectric and relaxor ferroelectric solid solutions because of their excellent dielectric, piezoelectric and electrostrictive properties that make them very attractive for various sensing, actuating and structural health monitoring (SHM) applications. We are interested in the development of highly sensitive and efficient PMN-PT sensors based on large single crystals for the structural health monitoring of composite materials that may be used in future spacecrafts. Highly sensitive sensors are needed for detection of defects in these materials because they often tend to fail by distributed and interacting damage modes and much of the damage occurs beneath the top surface of the laminate and not detectable by visual inspection. Research is being carried out for various combinations of solid solutions for PMN-PT piezoelectric materials and bigger size crystals are being sought for improved sensor applications. Single crystals of this material are of interest for sensor applications because of their high piezoelectric coefficient (d33 greater than 1700 pC/N) and electromechanical coefficients (k33 greater than 0.90). For comparison, the commonly used piezoelectric ceramic lead zirconate titanate (PZT) has a d33 of about 600 pC/N and electromechanical coefficients k33 of about 0.75. At the present time, these piezoelectric relaxor crystals are grown by high temperature flux growth method and the size of these crystals are rather small (3x4x5 mm(exp 3). In the present paper, we have attempted to grow bulk single crystals of PMN-PT in a 2 inch diameter platinum crucible and successfully grown a large size crystal of 67%PMN-33%PT using the vertical gradient freeze technique with no flux. Piezoelectric properties of the grown crystals are investigated. PMN-PT plates show excellent piezoelectric properties. Samples were poled under an applied electric field of 5 kV/cm. Dielectric properties at a frequency of 1 kHz are examined. The grown PMN-PT crystals show typical relaxor dielectric properties. Additionally, the thermal properties of the sample are tested. The results are in good agreement with those found in the literature and some are reported for the first time.
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NASA Astrophysics Data System (ADS)
Bondarenko, Yu. A.; Echin, A. B.; Surova, V. A.; Kolodyazhnyi, M. Yu.
2017-05-01
The effect of the conditions of directed crystallization (the temperature gradient and the crystallization rate) on the dendrite spacing, on the size of the particles of the hardening γ'-phase in the arms and arm spaces of the dendrites, on the volume fraction and size of the pores, on the size of the particles of the eutectic γ/γ'-phase, and on the features of dendritic segregation in a single-crystal castable refractory alloy is studied.
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NASA Astrophysics Data System (ADS)
Carlson, William D.
1989-09-01
The spatial disposition, compositional zoning profiles, and size distributions of garnet crystals in 11 specimens of pelitic schist from the Picuris Range of New Mexico (USA) demonstrate that the kinetics of intergranular diffusion controlled the nucleation and growth mechanisms of porphyroblasts in these rocks. An ordered disposition of garnet centers and a significant correlation between crystal radius and near-neighbor distances manifest suppressed nucleation of new crystals in diffusionally depleted zones surrounding pre-existing crystals. Compositional zoning profiles require diffusionally controlled growth, the rate of which increases exponentially as temperature increases with time; an acceleration factor for growth rate can be estimated from a comparison of compositional profiles for crystals of different sizes in each specimen. Crystal size distributions are interpreted as the result of nucleation rates that accelerate exponentially with increasing temperature early in the crystallization process, but decline in the later stages because of suppression effects in the vicinity of earlier-formed nuclei. Simulations of porphyroblast crystallization, based upon thermally accelerated diffusionally influenced nucleation kinetics and diffusionally controlled growth kinetics, quantitatively replicate textural relations in the rocks. The simulations employ only two variable parameters, which are evaluated by fitting of crystal size distributions. Both have physical significance. The first is an acceleration factor for nucleation, with a magnitude reflecting the prograde increase during the nucleation interval of the chemical affinity for the reaction in undepleted regions of the rock. The second is a measure of the relative sizes of the porphyroblast and the diffusionally depleted zone surrounding it. Crystal size distributions for the Picuris Range garnets correspond very closely to those in the literature from a variety of other localities for garnet and other minerals. The same kinetic model accounts quantitatively for crystal size distributions of porphyroblastic garnet, phlogopite, sphene, and pyroxene in rocks from both regional and contact metamorphic occurrences. These commonalities indicate that intergranular diffusion may be the dominant kinetic factor in the crystallization of porphyroblasts in a wide variety of metamorphic environments.
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NASA Astrophysics Data System (ADS)
Nanev, Christo N.; Petrov, Kostadin P.
2017-12-01
The use of the classical nucleation-growth-separation principle (NGSP) was restricted hitherto to nucleation kinetics studies only. A novel application of the NGSP is proposed. To reduce crystal polydispersity internal seeding of equally-sized crystals is suggested, the advantage being avoidance of crystal grinding, sieving and any introduction of impurities. In the present study, size distributions of grown insulin crystals are interpreted retrospectively to select the proper nucleation stage parameters. The conclusion is that when steering a crystallization process aimed at reducing crystal polydispersity, the shortest possible nucleation stage duration has to be chosen because it renders the closest size distribution of the nucleated crystal seeds. Causes of inherent propensity to increasing crystal polydispersity during prolonged growth are also explored. Step sources of increased activity, present in some crystals while absent in others, are pointed as the major polydispersity cause. Insulin crystal morphology is also considered since it determines the dissolution rate of a crystalline medicine.
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Fully automatic characterization and data collection from crystals of biological macromolecules.
Svensson, Olof; Malbet-Monaco, Stéphanie; Popov, Alexander; Nurizzo, Didier; Bowler, Matthew W
2015-08-01
Considerable effort is dedicated to evaluating macromolecular crystals at synchrotron sources, even for well established and robust systems. Much of this work is repetitive, and the time spent could be better invested in the interpretation of the results. In order to decrease the need for manual intervention in the most repetitive steps of structural biology projects, initial screening and data collection, a fully automatic system has been developed to mount, locate, centre to the optimal diffraction volume, characterize and, if possible, collect data from multiple cryocooled crystals. Using the capabilities of pixel-array detectors, the system is as fast as a human operator, taking an average of 6 min per sample depending on the sample size and the level of characterization required. Using a fast X-ray-based routine, samples are located and centred systematically at the position of highest diffraction signal and important parameters for sample characterization, such as flux, beam size and crystal volume, are automatically taken into account, ensuring the calculation of optimal data-collection strategies. The system is now in operation at the new ESRF beamline MASSIF-1 and has been used by both industrial and academic users for many different sample types, including crystals of less than 20 µm in the smallest dimension. To date, over 8000 samples have been evaluated on MASSIF-1 without any human intervention.
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Barnes, Cindy L; Snell, Edward H; Kundrot, Craig E
2002-05-01
This paper reports results from the first biological crystal-growth experiment on the International Space Station (ISS). Crystals of thaumatin were grown using liquid-liquid diffusion in Tygon tubing transported in the Enhanced Gaseous Nitrogen Dewar (EGN). Different volume ratios and concentrations of protein and precipitant were used to test different adaptations of the vapor-diffusion crystallization recipe to the liquid-liquid diffusion method. The EGN warmed up from 77 to 273 K in about 4 d, about the same time it took to warm from 273 to 293 K. The temperature within the EGN was 293-297 K for the majority of the experiment. Air gaps that blocked liquid-liquid diffusion formed in the tubes. Nonetheless, crystals were grown. Synchrotron diffraction data collected from the best space-grown crystal extended to 1.28 A, comparable to previous studies of space-grown thaumatin crystals. The resolution of the best ground-control crystal was only 1.47 A. It is not clear if the difference in diffraction limit arises from factors other than crystal size. Improvements in temperature control and the elimination of air gaps are needed, but the results show that the EGN on the ISS can be used to produce space-grown crystals that diffract to high resolution.
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NASA Technical Reports Server (NTRS)
Kundrot, Craig; Barnes, Cindy L.; Snell, Edward H.; Stinson, Thomas N. (Technical Monitor)
2002-01-01
This paper reports results from the first biological crystal growth experiment on the International Space Station (ISS). Crystals of thaumatin were grown using liquid-liquid diffusion in Tygon tubing transported in the Enhanced Gaseous Nitrogen Dewar (EGN). Different Volume ratios and concentrations of protein and precipitant were used to test different adaptations of the vapor diffusion crystallization recipe to the liquid-liquid diffusion method. The EGN warmed up from -196 C to 0 C in about four days, about the same time it took to warm from 0 C to 20 C. The temperature within the EGN was 20 - 24 C for the majority of the experiment. Air gaps that blocked liquid-liquid diffusion formed in the tubes. Nonetheless, crystals were grown. Synchrotron diffraction data collected from the best space grown crystal extended to 1.28 Angstroms, comparable to previous studies of space-grown thaumatin crystals. The resolution of the best ground control crystal was only 1.47 Angstroms. It is not clear if the difference in diffraction limit is due to factors other than crystal size. Improvements in temperature control and the elimination of air gaps are needed, but the results show that EGN on the ISS can be used to produce space grown crystals that diffract to high resolution.
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Iyer, Sneha R; Gogate, Parag R
2017-01-01
The current work investigates the application of low intensity ultrasonic irradiation for improving the cooling crystallization of Mefenamic Acid for the first time. The crystal shape and size has been analyzed with the help of optical microscope and image analysis software respectively. The effect of ultrasonic irradiation on crystal size, particle size distribution (PSD) and yield has been investigated, also establishing the comparison with conventional approach. It has been observed that application of ultrasound not only enhances the yield but also reduces the induction time for crystallization as compared to conventional cooling crystallization technique. In the presence of ultrasound, the maximum yield was obtained at optimum conditions of power dissipation of 30W and ultrasonic irradiation time of 10min. The yield was further improved by application of ultrasound in cycles where the formed crystals are allowed to grow in the absence of ultrasonic irradiation. It was also observed that the desired crystal morphology was obtained for the ultrasound assisted crystallization. The conventionally obtained needle shaped crystals transformed into plate shaped crystals for the ultrasound assisted crystallization. The particle size distribution was analyzed using statistical means on the basis of skewness and kurtosis values. It was observed that the skewness and excess kurtosis value for ultrasound assisted crystallization was significantly lower as compared to the conventional approach. XRD analysis also revealed better crystal properties for the processed mefenamic acid using ultrasound assisted approach. The overall process intensification benefits of mefenamic acid crystallization using the ultrasound assisted approach were reduced particle size, increase in the yield and uniform PSD coupled with desired morphology. Copyright © 2016 Elsevier B.V. All rights reserved.
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Bridgman growth of large-aperture yttrium calcium oxyborate crystal
DOE Office of Scientific and Technical Information (OSTI.GOV)
Wu, Anhua, E-mail: wuanhua@mail.sic.ac.cn; Jiang, Linwen; Qian, Guoxing
2012-09-15
Highlights: ► YCOB is a novel non-linear optical crystal possessing good thermal, mechanical and nonlinear optical properties. ► Large size crystal growth is key technology question for YCOB crystal. ► YCOB crystals 3 in. in diameter were grown with modified vertical Bridgman method. ► It is a more effective growth method to obtain large size and high quality YCOB crystal. -- Abstract: Large-aperture yttrium calcium oxyborate YCa{sub 4}O(BO{sub 3}){sub 3} (YCOB) crystals with 3 in. in diameter were grown with modified vertical Bridgman method, and the large crystal plate (63 mm × 68 mm × 20 mm) was harvested formore » high-average power frequency conversion system. The crack, facet growth and spiral growth can be effectively controlled in the as-grown crystal, and Bridgman method displays more effective in obtain large size and high quality YCOB crystal plate than Czochralski technique.« less
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NASA Astrophysics Data System (ADS)
Gaidies, Fred; Petley-Ragan, Arianne; Pattison, David
2016-04-01
The size, abundance, shape and spatial distribution of metamorphic minerals bears important information on the rates and mechanisms of fundamental processes that take place during metamorphic crystallization. X-ray computed tomography (XR-CT) has become the method of choice to study the three-dimensional (3D) disposition of minerals in rocks as it allows investigation of relatively large sample volumes at sufficiently high resolution required for statistically meaningful analyses, and as its non-destructive fashion permits further studies such as mineral chemical, isotopic or crystallographic analyses of select grains identified through XR-CT. We present results obtained through the quantification of the 3D disposition of cordierite and biotite crystals in a hornfels from the contact aureole of the Bugaboo Batholith (British Columbia, Canada) using XR-CT and global as well as scale-dependent pattern statistics (Petley-Ragan et al., 2016). The results demonstrate a random distribution of cordierite and biotite crystal sizes for all scales across the entire rock volume studied indicative of interface-controlled prograde metamorphic reaction kinetics. We show that the common approach to approximate the shape of crystals as spherical underestimates the influence of the Strauss hard-core process on rock texture which may be misinterpreted to reflect ordering of crystal sizes by inhibition of nucleation and growth commonly associated with diffusion-controlled reaction kinetics. According to our findings, Strauss hard-core ordering develops at length scales equal to and less than the average major axis of the crystal population. This is significantly larger than what is obtained if a spherical crystal geometry would be assumed, and increases with deviation from sphericity. For the cordierite and biotite populations investigated in this research, Strauss hard-core ordering developed at length scales of up to ˜2.2 and 1.25 mm, respectively, which is almost 1 mm longer than the scales that would be obtained if a spherical geometry would have been assumed. Our results highlight the importance of a critical assessment of the geometrical model assumptions commonly applied in the 3D analysis of crystal size distributions, and underline the need for a quantitative understanding of interface processes in order to appreciate their role in the kinetics of contact metamorphic reactions and rock texture formation. References: Petley-Ragan A, Gaidies F, Pattison DRM (2016) A statistical analysis of the distribution of cordierite and biotite in hornfels from the Bugaboo contact aureole: implications for the kinetics of porphyroblast crystallization. Journal of Metamorphic Geology 34:85-101
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Ice fog and light snow measurements using a high resolution camera system
NASA Astrophysics Data System (ADS)
Kuhn, Thomas; Gultepe, Ismail
2016-04-01
In this presentation, measurements collected by the ice crystal imaging (ICI) probe employed during FRAM (Fog Remote Sensing and Modeling) project for the Winter of 2010-2011 in Yellowknife, NWT, Canada are analysed to study small ice crystal impact on aviation operations. Ice fog, diamond dust, and light snow form during cold weather conditions and they affect aviation operations through visibility and deposition over the surfaces. In addition, these events influence the local heat budget through radiative cooling. Prediction of these hydrometeors using models is difficult because of limited knowledge of the microphysical properties at the small size ranges. These phenomena need to be better represented in forecast and climate models and this can only be done using accurate measurements from ground-based instrumentation. Imaging of ice particles' properties can complement other in-situ measurements being collected routinely. The newly developed ICI probe, aimed at measuring ice fog and light snow particles, is presented here. The ICI probe samples ice particles through a vertical inlet, where a laser beam and photodetector detect ice crystals contained in the flow. The detected particles are then imaged with high optical resolution between 10 to 1000 micron size range. An illuminating LED flash and image capturing for measurements are triggered by the photodetector. The results suggested that the majority of ice particles during the two-month long campaign were small with sizes between 300 μm and 800 μm. During ice fog events, the size distribution measured had a lower mode diameter of 300 μm compared to the overall campaign average with mode at 500 μm. In this presentation, challenges and issues related to small ice crystals are described and their importance for aviation operations and climate change are discussed.
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Chemical vapor deposition of high-quality large-sized MoS 2 crystals on silicon dioxide substrates
Chen, Jianyi; Tang, Wei; Tian, Bingbing; ...
2016-03-31
Large-sized MoS 2 crystals can be grown on SiO 2/Si substrates via a two-stage chemical vapor deposition method. The maximum size of MoS 2 crystals can be up to about 305 μm. The growth method can be used to grow other transition metal dichalcogenide crystals and lateral heterojunctions. Additionally, the electron mobility of the MoS 2 crystals can reach ≈30 cm 2 V –1 s –1, which is comparable to those of exfoliated flakes.
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Chemical Vapor Deposition of High-Quality Large-Sized MoS2 Crystals on Silicon Dioxide Substrates.
Chen, Jianyi; Tang, Wei; Tian, Bingbing; Liu, Bo; Zhao, Xiaoxu; Liu, Yanpeng; Ren, Tianhua; Liu, Wei; Geng, Dechao; Jeong, Hu Young; Shin, Hyeon Suk; Zhou, Wu; Loh, Kian Ping
2016-08-01
Large-sized MoS 2 crystals can be grown on SiO 2 /Si substrates via a two-stage chemical vapor deposition method. The maximum size of MoS 2 crystals can be up to about 305 μm. The growth method can be used to grow other transition metal dichalcogenide crystals and lateral heterojunctions. The electron mobility of the MoS 2 crystals can reach ≈30 cm 2 V -1 s -1 , which is comparable to those of exfoliated flakes.
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Polymer-dispersed liquid crystal elastomers
NASA Astrophysics Data System (ADS)
Rešetič, Andraž; Milavec, Jerneja; Zupančič, Blaž; Domenici, Valentina; Zalar, Boštjan
2016-10-01
The need for mechanical manipulation during the curing of conventional liquid crystal elastomers diminishes their applicability in the field of shape-programmable soft materials and future applications in additive manufacturing. Here we report on polymer-dispersed liquid crystal elastomers, novel composite materials that eliminate this difficulty. Their thermal shape memory anisotropy is imprinted by curing in external magnetic field, providing for conventional moulding of macroscopically sized soft, thermomechanically active elastic objects of general shapes. The binary soft-soft composition of isotropic elastomer matrix, filled with freeze-fracture-fabricated, oriented liquid crystal elastomer microparticles as colloidal inclusions, allows for fine-tuning of thermal morphing behaviour. This is accomplished by adjusting the concentration, spatial distribution and orientation of microparticles or using blends of microparticles with different thermomechanical characteristics. We demonstrate that any Gaussian thermomechanical deformation mode (bend, cup, saddle, left and right twist) of a planar sample, as well as beat-like actuation, is attainable with bilayer microparticle configurations.
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NASA Astrophysics Data System (ADS)
Koshiro, Yoko; Watanabe, Manabu; Takai, Rikuo; Hagiwara, Tomoaki; Suzuki, Toru
Size and shape of ice crystals in frozen food materials are very important because they affect not only quality of foods but also the viability of industrial processing such as freeze-drying of concentration. In this study, 30%wt sucrose solution is used as test samples. For examining the effect of stabilizerspectine and xantan gum is added to the sucrose solution. They are frozen on the cold stage of microscope to be observed their growing ice crystals under the circumstance of -10°C. Their size and shape are measured and quantitatively evaluated by applying fractal analysis. lce crystal of complicated shape has large fractal dimension, and vice versa. It successflly categorized the ice crystals into two groups; one is a group of large size and complicated shape, and the other is a group of small size and plain shape. The critical crystal size between the two groups is found to become larger with increasing holding time. It suggests a phenomenological model for metamorphoses process of ice crystals. Further, it is indicated that xantan gum is able to suppress the smoothing of ice crystals.
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Theory of the intermediate stage of crystal growth with applications to insulin crystallization
NASA Astrophysics Data System (ADS)
Barlow, D. A.
2017-07-01
A theory for the intermediate stage of crystal growth, where two defining equations one for population continuity and another for mass-balance, is used to study the kinetics of the supersaturation decay, the homogeneous nucleation rate, the linear growth rate and the final distribution of crystal sizes for the crystallization of bovine and porcine insulin from solution. The cited experimental reports suggest that the crystal linear growth rate is directly proportional to the square of the insulin concentration in solution for bovine insulin and to the cube of concentration for porcine. In a previous work, it was shown that the above mentioned system could be solved for the case where the growth rate is directly proportional to the normalized supersaturation. Here a more general solution is presented valid for cases where the growth rate is directly proportional to the normalized supersaturation raised to the power of any positive integer. The resulting expressions for the time dependent normalized supersaturation and crystal size distribution are compared with experimental reports for insulin crystallization. An approximation for the maximum crystal size at the end of the intermediate stage is derived. The results suggest that the largest crystal size in the distribution at the end of the intermediate stage is maximized when nucleation is restricted to be only homogeneous. Further, the largest size in the final distribution depends only weakly upon the initial supersaturation.
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NASA Astrophysics Data System (ADS)
Ma, Zhenye; Li, Cheng; Wu, Rujun; Chen, Rizhi; Gu, Zhenggui
2009-10-01
In this paper, a novel ceramic membrane anti-solvent crystallization (CMASC) method was proposed for the safe and rapid preparation ammonium perchlorate (AP) crystals, in which the acetone and ethyl acetate were chosen as solvent and anti-solvent, respectively. Comparing with the conventional liquid anti-solvent crystallization (LASC), CMASC which successfully introduces ceramic membrane with regular pore structure to the LASC as feeding medium, is favorable to control the rate of feeding rate and, therefore, to obtain size and morphology controllable AP. Several kinds of micro-sized AP particles with different morphology were obtained including polyhedral-like, quadrate-like to rod-like. The effect of processing parameters on the crystal size and shape of AP crystals such as volume ratio of anti-solvent to solvent, feeding pressure and crystallization temperature were investigated. It is found that higher volume ratio of anti-solvent to solvent, higher feeding pressure and higher temperature result in smaller particle size. Scaning electron microscopy (SEM) and X-ray diffraction (XRD) were used to characterize the resulting AP crystals. The nucleation and growth kinetic of the resulting AP crystals were also discussed.
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Synthesis, characterization, and ion-exchange properties of colloidal zeolite nanocrystals
NASA Astrophysics Data System (ADS)
Jawor, Anna; Jeong, Byeong-Heon; Hoek, Eric M. V.
2009-10-01
Here, we present physical-chemical properties of Linde type A (LTA) zeolite crystals synthesized via conventional hydrothermal and microwave heating methods. Both heating methods produced LTA crystals that were sub-micron in size, highly negatively charged, super-hydrophilic, and stable when dispersed in water. However, microwave heating produced relatively narrow crystal size distributions, required much shorter heating times, and did not significantly change composition, crystallinity, or surface chemistry. Moreover, microwave heating allowed systematic variation of crystal size by varying heating temperature and time during the crystallization reaction, thus producing a continuous gradient of crystal sizes ranging from about 90 to 300 nm. In ion-exchange studies, colloidal zeolites exhibited excellent sorption kinetics and capacity for divalent metal ions, suggesting their potential for use in water softening, scale inhibition, and scavenging of toxic metal ions from water.
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NASA Technical Reports Server (NTRS)
Judge, Russell A.; Snell, Edward H.
1999-01-01
Part of the challenge of macromolecular crystal growth for structure determination is obtaining an appropriate number of crystals with a crystal volume suitable for X-ray analysis. In this respect an understanding of the effect of solution conditions on macromolecule nucleation rates is advantageous. This study investigated the effects of solution conditions on the nucleation rate and final crystal size of two crystal systems; tetragonal lysozyme and glucose isomerase. Batch crystallization plates were prepared at given solution concentration and incubated at set temperatures over one week. The number of crystals per well with their size and axial ratios were recorded and correlated with solution conditions. Duplicate experiments indicate the reproducibility of the technique. Results for each system showing the effect of supersaturation, incubation temperature and solution pH on nucleation rates will be presented and discussed. In the case of lysozyme, having optimized solution conditions to produce an appropriate number of crystals of a suitable size, a batch of crystals were prepared under exactly the same conditions. Fifty of these crystals were analyzed by x-ray techniques. The results indicate that even under the same crystallization conditions, a marked variation in crystal properties exists.
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New developments on size-dependent growth applied to the crystallization of sucrose
NASA Astrophysics Data System (ADS)
Martins, P. M.; Rocha, F.
2007-12-01
The effect of crystal size on the growth rate of sucrose (C 12H 22O 11) at 40 °C is investigated from a theoretical and an experimental point of view. Based on new perspectives resulting from the recently introduced spiral nucleation model [P.M. Martins, F. Rocha, Surf. Sci. 601 (2007) 3400], crystal growth rates are expressed in terms of mass deposition per time and crystal volume units. This alternative definition is demonstrated to be size-independent over the considered supersaturation range. The conventional overall growth rate expressed per surface area units is found to be linearly dependent on crystal size. The advantages of the "volumetric" growth rate concept are discussed. Sucrose dissolution rates were measured under reciprocal conditions of the growth experiments in order to investigate the two-way effect of crystal size on mass transfer rates and on the integration kinetics. Both effects are adequately described by combining a well-established diffusion-integration model and the spiral nucleation mechanism.
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Characteristics of nanolite crystallization in volcanic pyroclasts
NASA Astrophysics Data System (ADS)
Mujin, M.; Nakamura, M.; Miyake, A.
2017-12-01
Crystal nucleation and initial growth in silicate melt may control the number density and later stage growth of crystals, such as twinning and morphology, and are therefore fundamental but still poorly understood processes in magma crystallization. Petrographic and experimental studies on groundmass microlites shed light on their importance for understanding eruption dynamics, but most studies did not focus on nanometer scale crystals. Recently, we reported "nanolites (30 nm-1 µm in width)" and "ultrananolites (< 30 nm in diameter)", which are nanoscale crystals with extremely high number density, in the interstices of microlites in pyroclasts. In this presentation, we summarize their mineralogical and petrological characteristics in pyroclasts of the 2011 eruption of Shinmoedake (Kirishima volcano group)1. By covering a wide size-range of crystals (down to 1 nm in diameter) based on scanning electron microscopy with tungsten filament (W-SEM), field emission (FE)-SEM, and transmission electron microscopy (TEM), we found a clear size gap (hiatus) in the size distribution and presence of minimum crystal size. In a dense juvenile fragment, crystals were absent or their number densities were too low to measure the sizes of pyroxene with a diameter of < 20 nm and a width of 30-100 nm, plagioclase with a width of < 100 nm, and Fe-Ti oxide with a diameter of 2-10 nm and a width of 20-100 nm. In pumice clasts, crystals smaller than 100 nm were not found. These observations show that nucleation of nanoscale crystals almost paused (froze) in the late stage of crystallization, possibly due to a decrease in undercooling, increase in interfacial free energy, and decrease in diffusivity in a dehydrated melt, whereas crystal growth was mostly continuous. Ultrananolites were found in pyroxene and Fe-Ti oxide; notably, these were spherical, whereas nanolites and microlites were rectangular. The observed ultrananolite-sized particles might partly include "subcritical clusters", which are particles smaller than the critical nucleation size assumed in the transient nucleation models. References 1) Mujin and Nakamura, 2014, Geology, v.42, p.611-614, and Mujin et al, in revision, Am. Min.
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A flow-free droplet-based device for high throughput polymorphic crystallization.
Yang, Shih-Mo; Zhang, Dapeng; Chen, Wang; Chen, Shih-Chi
2015-06-21
Crystallization is one of the most crucial steps in the process of pharmaceutical formulation. In recent years, emulsion-based platforms have been developed and broadly adopted to generate high quality products. However, these conventional approaches such as stirring are still limited in several aspects, e.g., unstable crystallization conditions and broad size distribution; besides, only simple crystal forms can be produced. In this paper, we present a new flow-free droplet-based formation process for producing highly controlled crystallization with two examples: (1) NaCl crystallization reveals the ability to package saturated solution into nanoliter droplets, and (2) glycine crystallization demonstrates the ability to produce polymorphic crystallization forms by controlling the droplet size and temperature. In our process, the saturated solution automatically fills the microwell array powered by degassed bulk PDMS. A critical oil covering step is then introduced to isolate the saturated solution and control the water dissolution rate. Utilizing surface tension, the solution is uniformly packaged in the form of thousands of isolating droplets at the bottom of each microwell of 50-300 μm diameter. After water dissolution, individual crystal structures are automatically formed inside the microwell array. This approach facilitates the study of different glycine growth processes: α-form generated inside the droplets and γ-form generated at the edge of the droplets. With precise temperature control over nanoliter-sized droplets, the growth of ellipsoidal crystalline agglomerates of glycine was achieved for the first time. Optical and SEM images illustrate that the ellipsoidal agglomerates consist of 2-5 μm glycine clusters with inner spiral structures of ~35 μm screw pitch. Lastly, the size distribution of spherical crystalline agglomerates (SAs) produced from microwells of different sizes was measured to have a coefficient variation (CV) of less than 5%, showing crystal sizes can be precisely controlled by microwell sizes with high uniformity. This new method can be used to reliably fabricate monodispersed crystals for pharmaceutical applications.
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NASA Astrophysics Data System (ADS)
Jang, Jisun; Kim, Il Won
2016-01-01
Polymeric additives to induce competitive crystallization of pharmaceutical compounds were explored. A cocrystal of theophylline and oxalic acid was used as a model system, and poly(acrylic acid), poly(caprolactone), and poly(ethylene glycol) were the additives. The cocrystal formation was selectively hindered with addition of poly(acrylic acid). First the size of the cocrystals were reduced, and eventually the cocrystallization was inhibited to generate neat theophylline crystals. The theophylline crystals were of a distinctively different crystal structure from known polymorphs, based on powder X-ray diffraction. They were also obtained in nanoscale size, when millimeter-scale crystals formed without poly(acrylic acid). Polymeric additives that could form specific interactions with crystallizing compounds seem to be useful tools for the phase and size control of pharmaceutical crystals.
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Single crystal growth of Ga3Ni2 by the Czochralski method
NASA Astrophysics Data System (ADS)
Wencka, Magdalena; Pillaca, Mirtha; Gille, Peter
2016-09-01
Intermetallic compounds have proved to be interesting alternatives to heterogeneous catalysts prepared from pure noble metals or their alloys. As to study their intrinsic properties, to determine the crystalline structures of specific surfaces and finally to understand elementary processes of heterogeneous catalysis, single crystals of these intermetallics are needed. Inspired by the recent discovery of Ga-Ni catalysts for carbon dioxide reduction to methanol, we have grown for the first time cm3-size single crystals of trigonal Ga3Ni2. We report in detail on the synthesis and Czochralski growth from high-temperature solution using Ga as native solvent. Inclusion formation of Ga-rich fluid proved to be the most severe problem that was minimized by using an extremely low pulling rate down to 25 μm/h.
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Diamond Lattice Colloidal Crystals from Binary DNA-grafted Microspheres
NASA Astrophysics Data System (ADS)
Crocker, John; Wang, Yifan; Jenkins, Ian; McGinley, James; Sinno, Talid
Future optical materials promise to do for photonics what semiconductors did for electronics, but the challenge has long been in creating the structure they require regular, three-dimensional array of transparent microspheres arranged like the atoms in a diamond crystal. Here we demonstrate a simple approach for spontaneously growing double-diamond (or B32) crystals from a binary suspension of sub-micron polymer microspheres with synthetic DNA grafted to their surfaces. While diamond symmetry crystals have previously been grown from much smaller nanoparticles, none of those methods appear workable for the larger particles needed for photonic applications, whose size must be comparable to the wavelength of visible light. Intriguingly, matched simulations fail to nucleate or grow B32 crystals from suspension; nor have they been predicted on the basis of theoretical arguments. We conjecture that the B32 crystals may form via transformation from a precursor with a different lattice structure in the bulk or on its surface. The feasibility of converting our self-assembled crystals into diamond-symmetry photonic templates will be discussed. This finding suggests that still other unexpected microstructures may be accessible using this approach. US National Science Foundation, CBET- 1403237.
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Fully automatic characterization and data collection from crystals of biological macromolecules
DOE Office of Scientific and Technical Information (OSTI.GOV)
Svensson, Olof; Malbet-Monaco, Stéphanie; Popov, Alexander
A fully automatic system has been developed that performs X-ray centring and characterization of, and data collection from, large numbers of cryocooled crystals without human intervention. Considerable effort is dedicated to evaluating macromolecular crystals at synchrotron sources, even for well established and robust systems. Much of this work is repetitive, and the time spent could be better invested in the interpretation of the results. In order to decrease the need for manual intervention in the most repetitive steps of structural biology projects, initial screening and data collection, a fully automatic system has been developed to mount, locate, centre to themore » optimal diffraction volume, characterize and, if possible, collect data from multiple cryocooled crystals. Using the capabilities of pixel-array detectors, the system is as fast as a human operator, taking an average of 6 min per sample depending on the sample size and the level of characterization required. Using a fast X-ray-based routine, samples are located and centred systematically at the position of highest diffraction signal and important parameters for sample characterization, such as flux, beam size and crystal volume, are automatically taken into account, ensuring the calculation of optimal data-collection strategies. The system is now in operation at the new ESRF beamline MASSIF-1 and has been used by both industrial and academic users for many different sample types, including crystals of less than 20 µm in the smallest dimension. To date, over 8000 samples have been evaluated on MASSIF-1 without any human intervention.« less
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Growing Larger Crystals for Neutron Diffraction
NASA Technical Reports Server (NTRS)
Pusey, Marc
2003-01-01
Obtaining crystals of suitable size and high quality has been a major bottleneck in macromolecular crystallography. With the advent of advanced X-ray sources and methods the question of size has rapidly dwindled, almost to the point where if one can see the crystal then it was big enough. Quality is another issue, and major national and commercial efforts were established to take advantage of the microgravity environment in an effort to obtain higher quality crystals. Studies of the macromolecule crystallization process were carried out in many labs in an effort to understand what affected the resultant crystal quality on Earth, and how microgravity improved the process. While technological improvements are resulting in a diminishing of the minimum crystal size required, neutron diffraction structural studies still require considerably larger crystals, by several orders of magnitude, than X-ray studies. From a crystal growth physics perspective there is no reason why these 'large' crystals cannot be obtained: the question is generally more one of supply than limitations mechanism. This talk will discuss our laboratory s current model for macromolecule crystal growth, with highlights pertaining to the growth of crystals suitable for neutron diffraction studies.
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Study on the temperature field of large-sized sapphire single crystal furnace
NASA Astrophysics Data System (ADS)
Zhai, J. P.; Jiang, J. W.; Liu, K. G.; Peng, X. B.; Jian, D. L.; Li, I. L.
2018-01-01
In this paper, the temperature field of large-sized (120kg, 200kg and 300kg grade) sapphire single crystal furnace was simulated. By keeping the crucible diameter ratio and the insulation system unchanged, the power consumption, axial and radial temperature gradient, solid-liquid surface shape, stress distribution and melt flow were studied. The simulation results showed that with the increase of the single crystal furnace size, the power consumption increased, the temperature field insulation effect became worse, the growth stress value increased and the stress concentration phenomenon occurred. To solve these problems, the middle and bottom insulation system should be enhanced during designing the large-sized sapphire single crystal furnace. The appropriate radial and axial temperature gradient was favorable to reduce the crystal stress and prevent the occurrence of cracking. Expanding the interface between the seed and crystal was propitious to avoid the stress accumulation phenomenon.
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Effect of hydrazine based deproteination protocol on bone mineral crystal structure.
Karampas, I A; Orkoula, M G; Kontoyannis, C G
2012-05-01
In several bone deproteination protocols the chemical agent used for protein cleavage is hydrazine. The effect of hydrazine deproteination method on the crystal size and crystallinity of the bone mineral was studied. Bovine bones were subjected to this protocol and the crystal size and crystallinity of the remaining bone mineral were determined by X-ray Diffraction (XRD), by measuring the width at the half of the maximum intensity of the (002) reflection. It was found that hydrazine deproteination induces noteworthy increase of crystal size and crystallinity. The effect was enhanced by increasing hydrazine temperature from 25 to 55°C. Furthermore, infrared spectroscopy revealed that hydrazine facilitates the removal of carbonate and acid phosphate ions from bone mineral. It is proposed that the mechanism of modification of crystal size and crystallinity lies on the removal of these ions thus, resulting in crystal re-organization.
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Radiopaque Strontium Fluoroapatite Glass-Ceramics.
Höland, Wolfram; Schweiger, Marcel; Dittmer, Marc; Ritzberger, Christian
2015-01-01
The controlled precipitation of strontium fluoroapatite crystals was studied in four base glass compositions derived from the SiO2-Al2O3-Y2O3-SrO-Na2O-K2O/Rb2O/Cs2O-P2O5-F system. The crystal phase formation of these glasses and the main properties of the glass-ceramics, such as thermal and optical properties and radiopacity were compared with a fifth, a reference glass-ceramic. The reference glass-ceramic was characterized as Ca-fluoroapatite glass-ceramic. The four strontium fluoroapatite glass-ceramics showed the following crystal phases: (a) Sr5(PO4)3F - leucite, KAlSi2O6, (b) Sr5(PO4)3F - leucite, KAlSi2O6, and nano-sized NaSrPO4, (c) Sr5(PO4)3F - pollucite, CsAlSi2O6, and nano-sized NaSrPO4, and (d) Sr5(PO4)3F - Rb-leucite, RbAlSi2O6, and nano-sized NaSrPO4. The proof of crystal phase formation was possible by X-ray diffraction. The microstructures, which were studied using scanning electron microscopy, demonstrated a uniform distribution of the crystals in the glass matrix. The Sr-fluoroapatites were precipitated based on an internal crystallization process, and the crystals demonstrated a needle-like morphology. The study of the crystal growth of needle-like Sr-fluoroapatites gave a clear evidence of an Ostwald ripening mechanism. The formation of leucite, pollucite, and Rb-leucite was based on a surface crystallization mechanism. Therefore, a twofold crystallization mechanism was successfully applied to develop these types of glass-ceramics. The main focus of this study was the controlled development of glass-ceramics exhibiting high radiopacity in comparison to the reference glass-ceramic. This goal could be achieved with all four glass-ceramics with the preferred development of the Sr-fluoroapatite - pollucite-type glass-ceramic. In addition to this main development, it was possible to control the thermal properties. Especially the Rb-leucite containing glass-ceramic showed the highest coefficient of thermal expansion (CTE). These glass-ceramics allow optical properties, especially the translucency and color, to be tailored to the needs of biomaterials for dental applications. The authors conclude that it is possible to use twofold crystallization processes to develop glass-ceramic biomaterials featuring different properties, such as specific radiopacity values, CTEs, and optical characteristics.
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Radiopaque Strontium Fluoroapatite Glass-Ceramics
Höland, Wolfram; Schweiger, Marcel; Dittmer, Marc; Ritzberger, Christian
2015-01-01
The controlled precipitation of strontium fluoroapatite crystals was studied in four base glass compositions derived from the SiO2–Al2O3–Y2O3–SrO–Na2O–K2O/Rb2O/Cs2O–P2O5–F system. The crystal phase formation of these glasses and the main properties of the glass-ceramics, such as thermal and optical properties and radiopacity were compared with a fifth, a reference glass-ceramic. The reference glass-ceramic was characterized as Ca-fluoroapatite glass-ceramic. The four strontium fluoroapatite glass-ceramics showed the following crystal phases: (a) Sr5(PO4)3F – leucite, KAlSi2O6, (b) Sr5(PO4)3F – leucite, KAlSi2O6, and nano-sized NaSrPO4, (c) Sr5(PO4)3F – pollucite, CsAlSi2O6, and nano-sized NaSrPO4, and (d) Sr5(PO4)3F – Rb-leucite, RbAlSi2O6, and nano-sized NaSrPO4. The proof of crystal phase formation was possible by X-ray diffraction. The microstructures, which were studied using scanning electron microscopy, demonstrated a uniform distribution of the crystals in the glass matrix. The Sr-fluoroapatites were precipitated based on an internal crystallization process, and the crystals demonstrated a needle-like morphology. The study of the crystal growth of needle-like Sr-fluoroapatites gave a clear evidence of an Ostwald ripening mechanism. The formation of leucite, pollucite, and Rb-leucite was based on a surface crystallization mechanism. Therefore, a twofold crystallization mechanism was successfully applied to develop these types of glass-ceramics. The main focus of this study was the controlled development of glass-ceramics exhibiting high radiopacity in comparison to the reference glass-ceramic. This goal could be achieved with all four glass-ceramics with the preferred development of the Sr-fluoroapatite – pollucite-type glass-ceramic. In addition to this main development, it was possible to control the thermal properties. Especially the Rb-leucite containing glass-ceramic showed the highest coefficient of thermal expansion (CTE). These glass-ceramics allow optical properties, especially the translucency and color, to be tailored to the needs of biomaterials for dental applications. The authors conclude that it is possible to use twofold crystallization processes to develop glass-ceramic biomaterials featuring different properties, such as specific radiopacity values, CTEs, and optical characteristics. PMID:26528470
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Ni, Xuewen; Ke, Fan; Xiao, Man; Wu, Kao; Kuang, Ying; Corke, Harold; Jiang, Fatang
2016-11-01
Konjac glucomannan (KGM)-based aerogels were prepared using a combination of sol-gel and freeze-drying methods. Preparation conditions were chosen to control ice crystal growth and aerogel structure formation. The ice crystals formed during pre-freezing were observed by low temperature polarizing microscopy, and images of aerogel pores were obtained by scanning electron microscopy. The size of ice crystals were calculated and size distribution maps were drawn, and similarly for aerogel pores. Results showed that ice crystal growth and aerogel pore sizes may be controlled by varying pre-freezing temperatures, KGM concentration and glyceryl monostearate concentration. The impact of pre-freezing temperatures on ice crystal growth was explained as combining ice crystal growth rate with nucleation rate, while the impacts of KGM and glyceryl monostearate concentration on ice crystal growth were interpreted based on their influences on sol network structure. Copyright © 2016 Elsevier B.V. All rights reserved.
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Modeling TiO2's refractive index function from bulk to nanoparticles
NASA Astrophysics Data System (ADS)
Jalava, Juho-Pertti; Taavitsainen, Veli-Matti; Lamminmäki, Ralf-Johan; Lindholm, Minna; Auvinen, Sami; Alatalo, Matti; Vartiainen, Erik; Haario, Heikki
2015-12-01
In recent decades, the use of nanomaterials has become very common. Different nanomaterials are being used in over 1600 consumer products. Nanomaterials have been defined as having at least one dimension in the range of 1-100 nm. Such materials often have unique properties. Despite some warnings of applying bulk optical constants for nano size materials, stated already in 1980s, bulk constants are still commonly used in the light scattering measurements of nano size particles. Titanium dioxide is one of the materials that is manufactured and used as an engineered nanomaterial in increasing quantities. Due to the aforementioned facts, it is quite crucial for successful research and production of nanoparticles to find out the dependence of the refractive index function (RIF) of the material on its crystal size. We have earlier performed several ab initio computations for obtaining the dependence of the RIF of TiO2 on the crystal or on the cluster size, for particles of size up to ca. 2 nm. Extending the calculations to greater sizes has turned out to be infeasible due to the unbearable increase in computational time. However, in this study we show how the crystal-size-dependent-RIF (CS-RIF), for both rutile and anatase can be modeled from measured extinction or turbidity spectra of samples with varying crystal and particle sizes. For computing the turbidity spectrum, we constructed a model including primary crystals whose distributions were parameterized by mean and standard deviation, and also including aggregates consisting of mean sized primary particles, parameterized just by mean aggregate size. Mainly because of the long computing times Mie calculation was used in the computation of extinction spectra. However, in practical process applications, the obtained RIF will be used together with the T-matrix method. We constructed the RIFs used in the model using generalized oscillator model (GOM) as expanded to crystal size dependence. The unknown parameters of the model were solved using nonlinear least squares estimation. When the crystal size becomes smaller than the bulk size the shape of the estimated CS-RIFs reveal two distinct regions for both rutile and anatase. In the first region, starting apparently already from ca. 200 nm, the height of both the real part and the imaginary part of CS-RIF decreases on crystal diameter. However, the band gap remains constant. In the second region, starting when the crystal diameter is decreased to ca. 3 nm, a blue shift starts to increase the band gap. The band gap dependence on crystal size is quite consistent with the existing experimental values. Consequently, it is of great importance to use CS-RIF in light scattering measurements for nanoparticle size determination. Neglecting this, the smaller particles in the size distribution will have too small values, already for sub-micrometer particles, naturally distorting also the mean value. To our knowledge, this is the first time ever that a CS-RIF from bulk to 1 nm size is determined for any material.
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An overview of inverted colloidal crystal systems for tissue engineering.
João, Carlos Filipe C; Vasconcelos, Joana Marta; Silva, Jorge Carvalho; Borges, João Paulo
2014-10-01
Scaffolding is at the heart of tissue engineering but the number of techniques available for turning biomaterials into scaffolds displaying the features required for a tissue engineering application is somewhat limited. Inverted colloidal crystals (ICCs) are inverse replicas of an ordered array of monodisperse colloidal particles, which organize themselves in packed long-range crystals. The literature on ICC systems has grown enormously in the past 20 years, driven by the need to find organized macroporous structures. Although replicating the structure of packed colloidal crystals (CCs) into solid structures has produced a wide range of advanced materials (e.g., photonic crystals, catalysts, and membranes) only in recent years have ICCs been evaluated as devices for medical/pharmaceutical and tissue engineering applications. The geometry, size, pore density, and interconnectivity are features of the scaffold that strongly affect the cell environment with consequences on cell adhesion, proliferation, and differentiation. ICC scaffolds are highly geometrically ordered structures with increased porosity and connectivity, which enhances oxygen and nutrient diffusion, providing optimum cellular development. In comparison to other types of scaffolds, ICCs have three major unique features: the isotropic three-dimensional environment, comprising highly uniform and size-controllable pores, and the presence of windows connecting adjacent pores. Thus far, this is the only technique that guarantees these features with a long-range order, between a few nanometers and thousands of micrometers. In this review, we present the current development status of ICC scaffolds for tissue engineering applications.
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Finite-size Scaling of the Density of States in Photonic Band Gap Crystals
NASA Astrophysics Data System (ADS)
Hasan, Shakeeb Bin; Mosk, Allard P.; Vos, Willem L.; Lagendijk, Ad
2018-06-01
The famous vanishing of the density of states (DOS) in a band gap, be it photonic or electronic, pertains to the infinite-crystal limit. In contrast, all experiments and device applications refer to finite crystals, which raises the question: Upon increasing the linear size L of a crystal, how fast does the DOS approach the infinite-crystal limit? We present a theory for finite crystals that includes Bloch-mode broadening due to the presence of crystal boundaries. Our results demonstrate that the DOS for frequencies inside a band gap has a 1 /L scale dependence for crystals in one, two and three dimensions.
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Kimura, Keisaku; Sato, Seiichi
2014-05-01
A conventional laser microscope can be used to derive the index of refractivity by the ratio of geometrical height of the transparent platelet to the apparent height of the normal incident light for very small crystals in the wide size range. We demonstrate that the simple method is effective for the samples from 100 μm to 16 μm in size using alkali halide crystals as a model system. The method is also applied for the surface fractured micro-crystals and an inclined crystal with microscopic size regime. Furthermore, we present two-dimensional refractive index mapping as well as two-dimensional height profile for the mixture of three alkali halides, KCl, KI, and NaCl, all are μm in size.
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Abendroth, Jan; McCormick, Michael S.; Edwards, Thomas E.; Staker, Bart; Loewen, Roderick; Gifford, Martin; Rifkin, Jeff; Mayer, Chad; Guo, Wenjin; Zhang, Yang; Myler, Peter; Kelley, Angela; Analau, Erwin; Hewitt, Stephen Nakazawa; Napuli, Alberto J.; Kuhn, Peter; Ruth, Ronald D.; Stewart, Lance J.
2010-01-01
Structural genomics discovery projects require ready access to both X-ray and NMR instrumentation which support the collection of experimental data needed to solve large numbers of novel protein structures. The most productive X-ray crystal structure determination laboratories make extensive frequent use of tunable synchrotron X-ray light to solve novel structures by anomalous diffraction methods. This requires that frozen cryo-protected crystals be shipped to large government-run synchrotron facilities for data collection. In an effort to eliminate the need to ship crystals for data collection, we have developed the first laboratory-scale synchrotron light source capable of performing many of the state-of-the-art synchrotron applications in X-ray science. This Compact Light Source is a first-in-class device that uses inverse Compton scattering to generate X-rays of sufficient flux, tunable wavelength and beam size to allow high-resolution X-ray diffraction data collection from protein crystals. We report on benchmarking tests of X-ray diffraction data collection with hen egg white lysozyme, and the successful high-resolution X-ray structure determination of the Glycine cleavage system protein H from Mycobacterium tuberculosis using diffraction data collected with the Compact Light Source X-ray beam. PMID:20364333
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Multiple electrokinetic actuators for feedback control of colloidal crystal size.
Juárez, Jaime J; Mathai, Pramod P; Liddle, J Alexander; Bevan, Michael A
2012-10-21
We report a feedback control method to precisely target the number of colloidal particles in quasi-2D ensembles and their subsequent assembly into crystals in a quadrupole electrode. Our approach relies on tracking the number of particles within a quadrupole electrode, which is used in a real-time feedback control algorithm to dynamically actuate competing electrokinetic transport mechanisms. Particles are removed from the quadrupole using DC-field mediated electrophoretic-electroosmotic transport, while high-frequency AC-field mediated dielectrophoretic transport is used to concentrate and assemble colloidal crystals. Our results show successful control of the size of crystals containing 20 to 250 colloidal particles with less than 10% error. Assembled crystals are characterized by their radius of gyration, crystallinity, and number of edge particles, and demonstrate the expected size-dependent properties. Our findings demonstrate successful ensemble feedback control of the assembly of different sized colloidal crystals using multiple actuators, which has broad implications for control over nano- and micro- scale assembly processes involving colloidal components.
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Snow Crystal Orientation Effects on the Scattering of Passive Microwave Radiation
NASA Technical Reports Server (NTRS)
Foster, J. L.; Barton, J. S.; Chang, A. T. C.; Hall, D. K.
1999-01-01
For this study, consideration is given to the role crystal orientation plays in scattering and absorbing microwave radiation. A discrete dipole scattering model is used to measure the passive microwave radiation, at two polarizations (horizontal and vertical), scattered by snow crystals oriented in random and non random positions, having various sizes (ranging between 1 micrometers to 10,000 micrometers in radius), and shapes (including spheroids, cylinders, hexagons). The model results demonstrate that for the crystal sizes typically found in a snowpack, crystal orientation is insignificant compared to crystal size in terms of scattering microwave energy in the 8,100 gm (37 GHz) region of the spectrum. Therefore, the assumption used in radiative transfer approaches, where snow crystals are modeled as randomly oriented spheres, is adequate to account for the transfer of microwave energy emanating from the ground and passing through a snowpack.
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Temperature and saturation dependence in the vapor sensing of butterfly wing scales.
Kertész, K; Piszter, G; Jakab, E; Bálint, Zs; Vértesy, Z; Biró, L P
2014-06-01
The sensing of gasses/vapors in the ambient air is the focus of attention due to the need to monitor our everyday environment. Photonic crystals are sensing materials of the future because of their strong light-manipulating properties. Natural photonic structures are well-suited materials for testing detection principles because they are significantly cheaper than artificial photonic structures and are available in larger sizes. Additionally, natural photonic structures may provide new ideas for developing novel artificial photonic nanoarchitectures with improved properties. In the present paper, we discuss the effects arising from the sensor temperature and the vapor concentration in air during measurements with a photonic crystal-type optical gas sensor. Our results shed light on the sources of discrepancy between simulated and experimental sensing behaviors of photonic crystal-type structures. Through capillary condensation, the vapors will condensate to a liquid state inside the nanocavities. Due to the temperature and radius of curvature dependence of capillary condensation, the measured signals are affected by the sensor temperature as well as by the presence of a nanocavity size distribution. The sensing materials used are natural photonic nanoarchitectures present in the wing scales of blue butterflies. Copyright © 2014 Elsevier B.V. All rights reserved.
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Kevorkyants, Ruslan; Wang, Xiqiao; Close, David M; Pavanello, Michele
2013-11-14
We present an application of the linear scaling frozen density embedding (FDE) formulation of subsystem DFT to the calculation of isotropic hyperfine coupling constants (hfcc's) of atoms belonging to a guanine radical cation embedded in a guanine hydrochloride monohydrate crystal. The model systems range from an isolated guanine to a 15,000 atom QM/MM cluster where the QM region is comprised of 36 protonated guanine cations, 36 chlorine anions, and 42 water molecules. Our calculations show that the embedding effects of the surrounding crystal cannot be reproduced by small model systems nor by a pure QM/MM procedure. Instead, a large QM region is needed to fully capture the complicated nature of the embedding effects in this system. The unprecedented system size for a relativistic all-electron isotropic hfcc calculation can be approached in this work because the local nature of the electronic structure of the organic crystals considered is fully captured by the FDE approach.
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cm-scale variations of crystal orientation fabric in cold Alpine ice core from Colle Gnifetti
NASA Astrophysics Data System (ADS)
Kerch, Johanna; Weikusat, Ilka; Eisen, Olaf; Wagenbach, Dietmar; Erhardt, Tobias
2015-04-01
Analysis of the microstructural parameters of ice has been an important part of ice core analyses so far mainly in polar cores in order to obtain information about physical processes (e.g. deformation, recrystallisation) on the micro- and macro-scale within an ice body. More recently the influence of impurities and climatic conditions during snow accumulation on these processes has come into focus. A deeper understanding of how palaeoclimate proxies interact with physical properties of the ice matrix bears relevance for palaeoclimatic interpretations, improved geophysical measurement techniques and the furthering of ice dynamical modeling. Variations in microstructural parameters e.g. crystal orientation fabric or grain size can be observed on a scale of hundreds and tens of metres but also on a centimetre scale. The underlying processes are not necessarily the same on all scales. Especially for the short-scale variations many questions remain unanswered. We present results from a study that aims to investigate following hypotheses: 1. Variations in grain size and fabric, i.e. strong changes of the orientation of ice crystals with respect to the vertical, occur on a centimetre scale and can be observed in all depths of an ice core. 2. Palaeoclimate proxies like dust and impurities have an impact on the microstructural processes and thus are inducing the observed short-scale variations in grain size and fabric. 3. The interaction of proxies with the ice matrix leads to depth intervals that show correlating behaviour as well as ranges with anticorrelation between microstructural parameters and palaeoclimatic proxies. The respective processes need to be identified. Fabric Analyser measurements were conducted on more than 80 samples (total of 8 m) from different depth ranges of a cold Alpine ice core (72 m length) drilled in 2013 at Colle Gnifetti, Switzerland/Italy. Results were obtained by automatic image processing, providing estimates for grain size distributions and crystal orientation fabric, and comparison with data from continuous flow analysis of chemical impurities. A microstructural characterisation of the analysed core is presented with emphasis on the observed variations in crystal orientation fabric. The relevance of these results for palaeoclimate reconstruction and geophysical applications in ice are discussed.
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Pb1-xMnxTe Crystals as a New Thermoelectric Material
NASA Astrophysics Data System (ADS)
Osinniy, V.; Jędrzejczak, A.; Domuchowski, W.; Dybko, K.; Witkowska, B.; Story, T.
2006-11-01
We studied experimentally thermoelectric properties of p-type bulk crystals of Pb1-xMnxTe and Pb1-x-yAgyMnxTe (0≤ x≤ 0.083 and y≤0.017) at room and liquid nitrogen temperatures. Model calculations of the thermoelectric figure of merit parameter (Z) involved the analysis of carrier concentration, carrier mobility, density of states as well as electronic and lattice contributions to the thermal conductivity of PbMnTe. In the analysis we took into account the main effect of Mn concentration on the band structure parameters of PbMnTe, i.e. the increase of the energy gap. The analysis of electrical, thermoelectric, and thermal properties of Pb1-xMnxTe crystals showed that, at room temperature, the maximum values of the parameter Z occur in crystals with Mn content 0.05≤ x≤0.07 and are comparable with a maximal value of Z observed in PbTe. At T=400 K the increase in the parameter Z by 10% is expected in Pb1-xMnxTe crystal (as compared to PbTe) for a very high concentration of holes of about p=5×1019 cm-3. The experimental data correctly reproduce the theoretical Z(p) dependence.
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Protein crystallization aboard the Space Shuttle and the Mir space station
NASA Technical Reports Server (NTRS)
Delbaere, Louis T. J.; Vandonselaar, Margaret; Prasad, Lata; Quail, J. W.; Birnbaum, George I.; Delucas, Lawrence J.; Moore, Karen; Bugg, Charles E.
1993-01-01
Two different protein crystallizations, namely ,the free Fab fragment of the Je142 monoclonal antibody and the complex of Fab fragment/HPr with antigen, were performed aboard the Discovery Space Shuttle flights and the Mir space station, respectively. Medium sized crystals of the Je142 Fab fragment were obtained. The Je142 Fab fragment/Hpr complex produced two medium-sized crystals after two months aboard the Mir space station. Microgravity was found to eliminate the tendency of these crystals to form clusters.
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NASA Astrophysics Data System (ADS)
Çakal, G. Ö.; Eroğlu, İ.; Özkar, S.
2006-04-01
Colemanite, one of the important boron minerals, is dissolved in aqueous sulfuric acid to produce boric acid. In this reaction, gypsum is obtained as a by-product. Gypsum crystals are in the shape of thin needles. These crystals should be grown to an easily filterable size in order to increase the production yield and purity of boric acid. In this paper, the particle size distributions and the volume-weighted mean diameters of the gypsum crystals obtained in batch and continuous flow systems were compared. Experiments in both batch and continuous reactors were performed at a temperature of 85 °C, a stirring rate of 400 rpm, and the inlet CaO to SO42- molar ratio of 1.0 using colemanite mineral in particle size smaller than 150 μm. The average diameter of the gypsum crystals obtained at 3.5 h from the batch reactor was found to be 37-41 μm. This value for the continuous system at steady state was observed to change between 44-163 μm. The particle size of the gypsum crystals was found to increase with the residence time of the solid in the continuous system.
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Selenium Derivatization of Nucleic Acids for Crystallography
DOE Office of Scientific and Technical Information (OSTI.GOV)
Jiang,J.; Sheng, J.; Carrasco, N.
2007-01-01
The high-resolution structure of the DNA (5'-GTGTACA-C-3') with the selenium derivatization at the 2'-position of T2 was determined via MAD and SAD phasing. The selenium-derivatized structure (1.28 {angstrom} resolution) with the 2'-Se modification in the minor groove is isomorphorous to the native structure (2.0 {angstrom}). To directly compare with the conventional bromine derivatization, we incorporated bromine into the 5-postion of T4, determined the bromine-derivatized DNA structure at 1.5 {angstrom} resolution, and found that the local backbone torsion angles and solvent hydration patterns were altered in the structure with the Br incorporation in the major groove. Furthermore, while the native andmore » Br-derivatized DNAs needed over a week to form reasonable-size crystals, we observed that the Se-derivatized DNAs grew crystals overnight with high-diffraction quality, suggesting that the Se derivatization facilitated the crystal formation. In addition, the Se-derivatized DNA sequences crystallized under a broader range of buffer conditions, and generally had a faster crystal growth rate. Our experimental results indicate that the selenium derivatization of DNAs may facilitate the determination of nucleic acid X-ray crystal structures in phasing and high-quality crystal growth. In addition, our results suggest that the Se derivatization can be an alternative to the conventional Br derivatization.« less
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Current trends in protein crystallization.
Gavira, José A
2016-07-15
Proteins belong to the most complex colloidal system in terms of their physicochemical properties, size and conformational-flexibility. This complexity contributes to their great sensitivity to any external change and dictate the uncertainty of crystallization. The need of 3D models to understand their functionality and interaction mechanisms with other neighbouring (macro)molecules has driven the tremendous effort put into the field of crystallography that has also permeated other fields trying to shed some light into reluctant-to-crystallize proteins. This review is aimed at revising protein crystallization from a regular-laboratory point of view. It is also devoted to highlight the latest developments and achievements to produce, identify and deliver high-quality protein crystals for XFEL, Micro-ED or neutron diffraction. The low likelihood of protein crystallization is rationalized by considering the intrinsic polypeptide nature (folded state, surface charge, etc) followed by a description of the standard crystallization methods (batch, vapour diffusion and counter-diffusion), including high throughput advances. Other methodologies aimed at determining protein features in solution (NMR, SAS, DLS) or to gather structural information from single particles such as Cryo-EM are also discussed. Finally, current approaches showing the convergence of different structural biology techniques and the cross-methodologies adaptation to tackle the most difficult problems, are presented. Current advances in biomacromolecules crystallization, from nano crystals for XFEL and Micro-ED to large crystals for neutron diffraction, are covered with special emphasis in methodologies applicable at laboratory scale. Copyright © 2015 Elsevier Inc. All rights reserved.
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Avramescu, M-L; Rasmussen, P E; Chénier, M; Gardner, H D
2017-01-01
Solubility is a critical component of physicochemical characterisation of engineered nanomaterials (ENMs) and an important parameter in their risk assessments. Standard testing methodologies are needed to estimate the dissolution behaviour and biodurability (half-life) of ENMs in biological fluids. The effect of pH, particle size and crystal form on dissolution behaviour of zinc metal, ZnO and TiO 2 was investigated using a simple 2 h solubility assay at body temperature (37 °C) and two pH conditions (1.5 and 7) to approximately frame the pH range found in human body fluids. Time series dissolution experiments were then conducted to determine rate constants and half-lives. Dissolution characteristics of investigated ENMs were compared with those of their bulk analogues for both pH conditions. Two crystal forms of TiO 2 were considered: anatase and rutile. For all compounds studied, and at both pH conditions, the short solubility assays and the time series experiments consistently showed that biodurability of the bulk analogues was equal to or greater than biodurability of the corresponding nanomaterials. The results showed that particle size and crystal form of inorganic ENMs were important properties that influenced dissolution behaviour and biodurability. All ENMs and bulk analogues displayed significantly higher solubility at low pH than at neutral pH. In the context of classification and read-across approaches, the pH of the dissolution medium was the key parameter. The main implication is that pH and temperature should be specified in solubility testing when evaluating ENM dissolution in human body fluids, even for preliminary (tier 1) screening.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Coughlan, H. D.; Darmanin, C.; Kirkwood, H. J.
2016-03-14
Three-dimensional imaging of protein crystals during X-ray diffraction experiments opens up a range of possibilities for optimising crystal quality and gaining new insights into the fundamental processes that drive radiation damage. Obtaining this information at the appropriate lengthscales however is extremely challenging. One approach that has been recently demonstrated as a promising avenue for charactering the size and shape of protein crystals at nanometre lengthscales is Bragg Coherent Diffractive Imaging (BCDI). BCDI is a recently developed technique that is able to recover the phase of the continuous diffraction intensity signal around individual Bragg peaks. When data is collected at multiplemore » points on a rocking curve a Reciprocal Space Map (RSM) can be assembled and then inverted using BCDI to obtain a three-dimensional image of the crystal. The first demonstration of two-dimensional BCDI of protein crystals was reported by Boutet at al., recently this work was extended to the study of radiation damage of micron-sized crystals. Here we present the first three-dimensional reconstructions of a Lysozyme protein crystal using BDI. The results are validated against RSM and TEM data and have implications for both radiation damage studies and for developing new approaches to structure retrieval from micron-sized protein crystals.« less
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Studies on Aspirin Crystals Generated by a Modified Vapor Diffusion Method.
Mittal, Amit; Malhotra, Deepak; Jain, Preeti; Kalia, Anupama; Shunmugaperumal, Tamilvanan
2016-08-01
The objectives of the current investigation were (1) to study the influence of selected two different non-solvents (diethylether and dichloromethane) on the drug crystal formation of a model drug, aspirin (ASP-I) by the modified vapor diffusion method and (2) to characterize and compare the generated crystals (ASP-II and ASP-III) using different analytical techniques with that of unprocessed ASP-I. When compared to the classical vapor diffusion method which consumes about 15 days to generate drug crystals, the modified method needs only 12 h to get the same. Fourier transform-infrared spectroscopy (FT-IR) reveals that the internal structures of ASP-II and ASP-III crystals were identical when compared with ASP-I. Although the drug crystals showed a close similarity in X-ray diffraction patterns, the difference in the relative intensities of some of the diffraction peaks (especially at 2θ values of around 7.7 and 15.5) could be attributed to the crystal habit or crystal size modification. Similarly, the differential scanning calorimetry (DSC) study speculates that only the crystal habit modifications might occur but without involving any change in internal structure of the generated drug polymorphic form I. This is further substantiated from the scanning electron microscopy (SEM) pictures that indicated the formation of platy shape for the ASP-II crystals and needle shape for the ASP-III crystals. In addition, the observed slow dissolution of ASP crystals should indicate polymorph form I formation. Thus, the modified vapor diffusion method could routinely be used to screen and legally secure all possible forms of other drug entities too.
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NASA Technical Reports Server (NTRS)
Bugg, Charles E.
1993-01-01
Proteins account for 50% or more of the dry weight of most living systems and play a crucial role in virtually all biological processes. Since the specific functions of essentially all biological molecules are determined by their three-dimensional structures, it is obvious that a detailed understanding of the structural makeup of a protein is essential to any systematic research pertaining to it. At the present time, protein crystallography has no substitute, it is the only technique available for elucidating the atomic arrangements within complicated biological molecules. Most macromolecules are extremely difficult to crystallize, and many otherwise exciting and promising projects have terminated at the crystal growth stage. There is a pressing need to better understand protein crystal growth, and to develop new techniques that can be used to enhance the size and quality of protein crystals. There are several aspects of microgravity that might be exploited to enhance protein crystal growth. The major factor that might be expected to alter crystal growth processes in space is the elimination of density-driven convective flow. Another factor that can be readily controlled in the absence of gravity is the sedimentation of growing crystal in a gravitational field. Another potential advantage of microgravity for protein crystal growth is the option of doing containerless crystal growth. One can readily understand why the microgravity environment established by Earth-orbiting vehicles is perceived to offer unique opportunities for the protein crystallographer. The near term objectives of the Protein Crystal Growth in a Microgravity Environment (PCG/ME) project is to continue to improve the techniques, procedures, and hardware systems used to grow protein crystals in Earth orbit.
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Crystallization of the Large Membrane Protein Complex Photosystem I in a Microfluidic Channel
Abdallah, Bahige G.; Kupitz, Christopher; Fromme, Petra; Ros, Alexandra
2014-01-01
Traditional macroscale protein crystallization is accomplished non-trivially by exploring a range of protein concentrations and buffers in solution until a suitable combination is attained. This methodology is time consuming and resource intensive, hindering protein structure determination. Even more difficulties arise when crystallizing large membrane protein complexes such as photosystem I (PSI) due to their large unit cells dominated by solvent and complex characteristics that call for even stricter buffer requirements. Structure determination techniques tailored for these ‘difficult to crystallize’ proteins such as femtosecond nanocrystallography are being developed, yet still need specific crystal characteristics. Here, we demonstrate a simple and robust method to screen protein crystallization conditions at low ionic strength in a microfluidic device. This is realized in one microfluidic experiment using low sample amounts, unlike traditional methods where each solution condition is set up separately. Second harmonic generation microscopy via Second Order Nonlinear Imaging of Chiral Crystals (SONICC) was applied for the detection of nanometer and micrometer sized PSI crystals within microchannels. To develop a crystallization phase diagram, crystals imaged with SONICC at specific channel locations were correlated to protein and salt concentrations determined by numerical simulations of the time-dependent diffusion process along the channel. Our method demonstrated that a portion of the PSI crystallization phase diagram could be reconstructed in excellent agreement with crystallization conditions determined by traditional methods. We postulate that this approach could be utilized to efficiently study and optimize crystallization conditions for a wide range of proteins that are poorly understood to date. PMID:24191698
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Calculation Of Clinopyroxene And Olivine Growth Rates Using Plagioclase Residence Time
NASA Astrophysics Data System (ADS)
Kilinc, A. I.; Borell, A.; Leu, A.
2012-12-01
According to the Crystal Size Distribution theory (CSD) in a plot of logarithm of number of crystals of a given size range per unit volume [ln(n)], against crystal size [L] shows a straight line. Slope of that line is given by where is the crystal residence time and G is the crystal growth rate. Therefore if is known then G can be calculated. We used thin sections of the Kilauea basalt from Hawaii where olivine, clinopyroxene and plagioclase crystallized within a small temperature range, and the crystal growth rate of plagioclase is known. Assuming that crystal residence times of these three minerals are the same, we plotted ln(n) against L and using the slope and the known crystal growth rate of plagioclase we calculated the crystal growth rates of clinopyroxene and olivine. For the clinopyroxene growth rate we report 10-10.9cm/sec, which is in good agreement with Congdon's data of 10-10 cm/sec. We also calculated the growth rate of olivine is a basaltic melt as 10-8.5 cm/sec which is comparable to < 10-10 to 10-7 cm/sec given by Donaldson and Jambon.
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NASA Astrophysics Data System (ADS)
Lenka, Maheswata; Sarkar, Debasis
2018-03-01
This work investigates the effect of internal seeding and an initial cooling/heating cycle on the final crystal size distribution (CSD) during a combined cooling/antisolvent crystallization of L-asparagine monohydrate from it's aqueous solution using isopropyl-alcohol as antisolvent. Internal seeds were generated by one-pot addition of various amounts of antisolvent to the crystallizer. It was then followed by a cooling/heating cycle to dissolve the fines produced and thus obtain a suitable initial seed. A combined cooling/antisolvent crystallization was then followed by employing a linear cooling profile with simultaneous addition of antisolvent with a constant mass flow rate to promote the growth of the internally generated seeds. The amount of initial antisolvent influences the characteristics of the internal seeds generated and the effect of initial amount of antisolvent on the final CSD is investigated. It was found that the introduction of a single cooling/heating cycle significantly improves the reproducibility of final CSD as well as the mean size. Overall, the study indicates that the application of internal seeding with a single cooling/heating cycle for fines dissolution is an effective technique to tailor crystal size distribution.
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Synthesis and characterization of colloidal CdTe nanocrystals
NASA Astrophysics Data System (ADS)
Semendy, Fred; Jaganathan, Gomatam; Dhar, Nibir; Trivedi, Sudhir; Bhat, Ishwara; Chen, Yuanping
2008-08-01
We synthesized CdTe nano crystals (NCs) in uniform sizes and in good quality as characterized by photoluminescence (PL), AFM, and X-ray diffraction. In this growth procedure, CdTe nano-crystal band gap is strongly dependent on the growth time and not on the injection temperature or organic ligand concentration. This is very attractive because of nano-crystal size can be easily controlled by the growth time only and is very attractive for large scale synthesis. The color of the solution changes from greenish yellow to light orange then to deep orange and finally grayish black to black over a period of one hour. This is a clear indication of the gradual growth of different size (and different band gap) of CdTe nano-crystals as a function of the growth time. In other words, the size of the nano-crystal and its band gap can be controlled by adjusting the growth time after injection of the tellurium. The prepared CdTe NCs were characterized by absorption spectra, photoluminescence (PL), AFM and X-ray diffraction. Measured absorption maxima are at 521, 560, 600 and 603 nm corresponding to band gaps of 2.38, 2.21,2,07 and 2.04 eV respectively for growth times of 15, 30, 45 and 60 minutes. From the absorption data nano-crystal growth size saturates out after 45 minutes. AFM scanning of these materials indicate that the size of these particles is between 4 - 10 nm in diameter for growth time of 45 minutes. XD-ray diffraction indicates that these nano crystals are of cubic zinc blende phase. This paper will present growth and characterization data on CdTe nano crystals for various growth times.
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Miura, Hiroki; Bon, Volodymyr; Senkovska, Irena; Ehrling, Sebastian; Watanabe, Satoshi; Ohba, Masaaki; Kaskel, Stefan
2017-10-17
Controlled nucleation in a micromixer and further crystal growth were used to synthesize Ni 2 (2,6-ndc) 2 dabco (2,6-ndc - 2,6-naphthalenedicarboxylate, dabco - 1,4-diazabicyclo[2.2.2]octane), also termed DUT-8(Ni) (DUT = Dresden University of Technology), with narrow particle size distribution in a range of a few nm to several μm. The crystal size was found to significantly affect the switching characteristics, in particular the gate opening pressure in nitrogen adsorption isotherms at 77 K for this highly porous and flexible network. Below a critical size of about 500 nm, a type Ia isotherm typical of rigid MOFs is observed, while above approximately 1000 nm a pronounced gating behaviour is detected, starting at p/p 0 = 0.2. With increasing crystal size this transition gate becomes steeper indicating a more uniform distribution of activation energies within the crystal ensemble. At an intermediate size (500-1000 nm), the DUT-8(Ni) crystals close during activation but cannot be reopened by nitrogen at 77 K possibly indicating monodomain switching.
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Crystallization processes in Ge{sub 2}Sb{sub 2}Se{sub 4}Te glass
DOE Office of Scientific and Technical Information (OSTI.GOV)
Svoboda, Roman, E-mail: roman.svoboda@upce.cz; Bezdička, Petr; Gutwirth, Jan
2015-01-15
Highlights: • Crystallization kinetics of Ge{sub 2}Sb{sub 2}Se{sub 4}Te glass was studied in dependence on particle size by DSC. • All studied fractions were described in terms of the SB autocatalytic model. • Relatively high amount of Te enhances manifestation of bulk crystallization mechanisms. • XRD analysis of samples crystallized under different conditions showed correlation with DSC data. • XRD analysis revealed a new crystallization mechanism indistinguishable by DSC. - Abstract: Differential scanning calorimetry (DSC) and X-ray diffraction (XRD) analysis were used to study crystallization in Ge{sub 2}Sb{sub 2}Se{sub 4}Te glass under non-isothermal conditions as a function of the particlemore » size. The crystallization kinetics was described in terms of the autocatalytic Šesták–Berggren model. An extensive discussion of all aspects of a full-scale kinetic study of a crystallization process was undertaken. Dominance of the crystallization process originating from mechanically induced strains and heterogeneities was confirmed. Substitution of Se by Te was found to enhance the manifestation of the bulk crystallization mechanisms (at the expense of surface crystallization). The XRD analysis showed significant dependence of the crystalline structural parameters on the crystallization conditions (initial particle size of the glassy grains and applied heating rate). Based on this information, a new microstructural crystallization mechanism, indistinguishable by DSC, was proposed.« less
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Borissova, A; Goltz, G E; Kavanagh, J P; Wilkins, T A
2010-07-01
Crystallization of calcium oxalate monohydrate in a section of a single kidney nephron (distal convoluted tubule) is simulated using a model adapted from industrial crystallization. The nephron fluid dynamics is represented as a crystallizer/separator series with changing volume to allow for water removal along the tubule. The model integrates crystallization kinetics and crystal size distribution and allows the prediction of the calcium oxalate concentration profile and the nucleation and growth rates. The critical supersaturation ratio for the nucleation of calcium oxalate crystals has been estimated as 2 and the mean crystal size as 1 mum. The crystal growth order, determined as 2.2, indicates a surface integration mechanism of crystal growth and crystal growth dispersion. The model allows the exploration of the effect of varying the input calcium oxalate concentration and the rate of water extraction, simulating real life stressors for stone formation such as dietary loading and dehydration.
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NASA Astrophysics Data System (ADS)
Morikawa, Satoshi; Satake, Yuji; Takashiri, Masayuki
2018-06-01
The effects of crystal orientation and grain size on the thermoelectric properties of Bi2Te3 thin films were investigated by conducting experimental and theoretical analyses. To vary the crystal orientation and grain size, we performed oblique deposition, followed by thermal annealing treatment. The crystal orientation decreased as the oblique angle was increased, while the grain size was not changed significantly. The thermoelectric properties were measured at room temperature. A theoretical analysis was performed using a first principles method based on density functional theory. Then the semi-classical Boltzmann transport equation was used in the relaxation time approximation, with the effect of grain size included. Furthermore, the effect of crystal orientation was included in the calculation based on a simple semi-experimental model. A maximum power factor of 11.6 µW/(cm·K2) was obtained at an oblique angle of 40°. The calculated thermoelectric properties were in very good agreement with the experimentally measured values.
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Miao, Yu; Qiu, Yanxuan; Cai, Jiawei; Wang, Zizhou; Yu, Xinwei; Dong, Wen
2016-01-01
The in-situ nano-crystal-to-crystal transformation (SCCT) synthesis provides a powerful approach for tailoring controllable feature shapes and sizes of nano crystals. In this work, three nitrogen-rich energetic nano-crystals based on 5,5′-azotetrazolate(AZT2−) Cr(III) salts were synthesized by means of SCCT methodology. SEM and TEM analyses show that the energetic nano-crystals feature a composition- and structure-dependent together with size-dependent thermal stability. Moreover, nano-scale decomposition products can be obtained above 500 °C, providing a new method for preparing metallic oxide nano materials. PMID:27869221
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Human serum albumin crystals and method of preparation
NASA Technical Reports Server (NTRS)
Carter, Daniel C. (Inventor)
1989-01-01
Human serum albumin (HSA) crystals are provided in the form of tetragonal plates having the space groups P42(sub 1)2, the crystals being grown to sizes in excess of 0.5 mm in two dimensions and a thickness of 0.1 mm. Growth of the crystals is carried out by a hanging drop method wherein a precipitant solution containing polyethylene glycol (PEG) and a phosphate buffer is mixed with an HSA solution, and a droplet of mixed solution is suspended over a well of precipitant solution. Crystals grow to the desired size in 3 to 7 days. Concentration of reagents, pH and other parameters are controlled within prescribed limits. The resulting crystals exhibit a size and quality such as to allow performance of x ray diffraction studies and enable the conduct of drug binding studies as well as genetic engineering studies.
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Coughlan, H D; Darmanin, C; Phillips, N W; Hofmann, F; Clark, J N; Harder, R J; Vine, D J; Abbey, B
2015-07-01
For laboratory and synchrotron based X-ray sources, radiation damage has posed a significant barrier to obtaining high-resolution structural data from biological macromolecules. The problem is particularly acute for micron-sized crystals where the weaker signal often necessitates the use of higher intensity beams to obtain the relevant data. Here, we employ a combination of techniques, including Bragg coherent diffractive imaging to characterise the radiation induced damage in a micron-sized protein crystal over time. The approach we adopt here could help screen for potential protein crystal candidates for measurement at X-ray free election laser sources.
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Coughlan, H. D.; Darmanin, C.; Phillips, N. W.; Hofmann, F.; Clark, J. N.; Harder, R. J.; Vine, D. J.; Abbey, B.
2015-01-01
For laboratory and synchrotron based X-ray sources, radiation damage has posed a significant barrier to obtaining high-resolution structural data from biological macromolecules. The problem is particularly acute for micron-sized crystals where the weaker signal often necessitates the use of higher intensity beams to obtain the relevant data. Here, we employ a combination of techniques, including Bragg coherent diffractive imaging to characterise the radiation induced damage in a micron-sized protein crystal over time. The approach we adopt here could help screen for potential protein crystal candidates for measurement at X-ray free election laser sources. PMID:26798804
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Coughlan, H. D.; Darmanin, C.; Phillips, N. W.
For laboratory and synchrotron based X-ray sources, radiation damage has posed a significant barrier to obtaining high-resolution structural data from biological macromolecules. The problem is particularly acute for micron-sized crystals where the weaker signal often necessitates the use of higher intensity beams to obtain the relevant data. Here, we employ a combination of techniques, including Bragg coherent diffractive imaging to characterise the radiation induced damage in a micron-sized protein crystal over time. The approach we adopt here could help screen for potential protein crystal candidates for measurement at X-ray free election laser sources.
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Coughlan, H. D.; Darmanin, C.; Phillips, N. W.; ...
2015-04-29
For laboratory and synchrotron based X-ray sources, radiation damage has posed a significant barrier to obtaining high-resolution structural data from biological macromolecules. The problem is particularly acute for micron-sized crystals where the weaker signal often necessitates the use of higher intensity beams to obtain the relevant data. Here, we employ a combination of techniques, including Bragg coherent diffractive imaging to characterise the radiation induced damage in a micron-sized protein crystal over time. The approach we adopt here could help screen for potential protein crystal candidates for measurement at X-ray free election laser sources.
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Paquay, Stefan; Both, Gert-Jan; van der Schoot, Paul
2017-07-01
When colloidal particles form a crystal phase on a spherical template, their packing is governed by the effective interaction between them and the elastic strain of bending the growing crystal. For example, if growth commences under appropriate conditions, and the isotropic crystal that forms reaches a critical size, growth continues via the incorporation of defects to alleviate elastic strain. Recently, it was experimentally found that, if defect formation is somehow not possible, the crystal instead continues growing in ribbons that protrude from the original crystal. Here we report on computer simulations in which we observe both the formation of ribbons at short interaction ranges and packings that incorporate defects if the interaction is longer-ranged. The ribbons only form above some critical crystal size, below which the nucleus is disk-shaped. We find that the scaling of the critical crystal size differs slightly from the one proposed in the literature, and we argue that this is because the actual morphology transition is caused by the competition between line tension and elastic stress, rather than the competition between chemical potential and elastic stress.
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NASA Astrophysics Data System (ADS)
Paquay, Stefan; Both, Gert-Jan; van der Schoot, Paul
2017-07-01
When colloidal particles form a crystal phase on a spherical template, their packing is governed by the effective interaction between them and the elastic strain of bending the growing crystal. For example, if growth commences under appropriate conditions, and the isotropic crystal that forms reaches a critical size, growth continues via the incorporation of defects to alleviate elastic strain. Recently, it was experimentally found that, if defect formation is somehow not possible, the crystal instead continues growing in ribbons that protrude from the original crystal. Here we report on computer simulations in which we observe both the formation of ribbons at short interaction ranges and packings that incorporate defects if the interaction is longer-ranged. The ribbons only form above some critical crystal size, below which the nucleus is disk-shaped. We find that the scaling of the critical crystal size differs slightly from the one proposed in the literature, and we argue that this is because the actual morphology transition is caused by the competition between line tension and elastic stress, rather than the competition between chemical potential and elastic stress.
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Influence of computational domain size on the pattern formation of the phase field crystals
NASA Astrophysics Data System (ADS)
Starodumov, Ilya; Galenko, Peter; Alexandrov, Dmitri; Kropotin, Nikolai
2017-04-01
Modeling of crystallization process by the phase field crystal method (PFC) represents one of the important directions of modern computational materials science. This method makes it possible to research the formation of stable or metastable crystal structures. In this paper, we study the effect of computational domain size on the crystal pattern formation obtained as a result of computer simulation by the PFC method. In the current report, we show that if the size of a computational domain is changed, the result of modeling may be a structure in metastable phase instead of pure stable state. The authors present a possible theoretical justification for the observed effect and provide explanations on the possible modification of the PFC method to account for this phenomenon.
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3-Dimensional Colloidal Crystals From Hollow Spheres
NASA Astrophysics Data System (ADS)
Zhang, Jian; Work, William J.; Sanyal, Subrata; Lin, Keng-Hui; Yodh, A. G.
2000-03-01
We have succeeded in synthesizing submicron-sized, hollow PMMA spheres and self-assembling them into colloidal crystalline structures using the depletion force. The resulting structures can be used as templates to make high refractive-index contrast, porous, inorganic structures without the need to use calcination or chemical-etching. With the method of emulsion polymerization, we managed to coat a thin PMMA shell around a swellable P(MMA/MAA/EGDMA) core. After neutralization and heating above the glass transition temperature of PMMA, we obtained water-swollen hydrogel particles encapsulated in PMMA shells. These composite particles become hollow spheres after drying. We characterized the particles with both transmission electron microscopy (TEM) and dynamic light scattering (DLS). The TEM results confirmed that each sphere has a hollow core. The DLS results showed that our hollow spheres are submicron-sized, with a swelling ratio of at least 25%, and with a polydispersity less than 5%. We anticipate using this method in the near-future to encapsulate ferrofluid emulsion droplets and liquid crystal droplets.
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Ultrasonically controlled particle size distribution of explosives: a safe method.
Patil, Mohan Narayan; Gore, G M; Pandit, Aniruddha B
2008-03-01
Size reduction of the high energy materials (HEM's) by conventional methods (mechanical means) is not safe as they are very sensitive to friction and impact. Modified crystallization techniques can be used for the same purpose. The solute is dissolved in the solvent and crystallized via cooling or is precipitated out using an antisolvent. The various crystallization parameters such as temperature, antisolvent addition rate and agitation are adjusted to get the required final crystal size and morphology. The solvent-antisolvent ratio, time of crystallization and yield of the product are the key factors for controlling antisolvent based precipitation process. The advantages of cavitationally induced nucleation can be coupled with the conventional crystallization process. This study includes the effect of the ultrasonically generated acoustic cavitation phenomenon on the solvent antisolvent based precipitation process. CL20, a high-energy explosive compound, is a polyazapolycyclic caged polynitramine. CL-20 has greater energy output than existing (in-use) energetic ingredients while having an acceptable level of insensitivity to shock and other external stimuli. The size control and size distribution manipulation of the high energy material (CL20) has been successfully carried out safely and quickly along with an increase in the final mass yield, compared to the conventional antisolvent based precipitation process.
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Dynamically controlled crystal growth system
NASA Technical Reports Server (NTRS)
Bray, Terry L. (Inventor); Kim, Larry J. (Inventor); Harrington, Michael (Inventor); DeLucas, Lawrence J. (Inventor)
2002-01-01
Crystal growth can be initiated and controlled by dynamically controlled vapor diffusion or temperature change. In one aspect, the present invention uses a precisely controlled vapor diffusion approach to monitor and control protein crystal growth. The system utilizes a humidity sensor and various interfaces under computer control to effect virtually any evaporation rate from a number of different growth solutions simultaneously by means of an evaporative gas flow. A static laser light scattering sensor can be used to detect aggregation events and trigger a change in the evaporation rate for a growth solution. A control/follower configuration can be used to actively monitor one chamber and accurately control replicate chambers relative to the control chamber. In a second aspect, the invention exploits the varying solubility of proteins versus temperature to control the growth of protein crystals. This system contains miniature thermoelectric devices under microcomputer control that change temperature as needed to grow crystals of a given protein. Complex temperature ramps are possible using this approach. A static laser light scattering probe also can be used in this system as a non-invasive probe for detection of aggregation events. The automated dynamic control system provides systematic and predictable responses with regard to crystal size. These systems can be used for microgravity crystallization projects, for example in a space shuttle, and for crystallization work under terrestial conditions. The present invention is particularly useful for macromolecular crystallization, e.g. for proteins, polypeptides, nucleic acids, viruses and virus particles.
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Zhang, Zhenzhen; Guo, Jiawen; Sun, Yali; Tian, Beimin; Zheng, Xiaojuan; Zhou, Ming; He, Lin; Zhang, Shaofeng
2018-05-01
The purpose of this study is to improve wear resistance and mechanical properties of lithium disilicate glass-ceramics by refining their crystal sizes. After lithium disilicate glass-ceramics (LD) were melted to form precursory glass blocks, bar (N = 40, n = 10) and plate (N = 32, n = 8) specimens were prepared. According to the differential scanning calorimetry (DSC) of precursory glass, specimens G1-G4 were designed to form lithium disilicate glass-ceramics with different crystal sizes using a two-step thermal treatment. In the meantime, heat-pressed lithium disilicate glass-ceramics (GC-P) and original ingots (GC-O) were used as control groups. Glass-ceramics were characterized using X-ray diffraction (XRD) and were tested using flexural strength test, nanoindentation test and toughness measurements. The plate specimens were dynamically loaded in a chewing simulator with 350 N up to 2.4 × 10 6 loading cycles. The wear analysis of glass-ceramics was performed using a 3D profilometer after every 300,000 wear cycles. Wear morphologies and microstructures were analyzed by scanning electron microscopy (SEM). One-way analysis of variance (ANOVA) was used to analyze the data. Multiple pairwise comparisons of means were performed by Tukey's post-hoc test. Materials with different crystal sizes (p < 0.05) exhibited different properties. Specifically, G3 with medium-sized crystals presented the highest flexural strength, hardness, elastic modulus and fracture toughness. G1 and G2 with small-sized crystals showed lower flexural strength, whereas G4, GC-P, and GC-O with large-sized crystals exhibited lower hardness and elastic modulus. The wear behaviors of all six groups showed running-in wear stage and steady wear stage. G3 showed the best wear resistance while GC-P and GC-O exhibited the highest wear volume loss. After crystal refining, lithium disilicate glass-ceramic with medium-sized crystals showed the highest wear resistance and mechanical properties. Copyright © 2018 Elsevier Ltd. All rights reserved.
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NASA Astrophysics Data System (ADS)
Uribe, J.; Aykac, M.; Baghaei, H.; Li, Hongdi; Wang, Yu; Liu, Yaqiang; Wong, V.; Xing, Tao; Ramirez, R.; Wong, Wai-Hoi
2003-06-01
Recent approvals by CMS (HCFA) for reimbursement of positron emission tomography (PET) scans fuels the rapid grow of the PET market, thus creating the need for more affordable dedicated PET scanners. The objective of the work presented here was the development of a BGO position-sensitive block with similar detector area (40 mm /spl times/ 40 mm) and same number of crystals (8 /spl times/ 8) as the block of a commercial BGO PET, using the less expensive photomultiplier quadrant sharing (PQS) technique. This block is coupled to four single-anode 40-mm diameter photomultipliers (PMT) instead of the 19-mm PMT used in a popular commercial BGO PET, and each PMT is shared by four adjacent detector blocks. Potentially, this design needs only 25% of the number of PMT used in the commercial BGO PET. In order not to waste the unused half-row of PMT at the edges of a detector panel/module when the module is made up solely of square blocks, an extended rectangular block has to be developed for the edge-blocks in the module, which maximized the use of the PMT and minimized the gap between modules. Only the extended block needs to be developed to derive the design for all the blocks in the module because the symmetric square block uses the same light-distributing partitions as those along the short side of the extended rectangular block. White-paint masks applied with accurate templates and airbrush were fine-tuned for every pair of adjacent crystals. The experimental block developed in this study provided good crystal-decoding. The composite energy spectrum of all 64 crystals showed a prominent photopeak. The worst crystal sitting in the air space between 4 round PMTs still has 60% of the signal pulse height as the best crystal. The average energy resolution was 21.8% for 511 keV gamma (range 17% - 28.7%) that compared well with the 22% - 44% measured with GE and CTI blocks. The image resolution provided by the PQS blocks is expected to be comparable to that of commercial BGO PETs as similar size crystals were decoded.
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Hutnik, Nina; Kozik, Anna; Mazienczuk, Agata; Piotrowski, Krzysztof; Wierzbowska, Boguslawa; Matynia, Andrzej
2013-07-01
Continuous DT MSMPR (Draft Tube Mixed Suspension Mixed Product Removal) crystallizer was provided with typical wastewater from phosphorus mineral fertilizers industry (pH < 4, 0.445 mass % of PO4(3-), inorganic impurities presence), dissolved substrates (magnesium and ammonium chlorides) and solution alkalising the environment of struvite MgNH4PO4·6H2O reaction crystallization process. Research ran in constant temperature 298 K assuming stoichiometric proportions of substrates or 20% excess of magnesium ions. Influence of pH (8.5-10) and mean residence time (900-3600 s) on product size distribution, its chemical composition, crystals shape, size-homogeneity and process kinetics was identified. Crystals of mean size ca. 25-37 μm and homogeneity CV 70-83% were produced. The largest crystals, of acceptable homogeneity, were produced using 20% excess of magnesium ions, pH 9 and mean residence time 3600 s. Under these conditions nucleation rate did not exceed 9 × 10(7) 1/(s m(3)) according to SIG (Size Independent Growth) MSMPR kinetic model. Linear crystal growth rate was 4.27 × 10(-9) m/s. Excess of magnesium ions influenced struvite reaction crystallization process yield advantageously. Concentration of phosphate(V) ions decreased from 0.445 to 9.2 × 10(-4) mass %. This can be regarded as a very good process result. In product crystals, besides main component - struvite, all impurities from wastewater were detected analytically. Copyright © 2013 Elsevier Ltd. All rights reserved.
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Crystallization of calcium oxalate in minimally diluted urine
NASA Astrophysics Data System (ADS)
Bretherton, T.; Rodgers, A.
1998-09-01
Crystallization of calcium oxalate was studied in minimally diluted (92%) urine using a mixed suspension mixed product crystallizer in series with a Malvern particle sizer. The crystallization was initiated by constant flow of aqueous sodium oxalate and urine into the reaction vessel via two independent feed lines. Because the Malvern cell was in series with the reaction vessel, noninvasive measurement of particle sizes could be effected. In addition, aliquots of the mixed suspension were withdrawn and transferred to a Coulter counter for crystal counting and sizing. Steady-state particle size distributions were used to determine nucleation and growth kinetics while scanning electron microscopy was used to examine deposited crystals. Two sets of experiments were performed. In the first, the effect of the concentration of the exogenous sodium oxalate was investigated while in the second, the effect of temperature was studied. Calcium oxalate nucleation and growth rates were found to be dependent on supersaturation levels inside the crystallizer. However, while growth rate increased with increasing temperature, nucleation rates decreased. The favored phases were the trihydrate at 18°C, the dihydrate at 38° and the monohydrate at 58°C. The results of both experiments are in agreement with those obtained in other studies that have been conducted in synthetic and in maximally diluted urine and which have employed invasive crystal counting and sizing techniques. As such, the present study lends confidence to the models of urinary calcium oxalate crystallization processes which currently prevail in the literature.
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Phenytoin crystal growth rates in the presence of phosphate and chloride ions
NASA Astrophysics Data System (ADS)
Zipp, G. L.; Rodríguez-Hornedo, N.
1992-09-01
Phenytoin crystal growth kinetics have been measured as a function of supersaturation in pH 2.2 phosphoric acid and pH 2.2 hydrochloric acid solutions. Two different methods were used for the kinetic analysis. The first involved a zone-sensing device which provided an analysis of the distribution of crystals in a batch crystallizer. Crystal growth rates were calculated from the increase in the size of the distribution with time. In the second method, growth rates were evaluated from the change in size with time of individual crystals observed under an inverted microscope. The results from each method compare favorably. The use of both techniques provides an excellent opportunity to exploit the strengths of each: an average growth rate from a population of crystals from batch crystallization and insight into the effect of growth on the morphology of the crystals from the individual crystal measurements.
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Control of interface shape during high melting sesquioxide crystal growth by HEM technique
NASA Astrophysics Data System (ADS)
Hu, Kaiwei; Zheng, Lili; Zhang, Hui
2018-02-01
During crystal growth in heat exchanger method (HEM) system, the shape of the growth interface changes with the proceeding of the growth process, which limits the crystal size and reduces the quality of the crystal. In this paper, a modified HEM system is proposed to control the interface shape for growth of sesquioxide crystals. Numerical simulation is performed to predict heat transfer, melt flow and interface shape during growth of high melting sesquioxide crystals by the heat exchanger method. The results show that a flat or slightly convex interface shape is beneficial to reduce the solute pileup in front of the melt/crystal interface and decrease the radial temperature gradient inside the crystal during growth of sesquioxide crystals. The interface shape can be controlled by adjusting the gap size d and lower resistance heater power during growth. The growth rate and the melt/crystal interface position can be obtained by two measured temperatures.
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Eberl, Dennis D.; Drits, V.A.; Srodon, J.
2000-01-01
GALOPER is a computer program that simulates the shapes of crystal size distributions (CSDs) from crystal growth mechanisms. This manual describes how to use the program. The theory for the program's operation has been described previously (Eberl, Drits, and Srodon, 1998). CSDs that can be simulated using GALOPER include those that result from growth mechanisms operating in the open system, such as constant-rate nucleation and growth, nucleation with a decaying nucleation rate and growth, surface-controlled growth, supply-controlled growth, and constant-rate and random growth; and those that result from mechanisms operating in the closed system such as Ostwald ripening, random ripening, and crystal coalescence. In addition, CSDs for two types weathering reactions can be simulated. The operation of associated programs also is described, including two statistical programs used for comparing calculated with measured CSDs, a program used for calculating lognormal CSDs, and a program for arranging measured crystal sizes into size groupings (bins).
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Eberl, D.D.; Drits, V.A.; Środoń, Jan; Nüesch, R.
1996-01-01
Particle size may strongly influence the physical and chemical properties of a substance (e.g. its rheology, surface area, cation exchange capacity, solubility, etc.), and its measurement in rocks may yield geological information about ancient environments (sediment provenance, degree of metamorphism, degree of weathering, current directions, distance to shore, etc.). Therefore mineralogists, geologists, chemists, soil scientists, and others who deal with clay-size material would like to have a convenient method for measuring particle size distributions. Nano-size crystals generally are too fine to be measured by light microscopy. Laser scattering methods give only average particle sizes; therefore particle size can not be measured in a particular crystallographic direction. Also, the particles measured by laser techniques may be composed of several different minerals, and may be agglomerations of individual crystals. Measurement by electron and atomic force microscopy is tedious, expensive, and time consuming. It is difficult to measure more than a few hundred particles per sample by these methods. This many measurements, often taking several days of intensive effort, may yield an accurate mean size for a sample, but may be too few to determine an accurate distribution of sizes. Measurement of size distributions by X-ray diffraction (XRD) solves these shortcomings. An X-ray scan of a sample occurs automatically, taking a few minutes to a few hours. The resulting XRD peaks average diffraction effects from billions of individual nano-size crystals. The size that is measured by XRD may be related to the size of the individual crystals of the mineral in the sample, rather than to the size of particles formed from the agglomeration of these crystals. Therefore one can determine the size of a particular mineral in a mixture of minerals, and the sizes in a particular crystallographic direction of that mineral.
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NASA Technical Reports Server (NTRS)
Xie, Yu; Minnis, Patrick; Hu, Yong X.; Kattawar, George W.; Yang, Ping
2008-01-01
Spherical or spheroidal air bubbles are generally trapped in the formation of rapidly growing ice crystals. In this study the single-scattering properties of inhomogeneous ice crystals containing air bubbles are investigated. Specifically, a computational model based on an improved geometric-optics method (IGOM) has been developed to simulate the scattering of light by randomly oriented hexagonal ice crystals containing spherical or spheroidal air bubbles. A combination of the ray-tracing technique and the Monte Carlo method is used. The effect of the air bubbles within ice crystals is to smooth the phase functions, diminish the 22deg and 46deg halo peaks, and substantially reduce the backscatter relative to bubble-free particles. These features vary with the number, sizes, locations and shapes of the air bubbles within ice crystals. Moreover, the asymmetry factors of inhomogeneous ice crystals decrease as the volume of air bubbles increases. Cloud reflectance lookup tables were generated at wavelengths 0.65 m and 2.13 m with different air-bubble conditions to examine the impact of the bubbles on retrieving ice cloud optical thickness and effective particle size. The reflectances simulated for inhomogeneous ice crystals are slightly larger than those computed for homogenous ice crystals at a wavelength of 0.65 microns. Thus, the retrieved cloud optical thicknesses are reduced by employing inhomogeneous ice cloud models. At a wavelength of 2.13 microns, including air bubbles in ice cloud models may also increase the reflectance. This effect implies that the retrieved effective particle sizes for inhomogeneous ice crystals are larger than those retrieved for homogeneous ice crystals, particularly, in the case of large air bubbles.
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Nadra, Imad; Boccaccini, Aldo R; Philippidis, Pandelis; Whelan, Linda C; McCarthy, Geraldine M; Haskard, Dorian O; Landis, R Clive
2008-01-01
Macrophages may promote a vicious cycle of inflammation and calcification in the vessel wall by ingesting neointimal calcific deposits (predominantly hydroxyapatite) and secreting tumor necrosis factor (TNF)alpha, itself a vascular calcifying agent. Here we have investigated whether particle size affects the proinflammatory potential of hydroxyapatite crystals in vitro and whether the nuclear factor (NF)-kappaB pathway plays a role in the macrophage TNFalpha response. The particle size and nano-topography of nine different crystal preparations was analyzed by X-ray diffraction, Raman spectroscopy, scanning electron microscopy and gas sorbtion analysis. Macrophage TNFalpha secretion was inversely related to hydroxyapatite particle size (P=0.011, Spearman rank correlation test) and surface pore size (P=0.014). A necessary role for the NF-kappaB pathway was demonstrated by time-dependent I kappaB alpha degradation and sensitivity to inhibitors of I kappaB alpha degradation. To test whether smaller particles were intrinsically more bioactive, their mitogenic activity on fibroblast proliferation was examined. This showed close correlation between TNFalpha secretion and crystal-induced fibroblast proliferation (P=0.007). In conclusion, the ability of hydroxyapatite crystals to stimulate macrophage TNFalpha secretion depends on NF-kappaB activation and is inversely related to particle and pore size, with crystals of 1-2 microm diameter and pore size of 10-50 A the most bioactive. Microscopic calcific deposits in early stages of atherosclerosis may therefore pose a greater inflammatory risk to the plaque than macroscopically or radiologically visible deposits in more advanced lesions.
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Different Topological Quantum States in Ternary Zintl compounds: BaCaX (X = Si, Ge, Sn and Pb)
DOE Office of Scientific and Technical Information (OSTI.GOV)
Wang, Lin-Lin; Kaminski, Adam; Canfield, Paul C.
Topological quantum states require stringent combination of crystal symmetry and spin–orbit coupling (SOC) strength. Here in this paper, we report that the ternary Zintl compound series BaCaX (X = Si, Ge, Sn and Pb, Group IV) in the same crystal structure having eight valence electrons per formula unit can host two different topological quantum phases, controlled by atomic size and SOC strength. BaCaSi is a nodal-line semimetal (NLSM) with band inversion protected by mirror symmetry and hosts a strong topological insulator (TI) state when SOC is turned on, thus, a NLSM-TI phase. Moving to larger atomic sizes and heavier atoms,more » BaCaGe and BaCaSn are normal insulators (NIs); then, with the strongest SOC in BaCaPb, a different band inversion is induced, giving a strong TI phase without the need of NLSM. Thus, we also predict two types of topological transitions in a phase diagram for BaCaX: (1) NLSM-TI to NI, then to TI by tuning atomic size and SOC strength via alloying, and (2) NI or TI to NLSM-TI via pressure.« less
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Enhanced Raman spectroscopy of 2,4,6-TNT in anatase and rutile titania nanocrystals
NASA Astrophysics Data System (ADS)
De La Cruz-Montoya, Edwin; Jeréz, Jaqueline I.; Balaguera-Gelves, Marcia; Luna-Pineda, Tatiana; Castro, Miguel E.; Hernández-Rivera, Samuel P.
2006-05-01
The majority of explosives found in antipersonnel and antitank landmines contain 2,4,6-trinitrotoluene (TNT). Chemical sensing of landmines and Improvised Explosive Devices (IED) requires detecting the chemical signatures of the explosive components in these devices. Nanotechnology is ideally suited to needs in microsensors development by providing new materials and methods that can be employed for trace explosive detection. This work is focused on modification of nano-scaled colloids of titanium dioxide (Titania: anatase, rutile and brookite) and thin layer of the oxides as substrates for use in Enhanced Raman Scattering (ERS) spectroscopy. Ultrafine particles have been generated by hydrothermally treating the sol-gel derived hydrous oxides. ERS spectra of nanocrystalline anatase Titania samples prepared with different average sizes: 38 nm (without acid), 24 nm (without acid) and 7 nm (with HCl). Bulk phase (commercial) and KBr were also used to prepare mixtures with TNT to look for Enhanced Raman Effect of the nitroaromatic explosive on the test surfaces. The studies clearly indicated that the anatase crystal size affects the enhancement of the TNT Raman signal. This enhancement was highest for the samples with Titania average crystal size of 7 nm.
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Different Topological Quantum States in Ternary Zintl compounds: BaCaX (X = Si, Ge, Sn and Pb)
Wang, Lin-Lin; Kaminski, Adam; Canfield, Paul C.; ...
2017-12-14
Topological quantum states require stringent combination of crystal symmetry and spin–orbit coupling (SOC) strength. Here in this paper, we report that the ternary Zintl compound series BaCaX (X = Si, Ge, Sn and Pb, Group IV) in the same crystal structure having eight valence electrons per formula unit can host two different topological quantum phases, controlled by atomic size and SOC strength. BaCaSi is a nodal-line semimetal (NLSM) with band inversion protected by mirror symmetry and hosts a strong topological insulator (TI) state when SOC is turned on, thus, a NLSM-TI phase. Moving to larger atomic sizes and heavier atoms,more » BaCaGe and BaCaSn are normal insulators (NIs); then, with the strongest SOC in BaCaPb, a different band inversion is induced, giving a strong TI phase without the need of NLSM. Thus, we also predict two types of topological transitions in a phase diagram for BaCaX: (1) NLSM-TI to NI, then to TI by tuning atomic size and SOC strength via alloying, and (2) NI or TI to NLSM-TI via pressure.« less
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Tetragonal Lysozyme Nucleation and Crystal Growth: The Role of the Solution Phase
NASA Technical Reports Server (NTRS)
Pusey, Marc L.; Forsythe, Elizabeth; Sumida, John; Maxwell, Daniel; Gorti, Sridhar
2002-01-01
Lysozyme, and most particularly the tetragonal form of the protein, has become the default standard protein for use in macromolecule crystal nucleation and growth studies. There is a substantial body of experimental evidence, from this and other laboratories, that strongly suggests this proteins crystal nucleation and growth is by addition of associated species that are preformed by standard reversible concentration-driven self association processes in the bulk solution. The evidence includes high resolution AFM studies of the surface packing and of growth unit size at incorporation, fluorescence resonance energy transfer measurements of intermolecular distances in dilute solution, dialysis kinetics, and modeling of the growth rate data. We have developed a selfassociation model for the proteins crystal nucleation and growth. The model accounts for the obtained crystal symmetry, explains the observed surface structures, and shows the importance of the symmetry obtained by self-association in solution to the process as a whole. Further, it indicates that nucleation and crystal growth are not distinct mechanistically, but identical, with the primary difference being the probability that the particle will continue to grow or dissolve. This model also offers a possible mechanism for fluid flow effects on the growth process and how microgravity may affect it. While a single lysozyme molecule is relatively small (M.W. = 14,400), a structured octamer in the 4(sub 3) helix configuration (the proposed average sized growth unit) would have a M.W. = 115,000 and dimensions of 5.6 x 5.6 x 7.6 nm. Direct AFM measurements of growth unit incorporation indicate that units as wide as 11.2 nm and as long as 11.4 nm commonly attach to the crystal. These measurements were made at approximately saturation conditions, and they reflect the sizes of species that both added or desorbed from the crystal surface. The larger and less isotropic the associated species the more likely that it will be oriented to some degree in a flowing boundary layer, even at the low flow velocities measured about macromolecule crystals. Flow-driven effects resulting in misorientation upon addition to and incorporation into the crystal need only be a small fraction of a percentage to significantly affect the resulting crystal. One Earth, concentration gradient driven flow will maintain a high interfacial concentration, i.e., a high level (essentially that of the bulk solution) of solute association at the interface and higher growth rate. Higher growth rates mean an increased probability that misaligned growth units are trapped by subsequent growth layers before they can be desorbed and try again, or that the desorbing species will be smaller than the adsorbing species. In microgravity the extended diffusive boundary layer will lower the interfacial concentration. This results in a net dissociation of aggregated species that diffuse in from the bulk solution, i.e., smaller associated species, which are more likely able to make multiple attempts to correctly bind, yielding higher quality crystals.
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Purification of a Multidrug Resistance Transporter for Crystallization Studies
Alegre, Kamela O.; Law, Christopher J.
2015-01-01
Crystallization of integral membrane proteins is a challenging field and much effort has been invested in optimizing the overexpression and purification steps needed to obtain milligram amounts of pure, stable, monodisperse protein sample for crystallography studies. Our current work involves the structural and functional characterization of the Escherichia coli multidrug resistance transporter MdtM, a member of the major facilitator superfamily (MFS). Here we present a protocol for isolation of MdtM to increase yields of recombinant protein to the milligram quantities necessary for pursuit of structural studies using X-ray crystallography. Purification of MdtM was enhanced by introduction of an elongated His-tag, followed by identification and subsequent removal of chaperonin contamination. For crystallization trials of MdtM, detergent screening using size exclusion chromatography determined that decylmaltoside (DM) was the shortest-chain detergent that maintained the protein in a stable, monodispersed state. Crystallization trials of MdtM performed using the hanging-drop diffusion method with commercially available crystallization screens yielded 3D protein crystals under several different conditions. We contend that the purification protocol described here may be employed for production of high-quality protein of other multidrug efflux members of the MFS, a ubiquitous, physiologically and clinically important class of membrane transporters. PMID:27025617
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THF water hydrate crystallization: an experimental investigation
NASA Astrophysics Data System (ADS)
Devarakonda, Surya; Groysman, Alexander; Myerson, Allan S.
1999-08-01
Supersaturated solutions of THF-water hydrate system were experimentally studied before and during crystallization, to examine the system's behavior in the metastable zone and observe any anomalies suggesting cluster formation. Nucleation induction time measurements, with and without additives, were performed to screen potential growth inhibitors. Shifts in the onset points of crystallization for water and THF-water mixtures with additives were measured using differential scanning calorimetry (DSC). Aspartame was among one of the few successfully screened inhibitors. Preliminary on-line crystal size distribution (CSD) measurements were performed on this system to monitor the crystal size during crystallization. The CSD data was also used to compute the hydrate crystal growth rates, which were found to be in the order of 145 μm/h.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Matyas, Josef; Amonette, James E.; Kukkadapu, Ravi K.
2014-10-31
Precipitation of large crystals/agglomerates of spinel and their accumulation in the pour spout riser of a Joule-heated ceramic melter during idling can plug the melter and prevent pouring of molten glass into canisters. Thus, there is a need to understand the effects of spinel-forming components, temperature, and time on the growth of crystals in connection with an accumulation rate. In our study, crystals of spinel [Fe, Ni, Mn, Zn, Sn][Fe, Cr]₂O₄ were precipitated from simulated high-level waste borosilicate glasses containing different concentrations of Ni, Fe, and Cr by heat treating at 850 and 900°C for different times. These crystals weremore » extracted from the glasses and analyzed with scanning electron microscopy and image analysis for size and shape, with inductively coupled plasma-atomic emission spectroscopy and atom probe tomography for concentration of spinel-forming components, and with wet colorimetry and Mössbauer spectroscopy for Fe²⁺/Fe total ratio. High concentrations of Ni, Fe, and Cr in glasses resulted in the precipitation of crystals larger than 100 µm in just two days. Crystals were a solid solution of NiFe₂O₄, NiCr₂O₄, and -Fe₂O₃ (identified only in the high-Ni-Fe glass) and also contained small concentrations of less than 1 at% of Li, Mg, Mn, and Al.« less
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The Impact of Aerosols on Cloud and Precipitation Processes: Cloud-Resolving Model Simulations
NASA Technical Reports Server (NTRS)
Tao, Wei-Kuo; Li, X.; Khain, A.; Simpson, S.
2005-01-01
Cloud microphysics are inevitable affected by the smoke particle (CCN, cloud condensation nuclei) size distributions below the clouds, Therefore, size distributions parameterized as spectral bin microphysics are needed to explicitly study the effect of atmospheric aerosol concentration on cloud development, rainfall production, and rainfall rates for convective clouds. Recently, a detailed spectral-bin microphysical scheme was implemented into the the Goddard Cumulus Ensemble (GCE) model. The formulation for the explicit spectral-bim microphysical processes is based on solving stochastic kinetic equations for the size distribution functions of water droplets (i.e., cloud droplets and raindrops), and several types of ice particles [i.e., pristine ice crystals (columnar and plate-like), snow (dendrites and aggregates), graupel and frozen drops/hail]. Each type is described by a special size distribution function containing many categories (i.e., 33 bins). Atmospheric aerosols are also described using number density size-distribution functions.
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Analysis of Crystallization Kinetics
NASA Technical Reports Server (NTRS)
Kelton, Kenneth F.
1997-01-01
A realistic computer model for polymorphic crystallization (i.e., initial and final phases with identical compositions), which includes time-dependent nucleation and cluster-size-dependent growth rates, is developed and tested by fits to experimental data. Model calculations are used to assess the validity of two of the more common approaches for the analysis of crystallization data. The effects of particle size on transformation kinetics, important for the crystallization of many systems of limited dimension including thin films, fine powders, and nanoparticles, are examined.
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NASA Astrophysics Data System (ADS)
Miyajima, Kensuke; Akatsu, Tatsuro; Itoh, Ken
2018-05-01
We evaluated the crystal size, shape, and alignment of the lattice planes of CuCl quantum dots (QDs) embedded in NaCl single crystals by optical measurements, X-ray diffraction (XRD) patterns, and transmission electron microscopy (TEM). We obtained, for the first time, an XRD pattern and TEM images for CuCl QDs in NaCl crystals. The XRD pattern showed that the lattice planes of the CuCl QDs were parallel to those of the NaCl crystals. In addition, the size of the QDs was estimated from the diffraction width. It was apparent from the TEM images that almost all CuCl QDs were polygonal, although some cubic QDs were present. The mean size and size distribution of the QDs were also obtained. The dot size obtained from optical measurements, XRD, and TEM image were almost consistent. Our new findings can help to reveal the growth mechanism of semiconductor QDs embedded in a crystallite matrix. In addition, this work will play an important role in progressing the study of optical phenomena originating from assembled semiconductor QDs.
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Self-cavity lasing in optically pumped single crystals of p-sexiphenyl
NASA Astrophysics Data System (ADS)
Yanagi, Hisao; Tamura, Kenji; Sasaki, Fumio
2016-08-01
Organic single-crystal self-cavities are prepared by solution growth of p-sexiphenyl (p-6P). Based on Fabry-Pérot feedback inside a quasi-lozenge-shaped platelet crystal, edge-emitting laser is obtained under optical pumping. The multimode lasing band appears at the 0-1 or 0-2 vibronic progressions depending on the excitation conditions which affect the self-absorption effect. Cavity-size dependence of amplified spontaneous emission (ASE) is investigated with laser-etched single crystals of p-6P. As the cavity length of square-shaped crystal is reduced from 100 to 10 μm, ASE threshold fluence is decreased probably due to size-dependent light confinement in the crystal cavity.
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Size effects on negative thermal expansion in cubic ScF{sub 3}
DOE Office of Scientific and Technical Information (OSTI.GOV)
Yang, C.; Guo, X. G.; Zhang, K.
2016-07-11
Scandium trifluoride (ScF{sub 3}), adopting a cubic ReO{sub 3}-type structure at ambient pressure, undergoes a pronounced negative thermal expansion (NTE) over a wide range of temperatures (10 K–1100 K). Here, we report the size effects on the NTE properties of ScF{sub 3}. The magnitude of NTE is reduced with diminishing the crystal size. As revealed by the specific heat measurement, the low-energy phonon vibrations which account for the NTE behavior are stiffened as the crystal size decreases. With decreasing the crystal size, the peaks in high-energy X-ray pair distribution function (PDF) become broad, which cannot be illuminated by local symmetry breaking. Instead,more » the broadened PDF peaks are strongly indicative of enhanced atomic displacements which are suggested to be responsible for the stiffening of NTE-related lattice vibrations. The present study suggests that the NTE properties of ReO{sub 3}-type and other open-framework materials can be effectively adjusted by controlling the crystal size.« less
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Espinosa, J R; Young, J M; Jiang, H; Gupta, D; Vega, C; Sanz, E; Debenedetti, P G; Panagiotopoulos, A Z
2016-10-21
Direct coexistence molecular dynamics simulations of NaCl solutions and Lennard-Jones binary mixtures were performed to explore the origin of reported discrepancies between solubilities obtained by direct interfacial simulations and values obtained from the chemical potentials of the crystal and solution phases. We find that the key cause of these discrepancies is the use of crystal slabs of insufficient width to eliminate finite-size effects. We observe that for NaCl crystal slabs thicker than 4 nm (in the direction perpendicular to the interface), the same solubility values are obtained from the direct coexistence and chemical potential routes, namely, 3.7 ± 0.2 molal at T = 298.15 K and p = 1 bar for the JC-SPC/E model. Such finite-size effects are absent in the Lennard-Jones system and are likely caused by surface dipoles present in the salt crystals. We confirmed that μs-long molecular dynamics runs are required to obtain reliable solubility values from direct coexistence calculations, provided that the initial solution conditions are near the equilibrium solubility values; even longer runs are needed for equilibration of significantly different concentrations. We do not observe any effects of the exposed crystal face on the solubility values or equilibration times. For both the NaCl and Lennard-Jones systems, the use of a spherical crystallite embedded in the solution leads to significantly higher apparent solubility values relative to the flat-interface direct coexistence calculations and the chemical potential values. Our results have broad implications for the determination of solubilities of molecular models of ionic systems.
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Klijn, Marieke E; Hubbuch, Jürgen
2018-04-27
Protein phase diagrams are a tool to investigate cause and consequence of solution conditions on protein phase behavior. The effects are scored according to aggregation morphologies such as crystals or amorphous precipitates. Solution conditions affect morphological features, such as crystal size, as well as kinetic features, such as crystal growth time. Common used data visualization techniques include individual line graphs or symbols-based phase diagrams. These techniques have limitations in terms of handling large datasets, comprehensiveness or completeness. To eliminate these limitations, morphological and kinetic features obtained from crystallization images generated with high throughput microbatch experiments have been visualized with radar charts in combination with the empirical phase diagram (EPD) method. Morphological features (crystal size, shape, and number, as well as precipitate size) and kinetic features (crystal and precipitate onset and growth time) are extracted for 768 solutions with varying chicken egg white lysozyme concentration, salt type, ionic strength and pH. Image-based aggregation morphology and kinetic features were compiled into a single and easily interpretable figure, thereby showing that the EPD method can support high throughput crystallization experiments in its data amount as well as its data complexity. Copyright © 2018. Published by Elsevier Inc.
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Crystallization Physics in Biomacromolecular Systems
NASA Technical Reports Server (NTRS)
Chernov, A. A.
2003-01-01
The crystals are built of molecules of protein, nucleic acid and their complexes, like viruses, approx. 5x10(exp 3)+ 3x10(exp 6) Da in weight and 2 + 20 nm in effective diameter. This size strongly exceeds action range of molecular forces and makes a big difference with inorganic crystals. Intermolecular contacts form patches on the biomacromolecular surface. Each patch may occupy only a small percent of the whole surface and vary from polymorph to polymorph of the same protein. Thus, under different conditions (pH, solution chemistry, temperature, any area on the macromolecular surface may form a contact. The crystal Young moduli, E approx. equals 0.1 + 0.5 GPa are more than 10 times lower than that of inorganics and the biomolecules themselves. Water within biocrystals (30-70%) is unable to flow unless typical deformation time is longer than approx. 10(exp -5)s. This explains the discrepancy between light scattering and static measurements of E. Nucleation and Growth requires typically concentrations exceeding the equilibrium ones up to 100 times - because of the new size scale results in 10 - 10(exp 3) times lower kinetic coefficients than that needed for inorganic solution growth. All phenomena observed in the latter occur with protein crystallization and are even better studied by AFM. Crystals are typically facetted. Among unexpected findings of general significance are - net molecular exchange flux at kinks is much lower than that expected from supersaturation, steps with low (< approx. 10(exp -2)) kink density at steps follow Gibbs-Thomson law only at very low supersaturations, step segment growth rate may be independent of step energy. Crystal perfection is a must of biocrystallization to achieve the major goal to find 3-D atomic structure of biomacromolecules by x-ray diffraction. Poor diffraction resolution (> 3Angstrom) makes crystallization a bottleneck for structural biology. All defects typical of small molecule crystals are found in biocrystals, but the defects responsible for poor resolution are not identified. Conformational changes are one of them. Biocrystallization in microgravity reportedly results in 20% cases of better crystals. The mechanism of how lack of convection can do this is still not clear. Lower supersaturation, self-purification &om preferentially trapped homologous impurities and step bunching are viable hypotheses.
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Utilization of biogenic tea waste silver nanoparticles for the reduction of organic dyes
NASA Astrophysics Data System (ADS)
Kaur, H.; Jaryal, N.
2018-05-01
Eco-friendly synthesis of nanoparticles is the need of the society today. Present study has been undertaken to investigate the greener approach for the preparation of medicinally and chemically important nanoparticles. Tea waste has been taken to synthesis silver nanoparticles. The nanoparticles are characterized by x-ray Diffraction, and Transmission Emission Microscopy studies. The particle size varied from 2 to 34 nm. These silver nanoparticles were evaluated for their reducing activity against four organic dyes viz crystal violet, methylene blue, Congo red and brilliant green. The particles exhibited good catalytic activity against crystal violet, methylene blue and brilliant green but no activity was visible for Congo red. Furthermore, AgNPs shows very promising and prominent antioxidant activity.
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Large-volume protein crystal growth for neutron macromolecular crystallography.
Ng, Joseph D; Baird, James K; Coates, Leighton; Garcia-Ruiz, Juan M; Hodge, Teresa A; Huang, Sijay
2015-04-01
Neutron macromolecular crystallography (NMC) is the prevailing method for the accurate determination of the positions of H atoms in macromolecules. As neutron sources are becoming more available to general users, finding means to optimize the growth of protein crystals to sizes suitable for NMC is extremely important. Historically, much has been learned about growing crystals for X-ray diffraction. However, owing to new-generation synchrotron X-ray facilities and sensitive detectors, protein crystal sizes as small as in the nano-range have become adequate for structure determination, lessening the necessity to grow large crystals. Here, some of the approaches, techniques and considerations for the growth of crystals to significant dimensions that are now relevant to NMC are revisited. These include experimental strategies utilizing solubility diagrams, ripening effects, classical crystallization techniques, microgravity and theoretical considerations.
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Armstrong, Mitchell R; Senthilnathan, Sethuraman; Balzer, Christopher J; Shan, Bohan; Chen, Liang; Mu, Bin
2017-01-01
Systematic studies of key operating parameters for the sonochemical synthesis of the metal organic framework (MOF) HKUST-1(also called CuBTC) were performed including reaction time, reactor volume, sonication amplitude, sonication tip size, solvent composition, and reactant concentrations analyzed through SEM particle size analysis. Trends in the particle size and size distributions show reproducible control of average particle sizes between 1 and 4μm. These results along with complementary studies in sonofragmentation and temperature control were conducted to compare these results to kinetic crystal growth models found in literature to develop a plausible hypothetical mechanism for ultrasound-assisted growth of metal-organic-frameworks composed of a competitive mechanism including constructive solid-on-solid (SOS) crystal growth and a deconstructive sonofragmentation. Copyright © 2016 Elsevier B.V. All rights reserved.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Zipper, Lauren E.; Binghamton University, 4400 Vestal Parkway East, Vestal, NY 13902; Aristide, Xavier
This article describes the use of evaporation control lids that are fitted to crystallization plates to improve the reproducibility of trials using as little as 5 nl. The plate lids contain apertures which are large enough for the transfer of protein containing droplets, but small enough to greatly reduce the rate of evaporation during the time needed to prepare the plate. A method is described for using plate lids to reduce evaporation in low-volume vapor-diffusion crystallization experiments. The plate lids contain apertures through which the protein and precipitants were added to different crystallization microplates (the reservoir was filled before fittingmore » the lids). Plate lids were designed for each of these commonly used crystallization microplates. This system minimizes the dehydration of crystallization droplets containing just a few nanolitres of protein and precipitant, and results in more reproducible diffraction from the crystals. For each lid design, changes in the weight of the plates were used to deduce the rate of evaporation under different conditions of temperature, air movement, droplet size and precipitant. For comparison, the state of dehydration was also visually assessed throughout the experiment. Finally, X-ray diffraction methods were used to compare the diffraction of protein crystals that were conventionally prepared against those that were prepared on plates with plate lids. The measurements revealed that the plate lids reduced the rate of evaporation by 63–82%. Crystals grown in 5 nl drops that were set up with plate lids diffracted to higher resolution than similar crystals from drops that were set up without plate lids. The results demonstrate that plate lids can be instrumental for improving few-nanolitre crystallizations.« less
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The Effect of Solution Conditions on the Nucleation Kinetics of Tetragonal Lysozyme Crystals
NASA Technical Reports Server (NTRS)
Judge, Russell A.; Baird, James K.; Pusey, Marc L.
1998-01-01
An understanding of protein crystal nucleation rates and the effect of solution conditions upon them, is fundamental to the preparation of protein crystals of the desired size and shape for X-ray diffraction analysis. The ability to predict the effect of supersaturation, temperature, pH and precipitant concentration on the number and size of crystals formed is of great benefit in the pursuit of protein structure analysis. In this study we experimentally examine the effect of supersaturation, temperature, pH and sodium chloride concentration on the nucleation rate of tetragonal chicken egg white lysozyme crystals. In order to do this batch crystallization plates were prepared at given solution concentrations and incubated at three different temperatures over the period of one week. The number of crystals per well with their size and dimensions were recorded and correlated against solution conditions. Duplicate experiments indicate the reproducibility of the technique. Although it is well known that crystal numbers increase with increasing supersaturation, large changes in crystal number were also correlated against solution conditions of temperature, pH and salt concentration over the same supersaturation ranges. Analysis of these results enhance our understanding of the effect of solution conditions such as the dramatic effect that small changes in charge and ionic strength can have on the number of tetragonal lysozyme crystals that form and grow in solution.
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The effect of crystal size on tunneling phenomena in luminescent nanodosimetric materials
NASA Astrophysics Data System (ADS)
Pagonis, Vasilis; Bernier, Shannon; Vieira, Francisco Marques dos Santos; Steele, Shane
2017-12-01
The study of luminescence signals from nanodosimetric materials is an active research area, due to the many possible practical applications of such materials. In several of these materials it has been shown that quantum tunneling is a dominant mechanism for recombination processes associated with luminescence phenomena. This paper examines the effect of crystal size on quantum tunneling phenomena in nanocrystals, based on the assumption of a random distribution of electrons and positive ions. The behavior of such random distributions is determined by three characteristic lengths: the radius of the crystal R, the tunneling length a, and the initial average distance 〈d〉 between electrons and positive ions (which is directly related to the density of charges in the material). Two different cases are examined, depending on the relative concentrations of electrons and ions. In the first case the concentration of electrons is assumed to be much smaller than the concentration of positive ions. Examination of a previously derived analytical equation demonstrates two different types of crystal size effects. When the tunneling length a is much smaller than both R and 〈d〉, the analytical equations show that smaller crystals exhibit a faster tunneling recombination rate. However, when the tunneling length a is of the same order of magnitude as both R and 〈d〉, the opposite effect is observed, with smaller crystals exhibiting a slower tunneling recombination rate. As the crystal size increases, the rate of tunneling in both cases reaches the limit expected for bulk materials. In the second case we examine the situation where the concentrations of electrons and positive ions are equal at all times. In this situation there is no analytical equation available to describe the process, and the crystal size effects are simulated by using Monte Carlo (MC) techniques. The two opposite behaviors as a function of the crystal size are also observed in these MC simulations. The effect of sample temperature is also studied by extending the MC simulations to include thermal characteristics of the defects. The relevance of the simulated results for luminescence dosimetry is discussed.
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Global statistics of microphysical properties of cloud-top ice crystals
NASA Astrophysics Data System (ADS)
van Diedenhoven, B.; Fridlind, A. M.; Cairns, B.; Ackerman, A. S.; Riedi, J.
2017-12-01
Ice crystals in clouds are highly complex. Their sizes, macroscale shape (i.e., habit), mesoscale shape (i.e., aspect ratio of components) and microscale shape (i.e., surface roughness) determine optical properties and affect physical properties such as fall speeds, growth rates and aggregation efficiency. Our current understanding on the formation and evolution of ice crystals under various conditions can be considered poor. Commonly, ice crystal size and shape are related to ambient temperature and humidity, but global observational statistics on the variation of ice crystal size and particularly shape have not been available. Here we show results of a project aiming to infer ice crystal size, shape and scattering properties from a combination of MODIS measurements and POLDER-PARASOL multi-angle polarimetry. The shape retrieval procedure infers the mean aspect ratios of components of ice crystals and the mean microscale surface roughness levels, which are quantifiable parameters that mostly affect the scattering properties, in contrast to "habit". We present global statistics on the variation of ice effective radius, component aspect ratio, microscale surface roughness and scattering asymmetry parameter as a function of cloud top temperature, latitude, location, cloud type, season, etc. Generally, with increasing height, sizes decrease, roughness increases, asymmetry parameters decrease and aspect ratios increase towards unity. Some systematic differences are observed for clouds warmer and colder than the homogeneous freezing level. Uncertainties in the retrievals will be discussed. These statistics can be used as observational targets for modeling efforts and to better constrain other satellite remote sensing applications and their uncertainties.
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Global Statistics of Microphysical Properties of Cloud-Top Ice Crystals
NASA Technical Reports Server (NTRS)
Van Diedenhoven, Bastiaan; Fridlind, Ann; Cairns, Brian; Ackerman, Andrew; Riedl, Jerome
2017-01-01
Ice crystals in clouds are highly complex. Their sizes, macroscale shape (i.e., habit), mesoscale shape (i.e., aspect ratio of components) and microscale shape (i.e., surface roughness) determine optical properties and affect physical properties such as fall speeds, growth rates and aggregation efficiency. Our current understanding on the formation and evolution of ice crystals under various conditions can be considered poor. Commonly, ice crystal size and shape are related to ambient temperature and humidity, but global observational statistics on the variation of ice crystal size and particularly shape have not been available. Here we show results of a project aiming to infer ice crystal size, shape and scattering properties from a combination of MODIS measurements and POLDER-PARASOL multi-angle polarimetry. The shape retrieval procedure infers the mean aspect ratios of components of ice crystals and the mean microscale surface roughness levels, which are quantifiable parameters that mostly affect the scattering properties, in contrast to a habit. We present global statistics on the variation of ice effective radius, component aspect ratio, microscale surface roughness and scattering asymmetry parameter as a function of cloud top temperature, latitude, location, cloud type, season, etc. Generally, with increasing height, sizes decrease, roughness increases, asymmetry parameters decrease and aspect ratios increase towards unity. Some systematic differences are observed for clouds warmer and colder than the homogeneous freezing level. Uncertainties in the retrievals will be discussed. These statistics can be used as observational targets for modeling efforts and to better constrain other satellite remote sensing applications and their uncertainties.
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The Effect of Temperature and Solution pH on the Nucleation of Tetragonal Lysozyme Crystals
NASA Technical Reports Server (NTRS)
Judge, Russell A.; Jacobs, Randolph S.; Frazier, Tyralynn; Snell, Edward H.; Pusey, Marc L.
1999-01-01
Part of the challenge of macromolecular crystal growth for structure determination is obtaining crystals with a volume suitable for x-ray analysis. In this respect an understanding of the effect of solution conditions on macromolecule nucleation rates is advantageous. This study investigated the effects of supersaturation, temperature, and pH on the nucleation rate of tetragonal lysozyme crystals. Batch crystallization plates were prepared at given solution concentrations and incubated at set temperatures over 1 week. The number of crystals per well with their size and axial ratios were recorded and correlated with solution conditions. Crystal numbers were found to increase with increasing supersaturation and temperature. The most significant variable, however, was pH; crystal numbers changed by two orders of magnitude over the pH range 4.0-5.2. Crystal size also varied with solution conditions, with the largest crystals obtained at pH 5.2. Having optimized the crystallization conditions, we prepared a batch of crystals under the same initial conditions, and 50 of these crystals were analyzed by x-ray diffraction techniques. The results indicate that even under the same crystallization conditions, a marked variation in crystal properties exists.
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NASA Astrophysics Data System (ADS)
Guo, Yun-Zhu; Sun, Li-Hua; Oberthuer, Dominik; Zhang, Chen-Yan; Shi, Jian-Yu; di, Jiang-Lei; Zhang, Bao-Liang; Cao, Hui-Ling; Liu, Yong-Ming; Li, Jian; Wang, Qian; Huang, Huan-Huan; Liu, Jun; Schulz, Jan-Mirco; Zhang, Qiu-Yu; Zhao, Jian-Lin; Betzel, Christian; He, Jian-Hua; Yin, Da-Chuan
2014-12-01
High-quality protein crystals of suitable size are an important prerequisite for applying X-ray crystallography to determine the 3-dimensional structure of proteins. However, it is often difficult to obtain protein crystals of appropriate size and quality because nucleation and growth processes can be unsuccessful. Here, we show that by adsorbing proteins onto porous polystyrene-divinylbenzene microspheres (SDB) floating on the surface of the crystallisation solution, a localised high supersaturation region at the surface of the microspheres and a low supersaturation region below the microspheres can coexist in a single solution. The crystals will easily nucleate in the region of high supersaturation, but when they grow to a certain size, they will sediment to the region of low supersaturation and continue to grow. In this way, the probability of crystallisation and crystal quality can be simultaneously increased in a single solution without changing other crystallisation parameters.
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Influence of mixing and ultrasound frequency on antisolvent crystallisation of sodium chloride.
Lee, Judy; Ashokkumar, Muthupandian; Kentish, Sandra E
2014-01-01
Ultrasound is known to promote nucleation of crystals and produce a narrower size distribution in a controlled and reproducible manner for the crystallisation process. Although there are various theories that suggest cavitation bubbles are responsible for sonocrystallisation, most studies use power ultrasonic horns that generate both intense shear and cavitation and this can mask the role that cavitation bubbles play. High frequency ultrasound from a plate transducer can be used to examine the effect of cavitation bubbles without the intense shear effect. This study reports the crystal size and morphology with various mixing speeds and ultrasound frequencies. The results show high frequency ultrasound produced sodium chloride crystals of similar size distribution as an ultrasonic horn. In addition, ultrasound generated sodium chloride crystals having a more symmetrical cubic structure compared to crystals produced by a high shear mixer. Copyright © 2013 Elsevier B.V. All rights reserved.
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Nanoscale effects of silica particle supports on the formation and properties of TiO2 nanocatalysts
NASA Astrophysics Data System (ADS)
Li, Aize; Jin, Yuhui; Muggli, Darrin; Pierce, David T.; Aranwela, Hemantha; Marasinghe, Gaya K.; Knutson, Theodore; Brockman, Greg; Zhao, Julia Xiaojun
2013-06-01
Small TiO2 crystals in the anatase phase are in high demand as photocatalysts. Stable TiO2 crystals in the anatase phase were obtained using a silica nanoparticle as a support. The focus of this study was to investigate the nanoscale effect of the silica support on the formation and properties of small anatase crystals. The experiments were carried out using powder X-ray diffraction, differential thermal analysis, transmission electron microscopy, and energy dispersion spectroscopy. The results showed that the size of the silica support played a crucial role in crystallization of TiO2 and regulation of TiO2 properties, including phase transition, crystal size, thermodynamic property and catalytic activity. A nanoscale curvature model of the spherical silica support was proposed to explain these size effects. Finally, the developed TiO2 catalysts were applied to the oxidation of methanol using a high-throughput photochemical reactor. The size effect of the silica supports on the TiO2 catalytic efficiency was demonstrated using this system.
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1992-06-25
Zeolites are crystalline aluminosilicates that have complex framework structures. However, there are several features of zeolite crystals that make unequivocal structure determinations difficult. The acquisition of reliable structural information on zeolites is greatly facilitated by the availability of high-quality specimens. For structure determinations by conventional diffraction techniques, large single-crystal specimens are essential. Alternatively, structural determinations by powder profile refinement methods relax the constraints on crystal size, but still require materials with a high degree of crystalline perfection. Studies conducted at CAMMP (Center for Advanced Microgravity Materials Processing) have demonstrated that microgravity processing can produce larger crystal sizes and fewer structural defects relative to terrestrial crystal growth. Principal Investigator: Dr. Albert Sacco
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NASA Technical Reports Server (NTRS)
1992-01-01
Zeolites are crystalline aluminosilicates that have complex framework structures. However, there are several features of zeolite crystals that make unequivocal structure determinations difficult. The acquisition of reliable structural information on zeolites is greatly facilitated by the availability of high-quality specimens. For structure determinations by conventional diffraction techniques, large single-crystal specimens are essential. Alternatively, structural determinations by powder profile refinement methods relax the constraints on crystal size, but still require materials with a high degree of crystalline perfection. Studies conducted at CAMMP (Center for Advanced Microgravity Materials Processing) have demonstrated that microgravity processing can produce larger crystal sizes and fewer structural defects relative to terrestrial crystal growth. Principal Investigator: Dr. Albert Sacco
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Scanning electron microscope view of iron crystal growing on pyroxene crystal
NASA Technical Reports Server (NTRS)
1972-01-01
A scanning electron microscope photograph of a four-micron size iron crystal growing on a pyroxene crystal (calcium-magnesium-iron silicate) from the Apollo 15 Hadley-Apennino lunar landing site. The well developed crystal faces indicate that the crystal was formed from a hot vapor as the rock was cooling.
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NASA Astrophysics Data System (ADS)
Ren, Xiaodong; Yang, Zhou; Yang, Dong; Zhang, Xu; Cui, Dong; Liu, Yucheng; Wei, Qingbo; Fan, Haibo; Liu, Shengzhong (Frank)
2016-02-01
Regulating the temperature during the direction contact and intercalation process (DCIP) for the transition from PbI2 to CH3NH3PbI3 modulated the crystallinity, crystal grain size and crystal grain orientation of the perovskite films. Higher temperatures produced perovskite films with better crystallinity, larger grain size, and better photovoltaic performance. The best cell, which had a PCE of 12.9%, was obtained on a film prepared at 200 °C. Further open circuit voltage decay and film resistance characterization revealed that the larger grain size contributed to longer carrier lifetime and smaller carrier transport resistance, both of which are beneficial for solar cell devices.Regulating the temperature during the direction contact and intercalation process (DCIP) for the transition from PbI2 to CH3NH3PbI3 modulated the crystallinity, crystal grain size and crystal grain orientation of the perovskite films. Higher temperatures produced perovskite films with better crystallinity, larger grain size, and better photovoltaic performance. The best cell, which had a PCE of 12.9%, was obtained on a film prepared at 200 °C. Further open circuit voltage decay and film resistance characterization revealed that the larger grain size contributed to longer carrier lifetime and smaller carrier transport resistance, both of which are beneficial for solar cell devices. Electronic supplementary information (ESI) available: XRD patterns and statistic results of solar cell performance. See DOI: 10.1039/c5nr08935b
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NASA Astrophysics Data System (ADS)
Wang, Chunyang; Du, Kui; Song, Kepeng; Ye, Xinglong; Qi, Lu; He, Suyun; Tang, Daiming; Lu, Ning; Jin, Haijun; Li, Feng; Ye, Hengqiang
2018-05-01
Low-angle grain boundaries generally exist in the form of dislocation arrays, while high-angle grain boundaries (misorientation angle >15 ° ) exist in the form of structural units in bulk metals. Here, through in situ atomic resolution aberration corrected electron microscopy observations, we report size-dependent grain-boundary structures improving both stabilities of electrical conductivity and mechanical properties in sub-10-nm-sized gold crystals. With the diameter of a nanocrystal decreasing below 10 nm, the high-angle grain boundary in the crystal exists as an array of dislocations. This size effect may be of importance to a new generation of interconnects applications.
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NASA Astrophysics Data System (ADS)
Hoffman, Tim
Hexagonal boron nitride (hBN) is a wide bandgap III-V semiconductor that has seen new interest due to the development of other III-V LED devices and the advent of graphene and other 2-D materials. For device applications, high quality, low defect density materials are needed. Several applications for hBN crystals are being investigated, including as a neutron detector and interference-less infrared-absorbing material. Isotopically enriched crystals were utilized for enhanced propagation of phonon modes. These applications exploit the unique physical, electronic and nanophotonics applications for bulk hBN crystals. In this study, bulk hBN crystals were grown by the flux method using a molten Ni-Cr solvent at high temperatures (1500°C) and atmospheric pressures. The effects of growth parameters, source materials, and gas environment on the crystals size, morphology and purity were established and controlled, and the reliability of the process was greatly improved. Single-crystal domains exceeding 1mm in width and 200microm in thickness were produced and transferred to handle substrates for analysis. Grain size dependence with respect to dwell temperature, cooling rate and cooling temperature were analyzed and modeled using response surface morphology. Most significantly, crystal grain width was predicted to increase linearly with dwell temperature, with single-crystal domains exceeding 2mm in at 1700°C. Isotopically enriched 10B and 11B hBN crystal were produced using a Ni-Cr-B flux method, and their properties investigated. 10B concentration was evaluated using SIMS and correlated to the shift in the Raman peak of the E2g mode. Crystals with enrichment of 99% 10B and >99% 11B were achieved, with corresponding Raman shift peaks at 1392.0 cm-1 and 1356.6 cm-1, respectively. Peak FWHM also decreased as isotopic enrichment approached 100%, with widths as low as 3.5 cm-1 achieved, compared to 8.0 cm-1 for natural abundance samples. Defect selective etching was performed using a molten NaOH-KOH etchant at 425°C-525°C, to quantify the quality of the crystals. Three etch pit shapes were identified and etch pit width was investigated as a function of temperature. Etch pit density and etch pit activation energy was estimated at 5x107 cm-2 and 60 kJ/mol, respectively. Screw and mixed-type dislocations were identified using diffraction-contrast TEM imaging.
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Lansiquot, Carisse; Boone-Kukoyi, Zainab; Shortt, Raquel; Thompson, Nishone; Ajifa, Hillary; Kioko, Bridgit; Constance, Edward Ned; Clement, Travis; Ozturk, Birol; Aslan, Kadir
2017-01-01
The use of indium tin oxide (ITO) and focused monomode microwave heating for the ultra-rapid crystallization of L-alanine (a model amino acid) is reported. Commercially available ITO dots (< 5 mm) attached to blank poly(methyl)methacrylate (PMMA, 5 cm in diameter with 21-well silicon isolators: referred to as the iCrystal plates) were found to withstand prolonged microwave heating during crystallization experiments. Crystallization of L-alanine was performed at room temperature (a control experiment), with the use of two microwave sources: a 2.45 GHz conventional microwave (900 W, power level 1, a control experiment) and 8 GHz (20 W) solid state, monomode microwave source with an applicator tip that focuses the microwave field to a 5-mm cavity. Initial appearance of L-alanine crystals and on iCrystal plates with ITO dots took 47 ± 2.9 min, 12 ± 7.6 min and 1.5 ± 0.5 min at room temperature, using a conventional microwave and focused monomode microwave heating, respectively. Complete evaporation of the solvent using the focused microwaves was achieved in 3.2 ± 0.5 min, which is ~52-fold and ~172-fold faster than that observed at room temperature and using conventional microwave heating, respectively. The size and number of L-alanine crystals was dependent on the type of the 21-well iCrystal plates and the microwave heating method: 33 crystals of 585 ± 137 μm in size at room temperature > 37 crystals of 542 ± 100 μm in size with conventional microwave heating > 331 crystals of 311 ± 190 μm in size with focused monomode microwave. FTIR, optical microscopy and powder X-ray diffraction analysis showed that the chemical composition and crystallinity of the L-alanine crystals did not change when exposed to microwave heating and ITO surfaces. In addition, theoretical simulations for the binding of L-alanine molecules to ITO and other metals showed the predicted nature of hydrogen bonds formed between L-alanine and these surfaces.
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Lansiquot, Carisse; Boone-Kukoyi, Zainab; Shortt, Raquel; Thompson, Nishone; Ajifa, Hillary; Kioko, Bridgit; Constance, Edward Ned; Clement, Travis; Ozturk, Birol; Aslan, Kadir
2018-01-01
The use of indium tin oxide (ITO) and focused monomode microwave heating for the ultra-rapid crystallization of L-alanine (a model amino acid) is reported. Commercially available ITO dots (< 5 mm) attached to blank poly(methyl)methacrylate (PMMA, 5 cm in diameter with 21-well silicon isolators: referred to as the iCrystal plates) were found to withstand prolonged microwave heating during crystallization experiments. Crystallization of L-alanine was performed at room temperature (a control experiment), with the use of two microwave sources: a 2.45 GHz conventional microwave (900 W, power level 1, a control experiment) and 8 GHz (20 W) solid state, monomode microwave source with an applicator tip that focuses the microwave field to a 5-mm cavity. Initial appearance of L-alanine crystals and on iCrystal plates with ITO dots took 47 ± 2.9 min, 12 ± 7.6 min and 1.5 ± 0.5 min at room temperature, using a conventional microwave and focused monomode microwave heating, respectively. Complete evaporation of the solvent using the focused microwaves was achieved in 3.2 ± 0.5 min, which is ~52-fold and ~172-fold faster than that observed at room temperature and using conventional microwave heating, respectively. The size and number of L-alanine crystals was dependent on the type of the 21-well iCrystal plates and the microwave heating method: 33 crystals of 585 ± 137 μm in size at room temperature > 37 crystals of 542 ± 100 μm in size with conventional microwave heating > 331 crystals of 311 ± 190 μm in size with focused monomode microwave. FTIR, optical microscopy and powder X-ray diffraction analysis showed that the chemical composition and crystallinity of the L-alanine crystals did not change when exposed to microwave heating and ITO surfaces. In addition, theoretical simulations for the binding of L-alanine molecules to ITO and other metals showed the predicted nature of hydrogen bonds formed between L-alanine and these surfaces. PMID:29657884
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Albasan, Hasan; Lulich, Jody P; Osborne, Carl A; Lekcharoensuk, Chalermpol; Ulrich, Lisa K; Carpenter, Kathleen A
2003-01-15
To determine effects of storage temperature and time on pH and specific gravity of and number and size of crystals in urine samples from dogs and cats. Randomized complete block design. 31 dogs and 8 cats. Aliquots of each urine sample were analyzed within 60 minutes of collection or after storage at room or refrigeration temperatures (20 vs 6 degrees C [68 vs 43 degrees F]) for 6 or 24 hours. Crystals formed in samples from 11 of 39 (28%) animals. Calcium oxalate (CaOx) crystals formed in vitro in samples from 1 cat and 8 dogs. Magnesium ammonium phosphate (MAP) crystals formed in vitro in samples from 2 dogs. Compared with aliquots stored at room temperature, refrigeration increased the number and size of crystals that formed in vitro; however, the increase in number and size of MAP crystals in stored urine samples was not significant. Increased storage time and decreased storage temperature were associated with a significant increase in number of CaOx crystals formed. Greater numbers of crystals formed in urine aliquots stored for 24 hours than in aliquots stored for 6 hours. Storage time and temperature did not have a significant effect on pH or specific gravity. Urine samples should be analyzed within 60 minutes of collection to minimize temperature- and time-dependent effects on in vitro crystal formation. Presence of crystals observed in stored samples should be validated by reevaluation of fresh urine.
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NASA Astrophysics Data System (ADS)
Tsai, Chun-Chien; Lee, Yao-Jen; Chiang, Ko-Yu; Wang, Jyh-Liang; Lee, I.-Che; Chen, Hsu-Hsin; Wei, Kai-Fang; Chang, Ting-Kuo; Chen, Bo-Ting; Cheng, Huang-Chung
2007-11-01
In this paper, location-controlled silicon crystal grains are fabricated by the excimer laser crystallization method which employs amorphous silicon spacer structure and prepatterned thin films. The amorphous silicon spacer in nanometer-sized width formed using spacer technology is served as seed crystal to artificially control superlateral growth phenomenon during excimer laser irradiation. An array of 1.8-μm-sized disklike silicon grains is formed, and the n-channel thin-film transistors whose channels located inside the artificially-controlled crystal grains exhibit higher performance of field-effect-mobility reaching 308cm2/Vs as compared with the conventional ones. This position-manipulated silicon grains are essential to high-performance and good uniformity devices.
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Oriented attachment by enantioselective facet recognition in millimeter-sized gypsum crystals.
Viedma, Cristóbal; Cuccia, Louis A; McTaggart, Alicia; Kahr, Bart; Martin, Alexander T; McBride, J Michael; Cintas, Pedro
2016-09-22
Crystal growth by oriented attachment involves the spontaneous self-assembly of adjoining crystals with common crystallographic orientations. Herein, we report the oriented attachment of gypsum crystals on agitation to form stereoselective mesoscale aggregates.
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Investigation of the milling capabilities of the F10 Fine Grind mill using Box-Behnken designs.
Tan, Bernice Mei Jin; Tay, Justin Yong Soon; Wong, Poh Mun; Chan, Lai Wah; Heng, Paul Wan Sia
2015-01-01
Size reduction or milling of the active is often the first processing step in the design of a dosage form. The ability of a mill to convert coarse crystals into the target size and size distribution efficiently is highly desirable as the quality of the final pharmaceutical product after processing is often still dependent on the dimensional attributes of its component constituents. The F10 Fine Grind mill is a mechanical impact mill designed to produce unimodal mid-size particles by utilizing a single-pass two-stage size reduction process for fine grinding of raw materials needed in secondary processing. Box-Behnken designs were used to investigate the effects of various mill variables (impeller, blower and feeder speeds and screen aperture size) on the milling of coarse crystals. Response variables included the particle size parameters (D10, D50 and D90), span and milling rate. Milled particles in the size range of 5-200 μm, with D50 ranging from 15 to 60 μm, were produced. The impeller and feeder speeds were the most critical factors influencing the particle size and milling rate, respectively. Size distributions of milled particles were better described by their goodness-of-fit to a log-normal distribution (i.e. unimodality) rather than span. Milled particles with symmetrical unimodal distributions were obtained when the screen aperture size was close to the median diameter of coarse particles employed. The capacity for high throughput milling of particles to a mid-size range, which is intermediate between conventional mechanical impact mills and air jet mills, was demonstrated in the F10 mill. Prediction models from the Box-Behnken designs will aid in providing a better guide to the milling process and milled product characteristics. Copyright © 2014 Elsevier B.V. All rights reserved.
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Large-volume protein crystal growth for neutron macromolecular crystallography
Ng, Joseph D.; Baird, James K.; Coates, Leighton; ...
2015-03-30
Neutron macromolecular crystallography (NMC) is the prevailing method for the accurate determination of the positions of H atoms in macromolecules. As neutron sources are becoming more available to general users, finding means to optimize the growth of protein crystals to sizes suitable for NMC is extremely important. Historically, much has been learned about growing crystals for X-ray diffraction. However, owing to new-generation synchrotron X-ray facilities and sensitive detectors, protein crystal sizes as small as in the nano-range have become adequate for structure determination, lessening the necessity to grow large crystals. Here, some of the approaches, techniques and considerations for themore » growth of crystals to significant dimensions that are now relevant to NMC are revisited. We report that these include experimental strategies utilizing solubility diagrams, ripening effects, classical crystallization techniques, microgravity and theoretical considerations.« less
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Large-volume protein crystal growth for neutron macromolecular crystallography
Ng, Joseph D.; Baird, James K.; Coates, Leighton; Garcia-Ruiz, Juan M.; Hodge, Teresa A.; Huang, Sijay
2015-01-01
Neutron macromolecular crystallography (NMC) is the prevailing method for the accurate determination of the positions of H atoms in macromolecules. As neutron sources are becoming more available to general users, finding means to optimize the growth of protein crystals to sizes suitable for NMC is extremely important. Historically, much has been learned about growing crystals for X-ray diffraction. However, owing to new-generation synchrotron X-ray facilities and sensitive detectors, protein crystal sizes as small as in the nano-range have become adequate for structure determination, lessening the necessity to grow large crystals. Here, some of the approaches, techniques and considerations for the growth of crystals to significant dimensions that are now relevant to NMC are revisited. These include experimental strategies utilizing solubility diagrams, ripening effects, classical crystallization techniques, microgravity and theoretical considerations. PMID:25849493
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Large-volume protein crystal growth for neutron macromolecular crystallography
DOE Office of Scientific and Technical Information (OSTI.GOV)
Ng, Joseph D.; Baird, James K.; Coates, Leighton
Neutron macromolecular crystallography (NMC) is the prevailing method for the accurate determination of the positions of H atoms in macromolecules. As neutron sources are becoming more available to general users, finding means to optimize the growth of protein crystals to sizes suitable for NMC is extremely important. Historically, much has been learned about growing crystals for X-ray diffraction. However, owing to new-generation synchrotron X-ray facilities and sensitive detectors, protein crystal sizes as small as in the nano-range have become adequate for structure determination, lessening the necessity to grow large crystals. Here, some of the approaches, techniques and considerations for themore » growth of crystals to significant dimensions that are now relevant to NMC are revisited. We report that these include experimental strategies utilizing solubility diagrams, ripening effects, classical crystallization techniques, microgravity and theoretical considerations.« less
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GCSS Cirrus Parcel Model Comparison Project
NASA Technical Reports Server (NTRS)
Lin, Ruei-Fong; Starr, David OC.; DeMott, Paul J.; Cotton, Richard; Jensen, Eric; Sassen, Kenneth; Einaudi, Franco (Technical Monitor)
2000-01-01
The Cirrus Parcel Model Comparison Project, a project of GCSS Working Group on Cirrus Cloud Systems (WG2), involves the systematic comparison of current models of ice crystal nucleation and growth for specified, typical, cirrus cloud environments. The goal of this project is to document and understand the factors resulting in significant inter-model differences. The intent is to foment research leading to model improvement and validation. In Phase 1 of the project reported here, simulated cirrus cloud microphysical properties are compared for situations of "warm" (-40 C) and "cold" (-60 C) cirrus subject to updrafts of 4, 20 and 100 cm/s, respectively. Five models participated. These models employ explicit microphysical schemes wherein the size distribution of each class of particles (aerosols and ice crystals) is resolved into bins. Simulations are made including both homogeneous and heterogeneous ice nucleation mechanisms. A single initial aerosol population of sulfuric acid particles is prescribed for all simulations. To isolate the treatment of the homogeneous freezing (of haze drops) nucleation process, the heterogeneous nucleation mechanism is disabled for a second parallel set of simulations. Qualitative agreement is found for the homogeneous-nucleation-only simulations, e.g., the number density of nucleated ice crystals increases with the strength of the prescribed updraft. However, non-negligible quantitative differences are found. Detailed analysis reveals that the homogeneous nucleation formulation, aerosol size, ice crystal growth rate (particularly the deposition coefficient), and water vapor uptake rate are critical components that lead to differences in predicted microphysics. Systematic bias exists between results based on a modified classical theory approach and models using an effective freezing temperature approach to the treatment of nucleation. Each approach is constrained by critical freezing data from laboratory studies, but each includes assumptions that can only be justified by further laboratory data. Consequently, it is not yet clear if the two approaches can be made consistent. Large haze particles may deviate considerably from equilibrium size in moderate to strong updrafts (20-100 cm/s) at -60 C when the commonly invoked equilibrium assumption is lifted. The resulting difference in particle-size-dependent solution concentration of haze particles may significantly affect the ice nucleation rate during the initial nucleation interval. The uptake rate for water vapor excess by ice crystals is another key component regulating the total number of nucleated ice crystals. This rate, the product of ice number concentration and ice crystal diffusional growth rate, which is sensitive to the deposition coefficient when ice particles are small, partially controls the peak nucleation rate achieved in an air parcel and the duration of the active nucleation time period. The effects of heterogeneous nucleation are most pronounced in weak updraft situations. Vapor competition by the nucleated (heterogeneous) ice crystals limits the achieved ice supersaturation and thus suppresses the contribution of homogeneous nucleation. Correspondingly, ice crystal number density is markedly reduced. Definitive laboratory and atmospheric benchmark data are needed for the heterogeneous nucleation process. Inter-model differences are correspondingly greater than in the case of the homogeneous nucleation process acting alone.
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The Nucleation and Growth of Protein Crystals
NASA Technical Reports Server (NTRS)
Pusey, Marc
2004-01-01
Obtaining crystals of suitable size and high quality continues to be a major bottleneck in macromolecular crystallography. Currently, structural genomics efforts are achieving on average about a 10% success rate in going from purified protein to a deposited crystal structure. Growth of crystals in microgravity was proposed as a means of overcoming size and quality problems, which subsequently led to a major NASA effort in microgravity crystal growth, with the agency also funding research into understanding the process. Studies of the macromolecule crystal nucleation and growth process were carried out in a number of labs in an effort to understand what affected the resultant crystal quality on Earth, and how microgravity improved the process. Based upon experimental evidence, as well as simple starting assumptions, we have proposed that crystal nucleation occurs by a series of discrete self assembly steps, which 'set' the underlying crystal symmetry. This talk will review the model developed, and its origins, in our laboratory for how crystals nucleate and grow, and will then present, along with preliminary data, how we propose to use this model to improve the success rate for obtaining crystals from a given protein.
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Saw, M H; Hishamuddin, E; Chong, C L; Yeoh, C B; Lim, W H
2017-01-01
The effect of 0.1-0.7% (w/w) of polyglycerol esters (PGEmix-8) on palm oil crystallization was studied using focused beam reflectance measurement (FBRM) to analyze the in-line changes of crystal size distribution during the crystallization. FBRM results show that 0.1-0.5% (w/w) of PGEmix-8 did not significantly affect nucleation but slightly retarded crystal growth. The use of 0.7% (w/w) additive showed greater heterogeneous nucleation compared to those with lower dosages of additive. Crystal growth was also greatly reduced when using 0.7% (w/w) dosage. The morphological study indicated that the palm oil crystals were smaller and more even in size than when more additive was added. Isothermal crystallization studies using differential scanning calorimetry (DSC) showed increased inhibitory effects on palm oil crystal growth with increasing concentration of PGEmix-8. These results imply that PGEmix-8 is a nucleation enhancing and crystal growth retarding additive in palm oil crystallization at 0.7% (w/w) dosage. Copyright © 2016 The Author(s). Published by Elsevier Ltd.. All rights reserved.
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Farley, Christopher; Burks, Geoffry; Siegert, Thomas; Juers, Douglas H
2014-08-01
In macromolecular cryocrystallography unit-cell parameters can have low reproducibility, limiting the effectiveness of combining data sets from multiple crystals and inhibiting the development of defined repeatable cooling protocols. Here, potential sources of unit-cell variation are investigated and crystal dehydration during loop-mounting is found to be an important factor. The amount of water lost by the unit cell depends on the crystal size, the loop size, the ambient relative humidity and the transfer distance to the cooling medium. To limit water loss during crystal mounting, a threefold strategy has been implemented. Firstly, crystal manipulations are performed in a humid environment similar to the humidity of the crystal-growth or soaking solution. Secondly, the looped crystal is transferred to a vial containing a small amount of the crystal soaking solution. Upon loop transfer, the vial is sealed, which allows transport of the crystal at its equilibrated humidity. Thirdly, the crystal loop is directly mounted from the vial into the cold gas stream. This strategy minimizes the exposure of the crystal to relatively low humidity ambient air, improves the reproducibility of low-temperature unit-cell parameters and offers some new approaches to crystal handling and cryoprotection.
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Farley, Christopher; Burks, Geoffry; Siegert, Thomas; Juers, Douglas H.
2014-01-01
In macromolecular cryocrystallography unit-cell parameters can have low reproducibility, limiting the effectiveness of combining data sets from multiple crystals and inhibiting the development of defined repeatable cooling protocols. Here, potential sources of unit-cell variation are investigated and crystal dehydration during loop-mounting is found to be an important factor. The amount of water lost by the unit cell depends on the crystal size, the loop size, the ambient relative humidity and the transfer distance to the cooling medium. To limit water loss during crystal mounting, a threefold strategy has been implemented. Firstly, crystal manipulations are performed in a humid environment similar to the humidity of the crystal-growth or soaking solution. Secondly, the looped crystal is transferred to a vial containing a small amount of the crystal soaking solution. Upon loop transfer, the vial is sealed, which allows transport of the crystal at its equilibrated humidity. Thirdly, the crystal loop is directly mounted from the vial into the cold gas stream. This strategy minimizes the exposure of the crystal to relatively low humidity ambient air, improves the reproducibility of low-temperature unit-cell parameters and offers some new approaches to crystal handling and cryoprotection. PMID:25084331
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Lee, Tu; Lin, Yu Kun; Tsai, Ya Chung; Lee, Hung Lin
2013-11-01
All experimental procedures discussed could be treated as a screening tool for probing the existence of molecular association among the chiral molecules and the solvent system. The molecular association phases of a racemic conglomerate solution (CS) and a racemic compound solution (RCS), and the templating effect of aspartic acid solid surface were observed to minimize the chance of redissolving racemic conglomerate and racemic compound aspartic acid in water and reforming an RCS in crossovers experiments. Only 1 %wt% of l-aspartic acid was adequate enough to induce a transformation from a racemic compound aspartic acid to a racemic conglomerate aspartic acid. This would make the propagation of biochirality more feasible and sound. However, tetrapeptide, (l-aspartic acid)4 , failed to induce enantioseparation as templates purely by crystallization. Nonclassical crystallization theory was needed to take into account the existence of a CS. Fundamental parameters of the crystallization kinetics such as the induction time, interfacial energy, Gibbs energetic barrier, nucleation rate, and critical size of stable nuclei of: (i) racemic compound aspartic acid, (ii) racemic compound aspartic acid seeded with 1 %wt% l-aspartic acid, (iii) racemic conglomerate aspartic acid, and (iv) l-aspartic acid were evaluated and compared with different initial supersaturation ratios. Morphological studies of crystals grown from the crystallization kinetics were also carried out. © 2013 Wiley Periodicals, Inc.
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Resonant spin tunneling in randomly oriented nanospheres of Mn 12 acetate
Lendínez, S.; Zarzuela, R.; Tejada, J.; ...
2015-01-06
We report measurements and theoretical analysis of resonant spin tunneling in randomly oriented nanospheres of a molecular magnet. Amorphous nanospheres of Mn₁₂ acetate have been fabricated and characterized by chemical, infrared, TEM, X-ray, and magnetic methods. Magnetic measurements have revealed sharp tunneling peaks in the field derivative of the magnetization that occur at the typical resonant field values for the Mn₁₂ acetate crystal in the field parallel to the easy axis.Theoretical analysis is provided that explains these observations. We argue that resonant spin tunneling in a molecular magnet can be established in a powder sample, without the need for amore » single crystal and without aligning the easy magnetization axes of the molecules. This is confirmed by re-analyzing the old data on a powdered sample of non-oriented micron-size crystals of Mn₁₂ acetate. In conclusion, our findings can greatly simplify the selection of candidates for quantum spin tunneling among newly synthesized molecular magnets.« less
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Resonant spin tunneling in randomly oriented nanospheres of Mn 12 acetate
DOE Office of Scientific and Technical Information (OSTI.GOV)
Lendínez, S.; Zarzuela, R.; Tejada, J.
We report measurements and theoretical analysis of resonant spin tunneling in randomly oriented nanospheres of a molecular magnet. Amorphous nanospheres of Mn₁₂ acetate have been fabricated and characterized by chemical, infrared, TEM, X-ray, and magnetic methods. Magnetic measurements have revealed sharp tunneling peaks in the field derivative of the magnetization that occur at the typical resonant field values for the Mn₁₂ acetate crystal in the field parallel to the easy axis.Theoretical analysis is provided that explains these observations. We argue that resonant spin tunneling in a molecular magnet can be established in a powder sample, without the need for amore » single crystal and without aligning the easy magnetization axes of the molecules. This is confirmed by re-analyzing the old data on a powdered sample of non-oriented micron-size crystals of Mn₁₂ acetate. In conclusion, our findings can greatly simplify the selection of candidates for quantum spin tunneling among newly synthesized molecular magnets.« less
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Boonna, Sureeporn; Tongta, Sunanta
2018-07-01
Structural transformation of crystallized debranched cassava starch prepared by temperature cycling (TC) treatment and then subjected to annealing (ANN), heat-moisture treatment (HMT) and dual hydrothermal treatments of ANN and HMT was investigated. The relative crystallinity, lateral crystal size, melting temperature and resistant starch (RS) content increased for all hydrothermally treated samples, but the slowly digestible starch (SDS) content decreased. The RS content followed the order: HMT → ANN > HMT > ANN → HMT > ANN > TC, respectively. The HMT → ANN sample showed a larger lateral crystal size with more homogeneity, whereas the ANN → HMT sample had a smaller lateral crystal size with a higher melting temperature. After cooking at 50% moisture, the increased RS content of samples was observed, particularly for the ANN → HMT sample. These results suggest that structural changes of crystallized debranched starch during hydrothermal treatments depend on initial crystalline characteristics and treatment sequences, influencing thermal stability, enzyme digestibility, and cooking stability. Copyright © 2018 Elsevier Ltd. All rights reserved.
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Analysis of stochastic crystallization in micron-sized droplets of undercooled liquid l-arabitol.
Guinet, Yannick; Carpentier, Laurent; Paccou, Laurent; Derollez, Patrick; Hédoux, Alain
2016-11-29
Kinetics of isothermal crystallization of l-arabitol were analyzed from the undercooled liquid state within micron-sized droplets from micro-Raman spectroscopy. This study reveals that crystallization slightly above T g is controlled by stochastic heterogeneous nucleation inherent to the droplet size. Microscopic Raman investigations performed in droplets give the unique opportunity to analyze the pure metastable Form II of l-arabitol. It was found that Form II is characterized by a molecular packing more compact than that of the stable Form I, inherent to strong intermolecular hydrogen bonding. Kinetics laws obtained by analyzing several droplets at different temperatures, reveal the transient character of Form II, quasi systematically detected during the crystallization process of form I. Form II appears as the first step of crystallization prior to successive short-living metastable states which is necessary to achieve a complete crystallization in Form I. It was found that the kinetics of conversion between the metastable states (Form II) into Form I is dependent on the amount of strong hydrogen bonding distinctive of Form II. Copyright © 2016 Elsevier Ltd. All rights reserved.
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Hydrothermal Synthesis of Metal Oxide Nanoparticles in Supercritical Water
Hayashi, Hiromichi; Hakuta, Yukiya
2010-01-01
This paper summarizes specific features of supercritical hydrothermal synthesis of metal oxide particles. Supercritical water allows control of the crystal phase, morphology, and particle size since the solvent's properties, such as density of water, can be varied with temperature and pressure, both of which can affect the supersaturation and nucleation. In this review, we describe the advantages of fine particle formation using supercritical water and describe which future tasks need to be solved. PMID:28883312
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Crystallization in a model glass: Influence of the boundary conditions
NASA Astrophysics Data System (ADS)
Jund, P.; Jullien, R.
1998-06-01
Using molecular dynamics calculations and the Voronoï tessellation, we study the evolution of the local structure of a soft-sphere glass vs. temperature starting from the liquid phase at different quenching rates. This study is done for different sizes and for two different boundary conditions, namely the usual cubic periodic boundary conditions and the isotropic hyperspherical boundary conditions for which the particles evolve on the surface of a hypersphere in four dimensions. Our results show that for small system sizes, crystallization can indeed be induced by the cubic boundary conditions. On the other hand, we show that finite-size effects are more pronounced on the hypersphere and that crystallization is artificially inhibited even for large system sizes.
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Coupled crystal orientation-size effects on the strength of nano crystals
Yuan, Rui; Beyerlein, Irene J.; Zhou, Caizhi
2016-01-01
We study the combined effects of grain size and texture on the strength of nanocrystalline copper (Cu) and nickel (Ni) using a crystal-plasticity based mechanics model. Within the model, slip occurs in discrete slip events exclusively by individual dislocations emitted statistically from the grain boundaries. We show that a Hall-Petch relationship emerges in both initially texture and non-textured materials and our values are in agreement with experimental measurements from numerous studies. We find that the Hall-Petch slope increases with texture strength, indicating that preferred orientations intensify the enhancements in strength that accompany grain size reductions. These findings reveal that texture is too influential to be neglected when analyzing and engineering grain size effects for increasing nanomaterial strength. PMID:27185364
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Descamps, Marc; Willart, Jean-François
2018-05-05
In the present paper we review different aspects of the crystallization of amorphous compounds in relation to specificities of the nucleation and growth rates. Its main purpose is: i) to underline the interest of a scaling analysis of recrystallization kinetics to identify similarities or disparities of experimental kinetic regimes. ii) to highlight the intrinsic link between the nucleation rate and growth rate with a temperature dependent characteristic transformation time τ(T), and a characteristic size ξ(T). The consequences on the influence of the sample size on kinetics of crystallization is considered. The significance of size effect and confinement for amorphous stabilization in the pharmaceutical sciences is discussed. Copyright © 2018. Published by Elsevier B.V.
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The Effect of Temperature and Solution pH on Tetragonal Lysozyme Nucleation Kinetics
NASA Technical Reports Server (NTRS)
Judge, Russell A.; Jacobs, Randolph S.; Frazier, Tyralynn; Snell, Edward H.; Pusey, Marc L.
1998-01-01
Part of the challenge of macromolecular crystal growth for structure determination is obtaining an appropriate number of crystals with a crystal volume suitable for x-ray analysis. In this respect an understanding of the effect of solution conditions on macromolecule nucleation rates is advantageous. This study investigated the effects of supersaturation, temperature and pH on the nucleation rate of tetragonal lysozyme crystals. Batch crystallization plates were prepared at given solution concentrations and incubated at set temperatures over one week. The number of crystals per well with their size and axial ratios were recorded and correlated with solution conditions, Duplicate experiments indicate the reproducibility of the technique, Crystal numbers were found to increase with increasing supersaturation and temperature. The most significant variable however, was pH, where crystal numbers changed by two orders of magnitude over the pH range 4.0 to 5.2. Crystal size varied also with solution conditions, with the largest crystals being obtained at pH 5.2. Having optimized the crystallization conditions, a batch of crystals were prepared under exactly the same conditions and fifty of these crystals were analyzed by x-ray techniques. The results indicate that even under the same crystallization conditions, a marked variation in crystal properties exists.
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Bolzoni, Leandro; Xia, Mingxu; Babu, Nadendla Hari
2016-01-01
The design of chemical compositions containing potent nuclei for the enhancement of heterogeneous nucleation in aluminium, especially cast alloys such as Al-Si alloys, is a matter of importance in order to achieve homogeneous properties in castings with complex geometries. We identified that Al3Nb/NbB2 compounds are effective heterogeneous nuclei and are successfully produced in the form of Al-2Nb-xB (x = 0.5, 1 and 2) master alloys. Our study shows that the inoculation of Al-10Si braze alloy with these compounds effectively promotes the heterogeneous nucleation of primary α-Al crystals and reduces the undercooling needed for solidification to take place. Moreover, we present evidences that these Nb-based compounds prevent the growth of columnar crystals and permit to obtain, for the first time, fine and equiaxed crystals in directionally solidified Al-10Si braze alloy. As a consequence of the potent heterogeneous particles, the size of the α-Al crystals was found to be less dependent on the processing conditions, especially the thermal gradient. Finally, we also demonstrate that the enhanced nucleation leads to the refinement of secondary phases such as eutectic silicon and primary silicon particles. PMID:28008967
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Susceptibility of contrail ice crystal numbers to aircraft soot particle emissions
NASA Astrophysics Data System (ADS)
Kärcher, B.; Voigt, C.
2017-08-01
We develop an idealized, physically based model describing combined effects of ice nucleation and sublimation on ice crystal number during persistent contrail formation. Our study represents the first effort to predict ice numbers at the point where contrails transition into contrail cirrus—several minutes past formation—by connecting them to aircraft soot particle emissions and atmospheric supersaturation with respect to ice. Results averaged over an observed exponential distribution of ice supersaturation (mean value 15%) indicate that large reductions in soot particle numbers are needed to lower contrail ice crystal numbers significantly for soot emission indices around 1015 (kg fuel)-1, because reductions in nucleated ice number are partially compensated by sublimation losses. Variations in soot particle (-50%) and water vapor (+10%) emission indices at threefold lower soot emissions resulting from biofuel blending cause ice crystal numbers to change by -35% and <5%, respectively. The efficiency of reduction depends on ice supersaturation and the size distribution of nucleated ice crystals in jet exhaust plumes and on atmospheric ice supersaturation, making the latter another key factor in contrail mitigation. We expect our study to have important repercussions for planning airborne measurements targeting contrail formation, designing parameterization schemes for use in large-scale models, reducing uncertainties in predicting contrail cirrus, and mitigating the climate impact of aviation.
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Actinide/beryllium neutron sources with reduced dispersion characteristics
Schulte, Louis D.
2012-08-14
Neutron source comprising a composite, said composite comprising crystals comprising BeO and AmBe.sub.13, and an excess of beryllium, wherein the crystals have an average size of less than 2 microns; the size distribution of the crystals is less than 2 microns; and the beryllium is present in a 7-fold to a 75-fold excess by weight of the amount of AmBe.sub.13; and methods of making thereof.
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Does size matter? Statistical limits of paleomagnetic field reconstruction from small rock specimens
NASA Astrophysics Data System (ADS)
Berndt, Thomas; Muxworthy, Adrian R.; Fabian, Karl
2016-01-01
As samples of ever decreasing sizes are being studied paleomagnetically, care has to be taken that the underlying assumptions of statistical thermodynamics (Maxwell-Boltzmann statistics) are being met. Here we determine how many grains and how large a magnetic moment a sample needs to have to be able to accurately record an ambient field. It is found that for samples with a thermoremanent magnetic moment larger than 10-11Am2 the assumption of a sufficiently large number of grains is usually given. Standard 25 mm diameter paleomagnetic samples usually contain enough magnetic grains such that statistical errors are negligible, but "single silicate crystal" works on, for example, zircon, plagioclase, and olivine crystals are approaching the limits of what is physically possible, leading to statistic errors in both the angular deviation and paleointensity that are comparable to other sources of error. The reliability of nanopaleomagnetic imaging techniques capable of resolving individual grains (used, for example, to study the cloudy zone in meteorites), however, is questionable due to the limited area of the material covered.
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Unusually large unit cell of lipid bicontinuous cubic phase: towards nature's length scales
NASA Astrophysics Data System (ADS)
Kim, Hojun; Leal, Cecilia
Lipid bicontinuous cubic phases are of great interest for drug delivery, protein crystallization, biosensing, and templates for directing hard material assembly. Structural modulations of lipid mesophases regarding phase identity and unit cell size are often necessary to augment loading and gain pore size control. One important example is the need for unit cells large enough to guide the crystallization of bigger proteins without distortion of the templating phase. In nature, bicontinuous cubic constructs achieve unit cell dimensions as high as 300 nm. However, the largest unit cell of lipid mesophases synthesized in the lab is an order of magnitude lower. In fact, it has been predicted theoretically that lipid bicontinuous cubic phases of unit cell dimensions exceeding 30 nm could not exist, as high membrane fluctuations would damp liquid crystalline order. Here we report non-equilibrium assembly methods of synthesizing metastable bicontinuous cubic phases with unit cell dimensions as high as 70 nm. The phases are stable for very long periods and become increasingly ordered as time goes by without changes to unit cell dimensions. We acknowledge the funding source as a NIH.
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Controlling ZIF-67 crystals formation through various cobalt sources in aqueous solution
DOE Office of Scientific and Technical Information (OSTI.GOV)
Guo, Xiangli; Jiangsu Key Laboratory of Advanced Metallic Materials, Nanjing 211189; Xing, Tiantian
2016-03-15
Zeolitic imidazolate frameworks ZIF-67 were prepared under hydrothermal (120 °C) and non-hydrothermal (room temperature) from various cobalt sources and 2-methylimidazolate (Hmim) in aqueous solution within 30 min. The particle size and morphology were found to be related to the reactivity of the cobalt salt, Hmim/Co{sup 2+} molar ratios and experimental condition. Using Co(NO{sub 3}){sub 2} as cobalt source, small-sized ZIF-67 crystals with agglomeration were formed. For CoCl{sub 2}, small-sized rhombic dodecahedron were obtained. While large-sized crystals of rhombic dodecahedron structure were obtained from CoSO{sub 4} and Co(OAc){sub 2}. Under hydrothermal condition, the size of ZIF-67 crystals tended to be moremore » uniform and the morphology were more regular comparing to non-hydrothermal condition. This study provides a simple way to control the size and morphology of ZIF-67 crystals prepared in aqueous solution. - Graphical abstract: Zeolitic imidazolate frameworks ZIF-67 were prepared under hydrothermal (120 °C) and non-hydrothermal (room temperature) from four different cobalt sources (Co(NO{sub 3}){sub 2}, CoCl{sub 2}, CoSO{sub 4} and Co(OAc){sub 2}) in aqueous solution within 30 min. The particle size and morphology were found to be related to the reactivity of the cobalt salt, Hmim/Co{sup 2+} molar ratios and experimental condition. - Highlights: • The particle size and morphology were determined by the reactivity of cobalt salt. • ZIF-67 could be prepared from CoSO{sub 4} and Co(OAc){sub 2} at Hmim/Co{sup 2+} molar ratio of 10. • Uniform and regular particles were obtained under hydrothermal condition.« less
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ERIC Educational Resources Information Center
Lange, Catherine
2008-01-01
In this inquiry-based, integrative art and science activity, Grade 5-8 students use multicolored Epsom salt (magnesium sulfate) crystallizing solutions to reveal beautiful, cylindrical, 3-dimensional, needle-shaped structures. Through observations of the crystal art, students analyze factors that contribute to crystal size and formation, compare…
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NASA Astrophysics Data System (ADS)
Mudalip, S. K. Abdul; Adam, F.; Parveen, J.; Abu Bakar, M. R.; Amran, N.; Sulaiman, S. Z.; Che Man, R.; Arshad, Z. I. Mohd; Shaarani, S. Md.
2017-06-01
This study investigate the effect of cooling rates on mefenamic acid crystallisation in ethyl acetate. The cooling rate was varied from 0.2 to 5 °C/min. The in-line conductivity system and turbidity system were employed to detect the onset of the crystallization process. The crystals produced were analysed using optical microscopy and Fourier transform infrared spectroscopy (FTIR). It was found that the crystals produced at different cooling rates were needle-like and exhibit polymorphic form type I. However, the aspect ratio and crystal size distributions were varied with the increased of cooling rate. A high crystals aspect ratio and narrower CSD (100-900 μm) was obtained at cooling rate of 0.5 °C/min. Thus, can be suggested as the most suitable cooling rate for crystallization of mefenamic acid in ethyl acetate.
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Choudhary, Muhammad Ajmal; Kundin, Julia; Emmerich, Heike; Oettel, Martin
2014-08-01
Phase-field-crystal (PFC) modeling has emerged as a computationally efficient tool to address crystal growth phenomena on atomistic length and diffusive time scales. We use a two-dimensional phase-field-crystal model for a binary system based on Elder et al. [Phys. Rev. B 75, 064107 (2007)] to study critical nuclei and their liquid-solid phase boundaries, in particular the nucleus size dependence of the liquid-solid interface tension as well as of the nucleation barrier. Critical nuclei are stabilized in finite systems of various sizes, however, the extracted interface tension as function of the nucleus radius r is independent of system size. We suggest a phenomenological expression to describe the dependence of the extracted interface tension on the nucleus radius r for the liquid-solid system. Moreover, the numerical PFC results show that this dependency can not be fully described by the nonclassical Tolman formula.
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Deducing growth mechanisms for minerals from the shapes of crystal size distributions
Eberl, D.D.; Drits, V.A.; Srodon, J.
1998-01-01
Crystal size distributions (CSDs) of natural and synthetic samples are observed to have several distinct and different shapes. We have simulated these CSDs using three simple equations: the Law of Proportionate Effect (LPE), a mass balance equation, and equations for Ostwald ripening. The following crystal growth mechanisms are simulated using these equations and their modifications: (1) continuous nucleation and growth in an open system, during which crystals nucleate at either a constant, decaying, or accelerating nucleation rate, and then grow according to the LPE; (2) surface-controlled growth in an open system, during which crystals grow with an essentially unlimited supply of nutrients according to the LPE; (3) supply-controlled growth in an open system, during which crystals grow with a specified, limited supply of nutrients according to the LPE; (4) supply- or surface-controlled Ostwald ripening in a closed system, during which the relative rate of crystal dissolution and growth is controlled by differences in specific surface area and by diffusion rate; and (5) supply-controlled random ripening in a closed system, during which the rate of crystal dissolution and growth is random with respect to specific surface area. Each of these mechanisms affects the shapes of CSDs. For example, mechanism (1) above with a constant nucleation rate yields asymptotically-shaped CSDs for which the variance of the natural logarithms of the crystal sizes (??2) increases exponentially with the mean of the natural logarithms of the sizes (??). Mechanism (2) yields lognormally-shaped CSDs, for which ??2 increases linearly with ??, whereas mechanisms (3) and (5) do not change the shapes of CSDs, with ??2 remaining constant with increasing ??. During supply-controlled Ostwald ripening (4), initial lognormally-shaped CSDs become more symmetric, with ??2 decreasing with increasing ??. Thus, crystal growth mechanisms often can be deduced by noting trends in ?? versus ??2 of CSDs for a series of related samples.
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NASA Astrophysics Data System (ADS)
Falkner, Joshua Charles
The three projects within this work address the difficulties of controlling biomolecular crystal formats (i.e. size and shape), producing 3-D ordered composite materials from biomolecular crystal templates, and understanding the mechanism of a practical iron oxide synthesis. The unifying thread consistent throughout these three topics is the development of methods to manipulate nanomaterials using a bottom-up approach. Biomolecular crystals are nanometer to millimeter sized crystals that have well ordered mesoporous solvent channels. The overall physical dimensions of these crystals are highly dependent on crystallization conditions. The controlled growth of micro- and nanoprotein crystals was studied to provide new pathways for creating smaller crystalline protein materials. This method produced tetragonal hen egg-white lysozyme crystals (250--100,000 nm) with near monodisperse size distributions (<15%). With this degree of control, existing protein crystal applications such as drug delivery and analytical sensors can reach their full potential. Applications for larger crystals with inherently ubiquitous pore structures could extend to materials used for membranes or templates. In this work, the porous structure of larger cowpea mosaic virus crystals was used to template metal nanoparticle growth within the body centered cubic crystalline network. The final composite material was found to have long range ordering of palladium and platinum nonocrystal aggregates (10nm) with symmetry consistent to the virus template. Nanoparticle synthesis itself is an immense field of study with an array of diverse applications. The final piece of this work investigates the mechanism behind a previously developed iron oxide synthesis to gain more understanding and direction to future synthesis strategies. The particle growth mechanism was found to proceed by the formation of a solvated iron(III)oleate complex followed by a reduction of iron (III) to iron (II). This unstable iron(II) nucleates to form a wustite (FeO) core which serves as an epitaxial surface for the magnetite (Fe3O4) shell growth. This method produces spherical particles (6-60nm) with relative size distributions of less than 15%.
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Synthesis of nanometer-sized sodalite without adding organic additives.
Fan, Wei; Morozumi, Kazumasa; Kimura, Riichiro; Yokoi, Toshiyuki; Okubo, Tatsuya
2008-06-01
Aggregates (80 nm) of sodalite nanocrystals with crystallite sizes ranging from 20 to 40 nm have been synthesized from a sodium aluminosilicate solution at low temperature, without adding any organic additives, while paying attention to the key factors for the synthesis of nanosized zeolite crystals. The physical properties of nanosized sodalite crystals were characterized by X-ray diffraction, scanning electron microscopy, high-resolution transmission electron microscopy, 29Si solid-state magic-angle spinning (MAS) NMR, and N2 adsorption. As expected, the external surface area of nanosized sodalite crystals is significantly increased compared with that of microsized sodalite crystals. The size of synthesized sodalite crystals can be controlled from 20 nm to 10 microm. It is found that the preparation of a homogeneous aluminosilicate solution followed by the formation of an aluminosilicate hard gel by adjusting the initial composition, for example, SiO2/Al2O3 and Na2O/H2O ratios, is critical for synthesis.
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NASA Astrophysics Data System (ADS)
Deleer, B. G. M.
1981-11-01
Based on population balance, CSD behavior as a function of geometrical and operating variables was studied, using a crystallizer. A potash alum-water system, involving a separation technique which uses surface active agents and an apolar, organic liquid to separate potash alum crystals from mother liquid under the influence of gravity was used to check experimental findings against literature data. Results show action of annular settling spaces is strongly influenced by fluid velocities perpendicular to those directed upwards. The well-mixed volume decreases with increasing crystallizer size until a minimum effective volume is reached. As supersaturation is constant throughout the crystallizer volume under stationary operating conditions, the annular settling space behaves like a growth chamber for crystals in its volume. Swirl in the lower part of the annular volume introduces significant back mixing. Crystals within this space either grow and return to the well-mixed part, or withdraw from the annular volume permanently.
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Preparation of fine single crystals of magnetic superconductor RuSr2GdCu2O8-δ by partial melting
NASA Astrophysics Data System (ADS)
Yamaki, Kazuhiro; Bamba, Yoshihiro; Irie, Akinobu
2018-03-01
In this study, fine uniform RuSr2GdCu2O8-δ (RuGd-1212) single crystals have been successfully prepared by partial melting. Synthesis temperature could be lowered to a value not exceeding the decomposition temperature of RuGd-1212 using the Sr-Gd-Cu-O flux. The crystals grown by alumina boats are cubic, which coincides with the result of a previous study of RuGd-1212 single crystals using platinum crucibles. The single crystals were up to 15 × 15 × 15 µm3 in size and their lattice constants were consistent with those of polycrystalline samples reported previously. Although the present size of single crystals is not sufficient for measurements, the partial melting technique will be beneficial for future progress of research using RuGd-1212 single crystals. Appropriate nominal composition, sintering atmosphere, and temperature are essential factors for growing RuGd-1212 single crystals.
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Er3+-doped transparent glass ceramics containing micron-sized SrF2 crystals for 2.7 μm emissions
Jiang, Yiguang; Fan, Jintai; Jiang, Benxue; Mao, Xiaojian; Tang, Junzhou; Xu, Yinsheng; Dai, Shixun; Zhang, Long
2016-01-01
Er3+-doped transparent glass ceramics containing micron-sized SrF2 crystals were obtained by direct liquid-phase sintering of a mixture of SrF2 powders and precursor glass powders at 820 °C for 15 min. The appearance and microstructural evolution of the SrF2 crystals in the resulting glass ceramics were investigated using X-ray diffraction, field-emission scanning electron microscopy and transmission microscopy. The SrF2 crystals are ~15 μm in size and are uniformly distributed throughout the fluorophosphate glass matrix. The glass ceramics achieve an average transmittance of 75% in the visible region and more than 85% in the near-IR region. The high transmittance of the glass ceramics results from matching the refractive index of the SrF2 with that of the precursor glass. Energy dispersive spectroscopy, photoluminescence spectra, and photoluminescence lifetimes verified the incorporation of Er3+ into the micron-sized SrF2 crystals. Intense 2.7 μm emissions due to the 4I11/2 → 4I13/2 transition were observed upon excitation at 980 nm using a laser diode. The maximum value of the emission cross section of Er3+ around 2.7 μm is more than 1.2 × 10−20 cm2, which indicates the potential of using transparent glass ceramics containing micron-sized SrF2 crystals for efficient 2.7 μm lasers and amplifiers. PMID:27430595
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Er(3+)-doped transparent glass ceramics containing micron-sized SrF2 crystals for 2.7 μm emissions.
Jiang, Yiguang; Fan, Jintai; Jiang, Benxue; Mao, Xiaojian; Tang, Junzhou; Xu, Yinsheng; Dai, Shixun; Zhang, Long
2016-07-19
Er(3+)-doped transparent glass ceramics containing micron-sized SrF2 crystals were obtained by direct liquid-phase sintering of a mixture of SrF2 powders and precursor glass powders at 820 °C for 15 min. The appearance and microstructural evolution of the SrF2 crystals in the resulting glass ceramics were investigated using X-ray diffraction, field-emission scanning electron microscopy and transmission microscopy. The SrF2 crystals are ~15 μm in size and are uniformly distributed throughout the fluorophosphate glass matrix. The glass ceramics achieve an average transmittance of 75% in the visible region and more than 85% in the near-IR region. The high transmittance of the glass ceramics results from matching the refractive index of the SrF2 with that of the precursor glass. Energy dispersive spectroscopy, photoluminescence spectra, and photoluminescence lifetimes verified the incorporation of Er(3+) into the micron-sized SrF2 crystals. Intense 2.7 μm emissions due to the (4)I11/2 → (4)I13/2 transition were observed upon excitation at 980 nm using a laser diode. The maximum value of the emission cross section of Er(3+) around 2.7 μm is more than 1.2 × 10(-20) cm(2), which indicates the potential of using transparent glass ceramics containing micron-sized SrF2 crystals for efficient 2.7 μm lasers and amplifiers.
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NASA Technical Reports Server (NTRS)
Gibson, U. J.; Horrell, E. E.; Kou, Y.; Pusey, Marc
2000-01-01
We have measured the nucleation and aspect ratio of CEWL crystals grown by vapor diffusion in acetate, butyrate, carbonate, succinate, and phosphate buffers in a range of pH spanning the pK(sub a) of these buffers. The nucleation numbers drop off significantly in the vicinity of pK(sub a) for each of the buffers except the phosphate system, in which we used only the pH range around the second titration point(pK2). There is a concomitant increase in the sizes of the crystals. Some typical nucleation number results are shown. These data support and extend other observations. In addition, we have examined changes in aspect ratio which accompany the suppression of nucleation within each buffer system. The length of the face in the [001] direction was measured, and compared to the width of the (110) face in the [110] type directions. We find that while the aspect ratio of the crystals is affected by pH, it is dominated by a correlation with the size of the crystals. Small crystals are longer in the [0011 direction than crystals that are larger (higher pH within a buffer system). This relationship is found to hold independent of the choice of buffer. These results are consistent with those of Judge et al, who used a batch process which resulted in uniform sizing of crystals at each pH. In these experiments, we specifically avoid agitating the protein/salt buffer mixture when combining the two. This permits the formation of a range of sizes at a given pH. The results for a .05 M acetate 5% NaCl buffer are also shown. We will discuss these results in light of a growth model.
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Slotted Photonic Crystal Sensors
Scullion, Mark G.; Krauss, Thomas F.; Di Falco, Andrea
2013-01-01
Optical biosensors are increasingly being considered for lab-on-a-chip applications due to their benefits such as small size, biocompatibility, passive behaviour and lack of the need for fluorescent labels. The light guiding mechanisms used by many of them results in poor overlap of the optical field with the target molecules, reducing the maximum sensitivity achievable. This review article presents a new platform for optical biosensors, namely slotted photonic crystals, which provide higher sensitivities due to their ability to confine, spatially and temporally, the optical mode peak within the analyte itself. Loss measurements showed values comparable to standard photonic crystals, confirming their ability to be used in real devices. A novel resonant coupler was designed, simulated, and experimentally tested, and was found to perform better than other solutions within the literature. Combining with cavities, microfluidics and biological functionalization allowed proof-of-principle demonstrations of protein binding to be carried out. Higher sensitivities were observed in smaller structures than possible with most competing devices reported in the literature. This body of work presents slotted photonic crystals as a realistic platform for complete on-chip biosensing; addressing key design, performance and application issues, whilst also opening up exciting new ideas for future study. PMID:23503295
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Kim, Minjeong; Choi, Myoung Gil; Ra, Ho Won; Park, Seung Bin; Kim, Yong-Joo; Lee, Kyubock
2018-02-13
The encapsulation of living cells is appealing for its various applications to cell-based sensors, bioreactors, biocatalysts, and bioenergy. In this work, we introduce the encapsulation of multiple microalgal cells in hollow polymer shells of rhombohedral shape by the following sequential processes: embedding of microalgae in CaCO₃ crystals; layer-by-layer (LbL) coating of polyelectrolytes; and removal of sacrificial crystals. The microcapsule size was controlled by the alteration of CaCO₃ crystal size, which is dependent on CaCl₂/Na₂CO₃ concentration. The microalgal cells could be embedded in CaCO₃ crystals by a two-step process: heterogeneous nucleation of crystal on the cell surface followed by cell embedment by the subsequent growth of crystal. The surfaces of the microalgal cells were highly favorable for the crystal growth of calcite; thus, micrometer-sized microalgae could be perfectly occluded in the calcite crystal without changing its rhombohedral shape. The surfaces of the microcapsules, moreover, could be decorated with gold nanoparticles, Fe₃O₄ magnetic nanoparticles, and carbon nanotubes (CNTs), by which we would expect the functionalities of a light-triggered release, magnetic separation, and enhanced mechanical and electrical strength, respectively. This approach, entailing the encapsulation of microalgae in semi-permeable and hollow polymer microcapsules, has the potential for application to microbial-cell immobilization for high-biomass-concentration cultivation as well as various other bioapplications.
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Baghdasaryan, Tigran; Geernaert, Thomas; Chah, Karima; Caucheteur, Christophe; Schuster, Kay; Kobelke, Jens; Thienpont, Hugo; Berghmans, Francis
2018-04-03
It is common belief that photonic crystals behave similarly to isotropic and transparent media only when their feature sizes are much smaller than the wavelength of light. Here, we counter that belief and we report on photonic crystals that are transparent for anomalously high normalized frequencies up to 0.9, where the crystal's feature sizes are comparable with the free space wavelength. Using traditional photonic band theory, we demonstrate that the isofrequency curves can be circular in the region above the first stop band for triangular lattice photonic crystals. In addition, by simulating how efficiently a tightly focused Gaussian beam propagates through the photonic crystal slab, we judge on the photonic crystal's transparency rather than on isotropy only. Using this approach, we identified a wide range of photonic crystal parameters that provide anomalous transparency. Our findings indicate the possibility to scale up the features of photonic crystals and to extend their operational wavelength range for applications including optical cloaking and graded index guiding. We applied our result in the domain of femtosecond laser micromachining, by demonstrating what we believe to be the first point-by-point grating inscribed in a multi-ring photonic crystal fiber.
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Effects of organic matter on crystallization of struvite in biologically treated swine wastewater.
Capdevielle, Aurélie; Sýkorová, Eva; Béline, Fabrice; Daumer, Marie-Line
2016-01-01
A sustainable way to recover phosphorus (P) in swine wastewater involves a preliminary step of P dissolution followed by the separation of particulate organic matter (OM). The next two steps are firstly the precipitation of struvite crystals done by adding a crystallization reagent (magnesia) and secondly the filtration of the crystals. To develop the process successfully at an industrial scale, the control of the mechanisms of precipitation is the key point in order to obtain high value-added products, that is, big struvite crystals easy to harvest and handle. Experiments with process parameters optimized previously in a synthetic swine wastewater were performed on real swine wastewater to assess the role of the OM on struvite crystallization. After 24 h, with a pH increase to 6.8 only, 90% of the initial P was precipitated and 60% was precipitated as struvite. 80% of the solid recovered was in the fraction > 100 µm. The other forms recovered were brushite, amorphous calcium phosphate, NaCl, KCl and OM. The influence of OM on struvite precipitation in acidified swine wastewater was negative on the reaction kinetics but positive on the size of the struvite crystals. The presence of colloidal particles increased the size of the struvite crystals but slowed down the kinetics due to the viscosity induced by the repulsive force of the colloids. The maximum size of single struvite crystals (200 µm) was observed with the presence of particulate OM.
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Thompson, Nishone; Boone-Kukoyi, Zainab; Shortt, Raquel; Lansiquot, Carisse; Kioko, Bridgit; Bonyi, Enock; Toker, Salih; Ozturk, Birol; Aslan, Kadir
2017-01-01
Gout is caused by the overproduction of uric acid and the inefficient metabolism of dietary purines in humans. Current treatments of gout, which include anti-inflammatory drugs, cyclooxygenase-2 inhibitors, and systemic glucocorticoids, have harmful side-effects. Our research laboratory has recently introduced an innovative approach for the decrystallization of biological and chemical crystals using the Metal-Assisted and Microwave-Accelerated Evaporative Decrystallization (MAMAD) technique. In the MAMAD technique, microwave energy is used to heat and activate gold nanoparticles that behave as “nano-bullets” to rapidly disrupt the crystal structure of biological crystals placed on planar surfaces. In this study, crystals of various sizes and compositions were studied as models for tophaceous gout at different stages (i.e., uric acid as small crystals (~10–100 μm) and L-alanine as medium (~300 μm) and large crystals (~4400 μm). Our results showed that the use of the MAMAD technique resulted in the reduction of the size and number of uric acid and L-alanine crystals up to >40% when exposed to intermittent microwave heating (up to 20 W power at 8 GHz) in the presence of 20 nm gold nanoparticles up to 120 s. This study demonstrates that the MAMAD technique can be potentially used as an alternative therapeutic method for the treatment of gout by effective decrystallization of large crystals, similar in size to those that often occur in gout. PMID:27763557
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Lattice Boltzmann Simulation of Kinetic Isotope Effect During Snow Crystal Formation
NASA Astrophysics Data System (ADS)
Lu, G.; Depaolo, D. J.; Kang, Q.; Zhang, D.
2007-12-01
The isotopic composition of precipitation, especially that of snow, plays a special role in the global hydrological cycle and in reconstruction of past climates using polar ice cores. The fractionation of the major water isotope species (HHO, HDO, HHO-18) during ice crystal formation is critical to understanding the global distribution of isotopes in precipitation. Ice crystal growth in clouds is traditionally treated with a spherically-symmetric steady state diffusion model, with semi-empirical modifications added to account for ventilation and for complex crystal morphology. Although it is known that crystal growth rate, which depends largely on the degree of vapor over- saturation, determines crystal morphology, there are no quantitative models that relate morphology to the vapor saturation factor. Since kinetic (vapor phase diffusion-controlled) isotopic fractionation also depends on growth rate, there should be direct relationships between vapor saturation, crystal morphology, and crystal isotopic composition. We use a 2D lattice Boltzmann model to simulate diffusion-controlled ice crystal growth from vapor- oversaturated air. In the model, crystals grow solely according to the diffusive fluxes just above the crystal surfaces, and hence crystal morphology arises from the initial and boundary conditions in the model and does not need to be specified a priori. Crystal growth patterns can be varied between random growth and deterministic growth (along the maximum concentration gradient for example). The input parameters needed are the isotope- dependent vapor deposition rate constant (k) and the water vapor diffusivity in air (D). The values of both k and D can be computed from kinetic theory, and there are also experimentally determined values of D. The deduced values of k are uncertain to the extent that the condensation coefficient for ice is uncertain. The ratio D/k is a length (order 1 micron) that determines the minimum scale of dendritic growth features and allows us to scale the numerical calculations to atmospheric conditions. Our calculations confirm that the crystal/vapor isotopic fractionation approaches the equilibrium value, and the crystals are compact (circular in 2D) as the saturation factor approaches unity (S= 1.0). However, few natural crystals form under such conditions. At higher oversaturation (e.g. S = 1.2), dendritic crystals of millimeter size develop on timescales appropriate to cloud processes, and kinetic effects control isotopic fractionation. Fractionation factors for dendritic crystals are similar to those predicted by the spherical diffusion model, but the model also gives estimates of crystal heterogeneity. Dendritic crystals are constrained to be relatively large, with dimension much greater than about 20D/k. The most difficult aspect of the modeling is to account for the large density difference between air and ice, which requires us to use a fictitious higher density for the vapor-oversaturated air and scale the crystal growth time accordingly. An approach using a larger scale simulation and the domain decomposition method can provide a vapor flux for a nested smaller scale calculation. The results clarify the controls on crystal growth, and the relationships between saturation state, growth rate, crystal morphology and isotopic fractionation.
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Modeling solute clustering in the diffusion layer around a growing crystal.
Shiau, Lie-Ding; Lu, Yung-Fang
2009-03-07
The mechanism of crystal growth from solution is often thought to consist of a mass transfer diffusion step followed by a surface reaction step. Solute molecules might form clusters in the diffusion step before incorporating into the crystal lattice. A model is proposed in this work to simulate the evolution of the cluster size distribution due to the simultaneous aggregation and breakage of solute molecules in the diffusion layer around a growing crystal in the stirred solution. The crystallization of KAl(SO(4))(2)12H(2)O from aqueous solution is studied to illustrate the effect of supersaturation and diffusion layer thickness on the number-average degree of clustering and the size distribution of solute clusters in the diffusion layer.
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Crystal growth and annealing for minimized residual stress
Gianoulakis, Steven E.
2002-01-01
A method and apparatus for producing crystals that minimizes birefringence even at large crystal sizes, and is suitable for production of CaF.sub.2 crystals. The method of the present invention comprises annealing a crystal by maintaining a minimal temperature gradient in the crystal while slowly reducing the bulk temperature of the crystal. An apparatus according to the present invention includes a thermal control system added to a crystal growth and annealing apparatus, wherein the thermal control system allows a temperature gradient during crystal growth but minimizes the temperature gradient during crystal annealing.
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NASA Astrophysics Data System (ADS)
de Azevedo Jacqueline, Resende; Fabienne, Espitalier; Jean-Jacques, Letourneau; Inês, Ré Maria
2017-08-01
LASSBio-294 (3,4-methylenedioxybenzoyl-2-thienylhydrazon) is a poorly soluble drug which has been proposed to have major advantages over other cardiotonic drugs. Poorly water soluble drugs present limited bioavailability due to their low solubility and dissolution rate. An antisolvent crystallization processing can improve the dissolution rate by decreasing the crystals particle size. However, LASSBio-294 is also poorly soluble in organic solvents and this operation is limited. In order to open new perspectives to improve dissolution rate, this work has investigated LASSBio-294 in terms of its antisolvent crystallization in 1-ethyl-3-methylimidazolium methyl phosphonate [emim][CH3O(H)PO2] as solvent and water as antisolvent. Two modes of mixing are tested in stirred vessel with different pre-mixers (Roughton or T-mixers) in order to investigate the mixing effect on the crystal properties (crystalline structure, particle size distribution, residual solvent and in vitro dissolution rate). Smaller drug particles with unchanged crystalline structure were obtained. Despite the decrease of the elementary particles size, the recrystallized particles did not achieve a better dissolution profile. However, this study was able to highlight a certain number of findings such as the impact of the hydrodynamic conditions on the crystals formation and the presence of a gel phase limiting the dissolution rate.
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Influence of nano-size inclusions on spall fracture of copper single crystals
DOE Office of Scientific and Technical Information (OSTI.GOV)
Razorenov, S. V.; Ivanchihina, G. E.; Kanel, G. I.
2007-12-12
Spall experiments have been carried out for copper in different structural states. The samples were copper single crystals, crystals of Cu+0.1% Si, copper crystals with silica particles of 180 nm average size, and polycrystalline copper. In experiments, the free surface velocity histories were recorded with the VISAR. The recovered samples were studied using optical microscopy and SEM. Solid solution Cu+0.1% Si demonstrates slower spall process than pure copper crystals. At longer pulse durations its spall strength is slightly less than that of pure crystals but approaches the latter with decreasing pulse duration. Fracture of copper with silica inclusions is completedmore » much faster. The spall strength of this material is close to that of Cu+0.1% Si crystals at longer pulse duration and approaches the strength of polycrystalline copper with decreasing the load duration. Fractography of the spall surfaces correlates with the free surface velocity histories. The main fracture surface of the Cu+0.1% Si grains consists of net of dimples {approx}4 {mu}m to 40 {mu}m mean diameter. The fracture surfaces of copper with silica inclusions is covered by a net of dimples of 1 {mu}m to 5 {mu}m size.« less
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Hammond, Robert B; Pencheva, Klimentina; Roberts, Kevin J; Auffret, Tony
2007-08-01
The poor solubility of potential drug molecules is a significant problem in the design of pharmaceutical formulations. It is well known, however, that the solubility of crystalline materials is enhanced when the particle size is reduced to submicron levels and this factor can be expected to enhance drug product bioavailability. Direct estimation of solubility enhancement, as calculated via the Gibbs-Thompson relationship, demands reasonably accurate values for the particle/solution interfacial tension and, in particular, its anisotropy with respect to the crystal product's habit and morphology. In this article, an improved, more molecule-centered, approach is presented towards the calculation of solubility enhancement factors in which molecular modeling techniques are applied, and the effects associated with both crystal habit modification and solvent choice are examined. A case study for facetted, acetyl salicylic acid (aspirin) crystals in equilibrium with saturated aqueous ethanol solution reveals that their solubility will be enhanced in the range (7-58%) for a crystal size of 0.02 microm, with significantly higher enhancement for crystal morphologies in which the hydrophobic crystal faces are more predominant than the hydrophilic faces and for solvents in which the solubility is smaller. (c) 2007 Wiley-Liss, Inc. and the American Pharmacists Association.
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NASA Technical Reports Server (NTRS)
Gatsonis, Nikos A.; Alexandrou, Andreas; Shi, Hui; Ongewe, Bernard; Sacco, Albert, Jr.
1999-01-01
Crystals grown from liquid solutions have important industrial applications. Zeolites, for instance, a class of crystalline aluminosilicate materials, form the backbone of the chemical process industry worldwide, as they are used as adsorbents and catalysts. Many of the phenomena associated with crystal growth processes are not well understood due to complex microscopic and macroscopic interactions. Microgravity could help elucidate these phenomena and allow the control of defect locations, concentration, as well as size of crystals. Microgravity in an orbiting spacecraft could help isolate the possible effects of natural convection (which affects defect formation) and minimize sedimentation. In addition, crystals will stay essentially suspended in the nutrient pool under a diffusion-limited growth condition. This is expected to promote larger crystals by allowing a longer residence time in a high-concentration nutrient field. Among other factors, the crystal size distribution depends on the nucleation rate and crystallization. These two are also related to the "gel" polymerization/depolymerization rate. Macroscopic bulk mass and flow transport and especially gravity, force the crystals down to the bottom of the reactor, thus forming a sedimentation layer. In this layer, the growth rate of the crystals slows down as crystals compete for a limited amount of nutrients. The macroscopic transport phenomena under certain conditions can, however, enhance the nutrient supply and therefore, accelerate crystal growth. Several zeolite experiments have been performed in space with mixed results. The results from our laboratory have indicated an enhancement in size of 30 to 70 percent compared to the best ground based controls, and a reduction of lattice defects in many of the space grown crystals. Such experiments are difficult to interpret, and cannot be easily used to derive empirical or other laws since many physical parameters are simultaneously involved in the process. At the same time, however, there is increased urgency to develop such an understanding in order to more accurately quantify the process. In order to better understand the results obtained from our prior space experiments, and design future experiments, a detailed fluid dynamic model simulating the crystal growth mechanism is required. This will not only add to the fundamental knowledge on the crystallization of zeolites, but also be useful in predicting the limits of size and growth of these important industrial materials. Our objective is to develop macro/microscopic theoretical and computational models to study the effect of transport phenomena in the growth of crystals grown in solutions. Our effort has concentrated so far in the development of separate macroscopic and microscopic models. The major highlights of our accomplishments are described.
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Dependence of crystal size on the catalytic performance of a porous coordination polymer.
Kiyonaga, Tomokazu; Higuchi, Masakazu; Kajiwara, Takashi; Takashima, Yohei; Duan, Jingui; Nagashima, Kazuro; Kitagawa, Susumu
2015-02-14
Submicrosized MOF-76(Yb) exhibits a higher catalytic performance for esterification than microsized MOF-76(Yb). Control of the crystal size of porous heterogeneous catalysts, such as PCP/MOFs, offers a promising approach to fabricating high-performance catalysts based on accessibility to the internal catalytic sites.
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Determining ice water content from 2D crystal images in convective cloud systems
NASA Astrophysics Data System (ADS)
Leroy, Delphine; Coutris, Pierre; Fontaine, Emmanuel; Schwarzenboeck, Alfons; Strapp, J. Walter
2016-04-01
Cloud microphysical in-situ instrumentation measures bulk parameters like total water content (TWC) and/or derives particle size distributions (PSD) (utilizing optical spectrometers and optical array probes (OAP)). The goal of this work is to introduce a comprehensive methodology to compute TWC from OAP measurements, based on the dataset collected during recent HAIC (High Altitude Ice Crystals)/HIWC (High Ice Water Content) field campaigns. Indeed, the HAIC/HIWC field campaigns in Darwin (2014) and Cayenne (2015) provide a unique opportunity to explore the complex relationship between cloud particle mass and size in ice crystal environments. Numerous mesoscale convective systems (MCSs) were sampled with the French Falcon 20 research aircraft at different temperature levels from -10°C up to 50°C. The aircraft instrumentation included an IKP-2 (isokinetic probe) to get reliable measurements of TWC and the optical array probes 2D-S and PIP recording images over the entire ice crystal size range. Based on the known principle relating crystal mass and size with a power law (m=α•Dβ), Fontaine et al. (2014) performed extended 3D crystal simulations and thereby demonstrated that it is possible to estimate the value of the exponent β from OAP data, by analyzing the surface-size relationship for the 2D images as a function of time. Leroy et al. (2015) proposed an extended version of this method that produces estimates of β from the analysis of both the surface-size and perimeter-size relationships. Knowing the value of β, α then is deduced from the simultaneous IKP-2 TWC measurements for the entire HAIC/HIWC dataset. The statistical analysis of α and β values for the HAIC/HIWC dataset firstly shows that α is closely linked to β and that this link changes with temperature. From these trends, a generalized parameterization for α is proposed. Finally, the comparison with the initial IKP-2 measurements demonstrates that the method is able to predict TWC values larger than 0.3g/m3 with an error close to 20%. Fontaine, E., A. Schwarzenboeck, J. Delanoë, W. Wobrock, D. Leroy, R. Dupuy, C. Gourbeyre, and A. Protat, 2014: Constraining mass-diameter relations from hydrometeor images and cloud radar reflectivities in tropical continental and oceanic convective anvils. Atmos Chem Phys, 14, 11367-11392, doi:10.5194/acp-14-11367-2014. Leroy, D., E. Fontaine, A. Schwarzenboeck and J.W. Strapp : Ice Crystal Sizes in High Ice Water Content Clouds. Part 1: Mass-size Relationships Derived from Particle Images and TWC for Various Crystal Diameter Definitions and Impact on Median Mass Diameter. Submitted to Journal of Atmospheric and Oceanic Technology, 2015.
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Akino, Yuichi; Gautam, Archana; Coutinho, Len; Würfel, Jan; Das, Indra J
2015-11-01
A synthetic single crystal diamond detector (SCDD) is commercially available and is characterized for radiation dosimetry in various radiation beams in this study. The characteristics of the commercial SCDD model 60019 (PTW) with 6- and 15-MV photon beams, and 208-MeV proton beams, were investigated and compared with the pre-characterized detectors: Semiflex (model 31010) and PinPoint (model 31006) ionization chambers (PTW), the EDGE diode detector (Sun Nuclear Corp) and the SFD Stereotactic Dosimetry Diode Detector (IBA). To evaluate the effects of the pre-irradiation, the diamond detector, which had not been irradiated on the day, was set up in the water tank, and the response to 100 MU was measured every 20 s. The depth-dose and profiles data were collected for various field sizes and depths. For all radiation types and field sizes, the depth-dose data of the diamond chamber showed identical curves to those of the ionization chambers. The profile of the diamond detector was very similar to those of the EDGE and SFD detectors, although the Semiflex and PinPoint chambers showed volume-averaging effects in the penumbrae region. The temperature dependency was within 0.7% in the range of 4-41°C. A dose of 900 cGy and 1200 cGy was needed to stabilize the chamber to the level within 0.5% and 0.2%, respectively. The PTW type 60019 SCDD detector showed suitable characteristics for radiation dosimetry, for relative dose, depth-dose and profile measurements for a wide range of field sizes. However, at least 1000 cGy of pre-irradiation will be needed for accurate measurements. © The Author 2015. Published by Oxford University Press on behalf of The Japan Radiation Research Society and Japanese Society for Radiation Oncology.
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NASA Astrophysics Data System (ADS)
Coutris, Pierre; Leroy, Delphine; Fontaine, Emmanuel; Schwarzenboeck, Alfons; Strapp, J. Walter
2016-04-01
A new method to retrieve cloud water content from in-situ measured 2D particle images from optical array probes (OAP) is presented. With the overall objective to build a statistical model of crystals' mass as a function of their size, environmental temperature and crystal microphysical history, this study presents the methodology to retrieve the mass of crystals sorted by size from 2D images using a numerical optimization approach. The methodology is validated using two datasets of in-situ measurements gathered during two airborne field campaigns held in Darwin, Australia (2014), and Cayenne, France (2015), in the frame of the High Altitude Ice Crystals (HAIC) / High Ice Water Content (HIWC) projects. During these campaigns, a Falcon F-20 research aircraft equipped with state-of-the art microphysical instrumentation sampled numerous mesoscale convective systems (MCS) in order to study dynamical and microphysical properties and processes of high ice water content areas. Experimentally, an isokinetic evaporator probe, referred to as IKP-2, provides a reference measurement of the total water content (TWC) which equals ice water content, (IWC) when (supercooled) liquid water is absent. Two optical array probes, namely 2D-S and PIP, produce 2D images of individual crystals ranging from 50 μm to 12840 μm from which particle size distributions (PSD) are derived. Mathematically, the problem is formulated as an inverse problem in which the crystals' mass is assumed constant over a size class and is computed for each size class from IWC and PSD data: PSD.m = IW C This problem is solved using numerical optimization technique in which an objective function is minimized. The objective function is defined as follows: 2 J(m)=∥P SD.m - IW C ∥ + λ.R (m) where the regularization parameter λ and the regularization function R(m) are tuned based on data characteristics. The method is implemented in two steps. First, the method is developed on synthetic crystal populations in order to evaluate the behavior of the iterative algorithm, the influence of data noise on the quality of the results, and to set up a regularization strategy. Therefore, 3D synthetic crystals have been generated and numerically processed to recreate the noise caused by 2D projections of randomly oriented 3D crystals and by the discretization of the PSD into size classes of predefined width. Subsequently, the method is applied to the experimental datasets and the comparison between the retrieved TWC (this methodology) and the measured ones (IKP-2 data) will enable the evaluation of the consistency and accuracy of the mass solution retrieved by the numerical optimization approach as well as preliminary assessment of the influence of temperature and dynamical parameters on crystals' masses.
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NASA Astrophysics Data System (ADS)
Wu, Chenglai; Liu, Xiaohong; Diao, Minghui; Zhang, Kai; Gettelman, Andrew; Lu, Zheng; Penner, Joyce E.; Lin, Zhaohui
2017-04-01
In this study we evaluate cloud properties simulated by the Community Atmosphere Model version 5 (CAM5) using in situ measurements from the HIAPER Pole-to-Pole Observations (HIPPO) campaign for the period of 2009 to 2011. The modeled wind and temperature are nudged towards reanalysis. Model results collocated with HIPPO flight tracks are directly compared with the observations, and model sensitivities to the representations of ice nucleation and growth are also examined. Generally, CAM5 is able to capture specific cloud systems in terms of vertical configuration and horizontal extension. In total, the model reproduces 79.8 % of observed cloud occurrences inside model grid boxes and even higher (94.3 %) for ice clouds (T ≤ -40 °C). The missing cloud occurrences in the model are primarily ascribed to the fact that the model cannot account for the high spatial variability of observed relative humidity (RH). Furthermore, model RH biases are mostly attributed to the discrepancies in water vapor, rather than temperature. At the micro-scale of ice clouds, the model captures the observed increase of ice crystal mean sizes with temperature, albeit with smaller sizes than the observations. The model underestimates the observed ice number concentration (Ni) and ice water content (IWC) for ice crystals larger than 75 µm in diameter. Modeled IWC and Ni are more sensitive to the threshold diameter for autoconversion of cloud ice to snow (Dcs), while simulated ice crystal mean size is more sensitive to ice nucleation parameterizations than to Dcs. Our results highlight the need for further improvements to the sub-grid RH variability and ice nucleation and growth in the model.
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Compaction of Chromite Cumulates applying a Centrifuging Piston-Cylinder
NASA Astrophysics Data System (ADS)
Manoochehri, S.; Schmidt, M. W.
2012-12-01
Stratiform accumulations of chromite cumulates, such as the UG2 chromitite layer in the Bushveld Complex, is a common feature in most of the large layered mafic intrusions. The time scales and mechanics of gravitationally driven crystal settling and compaction and the feasibility of these processes for the formation of such cumulate layers is investigated through a series of high temperature (1280-1300 °C) centrifuge-assisted experiments at 100-2000 g, 0.4-0.6 GPa. A mixture of natural chromite, with defined grain sizes (means of 5 μm, 13 μm, and 52 μm), and a melt with a composition thought to represent the parental magma of the Bushveld Complex, was first chemically and texturally equilibrated at static conditions and then centrifuged. Centrifugation leads to a single cumulate layer formed at the gravitational bottom of the capsule. This layer was analysed for porosity, mean grain size, size distribution and also travelling distance of chromite crystals. The experimentally observed mechanical settling velocity of chromite grains in a suspension with ~ 24 vol% crystals is calculated to be about half (~ 0.53) of the Stokes settling velocity, consistent with a sedimentation exponent n of 2.35±0.3. The settling leads to a porosity of about 52 % in the chromite layer. Formation times of chromite orthocumulates with initial crystal content in the melt of 1 % and grain sizes of 2 mm are thus around 0.6 m/day. To achieve more compacted chromite piles, centrifugation times and acceleration were increased. Within each experiment the crystal content of the cumulate layer increases downward almost linearly at least in the lower 2/3 of the cumulate pile. Although porosity in the lowermost segment of the chromite layer decreases with increasing effective stress integrated over time, the absolute decrease is smaller than for experiments with olivine (from a previous study). Formation times of a ½ meter single chromite layer with 70 vol% chromite, is calculated to be around 20 years whereas this value is around 0.4 years for olivine cumulates. When considering a natural outcrop of a layered intrusion with multiple layers of about 50 meters height, adcumulate formation time decreases to a few months. With increasing the effective stress integrated over time, applied during centrifugation, crystal size distribution histograms move slightly toward larger grain sizes, but looking at mean grain sizes, a narrow range of changes can be observed. Classic crystal size distribution profiles corrected for real 3D sizes (CSDCorrectin program) of the chromite grains in different experiments illustrate a collection of parallel log-linear trends at larger grain sizes with a very slight overturn at small grain sizes. This is in close agreement with the idealized CSD plots of adcumulus growth.
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NASA Astrophysics Data System (ADS)
Kutluay, Sinan; Şahin, Ömer; Ceyhan, A. Abdullah; İzgi, M. Sait
2017-06-01
In crystallization studies, newly developed technologies, such as Focused Beam Reflectance Measurement (FBRM) and Particle Vision and Measurement (PVM) are applied for determining on-line monitoring of a representation of the Chord Length Distribution (CLD) and observe the photographs of crystals respectively; moreover recently they are widely used. Properly installed, the FBRM ensures on-line determination of the CLD, which is statistically associated to the Crystal Size Distribution (CSD). In industrial crystallization, CSD and mean crystal size as well as external habit and internal structure are important characteristics for further use of the crystals. In this paper, the effect of residence time, stirring speed, feeding rate, supersaturation level and the polyelectrolytes such as anionic polyacrylamide (APAM) and non-ionic polyacrylamide (NPAM) on the CLD as well as the shape of boric acid crystals were investigated by using the FBRM G600 and the PVM V819 probes respectively in an MSMPR (Mixed Suspension Mixed Product Removal) crystallizer. The CSD and kinetic data were determined experimentally using continuous MSMPR crystallizer running at steady state. The population density of nuclei, the nucleation rate and the growth rate were determined from the experimental population balance distribution when the steady state was reached.
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2017-01-01
Gout is a disease with elusive treatment options. Reduction of the size of l-alanine crystals as a model crystal for gouty tophi with the use of a monomode solid-state microwave was examined as a possible therapeutic aid. The effect of microwave heating on l-alanine crystals in the presence of gold nanoparticles (Au NPs) in solution and synovial fluid (SF) in a plastic pouch through a synthetic skin patch was investigated. In this regard, three experimental paradigms were employed: Paradigm 1 includes the effect of variable microwave power (5–10 W) and variable heating time (5–60 s) and Au NPs in water (20 nm size, volume of 10 μL) in a plastic pouch (1 × 2 cm2 in size). Paradigm 2 includes the effect of a variable volume of 20 nm Au NPs in a variable volume of SF up to 100 μL in a plastic pouch at a constant microwave power (10 W) for 30 s. Paradigm 3 includes the effect of constant microwave power (10 W) and microwave heating time (30 s), constant volume of Au NPs (100 μL), and variable size of Au NPs (20–200 nm) placed in a plastic pouch through a synthetic skin patch. In these experiments, an average of 60–100% reduction in the size of an l-alanine crystal (initial size = 450 μm) without damage to the synthetic skin or increasing the temperature of the samples beyond the physiological range was reported. PMID:28983527
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Chutipongtanate, Somchai; Chaiyarit, Sakdithep; Thongboonkerd, Visith
2012-08-15
Dissolution therapy of calcium oxalate monohydrate (COM) kidney stone disease has not yet been implemented due to a lack of well characterized COM dissolution agents. The present study therefore aimed to identify potential COM crystal dissolution compounds. COM crystals were treated with deionized water (negative control), 5 mM EDTA (positive control), 5 mM sodium citrate, or 5mM sodium phosphate. COM crystal dissolution activities of these compounds were evaluated by phase-contrast and video-assisted microscopic examinations, semi-quantitative analysis of crystal size, number and total mass, and spectrophotometric oxalate-dissolution assay. In addition, effects of these compounds on detachment of COM crystals, which adhered tightly onto renal tubular cell surface, were also investigated. The results showed that citrate, not phosphate, had a significant dissolution effect on COM crystals as demonstrated by significant reduction of crystal size (approximately 37% decrease), crystal number (approximately 53% decrease) and total crystal mass (approximately 72% decrease) compared to blank and negative controls. Spectrophotometric oxalate-dissolution assay successfully confirmed the COM crystal dissolution property of citrate. Moreover, citrate could detach up to 85% of the adherent COM crystals from renal tubular cell surface. These data indicate that citrate is better than phosphate for dissolution and detachment of COM crystals. Copyright © 2012 Elsevier B.V. All rights reserved.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Pareja-Rivera, Carina; Cuéllar-Cruz, Mayra; Esturau-Escofet, Nuria
Here, in this contribution we use nonconventional methods that help to increase the success rate of a protein crystal growth, and consequently of structural projects using X-ray diffraction techniques. In order to achieve this purpose, this contribution presents new approaches involving more sophisticated techniques of protein crystallization, not just for growing protein crystals of different sizes by using electric fields, but also for controlling crystal size and orientation. Also, this latter was possible through the use of magnetic fields that allow to obtain protein crystals suitable for both high-resolution X-ray and neutron diffraction crystallography where big crystals are required. Thismore » contribution discusses some pros, cons and realities of the role of electromagnetic fields in protein crystallization research, and their effect on protein crystal contacts. Additionally, we discuss the importance of room and low temperatures during data collection. Finally, we also discuss the effect of applying a rather strong magnetic field of 16.5 T, for shorts and long periods of time, on protein crystal growth, and on the 3D structure of two model proteins.« less
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Sparsity-based image monitoring of crystal size distribution during crystallization
NASA Astrophysics Data System (ADS)
Liu, Tao; Huo, Yan; Ma, Cai Y.; Wang, Xue Z.
2017-07-01
To facilitate monitoring crystal size distribution (CSD) during a crystallization process by using an in-situ imaging system, a sparsity-based image analysis method is proposed for real-time implementation. To cope with image degradation arising from in-situ measurement subject to particle motion, solution turbulence, and uneven illumination background in the crystallizer, sparse representation of a real-time captured crystal image is developed based on using an in-situ image dictionary established in advance, such that the noise components in the captured image can be efficiently removed. Subsequently, the edges of a crystal shape in a captured image are determined in terms of the salience information defined from the denoised crystal images. These edges are used to derive a blur kernel for reconstruction of a denoised image. A non-blind deconvolution algorithm is given for the real-time reconstruction. Consequently, image segmentation can be easily performed for evaluation of CSD. The crystal image dictionary and blur kernels are timely updated in terms of the imaging conditions to improve the restoration efficiency. An experimental study on the cooling crystallization of α-type L-glutamic acid (LGA) is shown to demonstrate the effectiveness and merit of the proposed method.
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Pareja-Rivera, Carina; Cuéllar-Cruz, Mayra; Esturau-Escofet, Nuria; ...
2016-12-05
Here, in this contribution we use nonconventional methods that help to increase the success rate of a protein crystal growth, and consequently of structural projects using X-ray diffraction techniques. In order to achieve this purpose, this contribution presents new approaches involving more sophisticated techniques of protein crystallization, not just for growing protein crystals of different sizes by using electric fields, but also for controlling crystal size and orientation. Also, this latter was possible through the use of magnetic fields that allow to obtain protein crystals suitable for both high-resolution X-ray and neutron diffraction crystallography where big crystals are required. Thismore » contribution discusses some pros, cons and realities of the role of electromagnetic fields in protein crystallization research, and their effect on protein crystal contacts. Additionally, we discuss the importance of room and low temperatures during data collection. Finally, we also discuss the effect of applying a rather strong magnetic field of 16.5 T, for shorts and long periods of time, on protein crystal growth, and on the 3D structure of two model proteins.« less
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Q-space analysis of light scattering by ice crystals
NASA Astrophysics Data System (ADS)
Heinson, Yuli W.; Maughan, Justin B.; Ding, Jiachen; Chakrabarti, Amitabha; Yang, Ping; Sorensen, Christopher M.
2016-12-01
Q-space analysis is applied to extensive simulations of the single-scattering properties of ice crystals with various habits/shapes over a range of sizes. The analysis uncovers features common to all the shapes: a forward scattering regime with intensity quantitatively related to the Rayleigh scattering by the particle and the internal coupling parameter, followed by a Guinier regime dependent upon the particle size, a complex power law regime with incipient two dimensional diffraction effects, and, in some cases, an enhanced backscattering regime. The effects of significant absorption on the scattering profile are also studied. The overall features found for the ice crystals are similar to features in scattering from same sized spheres.
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Rapid Crystallization of the Bishop Magma
NASA Astrophysics Data System (ADS)
Gualda, G. A.; Anderson, A. T.; Sutton, S. R.
2007-12-01
Substantial effort has been made to understand the longevity of rhyolitic magmas, and particular attention has been paid to the systems in the Long Valley area (California). Recent geochronological data suggest discrete magma bodies that existed for hundreds of thousands of years. Zircon crystallization ages for the Bishop Tuff span 100-200 ka, and were interpreted to reflect slow crystallization of a liquid-rich magma. Here we use the diffusional relaxation of Ti zoning in quartz to investigate the longevity of the Bishop magma. We have used such an approach to show the short timescales of crystallization of Ti-rich rims on quartz from early- erupted Bishop Tuff. We have now recognized Ti-rich cores in quartz that can be used to derive the timescales of their crystallization. We studied four samples of the early-erupted Bishop. Hand-picked crystals were mounted on glass slides and polished. Cathodoluminescence (CL) images were obtained using the electron microprobe at the University of Chicago. Ti zoning was documented using the GeoSoilEnviroCARS x-ray microprobe at the Advanced Photon Source (Argonne National Lab). Quartz crystals in all 4 samples include up to 3 Ti-bearing zones: a central core (50-100 μm in diameter, ca. 50 ppm Ti), a volumetrically predominant interior (~40 ppm Ti), and in some crystals a 50-100 μm thick rim (50 ppm Ti). Maximum estimates of core residence times were calculated using a 1D diffusion model, as the time needed to smooth an infinitely steep profile to fit the observed profile. Surprisingly, even for the largest crystals studied - ca. 2 mm in diameter - core residence times are less than 1 ka. Calculated growth rates imply that even cm-sized crystals crystallized in less than 10 ka. Crystal size distribution data show that crystals larger than 3 mm are exceedingly rare, such that the important inference is that the bulk of the crystallization of the early-erupted Bishop magma occurred in only a few thousand years. This timescale is 2 orders of magnitude smaller than the shortest durations derived from geochronology. In the current paradigm, this implies that the Bishop magma existed virtually free of crystals for 100-200 ka. Occasional recharge of the system could cause resorption of crystals. The challenge, however, is to explain how a large- volume, liquid- and volatile-rich system, was prevented from erupting for over 100 ka. The trouble is such that it puts into question the whole concept of a long-lived, liquid-rich magma body. Evidence has accumulated to show that the Bishop magma was stratified and did not convect during crystallization, the stratification was established prior to phenocryst crystallization, and crystal migration did not significantly perturb the stratification. All these are simpler to explain if liquid-rich magma only existed for a short period of time, and we estimate the time as being on the order of 1 ka. The geospeedometric timescale inferred can be reconciled with the geochronological evidence if we interpret zircon crystallization ages as reflecting episodic growth in response to waxing and waning of a mushy body, rather than continuous crystallization from liquid-rich magma in a long-lived, large-volume magma body. We speculate that only after 100-200 ka did favorable conditions emerge and allowed for the generation of a large volume of liquid-rich magma. Once such a body of magma was established, it progressed rather quickly towards eruption.
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NASA Astrophysics Data System (ADS)
Magee, N.; Moyle, A.; Lamb, D.
2003-12-01
An improved understanding of ice crystal growth, particularly at low temperatures, is much in demand for the advancement of numerical modeling of atmospheric processes. Cirrus models must contend with the complexity of ice crystals growing in cold temperatures, low pressures, low supersaturations, and with multiple nucleation mechanisms. Recent observations have allowed increasingly realistic parameterizations of cirrus ice crystal microphysics, but these observations need to be supplemented by a fundamental understanding of growth processes affecting low-temperature crystals. Several experimental studies have demonstrated that certain ice crystals require a minimum "critical" supersaturation before exhibiting detectable growth. These crystals are presumed to be essentially defect-free, preventing vicinal hillock growth at the site of crystal dislocations. In the case of crystal growth by spiral dislocation, advancement of faces begins as soon as supersaturation is present. The finding of conditional critical supersaturations have analogies in other materials (metals, semiconductors, potassium dihydrogen phosphate) and are thermodynamically predicted given a two-dimensional nucleation growth mechanism. Previous measurements have determined the critical supersaturation for ice as a function of temperature and crystallographic face from 0 to --15° C with extrapolation to --30° C. For both basal and prism faces, critical supersaturation is seen to increase with decreasing temperature, suggesting that low-temperature, low-supersaturation processes are most likely to be affected by this critical contingency. We present laboratory results to verify and extend prior critical supersaturation measurements using a novel approach for supersaturation generation, control, and measurement. The crystals are grown on the tip of a fine glass fiber ( ˜10 microns in diameter) under varying conditions of temperature, pressure, and saturation. Supersaturation is generated when a pre-saturated airflow passes over a coil of ice warmed by electrical resistance upstream from the growing crystal. Supersaturation is determined by a system of differential thermocouples calibrated to sulfuric acid drop size measurements. Measurements follow those made in earlier studies, but also extend to temperatures of --45° C, mimicking conditions found in some high altitude clouds.
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NASA Astrophysics Data System (ADS)
Klein, Johannes; Mueller, Sebastian P.; Helo, Christoph; Schweitzer, Silja; Gurioli, Lucia; Castro, Jonathan M.
2018-05-01
This study examines the combined effect of crystal-size distributions (CSD) and crystal shape on the rheology of vesicle free magmatic suspensions and provides the first practical application of an empirical model to estimate the relative effect of crystal content and CSD's on the viscosity of magma directly from textural image analysis of natural rock samples in the form of a user-friendly texture-rheology spreadsheet calculator. We extend and apply established relationships between the maximum packing fraction ϕm of a crystal bearing suspension and both its rheological properties and the polydispersity γ of a CSD. By using analogue rotational rheometric experiments with glass fibres and glass flakes in silicone oil acting as magma equivalent, this study also provides new insights in the relationship between ϕm and the aspect ratio rp of suspended particles.
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Response of Halimeda to ocean acidification: Field and laboratory evidence
Robbins, L.L.; Knorr, P.O.; Hallock, P.
2009-01-01
Rising atmospheric pCO2 levels are changing ocean chemistry more dramatically now than in the last 20 million years. In fact, pHvalues of the open ocean have decreased by 0.1 since the 1800s and are predicted to decrease 0.1-0.4 globally in the next 90 years. Ocean acidification will affect fundamental geochemical and biological processes including calcification and carbonate sediment production. The west Florida shelf is a natural laboratory to examine the effects of ocean acidification on aragonite production by calcareous green algae. Scanning electron microscopy (SEM) of crystal morphology of calcifying organisms reveals ultrastructural details of calcification that occurred at different saturation states. Comparison of archived and recent specimens of calcareous green alga Halimeda spp. from the west Florida shelf, demonstrates crystal changes in shape and abundance over a 40+ year time span. Halimeda crystal data from apical sections indicate that increases in crystal concentration and decreases in crystal width occurred over the last 40+ years. Laboratory experiments using living specimens of Halimeda grown in environments with known pH values were used to constrain historical observations. Percentages of organic and inorganic carbon per sample weight of pooled species did not significantly change. However, individual species showed decreased inorganic carbon and increased organic carbon in more recent samples, although the sample sizes were limited. These results indicate that the effect of increased pCO 2 and decreased pH on calcification is reflected in the crystal morphology of this organism. More data are needed to confirm the observed changes in mass of crystal and organic carbon. ?? Author(s) 2009.
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Kobayashi, Atsuko; Golash, Harry N; Kirschvink, Joseph L
2016-06-01
An outstanding biophysical puzzle is focused on the apparent ability of weak, extremely low-frequency oscillating magnetic fields to enhance cryopreservation of many biological tissues. A recent theory holds that these weak magnetic fields could be inhibiting ice-crystal nucleation on the nanocrystals of biological magnetite (Fe3O4, an inverse cubic spinel) that are present in many plant and animal tissues by causing them to oscillate. In this theory, magnetically-induced mechanical oscillations disrupt the ability of water molecules to nucleate on the surface of the magnetite nanocrystals. However, the ability of the magnetite crystal lattice to serve as a template for heterogeneous ice crystal nucleation is as yet unknown, particularly for particles in the 10-100 nm size range. Here we report that the addition of trace-amounts of finely-dispersed magnetite into ultrapure water samples reduces strongly the incidence of supercooling, as measured in experiments conducted using a controlled freezing apparatus with multiple thermocouples. SQUID magnetometry was used to quantify nanogram levels of magnetite in the water samples. We also report a relationship between the volume change of ice, and the degree of supercooling, that may indicate lower degassing during the crystallization of supercooled water. In addition to supporting the role of ice-crystal nucleation by biogenic magnetite in many tissues, magnetite nanocrystals could provide inexpensive, non-toxic, and non-pathogenic ice nucleating agents needed in a variety of industrial processes, as well as influencing the dynamics of ice crystal nucleation in many natural environments. Copyright © 2016 The Authors. Published by Elsevier Inc. All rights reserved.
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NASA Astrophysics Data System (ADS)
Scott, G. R.; Brownlee, S. J.; Feinberg, J. M.; Renne, P. R.
2008-12-01
Rocks provide a compound paleomagnetic signal from mixtures of various iron minerals with different grain sizes and magnetic stabilities. To unravel this complex signal, specific mineral phases with stable remanence can be individually examined as single crystals. In the case of the Ecstall Pluton (~91 Ma), intra-pluton discordance of paleomagnetic directions may be the result of post-crystallization deformation, or mineralogical changes caused by re-heating from the adjacent Quottoon Pluton (~52 Ma). In order to distinguish between these two hypotheses we conducted rock magnetic experiments on single crystals of finely-exsolved hematite-ilmenite along a transect approaching the Quottoon Pluton. Reflected light, and SEM observations show grains of hematite and ilmenite as the dominant Fe-oxide throughout the Ecstall. Nearest the Quottoon Pluton, the hematite-ilmenite grains exhibit the classic rutile blitz texture. The lamellar microstructure observed in the hematite-ilmenite grains, as well as the rutile blitz texture are linked to the thermal history of the Ecstall Pluton, and have important effects on the magnetic properties of these grains (i.e. lamellar magnetism). Our results include the magnetic unmixing of isothermal remanence magnetization (IRM) acquisition, First Order Reversal Curve (FORC) diagrams, temperature vs. remanence experiments (MPMS), and TEM studies. These data provide a spatially resolved record of rock magnetic variations across the Ecstall Pluton, showing evidence of thermally activated reduction of hematite to magnetite in samples within 13 km of the Quottoon Pluton. TEM analysis shows the magnetite is present as 20-50 nm-sized particles within hematite. This mineralogic change may be responsible for the variations in paleomagnetic directions across the Ecstall Pluton, and clear evidence for this reaction cannot be found by traditional rock characterization techniques, illustrating the need to couple detailed rock magnetic, paleomagnetic, and mineralogic analyses.
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Tabacchini, Valerio; Surti, Suleman; Borghi, Giacomo; Karp, Joel S; Schaart, Dennis R
2017-02-13
We have recently built and characterized the performance of a monolithic scintillator detector based on a 32 mm × 32 mm × 22 mm LYSO:Ce crystal read out by digital silicon photomultiplier (dSiPM) arrays coupled to the crystal front and back surfaces in a dual-sided readout (DSR) configuration. The detector spatial resolution appeared to be markedly better than that of a detector consisting of the same crystal with conventional back-sided readout (BSR). Here, we aim to evaluate the influence of this difference in the detector spatial response on the quality of reconstructed images, so as to quantify the potential benefit of the DSR approach for high-resolution, whole-body time-of-flight (TOF) positron emission tomography (PET) applications. We perform Monte Carlo simulations of clinical PET systems based on BSR and DSR detectors, using the results of our detector characterization experiments to model the detector spatial responses. We subsequently quantify the improvement in image quality obtained with DSR compared to BSR, using clinically relevant metrics such as the contrast recovery coefficient (CRC) and the area under the localized receiver operating characteristic curve (ALROC). Finally, we compare the results with simulated rings of pixelated detectors with DOI capability. Our results show that the DSR detector produces significantly higher CRC and increased ALROC values than the BSR detector. The comparison with pixelated systems indicates that one would need to choose a crystal size of 3.2 mm with three DOI layers to match the performance of the BSR detector, while a pixel size of 1.3 mm with three DOI layers would be required to get on par with the DSR detector.
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NASA Astrophysics Data System (ADS)
Tabacchini, Valerio; Surti, Suleman; Borghi, Giacomo; Karp, Joel S.; Schaart, Dennis R.
2017-03-01
We have recently built and characterized the performance of a monolithic scintillator detector based on a 32 mm × 32 mm × 22 mm LYSO:Ce crystal read out by digital silicon photomultiplier (dSiPM) arrays coupled to the crystal front and back surfaces in a dual-sided readout (DSR) configuration. The detector spatial resolution appeared to be markedly better than that of a detector consisting of the same crystal with conventional back-sided readout (BSR). Here, we aim to evaluate the influence of this difference in the detector spatial response on the quality of reconstructed images, so as to quantify the potential benefit of the DSR approach for high-resolution, whole-body time-of-flight (TOF) positron emission tomography (PET) applications. We perform Monte Carlo simulations of clinical PET systems based on BSR and DSR detectors, using the results of our detector characterization experiments to model the detector spatial responses. We subsequently quantify the improvement in image quality obtained with DSR compared to BSR, using clinically relevant metrics such as the contrast recovery coefficient (CRC) and the area under the localized receiver operating characteristic curve (ALROC). Finally, we compare the results with simulated rings of pixelated detectors with DOI capability. Our results show that the DSR detector produces significantly higher CRC and increased ALROC values than the BSR detector. The comparison with pixelated systems indicates that one would need to choose a crystal size of 3.2 mm with three DOI layers to match the performance of the BSR detector, while a pixel size of 1.3 mm with three DOI layers would be required to get on par with the DSR detector.
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NASA Astrophysics Data System (ADS)
Prabhakaran, SP.; Ramesh Babu, R.; Sukumar, M.; Bhagavannarayana, G.; Ramamurthi, K.
2014-03-01
Growth of bulk single crystal of 4-Aminobenzophenone (4-ABP) from the vertical dynamic gradient freeze (VDGF) setup designed with eight zone furnace was investigated. The experimental parameters for the growth of 4-ABP single crystal with respect to the design of VDGF setup are discussed. The eight zones were used to generate multiple temperature gradients over the furnace, and video imaging system helped to capture the real time growth and solid-liquid interface. 4-ABP single crystal with the size of 18 mm diameter and 40 mm length was grown from this investigation. Structural and optical quality of grown crystal was examined by high resolution X-ray diffraction and UV-visible spectral analysis, respectively and the blue emission was also confirmed from the photoluminescence spectrum. Microhardness number of the crystal was estimated at different loads using Vicker's microhardness tester. The size and quality of single crystal grown from the present investigation are compared with the vertical Bridgman grown 4-ABP.
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Liu, Lifeng; Ding, Xiangdong; Li, Ju; Lookman, Turab; Sun, Jun
2014-02-21
Martensitic transformation usually creates hierarchical internal structures beyond mere change of the atomic crystal structure. Multi-stage nucleation is thus required, where nucleation (level-1) of the underlying atomic crystal lattice does not have to be immediately followed by the nucleation of higher-order superstructures (level-2 and above), such as polysynthetic laths. Using in situ transmission electron microscopy (TEM), we directly observe the nucleation of the level-2 superstructure in a Cu-Al-Ni single crystal under compression, with critical super-nuclei size L2c around 500 nm. When the sample size D decreases below L2c, the superelasticity behavior changes from a flat stress plateau to a continuously rising stress-strain curve. Such size dependence definitely would impact the application of shape memory alloys in miniaturized MEMS/NEMS devices.
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Thomas g. Shelton; Laurent Cartier; Terence L. Wagner; Christian Becker
2007-01-01
We examined the efficacy of termiticidal baits comprised of powdered acellulose and a mineral insecticide, cryolite crystals, in laboratory bioassays against pseudergates of Eastern subterranean termites [Reticulitermes flavipes (Kollar)]. The influence of cryolite crystal size [0 (control), 0.2, and 20 pm diameter particles] on the overall mortality...
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Hsu, Wei-Hsiang; Hsiang, Hsing-I, E-mail: hsingi@mail.ncku.edu.tw; Chia, Chih-Ta
2013-12-15
CuIn{sub 0.7}Ga{sub 0.3}Se{sub 2}(CIGS) nano-crystals were successfully synthesized via a heating-up process. The non-coordinating solvent (1-octadecene) and selenium/cations ratio effects on the crystalline phase and crystallite size of CIGS nano-crystallites were investigated. It was observed that the CIGS nano-crystallite morphology changed from sheet into spherical shape as the amount of 1-octadecene addition was increased. CIGS nano-crystals were obtained in 9–20 nm sizes as the selenium/cations ratio increased. These results suggest that the monomer reactivity in the solution can be adjusted by changing the solvent type and selenium/cations ratio, hence affecting the crystallite size and distribution. - Graphical abstract: CuIn{sub 0.7}Ga{submore » 0.3}Se{sub 2}(CIGS) nano-crystals were successfully synthesized via a heating-up process in this study. The super-saturation in the solution can be adjusted by changing the OLA/ODE ratio and selenium/cation ratio.« less
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Cheraft-Bahloul, Nassima; Husson, Cécile; Ourtioualous, Meriam; Sinaeve, Sébastien; Atmani, Djebbar; Stévigny, Caroline; Nortier, Joëlle L; Antoine, Marie-Hélène
2017-09-14
The world prevalence of kidney stones is increasing and plants are frequently used to treat urolithiasis. Pistacia lentiscus L, a plant which freely grows around the Mediterranean basin areas, is widely used for various pathologies. P. lentiscus has an important impact as it has economical value on top of its pharmacological interest. Decoctions of its aerial parts and/or resin are used to treat kidney stones. To in vitro assess the potential nephroprotective effect of Pistacia lentiscus ethanolic fruit extract (PLEF) on proximal tubular cells in response to the adhesion of calcium oxalate monohydrate (COM) crystals. Human Kidney [HK]-2 cells were incubated with and without COM in the presence or absence of PLEF. Cell viability was measured by the resazurin assay. The expression of E-cadherin was analyzed by PCR. The extracellular production of H 2 O 2 was measured by Amplex® Red H 2 O 2 Assay. The numbers of detached or non-adherent COM crystals in the presence of PLEF were microscopically captured and counted using ImageJ software. The interaction of PLEF with COM and the effect of PLEF on crystal size were analyzed by flow cytometry. The spectrophotometric measurement of turbidity was performed for assessing the COM concentration. PLEF incubated with COM was able to increase the cell viability. The decrease of E-cadherin expression after incubation with COM was counteracted by PLEF. Overproduction of H 2 O 2 induced by COM was also inhibited by PLEF. Observations using flow cytometry showed that interactions between PLEF and the COM crystals occurred. PLEF was also effective in reducing the particles size and in lowering COM concentration. Our data show that COM tubulotoxicity can be significantly reversed by PLEF -at least in part- via an inhibition of COM crystals adhesion onto the apical membrane. This early beneficial effect of PLEF needs to be further investigated as a useful strategy in nephrolithiasis prevention. Copyright © 2017 Elsevier Ireland Ltd. All rights reserved.
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Su, Chia-Chi; Reano, Resmond L; Dalida, Maria Lourdes P; Lu, Ming-Chun
2014-06-01
The effects of process conditions, including upward velocity inside the column, the amount of added seed and seed size, the pH value of the precipitant or the phosphate stream and the Ba/P molar ratio in a fluidized-bed reactor (FBR) were studied with a view to producing BaHPO₄ crystals of significant size and maximize the removal of barium. XRD were used to identify the products that were collected from the FBR. Experimental results show that an upward velocity of 48 cmmin(-1) produced the largest BaHPO₄ crystals with a size of around 0.84-1.0mm. The addition of seed crystals has no effect on barium removal. The use of a seed of a size in the ranges unseeded<0.149-0.29 mm<0.149 mm<0.29-0.42 mm produced increasing amounts of increasingly large crystals. The largest BaHPO₄ crystals were obtained at pH 8.4-8.8 with a Ba/P molar ratio of 1.0. In the homogeneous and heterogeneous processes, around 98% of barium was removed at pH 8.4-8.6 and [Ba]/[P]=1.0. The XRD results show that a significant amount of barium phosphate (Ba₃(PO₄)₂) was obtained at pH 11. The compounds BaHPO₄ and BaO were present at a pH of below 10. Copyright © 2014 Elsevier Ltd. All rights reserved.
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NASA Astrophysics Data System (ADS)
Svoboda, Martin; Lísal, Martin
2018-06-01
To address a high salinity of flow-back water during hydraulic fracturing, we use molecular dynamics (MD) simulations and study the thermodynamics, structure, and diffusion of concentrated aqueous salt solution in clay nanopores. The concentrated solution results from the dissolution of a cubic NaCl nanocrystal, immersed in an aqueous NaCl solution of varying salt concentration and confined in clay pores of a width comparable to the crystal size. The size of the nanocrystal equals to about 18 Å which is above a critical nucleus size. We consider a typical shale gas reservoir condition of 365 K and 275 bar, and we represent the clay pores as pyrophyllite and Na-montmorillonite (Na-MMT) slits. We employ the Extended Simple Point Charge (SPC/E) model for water, Joung-Cheatham model for ions, and CLAYFF for the slit walls. We impose the pressure in the normal direction and the resulting slit width varies from about 20 to 25 Å when the salt concentration in the surrounding solution increased from zero to an oversaturated value. By varying the salt concentration, we observe two scenarios. First, the crystal dissolves and its dissolution time increases with increasing salt concentration. We describe the dissolution process in terms of the number of ions in the crystal, and the crystal size and shape. Second, when the salt concentration reaches a system solubility limit, the crystal grows and attains a new equilibrium size; the crystal comes into equilibrium with the surrounding saturated solution. After crystal dissolution, we carry out canonical MD simulations for the concentrated solution. We evaluate the hydration energy, density profiles, orientation distributions, hydrogen-bond network, radial distribution functions, and in-plane diffusion of water and ions to provide insight into the microscopic behaviour of the concentrated aqueous sodium chloride solution in interlayer galleries of the slightly hydrophobic pyrophyllite and hydrophilic Na-MMT pores.
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Primary and secondary fragmentation of crystal-bearing intermediate magma
NASA Astrophysics Data System (ADS)
Jones, Thomas J.; McNamara, Keri; Eychenne, Julia; Rust, Alison C.; Cashman, Katharine V.; Scheu, Bettina; Edwards, Robyn
2016-11-01
Crystal-rich intermediate magmas are subjected to both primary and secondary fragmentation processes, each of which may produce texturally distinct tephra. Of particular interest for volcanic hazards is the extent to which each process contributes ash to volcanic plumes. One way to address this question is by fragmenting pyroclasts under controlled conditions. We fragmented pumice samples from Soufriere Hills Volcano (SHV), Montserrat, by three methods: rapid decompression in a shock tube-like apparatus, impact by a falling piston, and milling in a ball mill. Grain size distributions of the products reveal that all three mechanisms produce fractal breakage patterns, and that the fractal dimension increases from a minimum of 2.1 for decompression fragmentation (primary fragmentation) to a maximum of 2.7 by repeated impact (secondary fragmentation). To assess the details of the fragmentation process, we quantified the shape, texture and components of constituent ash particles. Ash shape analysis shows that the axial ratio increases during milling and that particle convexity increases with repeated impacts. We also quantify the extent to which the matrix is separated from the crystals, which shows that secondary processes efficiently remove adhering matrix from crystals, particularly during milling (abrasion). Furthermore, measurements of crystal size distributions before (using x-ray computed tomography) and after (by componentry of individual grain size classes) decompression-driven fragmentation show not only that crystals influence particular size fractions across the total grain size distribution, but also that free crystals are smaller in the fragmented material than in the original pumice clast. Taken together, our results confirm previous work showing both the control of initial texture on the primary fragmentation process and the contributions of secondary processes to ash formation. Critically, however, our extension of previous analyses to characterisation of shape, texture and componentry provides new analytical tools that can be used to assess contributions of secondary processes to ash deposits of uncertain or mixed origin. We illustrate this application with examples from SHV deposits.
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Svoboda, Martin; Lísal, Martin
2018-06-14
To address a high salinity of flow-back water during hydraulic fracturing, we use molecular dynamics (MD) simulations and study the thermodynamics, structure, and diffusion of concentrated aqueous salt solution in clay nanopores. The concentrated solution results from the dissolution of a cubic NaCl nanocrystal, immersed in an aqueous NaCl solution of varying salt concentration and confined in clay pores of a width comparable to the crystal size. The size of the nanocrystal equals to about 18 Å which is above a critical nucleus size. We consider a typical shale gas reservoir condition of 365 K and 275 bar, and we represent the clay pores as pyrophyllite and Na-montmorillonite (Na-MMT) slits. We employ the Extended Simple Point Charge (SPC/E) model for water, Joung-Cheatham model for ions, and CLAYFF for the slit walls. We impose the pressure in the normal direction and the resulting slit width varies from about 20 to 25 Å when the salt concentration in the surrounding solution increased from zero to an oversaturated value. By varying the salt concentration, we observe two scenarios. First, the crystal dissolves and its dissolution time increases with increasing salt concentration. We describe the dissolution process in terms of the number of ions in the crystal, and the crystal size and shape. Second, when the salt concentration reaches a system solubility limit, the crystal grows and attains a new equilibrium size; the crystal comes into equilibrium with the surrounding saturated solution. After crystal dissolution, we carry out canonical MD simulations for the concentrated solution. We evaluate the hydration energy, density profiles, orientation distributions, hydrogen-bond network, radial distribution functions, and in-plane diffusion of water and ions to provide insight into the microscopic behaviour of the concentrated aqueous sodium chloride solution in interlayer galleries of the slightly hydrophobic pyrophyllite and hydrophilic Na-MMT pores.
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Monitoring and modeling of ultrasonic wave propagation in crystallizing mixtures
NASA Astrophysics Data System (ADS)
Marshall, T.; Challis, R. E.; Tebbutt, J. S.
2002-05-01
The utility of ultrasonic compression wave techniques for monitoring crystallization processes is investigated in a study of the seeded crystallization of copper II sulfate pentahydrate from aqueous solution. Simple models are applied to predict crystal yield, crystal size distribution and the changing nature of the continuous phase. A scattering model is used to predict the ultrasonic attenuation as crystallization proceeds. Experiments confirm that modeled attenuation is in agreement with measured results.
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Rice-like hollow nano-CaCO3 synthesis
NASA Astrophysics Data System (ADS)
Ulkeryildiz, Eda; Kilic, Sevgi; Ozdemir, Ekrem
2016-09-01
We have shown that Ca(OH)2 solution is a natural stabilizer for CaCO3 particles. We designed a CO2 bubbling crystallization reactor to produce nano-CaCO3 particles in homogenous size distribution without aggregation. In the experimental set-up, the crystallization region was separated from the stabilization region. The produced nanoparticles were removed from the crystallization region into the stabilization region before aggregation or crystal growth. It was shown that rice-like hollow nano-CaCO3 particles in about 250 nm in size were produced with almost monodispersed size distribution. The particles started to dissolve through their edges as CO2 bubbles were injected, which opened-up the pores inside the particles. At the late stages of crystallization, the open pores were closed as a result of dissolution-recrystallization of the newly synthesized CaCO3 particles. These particles were stable in Ca(OH)2 solution and no aggregation was detected. The present methodology can be used in drug encapsulation into inorganic CaCO3 particles for cancer treatment with some modifications.
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NASA Astrophysics Data System (ADS)
Rebai, M.; Giacomelli, L.; Milocco, A.; Nocente, M.; Rigamonti, D.; Tardocchi, M.; Camera, F.; Cazzaniga, C.; Chen, Z. J.; Du, T. F.; Fan, T. S.; Giaz, A.; Hu, Z. M.; Marchi, T.; Peng, X. Y.; Gorini, G.
2016-11-01
A Single-crystal Diamond (SD) detector prototype was installed at Joint European Torus (JET) in 2013 and the achieved results have shown its spectroscopic capability of measuring 2.5 MeV neutrons from deuterium plasmas. This paper presents measurements of the SD response function to monoenergetic neutrons, which is a key point for the development of a neutron spectrometer based on SDs and compares them with Monte Carlo simulations. The analysis procedure allows for a good reconstruction of the experimental results. The good pulse height energy resolution (equivalent FWHM of 80 keV at 2.5 MeV), gain stability, insensitivity to magnetic field, and compact size make SDs attractive as compact neutron spectrometers of high flux deuterium plasmas, such as for instance those needed for the ITER neutron camera.
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Laser-induced damage of coatings on Yb:YAG crystals at cryogenic condition
NASA Astrophysics Data System (ADS)
Wang, He; Zhang, Weili; Chen, Shunli; Zhu, Meiping; He, Hongbo; Fan, Zhengxiu
2011-12-01
As large amounts of heat need to be dissipated during laser operation, some diode pumped solid state lasers (DPSSL), especially Yb:YAG laser, operate at cryogenic condition. This work investigated the laser induced damage of coatings (high-reflective and anti-reflective coatings) on Yb:YAG crystals at cryogenic temperature and room temperature. The results show that the damage threshold of coatings at cryogenic temperature is lower than the one at room temperature. Field-emission scanning electron microscopy (FESEM), optical profiler, step profiler and Atomic force microscope (AFM) were used to obtain the damage morphology, size and depth. Taking alteration of physical parameters, microstructure of coatings and the environmental pollution into consideration, we analyzed the key factor of lowering the coating damage threshold at cryogenic conditions. The results are important to understand the mechanisms leading to damage at cryogenic condition.
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NASA Astrophysics Data System (ADS)
Zhong, Mianzeng; Zhou, Ke; Wei, Zhongming; Li, Yan; Li, Tao; Dong, Huanli; Jiang, Lang; Li, Jingbo; Hu, Wenping
2018-07-01
Orthorhombic MoO3 (α-MoO3) is a typical layered n-type semiconductor with optical band gap over 2.7 eV, which have been widely studied in catalysis, gas sensing, lithium-ion batteries, field-emission, photoelectrical, photochromic and electrochromic devices, supercapacitors and organic solar cells. However, the bottleneck of generation large size atomic thin two-dimensional (2D) α-MoO3 crystals remain challenging this field (normally several micrometers size). Herein, we developed a facile vapor–solid (VS) process for controllable growth of large-size 2D α-MoO3 single crystals with a few nanometers thick and over 300 μm in lateral size. High-performance solar-blind photodetectors were fabricated based on individual 2D α-MoO3 single crystal. The detectors demonstrate outstanding optoelectronic properties under solar-blind UV light (254 nm), with a photoresponsivity of 67.9 A W‑1, external quantum efficiency of 3.3 × 104%. More important, the devices showed strong in-plane anisotropy in optoelectronic response and transport properties, e.g. the photocurrent along b-axis was found to be 5 times higher than the values along c-axis under 254 nm UV light, and current ON/OFF ratio and mobility anisotropy is about 2 times high. Our work suggests an optimized synthesis routine for 2D crystals, and the great potential of 2D oxides in functional optoelectronics.
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Kim, Minjeong; Choi, Myoung Gil; Ra, Ho Won; Park, Seung Bin; Kim, Yong-Joo; Lee, Kyubock
2018-01-01
The encapsulation of living cells is appealing for its various applications to cell-based sensors, bioreactors, biocatalysts, and bioenergy. In this work, we introduce the encapsulation of multiple microalgal cells in hollow polymer shells of rhombohedral shape by the following sequential processes: embedding of microalgae in CaCO3 crystals; layer-by-layer (LbL) coating of polyelectrolytes; and removal of sacrificial crystals. The microcapsule size was controlled by the alteration of CaCO3 crystal size, which is dependent on CaCl2/Na2CO3 concentration. The microalgal cells could be embedded in CaCO3 crystals by a two-step process: heterogeneous nucleation of crystal on the cell surface followed by cell embedment by the subsequent growth of crystal. The surfaces of the microalgal cells were highly favorable for the crystal growth of calcite; thus, micrometer-sized microalgae could be perfectly occluded in the calcite crystal without changing its rhombohedral shape. The surfaces of the microcapsules, moreover, could be decorated with gold nanoparticles, Fe3O4 magnetic nanoparticles, and carbon nanotubes (CNTs), by which we would expect the functionalities of a light-triggered release, magnetic separation, and enhanced mechanical and electrical strength, respectively. This approach, entailing the encapsulation of microalgae in semi-permeable and hollow polymer microcapsules, has the potential for application to microbial-cell immobilization for high-biomass-concentration cultivation as well as various other bioapplications. PMID:29438340
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Li, Z Y; Lam, W M; Yang, C; Xu, B; Ni, G X; Abbah, S A; Cheung, K M C; Luk, K D K; Lu, W W
2007-03-01
Recently, strontium (Sr) as ranelate compound has become increasingly popular in the treatment of osteoporosis. However, the lattice structure of bone crystal after Sr incorporation is yet to be extensively reported. In this study, we synthesized strontium-substituted hydroxyapatite (Sr-HA) with different Sr content (0.3%, 1.5% and 15% Sr-HA in mole ratio) to simulate bone crystals incorporated with Sr. The changes in chemical composition and lattice structure of apetite after synthetic incorporation of Sr were evaluated to gain insight into bone crystal changes after incorporation of Sr. X-ray diffraction (XRD) patterns revealed that 0.3% and 1.5% Sr-HA exhibited single phase spectrum, which was similar to that of HA. However, 15% Sr-HA induced the incorporation of HPO4(2-) and more CO3(2-), the crystallinity reduced dramatically. Transmission electron microscopy (TEM) images showed that the crystal length and width of 0.3% and 1.5% Sr-HA increased slightly. Meanwhile, the length and width distribution were broadened and the aspect ratio decreased from 10.68+/-4.00 to 7.28+/-2.80. The crystal size and crystallinity of 15% Sr-HA dropped rapidly, which may suggest that the fundamental crystal structure is changed. The findings from this work indicate that current clinical dosage which usually results in Sr incorporation of below 1.5% may not change chemical composition and lattice structure of bone, while it will broaden the bone crystal size distribution and strengthen the bone.
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Historical and New Perspective of Moissanite in the Canyon Diablo Meteorite
NASA Astrophysics Data System (ADS)
Leung, I. S.; Winston, R.
2004-12-01
Silicon carbide (SiC) was reportedly found in the residue of a 50-kg sample of the Canyon Diablo meteorite dissolved in acid by Henri Moissan, and, in his honor, George F. Kunz coined the mineral name moissanite in 1904. Scholars of the same meteorite, unable to find SiC, believed that Moissan's sample might have been contaminated by synthetic SiC used in tools and abrasives. Thus, an intriguing mineralogical controversy ensued to this day. Recently, occurrence of SiC in carbonaceous chondrites has been confirmed. We present in this paper our finding of three varieties of SiC crystals in the Canyon Diablo meteorite. We found 5 crystals of SiC (size 70-150 microns) in a black nodule (1 cm in size), composed mostly of disordered graphite and diamond/lonsdaleite. The crystals are pale blue, but some have dark overgrowths of uneven thickness, and black spotty or feathery inclusions. Their forms are rounded and resorbed. Our second specimen is oxidized and friable, bearing a 2-cm nodule showing sandy and black magnetic layers. We found 3 apple-green crystals, up to 200 microns in size. Scattered over two of the sandy layers are many minute emerald-green SiC crystals. Carbon in these crystals might have a terrestrial origin. As Moissan's crystals are no longer available for re-examination, a study of large carbon nodules housed in museums might at least lend credence that meteoritic SiC crystals could be as large as ones reported by Moissan.
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NASA Astrophysics Data System (ADS)
Price, C. J.
1993-03-01
The distribution of gross imperfections amongst populations of copper sulphate pentahydrate crystals grown under different conditions of purity and temperature are examined. The frequency of imperfection increases with decreasing crystal size. The nature of the imperfections vary with growth temperature and impurities present.
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Paisana, Maria; Wahl, Martin; Pinto, João
2015-12-12
Hydrate formation is a phase transition which can occur during manufacturing processes involving water. This work considers the prevention of hydration of anhydrous olanzapine and hydrate conversions in the presence of water and polymers (polyethyleneglycol; hydroxypropylcellulose; polyvinylpyrrolidone) in forming pellets by wet extrusion and spheronisation. Anhydrous olanzapine was added to water with or without those polymers prior to extrusion with microcrystalline cellulose. Assessment of olanzapine conversion was made by XRP-Diffraction; FTIR spectroscopy; calorimetry (DSC) and microscopy (SEM for crystal size and shape). The addition of water converted the anhydrous form into dihydrate B and higher hydrate; whereas polyethyleneglycol promoted a selective hydrate conversion into the higher hydrate olanzapine form. Both polyvinylpyrrolidone and hydroxypropylcellulose prevented the hydrate transformations of the anhydrous drug; the latter even in the presence of hydrate seeds. This may be explained by the higher H-bond ability; higher network association and higher hydrophobicity of hydroxypropylcellulose by comparison with polyethyleneglycol and polyvinylpyrrolidone; which could contribute to its higher affinity to the crystal surfaces of the hydrate nuclei/initial crystals and promoting steric hindrance to the incorporation of other drug molecules into the crystal lattice; thus, preventing the crystal growth. The addition of microcrystalline cellulose needed for the pellets production (final product) did not eliminate the protector effect of both hydroxypropylcellulose and polyvinylpyrrolidone during pellets' processing and dissolution evaluation.
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NASA Technical Reports Server (NTRS)
Landis, W. J.; Hodgens, K. J.; Arena, J.; Song, M. J.; McEwen, B. F.
1996-01-01
Aspects of the ultrastructural interaction between collagen and mineral crystals in embryonic chick bone have been examined by the novel technique of high voltage electron microscopic tomography to obtain three-dimensional information concerning extracellular calcification in this tissue. Newly mineralizing osteoid along periosteal surfaces of mid-diaphyseal regions from normal chick tibiae was embedded, cut into 0.25 microns thick sections, and documented at 1.0 MV in the Albany AEI-EM7 high voltage electron microscope. The areas of the tissue studied contained electron dense mineral crystals associated with collagen fibrils, some marked by crystals disposed along their cylindrically shaped lengths. Tomographic reconstructions of one site with two mineralizing fibrils were computed from a 5 degrees tilt series of micrographs over a +/- 60 degrees range. Reconstructions showed that the mineral crystals were platelets of irregular shape. Their sizes were variable, measured here up to 80 x 30 x 8 nm in length, width, and thickness, respectively. The longest crystal dimension, corresponding to the c-axis crystallographically, was generally parallel to the collagen fibril long axis. Individual crystals were oriented parallel to one another in each fibril examined. They were also parallel in the neighboring but apparently spatially separate fibrils. Crystals were periodically (approximately 67 nm repeat distance) arranged along the fibrils and their location appeared to correspond to collagen hole and overlap zones defined by geometrical imaging techniques. The crystals appeared to be continuously distributed along a fibril, their size and number increasing in a tapered fashion from a relatively narrow tip containing smaller and infrequent crystals to wider regions having more densely packed and larger crystals. Defined for the first time by direct visual 3D imaging, these data describe the size, shape, location, orientation, and development of early crystals in normal bone collagen. The results suggest that platelet-shaped crystals are arranged in channels or grooves which are formed by collagen hole zones in register and that crystal sizes may exceed the dimensions of hole zones. Such data agree with those from mineral-matrix interaction in normally calcifying avian tendon obtained by similar high voltage tomographic means, but in addition they indicate a possible gradual and continuous deposition of crystals in collagen of bone unlike tendon and imply that individual collagen fibrils in local regions of osteoid are organized such that they all may be aligned in a coherent manner.
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An assessment of calcite crystal growth mechanisms based on crystal size distributions
Kile, D.E.; Eberl, D.D.; Hoch, A.R.; Reddy, M.M.
2000-01-01
Calcite crystal growth experiments were undertaken to test a recently proposed model that relates crystal growth mechanisms to the shapes of crystal size distributions (CSDs). According to this approach, CSDs for minerals have three basic shapes: (1) asymptotic, which is related to a crystal growth mechanism having constant-rate nucleation accompanied by surface-controlled growth; (2) lognormal, which results from decaying-rate nucleation accompanied by surface-controlled growth; and (3) a theoretical, universal, steady-state curve attributed to Ostwald ripening. In addition, there is a fourth crystal growth mechanism that does not have a specific CSD shape, but which preserves the relative shapes of previously formed CSDs. This mechanism is attributed to supply-controlled growth. All three shapes were produced experimentally in the calcite growth experiments by modifying nucleation conditions and solution concentrations. The asymptotic CSD formed when additional reactants were added stepwise to the surface of solutions that were supersaturated with respect to calcite (initial Ω = 20, where Ω = 1 represents saturation), thereby leading to the continuous nucleation and growth of calcite crystals. Lognormal CSDs resulted when reactants were added continuously below the solution surface, via a submerged tube, to similarly supersaturated solutions (initial Ω = 22 to 41), thereby leading to a single nucleation event followed by surface-controlled growth. The Ostwald CSD resulted when concentrated reactants were rapidly mixed, leading initially to high levels of supersaturation (Ω >100), and to the formation and subsequent dissolution of very small nuclei, thereby yielding CSDs having small crystal size variances. The three CSD shapes likely were produced early in the crystallization process, in the nanometer crystal size range, and preserved during subsequent growth. Preservation of the relative shapes of the CSDs indicates that a supply-controlled growth mechanism was established and maintained during the constant-composition experiments. CSDs having shapes intermediate between lognormal and Ostwald also were generated by varying the initial levels of supersaturation (initial Ω = 28.2 to 69.2) in rapidly mixed solutions. Lognormal CSDs were observed for natural calcite crystals that are found in septarian concretions occurring in southeastern Colorado. Based on the model described above, these CSDs indicate initial growth by surface control, followed by supply-controlled growth. Thus, CSDs may be used to deduce crystal growth mechanisms from which geologic conditions early in the growth history of a mineral can be inferred. Conversely, CSD shape can be predicted during industrial crystallization by applying the appropriate conditions for a particular growth mechanism.
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Microstructural indicators of convection: insights from the Little Minch Sill Complex, Scotland
NASA Astrophysics Data System (ADS)
Nicoli, Gautier; Holness, Marian; Neufeld, Jerome; Farr, Robert
2017-04-01
The fluid dynamic behaviour of crystal-bearing magmas is a key parameter to understand the formation of magmatic bodies. There are two opposite views on the subject: Some argue that solidification in intrusive bodies is affected by convection whereas others claim solidification happens in a static environment. A consensus on the question may be reached by carefully studying the grain size distribution in the settled accumulations of cargo crystals. In the absence of significant crystal growth or particle coarsening by agglomeration, settling of a polydisperse crystal load will always result in a fining-upwards sequence in static magmas as well as in convecting environments. If we assume the particle concentration is always sufficiently low to prevent hindered settling, gravitational settling in a static magma leads to the settling of individual crystals at a constant rate determined by their Stokes' velocity. Each size class is deposited at a constant rate, until all the grains of that size class have fallen out of suspension, leading to a well-stratified sequence and the complete disappearance of progressively smaller size classes upwards in the accumulation. In contrast, in a vigorously convecting magma crystals settle when they enter the stagnant basal boundary layer. In a system containing a polydisperse crystal population most of the bigger particles are removed rapidly from the bulk magma, leading to the creation of a fining-upwards sequence on the floor. However, in detail the structure of this fining-upwards sequence is critically different from that created by settling from a stagnant magma, with the gradual phasing out of each size class instead of the abrupt termination of size classes seen in static systems. This provides us with the opportunity to distinguish between settling from static or convecting magma using the spatial variation of grain size in settled accumulations. We focus on the Little Minch Sill Complex in Scotland, which formed from olivine-phyric magma and is characterised by both composite and single-injection bodies with significant accumulation of olivine on their lower margins. Comparison of the fining-upwards sequences in the picrodolerite/crinanite unit of the composite Shiant Isles Main Sill,and related single-injection sills on the Trotternish Peninsula, Skye, illustrate the ability of this method to distinguish between convecting and non-convecting magma bodies.
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NASA Astrophysics Data System (ADS)
Colucci, Simone; de'Michieli Vitturi, Mattia; Landi, Patrizia
2016-04-01
It is well known that nucleation and growth of crystals play a fundamental role in controlling magma ascent dynamics and eruptive behavior. Size- and shape-distribution of crystal populations can affect mixture viscosity, causing, potentially, transitions between effusive and explosive eruptions. Furthermore, volcanic samples are usually characterized in terms of Crystal Size Distribution (CSD), which provide a valuable insight into the physical processes that led to the observed distributions. For example, a large average size can be representative of a slow magma ascent, and a bimodal CSD may indicate two events of nucleation, determined by two degassing events within the conduit. The Method of Moments (MoM), well established in the field of chemical engineering, represents a mesoscopic modeling approach that rigorously tracks the polydispersity by considering the evolution in time and space of integral parameters characterizing the distribution, the moments, by solving their transport differential-integral equations. One important advantage of this approach is that the moments of the distribution correspond to quantities that have meaningful physical interpretations and are directly measurable in natural eruptive products, as well as in experimental samples. For example, when the CSD is defined by the number of particles of size D per unit volume of the magmatic mixture, the zeroth moment gives the total number of crystals, the third moment gives the crystal volume fraction in the magmatic mixture and ratios between successive moments provide different ways to evaluate average crystal length. Tracking these quantities, instead of volume fraction only, will allow using, for example, more accurate viscosity models in numerical code for magma ascent. Here we adopted, for the first time, a quadrature based method of moments to track the temporal evolution of CSD in a magmatic mixture and we verified and calibrated the model again experimental data. We also show how the equations and the tool developed can be integrated in a magma ascent numerical model, with application to eruptive events occurred at Stromboli volcano (Italy).
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McShane, Colleen M; Choi, Kyoung-Shin
2009-02-25
Cu(2)O electrodes composed of dendritic crystals were produced electrochemically using a slightly acidic medium (pH 4.9) containing acetate buffer. The buffer played a key role for stabilizing dendritic branching growth as a pH drop during the synthesis prevents formation of morphologically unstable branches and promotes faceted growth. Dendritic branching growth enabled facile coverage of the substrate with Cu(2)O while avoiding growth of a thicker Cu(2)O layer and increasing surface areas. The resulting electrodes showed n-type behavior by generating anodic photocurrent without applying an external bias (zero-bias photocurrent under short-circuit condition) in an Ar-purged 0.02 M K(2)SO(4) solution. The zero-bias photocurrent of crystalline dendritic electrodes was significantly higher than that of the electrodes containing micrometer-size faceted crystals deposited without buffer. In order to enhance photocurrent further a strategy of improving charge-transport properties by increasing dendritic crystal domain size was investigated. Systematic changes in nucleation density and size of the dendritic Cu(2)O crystals were achieved by altering the deposition potential, Cu(2+) concentration, and acetate concentration. Increasing dendritic crystal size consistently resulted in the improvement of photocurrent regardless of the method used to regulate crystal size. The electrode composed of dendritic crystals with the lateral dimension of ca. 12000 microm(2) showed more than 20 times higher zero-bias photocurrent than that composed of dendritic crystals with the lateral dimension of ca. 100 microm(2). The n-type nature of the Cu(2)O electrodes prepared by this study were confirmed by linear sweep voltammetry with chopped light and capacitance measurements (i.e., Mott-Schottky plots). The flatband potential in a 0.2 M K(2)SO(4) solution (pH 6) was estimated to be -0.78 vs Ag/AgCl reference electrode. The IPCE measured without applying an external bias was approximately 1% for the visible region. With appropriate doping studies and surface treatment to improve charge transport and interfacial kinetics more efficient n-type Cu(2)O electrodes will be prepared for use in various photoelectrochemical and photovoltaic devices.
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NASA Astrophysics Data System (ADS)
Bahtiar, A.; Rahmanita, S.; Inayatie, Y. D.
2017-05-01
Morphology of perovskite film is a key important for achieving high performance perovskite solar cells. Perovskite films are commonly prepared by two-step spin-coating method. However, pin-holes are frequently formed in perovskite films due to incomplete conversion of lead-iodide (PbI2) into perovskite CH3NH3PbI3. Pin-holes in perovskite film cause large hysteresis in current-voltage curve of solar cells due to large series resistance between perovskite layer-hole transport material. Moreover, crystal structure and grain size of perovskite crystal are also other important parameters for achieving high performance solar cells, which are significantly affected by preparation of perovskite film. We studied the effect of preparation of perovskite film using controlled spin-coating parameters on crystal structure and morphological properties of perovskite film. We used two-step spin-coating method for preparation of perovskite film with varied spinning speed, spinning time and temperature of spin-coating process to control growth of perovskite crystal aimed to produce high quality perovskite crystal with pin-hole free and large grain size. All experiment was performed in air with high humidity (larger than 80%). The best crystal structure, pin-hole free with large grain crystal size of perovskite film was obtained from film prepared at room temperature with spinning speed 1000 rpm for 20 seconds and annealed at 100°C for 300 seconds.
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Supersaturation of aqueous species and hydrothermal crystal growth of ZnO
NASA Astrophysics Data System (ADS)
Gelabert, M. C.
2015-05-01
Synthesis of ZnO crystals prepared with zinc acetate or chloride, disodium dihydrogen ethylenediaminetetraacetate (EDTA), potassium hydroxide and sodium triflate at 200 °C and variable pH 8-12 is reported. Crystals were imaged and size-analyzed with optical microscopy. Using aqueous speciation modeling software, supersaturation dependence on pH was calculated for five zinc species-Zn2+, Zn(OH)+, Zn(OH)2, Zn(OH)3- and Zn(OH)42- -to investigate connections between predominate crystal habits at different pH and dominant aqueous species. For zinc acetate and chloride systems, the zinc species with highest supersaturation was Zn(OH)42- throughout the pH 8-12 range, and the second highest was Zn2+ or Zn(OH)3-, with a crossover pH of 10.2-10.4 depending on counterion. The prominence of the tetrahydroxyl zinc species in ZnO crystal growth is supported by these calculations, and total supersaturation is inversely proportional to average crystal sizes, as expected. Optical microscopy and size analysis on products revealed crystals with a needle or prismatic habit throughout the studied pH range, and the change in aspect ratio correlates with supersaturation changes for the Zn2+ in this pH range, thus suggesting that growth rates along the [001] crystallographic direction are affected by small concentration changes of this ion.
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NASA Astrophysics Data System (ADS)
George, Freya; Gaidies, Fred
2016-04-01
Analysis of porphyroblast distribution in metamorphic rocks yields insight into the processes controlling metamorphic reaction rates. By coupling this textural record with microprobe analysis and phase-equilibria and diffusion modelling, a detailed view of the nucleation and growth history of metamorphic minerals can be obtained. In this study, we comprehensively characterise the 3D distribution and compositional variation of a garnet population in a garnet-grade pelitic schist of the Lesser Himalayan Sequence (Sikkim), in order to investigate both the rates and kinetic controls of porphyroblastic crystallisation. Quantification of the size, shape and spatial distribution of garnet using high-resolution μ-computed X-ray tomography and statistical analysis reveals a log-normal crystal size distribution, systematic variation of aspect ratio with crystal size, and a significantly clustered garnet texture in the study sample. The latter is indicative of interface-controlled nucleation and growth, with nucleation sites controlled principally by a heterogeneous precursor assemblage. At length-scales less than 0.7 mm, there is evidence for adjacent grains that are on average smaller than the mean size of the population; this minor ordering is attributed to secondary redistribution of porphyroblast centers and reduction of crystal sizes due to syn-kinematic growth and resorption, respectively. Geochemical traverses through centrally sectioned garnet crystals of variable size highlight several features: (1) core compositions of even the smallest crystals preserve primary prograde growth zonation, with little evidence for diffusional modification in any crystal size; (2) rim compositions are within error between grains, suggestive of sample-scale equilibration of the growth medium at the time of cessation of crystallisation; (3) different grains of equal radii display equivalent compositional zoning; and (4) gradients of compositional profiles display a steepening trend in progressively smaller grain sizes, converse to anticipated trends based on classic kinetic crystallisation theory. The observed systematic behaviour is interpreted to reflect interface-controlled rates of crystallisation, with a decrease in the rate of crystal growth of newly nucleated grains as the crystallisation interval proceeds. Numerical simulations of garnet growth successfully reproduce observed core and rim compositions, and simulations of intracrystalline diffusion yield rapid heating/cooling rates along the P-T path, in excess of 100 °C/Ma. Radial garnet crystallisation is correspondingly rapid, with minimum growth rates of 1.5 mm/Ma in the smallest crystals. Simulations suggest progressive nucleation of new generations of garnet occurred with an exponentially decreasing frequency along the prograde path; however, measured gradients indicate that core compositions developed more slowly than predicted by the model, potentially resulting in a more evenly distributed pattern of nucleation.
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Wu, Shuwang; Li, Linhai; Xue, Han; Liu, Kai; Fan, Qingrui; Bai, Guoying; Wang, Jianjun
2017-10-24
Ice templates have been widely utilized for the preparation of porous materials due to the obvious advantages, such as environmentally benign and applicable to a wide range of materials. However, it remains a challenge to have controlled pore size as well as dimension of the prepared porous materials with the conventional ice template, since it often employs the kinetically not-stable growing ice crystals as the template. For example, there is no report so far for the preparation of 2D metal meshes with tunable pore size based on the ice template, although facile and eco-friendly prepared metal meshes are highly desirable for wearable electronics. Here, we report the preparation of 2D silver meshes with tunable mesh size employing recrystallized ice crystals as templates. Ice recrystallization is a kinetically stable process; therefore, the grain size of recrystallized ice crystals can be easily tuned, e.g., by adding different salts and changing the annealing temperature. Consequently, the size and line width of silver meshes obtained after freeze-drying can be easily adjusted, which in turn varied the conductivity of the obtained 2D silver film. Moreover, the silver meshes are transparent and display stable conductivity after the repeated stretching and bending. It can be envisioned that this approach for the preparation of 2D conducting films is of practical importance for wearable electronics. Moreover, this study provides a generic approach for the fabrication of 2D meshes with a controllable pore size.
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The deformation mechanisms and size effects of single-crystal magnesium
NASA Astrophysics Data System (ADS)
Byer, Cynthia M.
In this work, we seek to understand the deformation mechanisms and size effects of single-crystal magnesium at the micrometer scale through both microcompression experiments and finite element simulations. Microcompression experiments are conducted to investigate the impact of initial dislocation density and orientation on size effects. Micropillars are fabricated using a focused ion beam and tested in a Nanoindenter using a diamond fiat tip as a compression platen. Two different initial dislocation densities are examined for [0001] oriented micropillars. Our results demonstrate that decreasing the initial dislocation density results in an increased size effect in terms of increased strength and stochasticity. Microcompression along the [23¯14] axis results in much lower strengths than for [0001] oriented samples. Post-mortem analysis reveals basal slip in both [0001] and [23¯14] micropillars. The application of a stochastic probability model shows good agreement between theoretical predictions and experimental results for size effects with our values of initial dislocation density and micropillar dimensions. Size effects are then incorporated into a single-crystal plasticity model (modified from Zhang and Joshi [1]) implemented in ABAQUS/STANDARD as a user-material subroutine. The model successfully captures the phenomena typically associated with size effects of increasing stochasticity and strength with decreasing specimen size and also accounts for the changing trends resulting from variations in initial dislocation density that we observe in the experiments. Finally, finite element simulations are performed with the original (traditional, without size effects) crystal plasticity model [1] to investigate the relative activities of the deformation modes of single-crystal magnesium for varying degrees of misalignment in microcompression. The simulations reveal basal activity in all micropillars, even for perfectly aligned compression along the [0001] axis. Pyramidal < c + a > activity dominates until the misalignment increases to 2°, when basal slip takes over as the dominant mode. The stress-strain curves for the case of 0° misalignment agrees well with experimental curves, indicating that good alignment was achieved during the experiments. Through this investigation, we gain a better understanding of how to control the size effects, as well as the deformation mechanisms operating at the small scale in magnesium.
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On the influence of crystal size and wavelength on native SAD phasing.
Liebschner, Dorothee; Yamada, Yusuke; Matsugaki, Naohiro; Senda, Miki; Senda, Toshiya
2016-06-01
Native SAD is an emerging phasing technique that uses the anomalous signal of native heavy atoms to obtain crystallographic phases. The method does not require specific sample preparation to add anomalous scatterers, as the light atoms contained in the native sample are used as marker atoms. The most abundant anomalous scatterer used for native SAD, which is present in almost all proteins, is sulfur. However, the absorption edge of sulfur is at low energy (2.472 keV = 5.016 Å), which makes it challenging to carry out native SAD phasing experiments as most synchrotron beamlines are optimized for shorter wavelength ranges where the anomalous signal of sulfur is weak; for longer wavelengths, which produce larger anomalous differences, the absorption of X-rays by the sample, solvent, loop and surrounding medium (e.g. air) increases tremendously. Therefore, a compromise has to be found between measuring strong anomalous signal and minimizing absorption. It was thus hypothesized that shorter wavelengths should be used for large crystals and longer wavelengths for small crystals, but no thorough experimental analyses have been reported to date. To study the influence of crystal size and wavelength, native SAD experiments were carried out at different wavelengths (1.9 and 2.7 Å with a helium cone; 3.0 and 3.3 Å with a helium chamber) using lysozyme and ferredoxin reductase crystals of various sizes. For the tested crystals, the results suggest that larger sample sizes do not have a detrimental effect on native SAD data and that long wavelengths give a clear advantage with small samples compared with short wavelengths. The resolution dependency of substructure determination was analyzed and showed that high-symmetry crystals with small unit cells require higher resolution for the successful placement of heavy atoms.
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Lattice Boltzmann Simulation of Water Isotope Fractionation During Growth of Ice Crystals in Clouds
NASA Astrophysics Data System (ADS)
Lu, G.; Depaolo, D.; Kang, Q.; Zhang, D.
2006-12-01
The isotopic composition of precipitation, especially that of snow, plays a special role in the global hydrological cycle and in reconstruction of past climates using polar ice cores. The fractionation of the major water isotope species (HHO, HDO, HHO-18) during ice crystal formation is critical to understanding the global distribution of isotopes in precipitation. Ice crystal growth in clouds is traditionally treated with a spherically- symmetric steady state diffusion model, with semi-empirical modifications added to account for ventilation and for complex crystal morphology. Although it is known that crystal growth rate, which depends largely on the degree of vapor over-saturation, determines crystal morphology, there are no existing quantitative models that directly relate morphology to the vapor saturation factor. Since kinetic (vapor phase diffusion-controlled) isotopic fractionation also depends on growth rate, there should be a direct relationship between vapor saturation, crystal morphology, and crystal isotopic composition. We use a 2D Lattice-Boltzmann model to simulate diffusion-controlled ice crystal growth from vapor- oversaturated air. In the model, crystals grow solely according to the diffusive fluxes just above the crystal surfaces, and hence crystal morphology arises from the initial and boundary conditions in the model and does not need to be specified a priori. The input parameters needed are the isotope-dependent vapor deposition rate constant (k) and the water vapor diffusivity in air (D). The values of both k and D can be computed from kinetic theory, and there are also experimentally determined values of D. The deduced values of k are uncertain to the extent that the sticking coefficient (or accommodation coefficient) for ice is uncertain. The ratio D/k is a length that determines the minimum scale of dendritic growth features and allows us to scale the numerical calculations to atmospheric conditions using a dimensionless Damkohler number: Da = kh/D, where h is the width of the 2D calculation domain. Varying the nondimensional Da in the model is equivalent to varying the scale (h) in the model. Our calculations confirm that the crystal/vapor isotopic fractionation approaches the equilibrium value, and the crystals are compact (circular in 2D) as the saturation factor approaches unity (S= 1.0). At higher oversaturation (e.g. S = 1.2), dendritic crystals of millimeter size develop on timescales appropriate to cloud processes, the isotopic fractionations are dominated by kinetic effects, and similar to those predicted by the spherical diffusion model. Dendritic crystals are constrained to be relatively large, with dimension much greater than D/k. The most difficult aspect of the modeling is to account for the large density difference between air and ice, which requires us to use a fictitious higher density for the vapor-oversaturated air and scale the crystal growth time accordingly. A different approach, using a larger scale simulation to derive boundary conditions for a nested smaller scale calculation is in progress. The results to date clarify the controls on dendritic crystal growth, the relationships between saturation state, growth rate, crystal morphology and isotopic fractionation, and provide limits on the value of the accommodation coefficient.
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Homogeneous crystal nucleation in Ni droplets
NASA Astrophysics Data System (ADS)
Kožíšek, Zdeněk; Demo, Pavel
2017-10-01
Crystal nucleation kinetics is often represented by induction times or metastable zone widths (Kulkarni et al., 2013; Bokeloh et al., 2011). Repeating measurements of supercooling or time delay, at which phase transition is detected, are statistically processed to determine the so-called survivorship function, from which nucleation rate is computed. The size distribution of nuclei is difficult to measure near the critical size directly, and it is not clear which amount of nuclei is formed at the moment when the phase transition is detected. In the present paper, kinetic nucleation equations are solved for the crystal nucleation in Ni liquid droplet to determine the number of nuclei formed within a considered system. Analysis of supercooling experimental data, based on the classical nucleation theory CNT), computes appropriate values of the nucleation rate. However, CNT underestimates the number of nuclei F (F ≪ 1 for supercritical sizes). Taking into account the dependence of the surface energy on nucleus size to data analysis overcomes this discrepancy and leads to reasonable values of the size distribution of nuclei.
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Crystallization features of normal alkanes in confined geometry.
Su, Yunlan; Liu, Guoming; Xie, Baoquan; Fu, Dongsheng; Wang, Dujin
2014-01-21
How polymers crystallize can greatly affect their thermal and mechanical properties, which influence the practical applications of these materials. Polymeric materials, such as block copolymers, graft polymers, and polymer blends, have complex molecular structures. Due to the multiple hierarchical structures and different size domains in polymer systems, confined hard environments for polymer crystallization exist widely in these materials. The confined geometry is closely related to both the phase metastability and lifetime of polymer. This affects the phase miscibility, microphase separation, and crystallization behaviors and determines both the performance of polymer materials and how easily these materials can be processed. Furthermore, the size effect of metastable states needs to be clarified in polymers. However, scientists find it difficult to propose a quantitative formula to describe the transition dynamics of metastable states in these complex systems. Normal alkanes [CnH2n+2, n-alkanes], especially linear saturated hydrocarbons, can provide a well-defined model system for studying the complex crystallization behaviors of polymer materials, surfactants, and lipids. Therefore, a deeper investigation of normal alkane phase behavior in confinement will help scientists to understand the crystalline phase transition and ultimate properties of many polymeric materials, especially polyolefins. In this Account, we provide an in-depth look at the research concerning the confined crystallization behavior of n-alkanes and binary mixtures in microcapsules by our laboratory and others. Since 2006, our group has developed a technique for synthesizing nearly monodispersed n-alkane containing microcapsules with controllable size and surface porous morphology. We applied an in situ polymerization method, using melamine-formaldehyde resin as shell material and nonionic surfactants as emulsifiers. The solid shell of microcapsules can provide a stable three-dimensional (3-D) confining environment. We have studied multiple parameters of these microencapsulated n-alkanes, including surface freezing, metastability of the rotator phase, and the phase separation behaviors of n-alkane mixtures using differential scanning calorimetry (DSC), temperature-dependent X-ray diffraction (XRD), and variable-temperature solid-state nuclear magnetic resonance (NMR). Our investigations revealed new direct evidence for the existence of surface freezing in microencapsulated n-alkanes. By examining the differences among chain packing and nucleation kinetics between bulk alkane solid solutions and their microencapsulated counterparts, we also discovered a mechanism responsible for the formation of a new metastable bulk phase. In addition, we found that confinement suppresses lamellar ordering and longitudinal diffusion, which play an important role in stabilizing the binary n-alkane solid solution in microcapsules. Our work also provided new insights into the phase separation of other mixed system, such as waxes, lipids, and polymer blends in confined geometry. These works provide a profound understanding of the relationship between molecular structure and material properties in the context of crystallization and therefore advance our ability to improve applications incorporating polymeric and molecular materials.
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Numerical Simulation of Nanostructure Growth
NASA Technical Reports Server (NTRS)
Hwang, Helen H.; Bose, Deepak; Govindan, T. R.; Meyyappan, M.
2004-01-01
Nanoscale structures, such as nanowires and carbon nanotubes (CNTs), are often grown in gaseous or plasma environments. Successful growth of these structures is defined by achieving a specified crystallinity or chirality, size or diameter, alignment, etc., which in turn depend on gas mixture ratios. pressure, flow rate, substrate temperature, and other operating conditions. To date, there has not been a rigorous growth model that addresses the specific concerns of crystalline nanowire growth, while demonstrating the correct trends of the processing conditions on growth rates. Most crystal growth models are based on the Burton, Cabrera, and Frank (BCF) method, where adatoms are incorporated into a growing crystal at surface steps or spirals. When the supersaturation of the vapor is high, islands nucleate to form steps, and these steps subsequently spread (grow). The overall bulk growth rate is determined by solving for the evolving motion of the steps. Our approach is to use a phase field model to simulate the growth of finite sized nanowire crystals, linking the free energy equation with the diffusion equation of the adatoms. The phase field method solves for an order parameter that defines the evolving steps in a concentration field. This eliminates the need for explicit front tracking/location, or complicated shadowing routines, both of which can be computationally expensive, particularly in higher dimensions. We will present results demonstrating the effect of process conditions, such as substrate temperature, vapor supersaturation, etc. on the evolving morphologies and overall growth rates of the nanostructures.
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Massey, Michael S; Ippolito, James A; Davis, Jessica G; Sheffield, Ron E
2010-02-01
Phosphorus (P) recovery and re-use will become increasingly important for water quality protection and sustainable nutrient cycling as environmental regulations become stricter and global P reserves decline. The objective of this study was to examine and characterize several magnesium phosphates recovered from actual wastewater under field conditions. Three types of particles were examined including crystalline magnesium ammonium phosphate hexahydrate (struvite) recovered from dairy wastewater, crystalline magnesium ammonium phosphate hydrate (dittmarite) recovered from a food processing facility, and a heterogeneous product also recovered from dairy wastewater. The particles were analyzed using "wet" chemical techniques, powder X-ray diffraction (XRD), and scanning electron microscopy in conjunction with energy dispersive X-ray spectroscopy (SEM-EDS). The struvite crystals had regular and consistent shape, size, and structure, and SEM-EDS analysis clearly showed the struvite crystals as a surface precipitate on calcium phosphate seed material. In contrast, the dittmarite crystals showed no evidence of seed material, and were not regular in size or shape. The XRD analysis identified no crystalline magnesium phosphates in the heterogeneous product and indicated the presence of sand particles. However, magnesium phosphate precipitates on calcium phosphate seed material were observed in this product under SEM-EDS examination. These substantial variations in the macroscopic and microscopic characteristics of magnesium phosphates recovered under field conditions could affect their potential for beneficial re-use and underscore the need to develop recovery processes that result in a uniform, consistent product.
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Far from the equilibrium crystallization of oxide quantum dots in dried inorganic gels
NASA Astrophysics Data System (ADS)
Costille, B.; Dumoulin, M.; Ntsame Abagha, A. M.; Thune, E.; Guinebretière, R.
2018-06-01
We synthesized, through the sol-gel process, far from the equilibrium amorphous materials in which heterogeneous crystallization allowed the formation of oxide quantum dots. The isothermal evolutions of the mean size of the nanocrystals and the crystallinity of the materials were determined through x-ray diffraction experiments. The heterogeneous crystallization is characterized by a kinetic behavior that is far from that expected, according to the classical nucleation theory. We demonstrate that the evolution of the crystallinity is characterized by an Avrami exponent largely smaller than 1. Finally, nanocrystals exhibiting a size significantly below their Bohr radius are obtained and the number of these nanocrystals increases during isothermal treatment, whereas their mean size remains quasi-constant.
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NASA Astrophysics Data System (ADS)
Golod, V. M.; Sufiiarov, V. Sh
2017-04-01
Gas atomization is a high-performance process for manufacturing superfine metal powders. Formation of the powder particles takes place primarily through the fragmentation of alloy melt flow with high-pressure inert gas, which leads to the formation of non-uniform sized micron-scale particles and subsequent their rapid solidification due to heat exchange with gas environment. The article presents results of computer modeling of crystallization process, simulation and experimental studies of the cellular-dendrite structure formation and microsegregation in different size particles. It presents results of adaptation of the approach for local nonequilibrium solidification to conditions of crystallization at gas atomization, detected border values of the particle size at which it is possible a manifestation of diffusionless crystallization.
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Key to enhance thermoelectric performance by controlling crystal size of strontium titanate
NASA Astrophysics Data System (ADS)
Wang, Jun; Ye, Xinxin; Yaer, Xinba; Wu, Yin; Zhang, Boyu; Miao, Lei
2015-09-01
One-step molten salt synthesis process was introduced to fabricate nano to micrometer sized SrTiO3 powders in which effects of synthesis temperature, oxide-to-flux ratios and raw materials on the generation of SrTiO3 powders were examined. 100 nm or above sized pure SrTiO3 particles were obtained at relatively lower temperature of 900∘C. Micro-sized rhombohedral crystals with a maximum size of approximately 12 μm were obtained from SrCO3 or Sr(NO3)2 strontium source with 1:1 O/S ratio. Controlled crystal size and morphology of Nb-doped SrTiO3 particles are prepared by using this method to confirm the performance of thermoelectric properties. The Seebeck coefficient obtained is significantly high when compared with the reported data, and the high ratio of nano particles in the sample has a positive effect on the increase of Seebeck coefficient too, which is likely due to the energy filtering effect at large numbers of grain boundaries resulting from largely distributed structure.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Pan, Bo; Shibutani, Yoji, E-mail: sibutani@mech.eng.osaka-u.ac.jp; Zhang, Xu
2015-07-07
Recent research has explained that the steeply increasing yield strength in metals depends on decreasing sample size. In this work, we derive a statistical physical model of the yield strength of finite single-crystal micro-pillars that depends on single-ended dislocation pile-up inside the micro-pillars. We show that this size effect can be explained almost completely by considering the stochastic lengths of the dislocation source and the dislocation pile-up length in the single-crystal micro-pillars. The Hall–Petch-type relation holds even in a microscale single-crystal, which is characterized by its dislocation source lengths. Our quantitative conclusions suggest that the number of dislocation sources andmore » pile-ups are significant factors for the size effect. They also indicate that starvation of dislocation sources is another reason for the size effect. Moreover, we investigated the explicit relationship between the stacking fault energy and the dislocation “pile-up” effect inside the sample: materials with low stacking fault energy exhibit an obvious dislocation pile-up effect. Our proposed physical model predicts a sample strength that agrees well with experimental data, and our model can give a more precise prediction than the current single arm source model, especially for materials with low stacking fault energy.« less
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Size-dependent and tunable crystallization of GeSbTe phase-change nanoparticles
NASA Astrophysics Data System (ADS)
Chen, Bin; Ten Brink, Gert H.; Palasantzas, George; Kooi, Bart J.
2016-12-01
Chalcogenide-based nanostructured phase-change materials (PCMs) are considered promising building blocks for non-volatile memory due to their high write and read speeds, high data-storage density, and low power consumption. Top-down fabrication of PCM nanoparticles (NPs), however, often results in damage and deterioration of their useful properties. Gas-phase condensation based on magnetron sputtering offers an attractive and straightforward solution to continuously down-scale the PCMs into sub-lithographic sizes. Here we unprecedentedly present the size dependence of crystallization for Ge2Sb2Te5 (GST) NPs, whose production is currently highly challenging for chemical synthesis or top-down fabrication. Both amorphous and crystalline NPs have been produced with excellent size and composition control with average diameters varying between 8 and 17 nm. The size-dependent crystallization of these NPs was carefully analyzed through in-situ heating in a transmission electron microscope, where the crystallization temperatures (Tc) decrease when the NPs become smaller. Moreover, methane incorporation has been observed as an effective method to enhance the amorphous phase stability of the NPs. This work therefore elucidates that GST NPs synthesized by gas-phase condensation with tailored properties are promising alternatives in designing phase-change memories constrained by optical lithography limitations.
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Review: Serial Femtosecond Crystallography: A Revolution in Structural Biology
Martin-Garcia, Jose M.; Conrad, Chelsie E.; Coe, Jesse; Roy-Chowdhury, Shatabdi; Fromme, Petra
2016-01-01
Macromolecular crystallography at synchrotron sources has proven to be the most influential method within structural biology, producing thousands of structures since its inception. While its utility has been instrumental in progressing our knowledge of structures of molecules, it suffers from limitations such as the need for large, well-diffracting crystals, and radiation damage that can hamper native structural determination. The recent advent of X-ray free electron lasers (XFELs) and their implementation in the emerging field of serial femtosecond crystallography (SFX) has given rise to a remarkable expansion upon existing crystallographic constraints, allowing structural biologists access to previously restricted scientific territory. SFX relies on exceptionally brilliant, micro-focused X-ray pulses, which are femtoseconds in duration, to probe nano/micrometer sized crystals in a serial fashion. This results in data sets comprised of individual snapshots, each capturing Bragg diffraction of single crystals in random orientations prior to their subsequent destruction. Thus structural elucidation while avoiding radiation damage, even at room temperature, can now be achieved. This emerging field has cultivated new methods for nanocrystallogenesis, sample delivery, and data processing. Opportunities and challenges within SFX are reviewed herein. PMID:27143509
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Serial femtosecond crystallography: A revolution in structural biology.
Martin-Garcia, Jose M; Conrad, Chelsie E; Coe, Jesse; Roy-Chowdhury, Shatabdi; Fromme, Petra
2016-07-15
Macromolecular crystallography at synchrotron sources has proven to be the most influential method within structural biology, producing thousands of structures since its inception. While its utility has been instrumental in progressing our knowledge of structures of molecules, it suffers from limitations such as the need for large, well-diffracting crystals, and radiation damage that can hamper native structural determination. The recent advent of X-ray free electron lasers (XFELs) and their implementation in the emerging field of serial femtosecond crystallography (SFX) has given rise to a remarkable expansion upon existing crystallographic constraints, allowing structural biologists access to previously restricted scientific territory. SFX relies on exceptionally brilliant, micro-focused X-ray pulses, which are femtoseconds in duration, to probe nano/micrometer sized crystals in a serial fashion. This results in data sets comprised of individual snapshots, each capturing Bragg diffraction of single crystals in random orientations prior to their subsequent destruction. Thus structural elucidation while avoiding radiation damage, even at room temperature, can now be achieved. This emerging field has cultivated new methods for nanocrystallogenesis, sample delivery, and data processing. Opportunities and challenges within SFX are reviewed herein. Published by Elsevier Inc.
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NASA Astrophysics Data System (ADS)
de Vries, B. L.; Maaskant, K. M.; Min, M.; Lombaert, R.; Waters, L. B. F. M.; Blommaert, J. A. D. L.
2015-04-01
Aims: We study the grain properties and location of the forsterite crystals in the circumstellar environment of the pre-planetary nebula (PPN) IRAS 17150-3224 in order to learn more about the as yet poorly understood evolutionary phase prior to the PPN. Methods: We use the best-fit model for IRAS 17150-3224 of Meixner et al. (2002, ApJ, 571, 936) and add forsterite to this model. We investigate different spatial distributions and grain sizes of the forsterite crystals in the circumstellar environment. We compare the spectral bands of forsterite in the mid-infrared and at 69 μm in radiative transport models to those in ISO-SWS and Herschel/ PACS observations. Results: We can reproduce the non-detection of the mid-infrared bands and the detection of the 69 μm feature with models where the forsterite is distributed in the whole outflow, in the superwind region, or in the AGB-wind region emitted previous to the superwind, but we cannot discriminate between these three models. To reproduce the observed spectral bands with these three models, the forsterite crystals need to be dominated by a grain size population of 2 μm up to 6 μm. We also tested models where the forsterite is located in a torus region or where it is concentrated in the equatorial plane, in a disk-like fashion. These models show either absorption features that are too strong or a 69 μm band that is too weak, respectively, so we exclude these cases. We observe a blue shoulder on the 69 μm band that cannot be explained by forsterite and we suggest a possible population of micron-sized ortho-enstatite grains. We hypothesise that the large forsterite crystals were formed after the superwind phase of IRAS 17150-3224, where the star developed an as yet unknown hyperwind with an extremely high mass-loss rate (≳10-3M⊙/yr). The high densities of such a hyperwind could be responsible for the efficient grain growth of both amorphous and crystalline dust in the outflow. Several mechanisms are discussed that might explain the lower-limit of ˜2 μm found for the forsterite grains, but none are satisfactory. Among the mechanisms explored is a possible selection effect due to radiation pressure based on photon scattering on micron-sized grains.
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NASA Astrophysics Data System (ADS)
Martínez-Cruz, Nancy; Carrillo-Romo, Felipe; Jaramillo-Vigueras, David
2004-10-01
This paper analyzes the effect of polystyrensulfonic acid sodium salt (NaPSS), obtained by kinetic precipitation from solutions of polymers of molecular weight 245 000 and 38 000 g mol-1 in sodium bicarbonate (NaHCO3) itself precipitated from synthetic brine. Crystal size, shape and the additive adsorbed are reported. X shaped and hexagonal prisms crystals with different aspect ratios were obtained. The results show that with increasing polymer concentration the crystal size decreases, from 0.27 to 0.48 mm. Additionally, the higher molecular weight polymer shows both higher adsorption capacity and higher crystal habit modification. Crystal shape patterns were similar for both polymers; however, the higher molecular weight material induced changes at lower concentration. It was observed that the precipitation rate reached a minimum with increasing additive concentration.
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Study on growth techniques and macro defects of large-size Nd:YAG laser crystal
NASA Astrophysics Data System (ADS)
Quan, Jiliang; Yang, Xin; Yang, Mingming; Ma, Decai; Huang, Jinqiang; Zhu, Yunzhong; Wang, Biao
2018-02-01
Large-size neodymium-doped yttrium aluminum garnet (Nd:YAG) single crystals were grown by the Czochralski method. The extinction ratio and wavefront distortion of the crystal were tested to determine the optical homogeneity. Moreover, under different growth conditions, the macro defects of inclusion, striations, and cracking in the as-grown Nd:YAG crystals were analyzed. Specifically, the inclusion defects were characterized using scanning electron microscopy and energy dispersive spectroscopy. The stresses of growth striations and cracking were studied via a parallel plane polariscope. These results demonstrate that improper growth parameters and temperature fields can enhance defects significantly. Thus, by adjusting the growth parameters and optimizing the thermal environment, high-optical-quality Nd:YAG crystals with a diameter of 80 mm and a total length of 400 mm have been obtained successfully.
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NASA Astrophysics Data System (ADS)
Scotti, A.; Gasser, U.; Herman, E. S.; Han, Jun; Menzel, A.; Lyon, L. A.; Fernandez-Nieves, A.
2017-09-01
We investigate the phase behavior of suspensions of poly(N -isopropylacrylamide) (pNIPAM) microgels with either bimodal or polydisperse size distribution. We observe a shift of the fluid-crystal transition to higher concentrations depending on the polydispersity or the fraction of large particles in suspension. Crystallization is observed up to polydispersities as high as 18.5%, and up to a number fraction of large particles of 29% in bidisperse suspensions. The crystal structure is random hexagonal close-packed as in monodisperse pNIPAM microgel suspensions. We explain our experimental results by considering the effect of bound counterions. Above a critical particle concentration, these cause deswelling of the largest microgels, which are the softest, changing the size distribution of the suspension and enabling crystal formation in conditions where incompressible particles would not crystallize.
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Crystal imperfection studies of pure and silicon substituted hydroxyapatite using Raman and XRD.
Zou, Shuo; Huang, Jie; Best, Serena; Bonfield, William
2005-12-01
Hydroxyapatite (HA) is important in biomedical applications because of its chemical similarity to the mineral content of bone and its consequent bioactivity. Silicon substitution into the hydroxyapatite crystal lattice was found to enhance its bioactivity both in vitro and in vivo [1, 2]. However, the mechanism for the enhancement is still not well understood. In this paper, the crystal imperfections introduced by silicon substitution were studied using XRD and Raman spectroscopy. It was found that silicon substitution did not introduce microstrain, but deceased the crystal size in the hk0 direction. Three new vibration modes and peak broadening were observed in Raman spectra following silicon incorporation. The imperfections introduced by silicon substitution may play a role in enhancing bioactivity. A phenomenological relationship between the width of the PO4 v1 peak and crystal size was established.
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Novel fluorescence adjustable photonic crystal materials
NASA Astrophysics Data System (ADS)
Zhu, Cheng; Liu, Xiaoxia; Ni, Yaru; Fang, Jiaojiao; Fang, Liang; Lu, Chunhua; Xu, Zhongzi
2017-11-01
Novel photonic crystal materials (PCMs) with adjustable fluorescence were fabricated by distributing organic fluorescent powders of Yb0.2Er0.4Tm0.4(TTA)3Phen into the opal structures of self-assembled silica photonic crystals (PCs). Via removing the silica solution in a constant speed, PCs with controllable thicknesses and different periodic sizes were obtained on glass slides. Yb0.2Er0.4Tm0.4(TTA)3Phen powders were subsequently distributed into the opal structures. The structures and optical properties of the prepared PCMs were investigated. Finite-difference-time-domain (FDTD) calculation was used to further analyze the electric field distributions in PCs with different periodic sizes while the relation between periodic sizes and fluorescent spectra of PCMs was discussed. The results showed that the emission color of the PCMs under irradiation of 980 nm laser can be easily adjusted from green to blue by increasing the periodic size from 250 to 450 nm.
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Economic analysis of crystal growth in space
NASA Technical Reports Server (NTRS)
Ulrich, D. R.; Chung, A. M.; Yan, C. S.; Mccreight, L. R.
1972-01-01
Many advanced electronic technologies and devices for the 1980's are based on sophisticated compound single crystals, i.e. ceramic oxides and compound semiconductors. Space processing of these electronic crystals with maximum perfection, purity, and size is suggested. No ecomonic or technical justification was found for the growth of silicon single crystals for solid state electronic devices in space.
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Imaging System For Measuring Macromolecule Crystal Growth Rates in Microgravity
NASA Technical Reports Server (NTRS)
Corder, Eric L.; Briscoe, Jeri
2004-01-01
In order to determine how macromolecule crystal quality improvement in microgravity is related to crystal growth characteristics, a team of scientists and engineers at NASA's Marshal Space Flight Center (MSFC) developed flight hardware capable of measuring the crystal growth rates of a population of crystals growing under the same conditions. As crystal growth rate is defined as the change or delta in a defined dimension or length (L) of crystal over time, the hardware was named Delta-L. Delta-L consists of three sub assemblies: a fluid unit including a temperature-controlled growth cell, an imaging unit, and a control unit (consisting of a Data Acquisition and Control Unit (DACU), and a thermal control unit). Delta-L will be used in connection with the Glovebox Integrated Microgravity Isolation Technology (g-LIMIT) inside the Microgravity Science Glovebox (MSG), onboard the International Space Station. This paper will describe the Delta-L imaging system. The Delta-L imaging system was designed to locate, resolve, and capture images of up to 10 individual crystals ranging in size from 10 to 500 microns with a point-to-point accuracy of +/- 2.0 microns within a quartz growth cell observation area of 20 mm x 10 mm x 1 mm. The optical imaging system is comprised of a video microscope camera mounted on computer controlled translation stages. The 3-axis translation stages and control units provide crewmembers the ability to search throughout the growth cell observation area for crystals forming in size of approximately 10 microns. Once the crewmember has selected ten crystals of interest, the growth of these crystals is tracked until the size reaches approximately 500 microns. In order to resolve these crystals an optical system with a magnification of 10X was designed. A black and white NTSC camera was utilized with a 20X microscope objective and a 0.5X custom designed relay lens with an inline light to meet the magnification requirement. The design allows a 500 pm crystal to be viewed in the vertical dimension on a standard NTSC monitor (4:3 aspect ratio). Images of the 10 crystals are collected periodically and stored in sets by the DACU.
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Structuring β-Ga2O3 photonic crystal photocatalyst for efficient degradation of organic pollutants.
Li, Xiaofang; Zhen, Xiuzheng; Meng, Sugang; Xian, Jiangjun; Shao, Yu; Fu, Xianzhi; Li, Danzhen
2013-09-03
Coupling photocatalysts with photonic crystals structure is based on the unique property of photonic crystals in confining, controlling, and manipulating the incident photons. This combination enhances the light absorption in photocatalysts and thus greatly improves their photocatalytic performance. In this study, Ga2O3 photonic crystals with well-arranged skeleton structures were prepared via a dip-coating infiltration method. The positions of the electronic band absorption for Ga2O3 photonic crystals could be made to locate on the red edge, on the blue edge, and away from the edge of their photonic band gaps by changing the pore sizes of the samples, respectively. Particularly, the electronic band absorption of the Ga2O3 photonic crystal with a pore size of 135 nm was enhanced more than other samples by making it locate on the red edge of its photonic band gap, which was confirmed by the higher instantaneous photocurrent and photocatalytic activity for the degradation of various organic pollutants under ultraviolet light irradiation. Furthermore, the degradation mechanism over Ga2O3 photonic crystals was discussed. The design of Ga2O3 photonic crystals presents a prospective application of photonic crystals in photocatalysis to address light harvesting and quantum efficiency problems through manipulating photons or constructing photonic crystal structure as groundwork.
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NASA Astrophysics Data System (ADS)
Choi, Byung Sang
Compared to overwhelming technical data available in other advanced technologies, knowledge about particle technology, especially in particle synthesis from a solution, is still poor due to the lack of available equipment to study crystallization phenomena in a crystallizer. Recent technical advances in particle size measurement such as Coulter counter and laser light scattering have made in/ex situ study of some of particle synthesis, i.e., growth, attrition, and aggregation, possible with simple systems. Even with these advancements in measurement technology, to grasp fully the crystallization phenomena requires further theoretical and technical advances in understanding such particle synthesis mechanisms. Therefore, it is the motive of this work to establish the general processing parameters and to produce rigorous experimental data with reliable performance and characterization that rigorously account for the crystallization phenomena of nucleation, growth, aggregation, and breakage including their variations with time and space in a controlled continuous mixed-suspension mixed-product removal (CMSMPR) crystallizer. This dissertation reports the results and achievements in the following areas: (1) experimental programs to support the development and validation of the phenomenological models and generation of laboratory data for the purpose of testing, refining, and validating the crystallization process, (2) development of laboratory well-mixed crystallizer system and experimental protocols to generate crystal size distribution (CSD) data, (3) the effects of feed solution concentration, crystallization temperature, feed flow rate, and mixing speed, as well as different types of mixers resulting in the evolution of CSDs with time from a concentrated brine solution, (4) with statistically designed experiments the effects of processing variables on the resultant particle structure and CSD at steady state were quantified and related to each of those operating conditions by studying the detailed crystallization processes, such as nucleation, growth, and breakage, as well as agglomeration. The purification of CaCl2 solution involving the crystallization of NaCl from the solution mixture of CaCl2, KCl, and NaCl as shipped from Dow Chemical, Ludington, in a CMSMPR crystallizer was studied as our model system because of its nucleation and crystal growth tendencies with less agglomeration. This project also generated a significant body of experimental data that are available at URL that is http://www.che.utah.edu/˜ring/CrystallizationWeb.
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Bubble migration in a compacting crystal-liquid mush
NASA Astrophysics Data System (ADS)
Boudreau, Alan
2016-04-01
Recent theoretical models have suggested that bubbles are unlikely to undergo significant migration in a compaction crystal mush by capillary invasion while the system remains partly molten. To test this, experiments of bubble migration during compaction in a crystal-liquid mush were modeled using deformable foam crystals in corn syrup in a volumetric burette, compacted with rods of varying weights. A bubble source was provided by sodium bicarbonate (Alka-Seltzer®). Large bubbles (>several crystal sizes) are pinched by the compacting matrix and become overpressured and deformed as the bubbles experience a load change from hydrostatic to lithostatic. Once they begin to move, they move much faster than the compaction-driven liquid. Bubbles that are about the same size as the crystals but larger than the narrower pore throats move by deformation or breaking into smaller bubbles as they are forced through pore restrictions. Bubbles that are less than the typical pore diameter generally move with the liquid: The liquid + bubble mixture behaves as a single phase with a lower density than the bubble-free liquid, and as a consequence it rises faster than bubble-free liquid and allows for faster compaction. The overpressure required to force a bubble through the matrix (max grain size = 5 mm) is modest, about 5 %, and it is estimated that for a grain size of 1 mm, the required overpressure would be about 25 %. Using apatite distribution in a Stillwater olivine gabbro as an analog for bubble nucleation and growth, it is suggested that relatively large bubbles initially nucleate and grow in liquid-rich channels that develop late in the compaction history. Overpressure from compaction allows bubbles to rise higher into hotter parts of the crystal pile, where they redissolve and increase the volatile content of the liquid over what it would have without the bubble migration, leading to progressively earlier vapor saturation during crystallization of the interstitial liquid. Bubbles can also move rapidly by `surfing' on porosity waves that can develop in a compacting mush.
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NASA Astrophysics Data System (ADS)
Tong, Huifen; Zhou, Yingying; Chang, Gang; Li, Pai; Zhu, Ruizhi; He, Yunbin
2018-06-01
Anatase TiO2 micro-crystals with 51% surface exposing highly active {0 0 1} facets are prepared by hydrothermal synthesis using TiF4 as Ti resource and HF as morphology control agent. In addition, anatase TiO2 single crystals exposing large {0 0 1} crystal facets are facilely synthesized with "green" NaF plus HCl replacing HF for the morphology control. A series of comparative experiments are carried out for separately studying the effects of F- and H+ concentrations on the growth of TiO2 crystals, which have not been understood very much in depth so far. The results indicate that both F- and H+ synergistically affect the synthesis of truncated anatase octahedrons, where F- is preferentially adsorbed on the {0 0 1} facets resulting in lateral growth of these facets and H+ adjusts the growth rate of anatase TiO2 along different orientations by tuning the hydrolysis rate. Based on this information, anatase TiO2 single crystals with small size (1.3 μm) and large exposure of {0 0 1} facets (45%) are successfully prepared under optimal conditions ([H+]/[F-] = 20:1). Photocatalytic activities of the as-prepared products toward methylene blue photo-degradation are further tested. It is revealed that both crystal size and percentage of {0 0 1} facets are decisive for the photocatalytic performance, and the crystals with a small size (1.3 μm) and large exposure of {0 0 1} facets (45%) are catalytically most active. This work has clarified the main factors that control the growth process and morphology of anatase TiO2 single crystals for achieving superior photocatalytic properties.
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Imaging transport phenomena during lysozyme protein crystal growth by the hanging drop technique
NASA Astrophysics Data System (ADS)
Sethia Gupta, Anamika; Gupta, Rajive; Panigrahi, P. K.; Muralidhar, K.
2013-06-01
The present study reports the transport process that occurs during the growth of lysozyme protein crystals by the hanging drop technique. A rainbow schlieren technique has been employed for imaging changes in salt concentration. A one dimensional color filter is used to record the deflection of the light beam. An optical microscope and an X-ray crystallography unit are used to characterize the size, tetragonal shape and Bravais lattice constants of the grown crystals. A parametric study on the effect of drop composition, drop size, reservoir height and number of drops on the crystal size and quality is reported. Changes in refractive index are not large enough to create a meaningful schlieren image in the air gap between the drop and the reservoir. However, condensation of fresh water over the reservoir solution creates large changes in the concentration of NaCl, giving rise to clear color patterns in the schlieren images. These have been analyzed to obtain salt concentration profiles near the free surface of the reservoir solution as a function of time. The diffusion of fresh water into the reservoir solution at the early stages of crystal growth followed by the mass flux of salt from the bulk solution towards the free surface has been recorded. The overall crystal growth process can be classified into two regimes, as demarcated by the changes in slope of salt concentration within the reservoir. The salt concentration in the reservoir equilibrates at long times when the crystallization process is complete. Thus, transport processes in the reservoir emerge as the route to monitor protein crystal growth in the hanging drop configuration. Results show that crystal growth rate is faster for a higher lysozyme concentration, smaller drops, and larger reservoir heights.
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Time-evolution of grain size distributions in random nucleation and growth crystallization processes
NASA Astrophysics Data System (ADS)
Teran, Anthony V.; Bill, Andreas; Bergmann, Ralf B.
2010-02-01
We study the time dependence of the grain size distribution N(r,t) during crystallization of a d -dimensional solid. A partial differential equation, including a source term for nuclei and a growth law for grains, is solved analytically for any dimension d . We discuss solutions obtained for processes described by the Kolmogorov-Avrami-Mehl-Johnson model for random nucleation and growth (RNG). Nucleation and growth are set on the same footing, which leads to a time-dependent decay of both effective rates. We analyze in detail how model parameters, the dimensionality of the crystallization process, and time influence the shape of the distribution. The calculations show that the dynamics of the effective nucleation and effective growth rates play an essential role in determining the final form of the distribution obtained at full crystallization. We demonstrate that for one class of nucleation and growth rates, the distribution evolves in time into the logarithmic-normal (lognormal) form discussed earlier by Bergmann and Bill [J. Cryst. Growth 310, 3135 (2008)]. We also obtain an analytical expression for the finite maximal grain size at all times. The theory allows for the description of a variety of RNG crystallization processes in thin films and bulk materials. Expressions useful for experimental data analysis are presented for the grain size distribution and the moments in terms of fundamental and measurable parameters of the model.
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Ma, Meng; He, Zhoukun; Li, Yuhan; Chen, Feng; Wang, Ke; Zhang, Qing; Deng, Hua; Fu, Qiang
2012-12-01
Thin films of polystyrene (PS)/poly(ε-caprolactone) (PCL) blends were prepared by spin-coating and characterized by tapping mode force microscopy (AFM). Effects of the relative concentration of PS in polymer solution on the surface phase separation and dewetting feature size of the blend films were systematically studied. Due to the coupling of phase separation, dewetting, and crystallization of the blend films with the evaporation of solvent during spin-coating, different size of PS islands decorated with various PCL crystal structures including spherulite-like, flat-on individual lamellae, and flat-on dendritic crystal were obtained in the blend films by changing the film composition. The average distance of PS islands was shown to increase with the relative concentration of PS in casting solution. For a given ratio of PS/PCL, the feature size of PS appeared to increase linearly with the square of PS concentration while the PCL concentration only determined the crystal morphology of the blend films with no influence on the upper PS domain features. This is explained in terms of vertical phase separation and spinodal dewetting of the PS rich layer from the underlying PCL rich layer, leading to the upper PS dewetting process and the underlying PCL crystalline process to be mutually independent. Copyright © 2012 Elsevier Inc. All rights reserved.
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NASA Astrophysics Data System (ADS)
Hu, Lin; Wirth, Brian D.; Maroudas, Dimitrios
2017-08-01
We report results on the lattice thermal conductivities of tungsten single crystals containing nanoscale-sized pores or voids and helium (He) nanobubbles as a function of void/bubble size and gas pressure in the He bubbles based on molecular-dynamics simulations. For reference, we calculated lattice thermal conductivities of perfect tungsten single crystals along different crystallographic directions at room temperature and found them to be about 10% of the overall thermal conductivity of tungsten with a weak dependence on the heat flux direction. The presence of nanoscale voids in the crystal causes a significant reduction in its lattice thermal conductivity, which decreases with increasing void size. Filling the voids with He to form He nanobubbles and increasing the bubble pressure leads to further significant reduction of the tungsten lattice thermal conductivity, down to ˜20% of that of the perfect crystal. The anisotropy in heat conduction remains weak for tungsten single crystals containing nanoscale-sized voids and He nanobubbles throughout the pressure range examined. Analysis of the pressure and atomic displacement fields in the crystalline region that surrounds the He nanobubbles reveals that the significant reduction of tungsten lattice thermal conductivity in this region is due to phonon scattering from the nanobubbles, as well as lattice deformation around the nanobubbles and formation of lattice imperfections at higher bubble pressure.
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Livi, Kenneth J T; Villalobos, Mario; Leary, Rowan; Varela, Maria; Barnard, Jon; Villacís-García, Milton; Zanella, Rodolfo; Goodridge, Anna; Midgley, Paul
2017-09-12
Two synthetic goethites of varying crystal size distributions were analyzed by BET, conventional TEM, cryo-TEM, atomic resolution STEM and HRTEM, and electron tomography in order to determine the effects of crystal size, shape, and atomic scale surface roughness on their adsorption capacities. The two samples were determined by BET to have very different site densities based on Cr VI adsorption experiments. Model specific surface areas generated from TEM observations showed that, based on size and shape, there should be little difference in their adsorption capacities. Electron tomography revealed that both samples crystallized with an asymmetric {101} tablet habit. STEM and HRTEM images showed a significant increase in atomic-scale surface roughness of the larger goethite. This difference in roughness was quantified based on measurements of relative abundances of crystal faces {101} and {201} for the two goethites, and a reactive surface site density was calculated for each goethite. Singly coordinated sites on face {210} are 2.5 more dense than on face {101}, and the larger goethite showed an average total of 36% {210} as compared to 14% for the smaller goethite. This difference explains the considerably larger adsorption capacitiy of the larger goethite vs the smaller sample and points toward the necessity of knowing the atomic scale surface structure in predicting mineral adsorption processes.
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Use of a miniature diamond-anvil cell in high-pressure single-crystal neutron Laue diffraction
Binns, Jack; Kamenev, Konstantin V.; McIntyre, Garry J.; Moggach, Stephen A.; Parsons, Simon
2016-01-01
The first high-pressure neutron diffraction study in a miniature diamond-anvil cell of a single crystal of size typical for X-ray diffraction is reported. This is made possible by modern Laue diffraction using a large solid-angle image-plate detector. An unexpected finding is that even reflections whose diffracted beams pass through the cell body are reliably observed, albeit with some attenuation. The cell body does limit the range of usable incident angles, but the crystallographic completeness for a high-symmetry unit cell is only slightly less than for a data collection without the cell. Data collections for two sizes of hexamine single crystals, with and without the pressure cell, and at 300 and 150 K, show that sample size and temperature are the most important factors that influence data quality. Despite the smaller crystal size and dominant parasitic scattering from the diamond-anvil cell, the data collected allow a full anisotropic refinement of hexamine with bond lengths and angles that agree with literature data within experimental error. This technique is shown to be suitable for low-symmetry crystals, and in these cases the transmission of diffracted beams through the cell body results in much higher completeness values than are possible with X-rays. The way is now open for joint X-ray and neutron studies on the same sample under identical conditions. PMID:27158503
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High-temperature crystallization of nanocrystals into three-dimensional superlattices.
Wu, Liheng; Willis, Joshua J; McKay, Ian Salmon; Diroll, Benjamin T; Qin, Jian; Cargnello, Matteo; Tassone, Christopher J
2017-08-10
Crystallization of colloidal nanocrystals into superlattices represents a practical bottom-up process with which to create ordered metamaterials with emergent functionalities. With precise control over the size, shape and composition of individual nanocrystals, various single- and multi-component nanocrystal superlattices have been produced, the lattice structures and chemical compositions of which can be accurately engineered. Nanocrystal superlattices are typically prepared by carefully controlling the assembly process through solvent evaporation or destabilization or through DNA-guided crystallization. Slow solvent evaporation or cooling of nanocrystal solutions (over hours or days) is the key element for successful crystallization processes. Here we report the rapid growth (seconds) of micrometre-sized, face-centred-cubic, three-dimensional nanocrystal superlattices during colloidal synthesis at high temperatures (more than 230 degrees Celsius). Using in situ small-angle X-ray scattering, we observe continuous growth of individual nanocrystals within the lattices, which results in simultaneous lattice expansion and fine nanocrystal size control due to the superlattice templates. Thermodynamic models demonstrate that balanced attractive and repulsive interparticle interactions dictated by the ligand coverage on nanocrystal surfaces and nanocrystal core size are responsible for the crystallization process. The interparticle interactions can also be controlled to form different superlattice structures, such as hexagonal close-packed lattices. The rational assembly of various nanocrystal systems into novel materials is thus facilitated for both fundamental research and for practical applications in the fields of magnetics, electronics and catalysis.
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High-temperature crystallization of nanocrystals into three-dimensional superlattices
NASA Astrophysics Data System (ADS)
Wu, Liheng; Willis, Joshua J.; McKay, Ian Salmon; Diroll, Benjamin T.; Qin, Jian; Cargnello, Matteo; Tassone, Christopher J.
2017-08-01
Crystallization of colloidal nanocrystals into superlattices represents a practical bottom-up process with which to create ordered metamaterials with emergent functionalities. With precise control over the size, shape and composition of individual nanocrystals, various single- and multi-component nanocrystal superlattices have been produced, the lattice structures and chemical compositions of which can be accurately engineered. Nanocrystal superlattices are typically prepared by carefully controlling the assembly process through solvent evaporation or destabilization or through DNA-guided crystallization. Slow solvent evaporation or cooling of nanocrystal solutions (over hours or days) is the key element for successful crystallization processes. Here we report the rapid growth (seconds) of micrometre-sized, face-centred-cubic, three-dimensional nanocrystal superlattices during colloidal synthesis at high temperatures (more than 230 degrees Celsius). Using in situ small-angle X-ray scattering, we observe continuous growth of individual nanocrystals within the lattices, which results in simultaneous lattice expansion and fine nanocrystal size control due to the superlattice templates. Thermodynamic models demonstrate that balanced attractive and repulsive interparticle interactions dictated by the ligand coverage on nanocrystal surfaces and nanocrystal core size are responsible for the crystallization process. The interparticle interactions can also be controlled to form different superlattice structures, such as hexagonal close-packed lattices. The rational assembly of various nanocrystal systems into novel materials is thus facilitated for both fundamental research and for practical applications in the fields of magnetics, electronics and catalysis.
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NASA Technical Reports Server (NTRS)
Curry, Judith; Khvorostyanov, V. I.
2005-01-01
This project used a hierarchy of cloud resolving models to address the following science issues of relevance to CRYSTAL-FACE: What ice crystal nucleation mechanisms are active in the different types of cirrus clouds in the Florida area and how do these different nucleation processes influence the evolution of the cloud system and the upper tropospheric humidity? How does the feedback between supersaturation and nucleation impact the evolution of the cloud? What is the relative importance of the large-scale vertical motion and the turbulent motions in the evolution of the crystal size spectra? How does the size spectra impact the life-cycle of the cloud, stratospheric dehydration, and cloud radiative forcing? What is the nature of the turbulence and waves in the upper troposphere generated by precipitating deep convective cloud systems? How do cirrus microphysical and optical properties vary with the small-scale dynamics? How do turbulence and waves in the upper troposphere influence the cross-tropopause mixing and stratospheric and upper tropospheric humidity? The models used in this study were: 2-D hydrostatic model with explicit microphysics that can account for 30 size bins for both the droplet and crystal size spectra. Notably, a new ice crystal nucleation scheme has been incorporated into the model. Parcel model with explicit microphysics, for developing and evaluating microphysical parameterizations. Single column model for testing bulk microphysics parameterizations
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Wu, Congcong; Sun, Zhaomei; Liu, Li-Shang
2017-07-10
The surface crystallization of CaCO 3 on gold was monitored by a quartz crystal microbalance (QCM). Quantitative control of the grown crystals was realized by adjusting the ratio of two functional groups, -N(CH 3 ) 3 and -COOH, on SAMs. Crystals with uniform size, morphology and polymorphism were obtained. The amount of crystals formed was found to increase with an increase in the -COOH group. The proposed quantitative control of crystallization can be an effective mass amplification strategy for QCM to enhance its assay sensitivity.
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NASA Technical Reports Server (NTRS)
Miller, Teresa Y.; He, Xiao-Min; Carter, Daniel C.
1992-01-01
Crystals of human serum albumin have been successfully grown in a variety of gels using crystallization conditions otherwise equivalent to those utilized in the popular hanging-drop vapor-equilibrium method. Preliminary comparisons of gel grown crystals with crystals grown by the vapor diffusion method via both ground-based and microgravity methods indicate that crystals superior in size and quality may be grown by limiting solutal convection. Preliminary X-ray diffraction statistics are presented.
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Advances in food crystallization.
Hartel, Richard W
2013-01-01
Crystals often play an important role in food product quality and shelf life. Controlling crystallization to obtain the desired crystal content, size distribution, shape, and polymorph is key to manufacturing products with desired functionality and shelf life. Technical developments in the field have improved the tools with which we study and characterize crystals in foods. These developments also help our understanding of the physico-chemical phenomena that govern crystallization and improve our ability to control it during processing and storage. In this review, some of the more important recent developments in measuring and controlling crystallization are discussed.
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NASA Astrophysics Data System (ADS)
Lindsey, Adam C.; Zhuravleva, Mariya; Wu, Yuntao; Stand, Luis; Loyd, Matthew; Gokhale, Sasmit; Koschan, Merry; Melcher, Charles L.
2016-09-01
KCaI3:Eu crystals have been identified as very promising for use in spectroscopic detector applications related to nuclear nonproliferation and domestic security efforts. Initial studies have shown for small crystals a few mm3 in size with 3% europium dopant concentration, a high light yield of >70,000 ph/MeV and energy resolution of ≈3% at 662 keV is attainable which is comparable with the highest performance scintillators discovered. In this work, single crystals of KCaI3 with a range of Eu2+ doping between 0 and 5 at% substituting for Ca2+ were grown at 22 mm diameter and their performance for gamma-ray spectroscopy studied. Comparisons among crystals approximately Ø22 mm×22 mm (8.4 cm3 or ≈0.5 in3) provide a more accurate understanding of how scintillation performance changes with Eu doping and increased crystal size. KCaI3 in the undoped form is shown to be a highly efficient intrinsic scintillator with a defect-related emission at 404 nm which coexists with the Eu2+ 5d-4f emission in low dopant concentrations and is completely re-absorbed in more heavily doped crystals. For larger crystals, effects from self-absorption due to Eu activation become more evident by a near doubling of decay time for 0.5 in3 crystals as the activator is increased from 0.5 to 5.0 at% Eu. Comparisons of pulse-height spectra obtained for Ø22 mm×22 mm cylinders with varying Eu concentration suggests best performance is achieved using lower Eu additions closer to 0.5-1.0 at%. Using a modified crystal packaging featuring an offset reflector geometry, 0.5 in3 crystals of KCaI3:Eu can attain under 4% energy resolution at 662 keV.
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Single crystals of selected titanates and tungstates
NASA Technical Reports Server (NTRS)
Loiacono, G. M.
1972-01-01
The compound preparation and crystal growth of a number of mixed titanate compositions was investigated. None of the compounds studied were found to melt congruently and therefore, crystal growth was extremely difficult. Various single crystal preparation methods always resulted in mixed phases from which 1-2 mm size crystals could be separated. It is concluded from this study that before successful single crystal growth can be accomplished, a detailed study of the phase diagrams in each of the systems of interest must be completed.
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Light scattering by hexagonal ice crystals with distributed inclusions
NASA Astrophysics Data System (ADS)
Panetta, R. Lee; Zhang, Jia-Ning; Bi, Lei; Yang, Ping; Tang, Guanlin
2016-07-01
Inclusions of air bubbles or soot particles have significant effects on the single-scattering properties of ice crystals, effects that in turn have significant impacts on the radiation budget of an atmosphere containing the crystals. This study investigates some of the single-scattering effects in the case of hexagonal ice crystals, including effects on the backscattering depolarization ratio, a quantity of practical importance in the interpretation of lidar observations. One distinguishing feature of the study is an investigation of scattering properties at a visible wavelength for a crystal with size parameter (x) above 100, a size regime where one expects some agreement between exact methods and geometrical optics methods. This expectation is generally borne out in a test comparison of how the sensitivity of scattering properties to the distribution of a given volume fraction of included air is represented using (i) an approximate Monte Carlo Ray Tracing (MCRT) method and (ii) a numerically exact pseudo-spectral time-domain (PSTD) method. Another distinguishing feature of the study is a close examination, using the numerically exact Invariant-Imbedding T-Matrix (II-TM) method, of how some optical properties of importance to satellite remote sensing vary as the volume fraction of inclusions and size of crystal are varied. Although such an investigation of properties in the x>100 regime faces serious computational burdens that force a large number of idealizations and simplifications in the study, the results nevertheless provide an intriguing glimpse of what is evidently a quite complex sensitivity of optical scattering properties to inclusions of air or soot as volume fraction and size parameter are varied.
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Computer Modeling of Non-Isothermal Crystallization
NASA Technical Reports Server (NTRS)
Kelton, K. F.; Narayan, K. Lakshmi; Levine, L. E.; Cull, T. C.; Ray, C. S.
1996-01-01
A realistic computer model for simulating isothermal and non-isothermal phase transformations proceeding by homogeneous and heterogeneous nucleation and interface-limited growth is presented. A new treatment for particle size effects on the crystallization kinetics is developed and is incorporated into the numerical model. Time-dependent nucleation rates, size-dependent growth rates, and surface crystallization are also included. Model predictions are compared with experimental measurements of DSC/DTA peak parameters for the crystallization of lithium disilicate glass as a function of particle size, Pt doping levels, and water content. The quantitative agreement that is demonstrated indicates that the numerical model can be used to extract key kinetic data from easily obtained calorimetric data. The model can also be used to probe nucleation and growth behavior in regimes that are otherwise inaccessible. Based on a fit to data, an earlier prediction that the time-dependent nucleation rate in a DSC/DTA scan can rise above the steady-state value at a temperature higher than the peak in the steady-state rate is demonstrated.
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Strength and fatigue properties of three-step sintered dense nanocrystal hydroxyapatite bioceramics
NASA Astrophysics Data System (ADS)
Guo, Wen-Guang; Qiu, Zhi-Ye; Cui, Han; Wang, Chang-Ming; Zhang, Xiao-Jun; Lee, In-Seop; Dong, Yu-Qi; Cui, Fu-Zhai
2013-06-01
Dense hydroxyapatite (HA) ceramic is a promising material for hard tissue repair due to its unique physical properties and biologic properties. However, the brittleness and low compressive strength of traditional HA ceramics limited their applications, because previous sintering methods produced HA ceramics with crystal sizes greater than nanometer range. In this study, nano-sized HA powder was employed to fabricate dense nanocrystal HA ceramic by high pressure molding, and followed by a three-step sintering process. The phase composition, microstructure, crystal dimension and crystal shape of the sintered ceramic were examined by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Mechanical properties of the HA ceramic were tested, and cytocompatibility was evaluated. The phase of the sintered ceramic was pure HA, and the crystal size was about 200 nm. The compressive strength and elastic modulus of the HA ceramic were comparable to human cortical bone, especially the good fatigue strength overcame brittleness of traditional sintered HA ceramics. Cell attachment experiment also demonstrated that the ceramics had a good cytocompatibility.
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Fabrication of crystals from single metal atoms
Barry, Nicolas P. E.; Pitto-Barry, Anaïs; Sanchez, Ana M.; Dove, Andrew P.; Procter, Richard J.; Soldevila-Barreda, Joan J.; Kirby, Nigel; Hands-Portman, Ian; Smith, Corinne J.; O’Reilly, Rachel K.; Beanland, Richard; Sadler, Peter J.
2014-01-01
Metal nanocrystals offer new concepts for the design of nanodevices with a range of potential applications. Currently the formation of metal nanocrystals cannot be controlled at the level of individual atoms. Here we describe a new general method for the fabrication of multi-heteroatom-doped graphitic matrices decorated with very small, ångström-sized, three-dimensional (3D)-metal crystals of defined size. We irradiate boron-rich precious-metal-encapsulated self-spreading polymer micelles with electrons and produce, in real time, a doped graphitic support on which individual osmium atoms hop and migrate to form 3D-nanocrystals, as small as 15 Å in diameter, within 1 h. Crystal growth can be observed, quantified and controlled in real time. We also synthesize the first examples of mixed ruthenium–osmium 3D-nanocrystals. This technology not only allows the production of ångström-sized homo- and hetero-crystals, but also provides new experimental insight into the dynamics of nanocrystals and pathways for their assembly from single atoms. PMID:24861089
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Plant ice-binding (antifreeze) proteins
USDA-ARS?s Scientific Manuscript database
Proteins that determine the temperature at which ice crystals will form in water-based solutions in cells and tissues, that bind to growing ice crystals, thus affecting their size, and that impact ice re-crystallization have been widely-documented and studied in many plant, bacterial, fungal, insect...
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Low-Temperature Growth of Two-Dimensional Layered Chalcogenide Crystals on Liquid.
Zhou, Yubing; Deng, Bing; Zhou, Yu; Ren, Xibiao; Yin, Jianbo; Jin, Chuanhong; Liu, Zhongfan; Peng, Hailin
2016-03-09
The growth of high-quality two-dimensional (2D) layered chalcogenide crystals is highly important for practical applications in future electronics, optoelectronics, and photonics. Current route for the synthesis of 2D chalcogenide crystals by vapor deposition method mainly involves an energy intensive high-temperature growth process on solid substrates, often suffering from inhomogeneous nucleation density and grain size distribution. Here, we first demonstrate a facile vapor-phase synthesis of large-area high-quality 2D layered chalcogenide crystals on liquid metal surface with relatively low surface energy at a growth temperature as low as ∼100 °C. Uniform and large-domain-sized 2D crystals of GaSe and GaxIn1-xSe were grown on liquid metal surface even supported on a polyimide film. As-grown 2D GaSe crystals have been fabricated to flexible photodetectors, showing high photoresponse and excellent flexibility. Our strategy of energy-sustainable low-temperature growth on liquid metal surface may open a route to the synthesis of high-quality 2D crystals of Ga-, In-, Bi-, Hg-, Pb-, or Sn-based chalcogenides and halides.
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Probabilistic approach to lysozyme crystal nucleation kinetics.
Dimitrov, Ivaylo L; Hodzhaoglu, Feyzim V; Koleva, Dobryana P
2015-09-01
Nucleation of lysozyme crystals in quiescent solutions at a regime of progressive nucleation is investigated under an optical microscope at conditions of constant supersaturation. A method based on the stochastic nature of crystal nucleation and using discrete time sampling of small solution volumes for the presence or absence of detectable crystals is developed. It allows probabilities for crystal detection to be experimentally estimated. One hundred single samplings were used for each probability determination for 18 time intervals and six lysozyme concentrations. Fitting of a particular probability function to experimentally obtained data made possible the direct evaluation of stationary rates for lysozyme crystal nucleation, the time for growth of supernuclei to a detectable size and probability distribution of nucleation times. Obtained stationary nucleation rates were then used for the calculation of other nucleation parameters, such as the kinetic nucleation factor, nucleus size, work for nucleus formation and effective specific surface energy of the nucleus. The experimental method itself is simple and adaptable and can be used for crystal nucleation studies of arbitrary soluble substances with known solubility at particular solution conditions.
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Characterization of Large Volume CLYC Scintillators for Nuclear Security Applications
NASA Astrophysics Data System (ADS)
Soundara-Pandian, Lakshmi; Tower, J.; Hines, C.; O'Dougherty, P.; Glodo, J.; Shah, K.
2017-07-01
We report on our development of large volume Cs2LiYCl6 (CLYC) detectors for nuclear security applications. Three-inch diameter boules have been grown and 3-in right cylinders have been fabricated. Crystals containing either >95% 6Li or >99% 7Li have been grown for applications specific to thermal or fast neutron detection, respectively. We evaluated their gamma and neutron detection properties and the performance is as good as small size crystals. Gamma and neutron efficiencies were measured for large crystals and compared with smaller size crystals. With their excellent performance characteristics, and the ability to detect fast neutrons, CLYC detectors are excellent triple-mode scintillators for use in handheld and backpack instruments for nuclear security applications.
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Fox-7 for Insensitive Boosters
2010-08-01
cavitation , and therefore nucleation, to occur at each frequency. As well as producing ultrasound at different frequencies, the method of delivery of...processing techniques using ultrasound , designed to optimise FOX-7 crystal size and morphology to improve booster formulations, and results from these...7 booster formulations. Also included are particle processing techniques using ultrasound , designed to optimise FOX-7 crystal size and morphology
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Scalable room-temperature conversion of copper(II) hydroxide into HKUST-1 (Cu3 (btc)2).
Majano, Gerardo; Pérez-Ramírez, Javier
2013-02-20
Copper(II) hydroxide is converted directly to HKUST-1 (Cu(3) (btc)(2) ) after only 5 min at room-temperature in aqueous ethanolic solution without the need of additional solvents. Scale up to the kilogram scale does not influence porous properties yielding pure-phase product with a remarkable total surface area exceeding 1700 m(2) g(-1) featuring aggregates of nanometer-sized crystals (<600 nm) and extremely high space-time yields. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Template-Directed Crystallization of High Energy Materials
2014-04-01
objectives of this grant were to (a) examine the solution crystallization of RDX , HMX and CL-20 from a variety of solvents, withdetailed analysis of...crystal nucleation templates and (c) to assess the growth of RDX , HMX and CL-20 on these templates. High explosives, crystallization, RDX , CL-20...crystallization of RDX , HMX and CL-20 from a variety of solvents, with detailed analysis of their phase, size, and morphological properties; (b) to
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Marshall, Thomas; Challis, Richard E; Holmes, Andrew K; Tebbutt, John S
2002-11-01
Ultrasonic compression wave absorption is investigated as a means to monitor the seeded crystallization of copper (II) sulphate pentahydrate from aqueous solution. Simple models are applied to predict crystal yield, crystal size distribution, and the changing nature of the continuous phase. The Allegra-Hawley scattering formulation is used to simulate ultrasonic absorption as crystallization proceeds. Experiments confirm that simulated attenuation is in agreement with measured results.
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Spatially resolved observation of crystal-face-dependent catalysis by single turnover counting
NASA Astrophysics Data System (ADS)
Roeffaers, Maarten B. J.; Sels, Bert F.; Uji-I, Hiroshi; de Schryver, Frans C.; Jacobs, Pierre A.; de Vos, Dirk E.; Hofkens, Johan
2006-02-01
Catalytic processes on surfaces have long been studied by probing model reactions on single-crystal metal surfaces under high vacuum conditions. Yet the vast majority of industrial heterogeneous catalysis occurs at ambient or elevated pressures using complex materials with crystal faces, edges and defects differing in their catalytic activity. Clearly, if new or improved catalysts are to be rationally designed, we require quantitative correlations between surface features and catalytic activity-ideally obtained under realistic reaction conditions. Transmission electron microscopy and scanning tunnelling microscopy have allowed in situ characterization of catalyst surfaces with atomic resolution, but are limited by the need for low-pressure conditions and conductive surfaces, respectively. Sum frequency generation spectroscopy can identify vibrations of adsorbed reactants and products in both gaseous and condensed phases, but so far lacks sensitivity down to the single molecule level. Here we adapt real-time monitoring of the chemical transformation of individual organic molecules by fluorescence microscopy to monitor reactions catalysed by crystals of a layered double hydroxide immersed in reagent solution. By using a wide field microscope, we are able to map the spatial distribution of catalytic activity over the entire crystal by counting single turnover events. We find that ester hydrolysis proceeds on the lateral {1010} crystal faces, while transesterification occurs on the entire outer crystal surface. Because the method operates at ambient temperature and pressure and in a condensed phase, it can be applied to the growing number of liquid-phase industrial organic transformations to localize catalytic activity on and in inorganic solids. An exciting opportunity is the use of probe molecules with different size and functionality, which should provide insight into shape-selective or structure-sensitive catalysis and thus help with the rational design of new or more productive heterogeneous catalysts.
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Extraordinary wavelength reduction in terahertz graphene-cladded photonic crystal slabs
Williamson, Ian A. D.; Mousavi, S. Hossein; Wang, Zheng
2016-01-01
Photonic crystal slabs have been widely used in nanophotonics for light confinement, dispersion engineering, nonlinearity enhancement, and other unusual effects arising from their structural periodicity. Sub-micron device sizes and mode volumes are routine for silicon-based photonic crystal slabs, however spectrally they are limited to operate in the near infrared. Here, we show that two single-layer graphene sheets allow silicon photonic crystal slabs with submicron periodicity to operate in the terahertz regime, with an extreme 100× wavelength reduction from graphene’s large kinetic inductance. The atomically thin graphene further leads to excellent out-of-plane confinement, and consequently photonic-crystal-slab band structures that closely resemble those of ideal two-dimensional photonic crystals, with broad band gaps even when the slab thickness approaches zero. The overall photonic band structure not only scales with the graphene Fermi level, but more importantly scales to lower frequencies with reduced slab thickness. Just like ideal 2D photonic crystals, graphene-cladded photonic crystal slabs confine light along line defects, forming waveguides with the propagation lengths on the order of tens of lattice constants. The proposed structure opens up the possibility to dramatically reduce the size of terahertz photonic systems by orders of magnitude. PMID:27143314
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Hendriks, Frank C; Schmidt, Joel E; Rombouts, Jeroen A; Lammertsma, Koop; Bruijnincx, Pieter C A; Weckhuysen, Bert M
2017-05-05
A micro-spectroscopic method has been developed to probe the accessibility of zeolite crystals using a series of fluorescent 4-(4-diethylaminostyryl)-1-methylpyridinium iodide (DAMPI) probes of increasing molecular size. Staining large zeolite crystals with MFI (ZSM-5) topology and subsequent mapping of the resulting fluorescence using confocal fluorescence microscopy reveal differences in structural integrity: the 90° intergrowth sections of MFI crystals are prone to develop structural imperfections, which act as entrance routes for the probes into the zeolite crystal. Polarization-dependent measurements provide evidence for the probe molecule's alignment within the MFI zeolite pore system. The developed method was extended to BEA (Beta) crystals, showing that the previously observed hourglass pattern is a general feature of BEA crystals with this morphology. Furthermore, the probes can accurately identify at which crystal faces of BEA straight or sinusoidal pores open to the surface. The results show this method can spatially resolve the architecture-dependent internal pore structure of microporous materials, which is difficult to assess using other characterization techniques such as X-ray diffraction. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
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NASA Technical Reports Server (NTRS)
Lin, Ruei-Fong; Starr, David OC; DeMott, Paul J.; Cotton, Richard; Sassen, Kenneth; Jensen, Eric; Einaudi, Franco (Technical Monitor)
2001-01-01
The Cirrus Parcel Model Comparison Project, a project of the GCSS (GEWEX Cloud System Studies) Working Group on Cirrus Cloud Systems, involves the systematic comparison of current models of ice crystal nucleation and growth for specified, typical, cirrus cloud environments. In Phase I of the project reported here, simulated cirrus cloud microphysical properties are compared for situations of "warm" (40 C) and "cold" (-60 C) cirrus, both subject to updrafts of 4, 20 and 100 centimeters per second. Five models participated. The various models employ explicit microphysical schemes wherein the size distribution of each class of particles (aerosols and ice crystals) is resolved into bins or treated separately. Simulations are made including both the homogeneous and heterogeneous ice nucleation mechanisms. A single initial aerosol population of sulfuric acid particles is prescribed for all simulations. To isolate the treatment of the homogeneous freezing (of haze droplets) nucleation process, the heterogeneous nucleation mechanism is disabled for a second parallel set of simulations. Qualitative agreement is found for the homogeneous-nucleation- only simulations, e.g., the number density of nucleated ice crystals increases with the strength of the prescribed updraft. However, significant quantitative differences are found. Detailed analysis reveals that the homogeneous nucleation rate, haze particle solution concentration, and water vapor uptake rate by ice crystal growth (particularly as controlled by the deposition coefficient) are critical components that lead to differences in predicted microphysics. Systematic bias exists between results based on a modified classical theory approach and models using an effective freezing temperature approach to the treatment of nucleation. Each approach is constrained by critical freezing data from laboratory studies, but each includes assumptions that can only be justified by further laboratory research. Consequently, it is not yet clear if the two approaches can be made consistent. Large haze particles may deviate considerably from equilibrium size in moderate to strong updrafts (20-100 centimeters per second) at -60 C when the commonly invoked equilibrium assumption is lifted. The resulting difference in particle-size- dependent solution concentration of haze particles may significantly affect the ice particle formation rate during the initial nucleation interval. The uptake rate for water vapor excess by ice crystals is another key component regulating the total number of nucleated ice crystals. This rate, the product of particle number concentration and ice crystal diffusional growth rate, which is particularly sensitive to the deposition coefficient when ice particles are small, modulates the peak particle formation rate achieved in an air parcel and the duration of the active nucleation time period. The effects of heterogeneous nucleation are most pronounced in weak updraft situations. Vapor competition by the heterogeneously nucleated ice crystals may limit the achieved ice supersaturation and thus suppresses the contribution of homogeneous nucleation. Correspondingly, ice crystal number density is markedly reduced. Definitive laboratory and atmospheric benchmark data are needed for the heterogeneous nucleation process. Inter-model differences are correspondingly greater than in the case of the homogeneous nucleation process acting alone.
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Silicon Carbide From a Carbon Nodule in the Canyon Diablo Meteorite
NASA Astrophysics Data System (ADS)
Leung, I. S.; Winston, R.
2011-12-01
The Canyon Diablo Meteorite fell in the Arizona desert 50,000 years ago, giving rise to the well-preserved Meteor Crater. Irons of various sizes were scattered around the crater rim and on the surrounding plains. We studied a rusty specimen containing a carbon nodule. We dug out small blocks of sooty carbon by means of a sharp tungsten carbide tip. These carbon materials contain traces of silicon carbide (SiC) and diamond/lonsdaleite. We report here our findigs of two groups of SiC grains. (1) Relatively large crystals, about 80-90 microns in size. Their colors are in shades of blue, green and neutral. One of the grains are composed of a cluster of 3 crystals of the 3C polytype, whereas, 7 other individual crystals are of hexagonal structure. All crystals in this group have dark, rounded resorption rims. (2) Small crystals, about 30-50 microns in size. They are pale blue in color, and they lack dark-colored rims. These two distinct groups probably have different modes of origin. The large crystals seem to be early-formed, but had been reheated or partially melted, as indicated by the bead-like rims. The complexities displayed by these SiC crystals might have resulted from a long residence time in the meteorite while it was still in space. Their origin might be akin to that of SiC occurring in carbonaceous chondrites and interplanetary dust particles.
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Shaping plasmon beams via the controlled illumination of finite-size plasmonic crystals
Bouillard, J.-S.; Segovia, P.; Dickson, W.; Wurtz, G. A.; Zayats, A. V.
2014-01-01
Plasmonic crystals provide many passive and active optical functionalities, including enhanced sensing, optical nonlinearities, light extraction from LEDs and coupling to and from subwavelength waveguides. Here we study, both experimentally and numerically, the coherent control of SPP beam excitation in finite size plasmonic crystals under focussed illumination. The correct combination of the illuminating spot size, its position relative to the plasmonic crystal, wavelength and polarisation enables the efficient shaping and directionality of SPP beam launching. We show that under strongly focussed illumination, the illuminated part of the crystal acts as an antenna, launching surface plasmon waves which are subsequently filtered by the surrounding periodic lattice. Changing the illumination conditions provides rich opportunities to engineer the SPP emission pattern. This offers an alternative technique to actively modulate and control plasmonic signals, either via micro- and nano-electromechanical switches or with electro- and all-optical beam steering which have direct implications for the development of new integrated nanophotonic devices, such as plasmonic couplers and switches and on-chip signal demultiplexing. This approach can be generalised to all kinds of surface waves, either for the coupling and discrimination of light in planar dielectric waveguides or the generation and control of non-diffractive SPP beams. PMID:25429786
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Non-Isothermal Calorimetric Studies of the Crystallization of Lithium Disilicate Glass
NASA Technical Reports Server (NTRS)
Ray, C. S.; Day, D. E.; Huang, W.; Narayan, K. Lakshmi; Cull, T. S.; Kelton, K. F.
1996-01-01
The influence of preannealing treatments on the polymorphic crystallization of lithium disilicate glasses is examined. As expected, glasses heated at different rates through the temperature range where there is significant nucleation develop widely different numbers of nuclei. This can dramatically influence the stability and transformation characteristics of the annealed glass. Non-isothermal differential scanning calorimetry (DSC) and differential thermal analysis (DTA) measurements are demonstrated to be useful to probe the nucleation behavior. The first systematic investigations of particle size effects on the non-isothermal transformation behavior are presented and discussed. Based on DTA and microscopy experiments, we show that small particles of lithium disilicate glasses crystallize primarily by surface crystallization. The relative importance of surface versus volume crystallization is examined by varying particle size, by introducing nucleating agents and by exposing glasses to atmospheres of different water content. These data are analyzed quantitatively using a numerical model developed in a second paper following in this volume.
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Gao, Libo; Ren, Wencai; Xu, Huilong; Jin, Li; Wang, Zhenxing; Ma, Teng; Ma, Lai-Peng; Zhang, Zhiyong; Fu, Qiang; Peng, Lian-Mao; Bao, Xinhe; Cheng, Hui-Ming
2012-02-28
Large single-crystal graphene is highly desired and important for the applications of graphene in electronics, as grain boundaries between graphene grains markedly degrade its quality and properties. Here we report the growth of millimetre-sized hexagonal single-crystal graphene and graphene films joined from such grains on Pt by ambient-pressure chemical vapour deposition. We report a bubbling method to transfer these single graphene grains and graphene films to arbitrary substrate, which is nondestructive not only to graphene, but also to the Pt substrates. The Pt substrates can be repeatedly used for graphene growth. The graphene shows high crystal quality with the reported lowest wrinkle height of 0.8 nm and a carrier mobility of greater than 7,100 cm(2) V(-1) s(-1) under ambient conditions. The repeatable growth of graphene with large single-crystal grains on Pt and its nondestructive transfer may enable various applications.
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Gao, Libo; Ren, Wencai; Xu, Huilong; Jin, Li; Wang, Zhenxing; Ma, Teng; Ma, Lai-Peng; Zhang, Zhiyong; Fu, Qiang; Peng, Lian-Mao; Bao, Xinhe; Cheng, Hui-Ming
2012-01-01
Large single-crystal graphene is highly desired and important for the applications of graphene in electronics, as grain boundaries between graphene grains markedly degrade its quality and properties. Here we report the growth of millimetre-sized hexagonal single-crystal graphene and graphene films joined from such grains on Pt by ambient-pressure chemical vapour deposition. We report a bubbling method to transfer these single graphene grains and graphene films to arbitrary substrate, which is nondestructive not only to graphene, but also to the Pt substrates. The Pt substrates can be repeatedly used for graphene growth. The graphene shows high crystal quality with the reported lowest wrinkle height of 0.8 nm and a carrier mobility of greater than 7,100 cm2 V−1 s−1 under ambient conditions. The repeatable growth of graphene with large single-crystal grains on Pt and its nondestructive transfer may enable various applications. PMID:22426220
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NASA Astrophysics Data System (ADS)
Prostomolotov, A. I.; Verezub, N. A.; Voloshin, A. E.
2014-09-01
A thermo-gravitational convection and impurity transfer in the melt were investigated using a simplified numerical model for Bridgman GaSb(Te) crystal growth in microgravity conditions. Simplifications were as follows: flat melt/crystal interface, fixed melt sizes and only lateral ampoule heating. Calculations were carried out by Ansys®Fluent® code employing a two-dimensional Navier-Stokes-Boussinesq and heat and mass transfer equations in a coordinate system moving with the melt/crystal interface. The parametric dependence of the effective segregation coefficient Keff at the melt/crystal interface was studied for various ampoule sizes and for microgravity conditions. For the uprising one-vortex flow, the resulting dependences were presented as Keff vs. Vmax-the maximum velocity value. These dependences were compared with the formulas by Burton-Prim-Slichter's, Ostrogorsky-Muller's, as well as with the semi-analytical solutions.
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Guo, Feng; Zhou, Weijie; Li, Peng; Mao, Zhangming; Yennawar, Neela H; French, Jarrod B; Huang, Tony Jun
2015-06-01
Advances in modern X-ray sources and detector technology have made it possible for crystallographers to collect usable data on crystals of only a few micrometers or less in size. Despite these developments, sample handling techniques have significantly lagged behind and often prevent the full realization of current beamline capabilities. In order to address this shortcoming, a surface acoustic wave-based method for manipulating and patterning crystals is developed. This method, which does not damage the fragile protein crystals, can precisely manipulate and pattern micrometer and submicrometer-sized crystals for data collection and screening. The technique is robust, inexpensive, and easy to implement. This method not only promises to significantly increase efficiency and throughput of both conventional and serial crystallography experiments, but will also make it possible to collect data on samples that were previously intractable. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Olivares, M; Larrañaga, A; Irazola, M; Sarmiento, A; Murelaga, X; Etxebarria, N
2012-08-30
The determination of crystal size of chert samples can provide suitable information about the raw material used for the manufacture of archeological items. X-ray diffraction (XRD) has been widely used for this purpose in several scientific areas. However, the historical value of archeological pieces makes this procedure sometimes unfeasible and thus, non-invasive new analytical approaches are required. In this sense, a new method was developed relating the crystal size obtained by means of XRD and infrared spectroscopy (IR) using partial least squares regression. The IR spectra collected from a large amount of different geological chert samples of archeological use were pre-processed following different treatments (i.e., derivatization or sample-wise normalization) to obtain the best regression model. The full cross-validation was satisfactorily validated using real samples and the experimental root mean standard error of precision value was 165 Å whereas the average precision of the estimated size value was 3%. The features of infrared bands were also evaluated in order to know the background of the prediction ability. In the studied case, the variance in the model was associated to the differences in the characteristic stretching and bending infrared bands of SiO(2). Based on this fact, it would be feasible to estimate the crystal size if it is built beforehand a chemometric model relating the size measured by standard methods and the IR spectra. Copyright © 2012 Elsevier B.V. All rights reserved.
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NASA Technical Reports Server (NTRS)
Nisbet, John S.
1988-01-01
General equations for the Reynolds number of a variety of types of ice crystals and water drops are given in terms of the Davies, Bond, and Knudsen numbers. The equations are in terms of the basic physical parameters of the system and are valid for calculating velocities in gravitational and electric fields over a very wide range of sizes and atmospheric conditions. The equations are asymptotically matched at the bottom and top of the size spectrum, useful when checking large computer codes. A numerical system for specifying the dimensional properties of ice crystals is introduced. Within the limits imposed by such variables as particle density, which have large deviations, the accuracy of velocities appears to be within 10 percent over the entire range of sizes of interest.
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de Waard, Hans; De Beer, Thomas; Hinrichs, Wouter L J; Vervaet, Chris; Remon, Jean-Paul; Frijlink, Henderik W
2010-12-01
We developed a novel process, "controlled crystallization during freeze-drying" to produce drug nanocrystals of poorly water-soluble drugs. This process involves freeze-drying at a relatively high temperature of a drug and a matrix material from a mixture of tertiary butyl alcohol and water, resulting in drug nanocrystals incorporated in a matrix. The aim of this study was to elucidate the mechanisms that determine the size of the drug crystals. Fenofibrate was used as a model lipophilic drug. To monitor the crystallization during freeze-drying, a Raman probe was placed just above the sample in the freeze-dryer. These in-line Raman spectroscopy measurements clearly revealed when the different components crystallized during freeze-drying. The solvents crystallized only during the freezing step, while the solutes only crystallized after the temperature was increased, but before drying started. Although the solutes crystallized only after the freezing step, both the freezing rate and the shelf temperature were critical parameters that determined the final crystal size. At a higher freezing rate, smaller interstitial spaces containing the freeze-concentrated fraction were formed, resulting in smaller drug crystals (based on dissolution data). On the other hand, when the solutes crystallized at a lower shelf temperature, the degree of supersaturation is higher, resulting in a higher nucleation rate and consequently more and therefore smaller crystals. In conclusion, for the model drug fenofibrate, a high freezing rate and a relatively low crystallization temperature resulted in the smallest crystals and therefore the highest dissolution rate.
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High efficiency machining technology and equipment for edge chamfer of KDP crystals
NASA Astrophysics Data System (ADS)
Chen, Dongsheng; Wang, Baorui; Chen, Jihong
2016-10-01
Potassium dihydrogen phosphate (KDP) is a type of nonlinear optical crystal material. To Inhibit the transverse stimulated Raman scattering of laser beam and then enhance the optical performance of the optics, the edges of the large-sized KDP crystal needs to be removed to form chamfered faces with high surface quality (RMS<5 nm). However, as the depth of cut (DOC) of fly cutting is usually several, its machining efficiency is too low to be accepted for chamfering of the KDP crystal as the amount of materials to be removed is in the order of millimeter. This paper proposes a novel hybrid machining method, which combines precision grinding with fly cutting, for crackless and high efficiency chamfer of KDP crystal. A specialized machine tool, which adopts aerostatic bearing linear slide and aerostatic bearing spindle, was developed for chamfer of the KDP crystal. The aerostatic bearing linear slide consists of an aerostatic bearing guide with linearity of 0.1 μm/100mm and a linear motor to achieve linear feeding with high precision and high dynamic performance. The vertical spindle consists of an aerostatic bearing spindle with the rotation accuracy (axial) of 0.05 microns and Fork type flexible connection precision driving mechanism. The machining experiment on flying and grinding was carried out, the optimize machining parameters was gained by a series of experiment. Surface roughness of 2.4 nm has been obtained. The machining efficiency can be improved by six times using the combined method to produce the same machined surface quality.
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Understanding dislocation mechanics at the mesoscale using phase field dislocation dynamics
Hunter, A.
2016-01-01
In this paper, we discuss the formulation, recent developments and findings obtained from a mesoscale mechanics technique called phase field dislocation dynamics (PFDD). We begin by presenting recent advancements made in modelling face-centred cubic materials, such as integration with atomic-scale simulations to account for partial dislocations. We discuss calculations that help in understanding grain size effects on transitions from full to partial dislocation-mediated slip behaviour and deformation twinning. Finally, we present recent extensions of the PFDD framework to alternative crystal structures, such as body-centred cubic metals, and two-phase materials, including free surfaces, voids and bi-metallic crystals. With several examples we demonstrate that the PFDD model is a powerful and versatile method that can bridge the length and time scales between atomistic and continuum-scale methods, providing a much needed understanding of deformation mechanisms in the mesoscale regime. PMID:27002063
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A general approach to DNA-programmable atom equivalents.
Zhang, Chuan; Macfarlane, Robert J; Young, Kaylie L; Choi, Chung Hang J; Hao, Liangliang; Auyeung, Evelyn; Liu, Guoliang; Zhou, Xiaozhu; Mirkin, Chad A
2013-08-01
Nanoparticles can be combined with nucleic acids to programme the formation of three-dimensional colloidal crystals where the particles' size, shape, composition and position can be independently controlled. However, the diversity of the types of material that can be used is limited by the lack of a general method for preparing the basic DNA-functionalized building blocks needed to bond nanoparticles of different chemical compositions into lattices in a controllable manner. Here we show that by coating nanoparticles protected with aliphatic ligands with an azide-bearing amphiphilic polymer, followed by the coupling of DNA to the polymer using strain-promoted azide-alkyne cycloaddition (also known as copper-free azide-alkyne click chemistry), nanoparticles bearing a high-density shell of nucleic acids can be created regardless of nanoparticle composition. This method provides a route to a virtually endless class of programmable atom equivalents for DNA-based colloidal crystallization.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Rebai, M., E-mail: marica.rebai@mib.infn.it; Nocente, M.; Rigamonti, D.
2016-11-15
A Single-crystal Diamond (SD) detector prototype was installed at Joint European Torus (JET) in 2013 and the achieved results have shown its spectroscopic capability of measuring 2.5 MeV neutrons from deuterium plasmas. This paper presents measurements of the SD response function to monoenergetic neutrons, which is a key point for the development of a neutron spectrometer based on SDs and compares them with Monte Carlo simulations. The analysis procedure allows for a good reconstruction of the experimental results. The good pulse height energy resolution (equivalent FWHM of 80 keV at 2.5 MeV), gain stability, insensitivity to magnetic field, and compactmore » size make SDs attractive as compact neutron spectrometers of high flux deuterium plasmas, such as for instance those needed for the ITER neutron camera.« less
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Polycrystalline magma behaviour in dykes: Insights from high-resolution numerical models
NASA Astrophysics Data System (ADS)
Yamato, Philippe; Duretz, Thibault; Tartèse, Romain; May, Dave
2013-04-01
The presence of a crystalline load in magmas modifies their effective rheology and thus their flow behaviour. In dykes, for instance, the presence of crystals denser than the melt reduces the ascent velocity and modifies the shape of the velocity profile from a Newtonian Poiseuille flow to a Bingham type flow. Nevertheless, several unresolved issues still remain poorly understood and need to be quantified: (1) What are the mechanisms controlling crystals segregation during magma ascent in dykes? (2) How does crystals transportation within a melt depend on their concentration, geometry, size and density? (3) Do crystals evolve in isolation to each other or as a cluster? (4) What is the influence of considering inertia of the melt within the system? In this study, we present numerical models following the setup previously used in Yamato et al. (2012). Our model setup simulates an effective pressure gradient between the base and the top of a channel (representing a dyke), by pushing a rigid piston into a magmatic mush that comprised crystals and melt and perforated by a hole. The initial resolution of the models (401x1551 nodes) has been doubled in order to ensure that the smallest crystalline fractions are sufficiently well resolved. Results show that the melt phase can be squeezed out from a crystal-rich magma when subjected to a given pressure gradient range and that clustering of crystals might be an important parameter controlling their behaviour. This demonstrates that crystal-melt segregation in dykes during magma ascent constitutes a viable mechanism for magmatic differentiation of residual melts. These results also explain how isolated crystal clusters and melt pockets, with different chemistry, can be formed. In addition, we discuss the impact of taking into account inertia in our models. Reference: Yamato, P., Tartèse, R., Duretz, T., May, D.A., 2012. Numerical modelling of magma transport in dykes. Tectonophysics 526-529, 97-109.
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Method of making macrocrystalline or single crystal semiconductor material
NASA Technical Reports Server (NTRS)
Shlichta, P. J. (Inventor); Holliday, R. J. (Inventor)
1986-01-01
A macrocrystalline or single crystal semiconductive material is formed from a primary substrate including a single crystal or several very large crystals of a relatively low melting material. This primary substrate is deposited on a base such as steel or ceramic, and it may be formed from such metals as zinc, cadmium, germanium, aluminum, tin, lead, copper, brass, magnesium silicide, or magnesium stannide. These materials generally have a melting point below about 1000 C and form on the base crystals the size of fingernails or greater. The primary substrate has an epitaxial relationship with a subsequently applied layer of material, and because of this epitaxial relationship, the material deposited on the primary substrate will have essentially the same crystal size as the crystals in the primary substrate. If required, successive layers are formed, each of a material which has an epitaxial relationship with the previously deposited layer, until a layer is formed which has an epitaxial relationship with the semiconductive material. This layer is referred to as the epitaxial substrate, and its crystals serve as sites for the growth of large crystals of semiconductive material. The primary substrate is passivated to remove or otherwise convert it into a stable or nonreactive state prior to deposition of the seconductive material.
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Structural Biology of Proteins of the Multi-enzyme Assembly Human Pyruvate Dehydrogenase Complex
NASA Technical Reports Server (NTRS)
2003-01-01
Objectives and research challenges of this effort include: 1. Need to establish Human Pyruvate Dehydrogenase Complex protein crystals; 2. Need to test value of microgravity for improving crystal quality of Human Pyruvate Dehydrogenase Complex protein crystals; 3. Need to improve flight hardware in order to control and understand the effects of microgravity on crystallization of Human Pyruvate Dehydrogenase Complex proteins; 4. Need to integrate sets of national collaborations with the restricted and specific requirements of flight experiments; 5. Need to establish a highly controlled experiment in microgravity with a rigor not yet obtained; 6. Need to communicate both the rigor of microgravity experiments and the scientific value of results obtained from microgravity experiments to the national community; and 7. Need to advance the understanding of Human Pyruvate Dehydrogenase Complex structures so that scientific and commercial advance is identified for these proteins.
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Crystal Growth of Undoped and Doped ZnSe
NASA Technical Reports Server (NTRS)
Davis, Swanson L.; Chen, K.-T.; George, M. A.; Shi, D. T.; Collins, W. E.; Burger, Arnold
1997-01-01
The surface morphology of freshly cleaved ZnSe single crystal grown by the physical vapor transport (PVT) method was investigated by Atomic Force Microscopy (AFM) and the results were correlated with Differential Scanning Calorimetry (DSC) data. Selenium precipitates have been revealed in undoped doped ZnSe crystals having a size of about 50 nm. A transition temperature around 221 C in the DSC measurements is interpreted as the eutectic temperature of Se-saturated ZnSe. The AFM images of doped ZnSe also show that possible Cr clusters are uniformly distributed and they have an estimated size of about 6 nm.
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Ukar, Estibalitz; Laubach, Stephen E.; Marrett, Randall
2016-03-09
Here, we evaluate a published model for crystal growth patterns in quartz cement in sandstone fractures by comparing crystal fracture-spanning predictions to quartz c-axis orientation distributions measured by electron backscatter diffraction (EBSD) of spanning quartz deposits. Samples from eight subvertical opening-mode fractures in four sandstone formations, the Jurassic– Cretaceous Nikanassin Formation, northwestern Alberta Foothills (Canada), Cretaceous Mesaverde Group (USA; Cozzette Sandstone Member of the Iles Formation), Piceance Basin, Colorado (USA), and upper Jurassic–lower Cretaceous Cotton Valley Group (Taylor sandstone) and overlying Travis Peak Formation, east Texas, have similar quartzose composition and grain size but contain fractures with different temperature historiesmore » and opening rates based on fluid inclusion assemblages and burial history. Spherical statistical analysis shows that, in agreement with model predictions, bridging crystals have a preferred orientation with c-axis orientations at a high angle to fracture walls. The second form of validation is for spanning potential that depends on the size of cut substrate grains. Using measured cut substrate grain sizes and c-axis orientations of spanning bridges, we calculated the required orientation for the smallest cut grain to span the maximum gap size and the required orientation of the crystal with the least spanning potential to form overgrowths that span across maximum measured gap sizes. We find that within a 10° error all spanning crystals conform to model predictions. Using crystals with the lowest spanning potential based on crystallographic orientation (c-axis parallel to fracture wall) and a temperature range for fracture opening measured from fluid inclusion assemblages, we calculate maximum fracture opening rates that allow crystals to span. These rates are comparable to those derived independently from fracture temperature histories based on burial history and multiple sequential fluid inclusion assemblages. Results support the R. Lander and S. Laubach model, which predicts that for quartz deposited synchronously with fracture opening, spanning potential, or likelihood of quartz deposits that are thick enough to span between fracture walls, depends on temperature history, fracture opening rate, size of opening increments, and size, mineralogy, and crystallographic orientation of substrates in the fracture wall (transected grains). Results suggest that EBSD maps, which can be more rapidly acquired than measurement of tens to hundreds of fluid inclusion assemblages, can provide a useful measure of relative opening rates within populations of quartz-filled fractures formed under sedimentary basin conditions. Such data are useful for evaluating fracture pattern development models.« less
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Ukar, Estibalitz; Laubach, Stephen E.; Marrett, Randall
Here, we evaluate a published model for crystal growth patterns in quartz cement in sandstone fractures by comparing crystal fracture-spanning predictions to quartz c-axis orientation distributions measured by electron backscatter diffraction (EBSD) of spanning quartz deposits. Samples from eight subvertical opening-mode fractures in four sandstone formations, the Jurassic– Cretaceous Nikanassin Formation, northwestern Alberta Foothills (Canada), Cretaceous Mesaverde Group (USA; Cozzette Sandstone Member of the Iles Formation), Piceance Basin, Colorado (USA), and upper Jurassic–lower Cretaceous Cotton Valley Group (Taylor sandstone) and overlying Travis Peak Formation, east Texas, have similar quartzose composition and grain size but contain fractures with different temperature historiesmore » and opening rates based on fluid inclusion assemblages and burial history. Spherical statistical analysis shows that, in agreement with model predictions, bridging crystals have a preferred orientation with c-axis orientations at a high angle to fracture walls. The second form of validation is for spanning potential that depends on the size of cut substrate grains. Using measured cut substrate grain sizes and c-axis orientations of spanning bridges, we calculated the required orientation for the smallest cut grain to span the maximum gap size and the required orientation of the crystal with the least spanning potential to form overgrowths that span across maximum measured gap sizes. We find that within a 10° error all spanning crystals conform to model predictions. Using crystals with the lowest spanning potential based on crystallographic orientation (c-axis parallel to fracture wall) and a temperature range for fracture opening measured from fluid inclusion assemblages, we calculate maximum fracture opening rates that allow crystals to span. These rates are comparable to those derived independently from fracture temperature histories based on burial history and multiple sequential fluid inclusion assemblages. Results support the R. Lander and S. Laubach model, which predicts that for quartz deposited synchronously with fracture opening, spanning potential, or likelihood of quartz deposits that are thick enough to span between fracture walls, depends on temperature history, fracture opening rate, size of opening increments, and size, mineralogy, and crystallographic orientation of substrates in the fracture wall (transected grains). Results suggest that EBSD maps, which can be more rapidly acquired than measurement of tens to hundreds of fluid inclusion assemblages, can provide a useful measure of relative opening rates within populations of quartz-filled fractures formed under sedimentary basin conditions. Such data are useful for evaluating fracture pattern development models.« less
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Towards true 3D textural analysis; using your crystal mush wisely.
NASA Astrophysics Data System (ADS)
Jerram, D. A.; Morgan, D. J.; Pankhurst, M. J.
2014-12-01
The crystal cargo that is found in volcanic and plutonic rocks contains a wealth of information about magmatic mush processes, crystallisation history, crystal entrainment and recycling. Phenocryst populations predominantly record episodes of growth/nucleation and bulk geochemical changes within an evolving crystal-melt body. Ante- and xeno-crysts provide useful clues to the nature of mush interaction with wall rock and with principal magma(s). Furthermore, crystal evolutions (core to rim) record pathways through pressure, temperature and compositional space. These can often illustrate complex recycling within systems, describing the plumbing architecture. Understanding this architecture underpins our knowledge of how igneous systems can interact with the crust, grow, freeze, re-mobilise and prime for eruption. Initially, 2D studies produced corrected 3D crystal size distributions to help provide information about nucleation and residence times. It immediately became clear that crystal shape is an important factor in determining the confidence placed upon 3D reconstructions of 2D data. Additionally studies utilised serial sections of medium- to coarse-grain-size populations which allowed 3D reconstruction using modelling software to be improved, since size and shape etc. can be directly constrained. Finally the advent of textural studies using X-ray tomography has revolutionised the way in which we can inspect the crystal cargo in mushy systems, allowing us to image in great detail crystal packing arrangements, 3D CSDs, shapes and orientations etc. The latest most innovative studies use X-ray micro-computed tomography to rapidly characterise chemical populations within the crystal cargo, adding a further dimension to this approach, and implies the ability to untangle magmatic chemical components to better understand their individual and combined evolution. In this contribution key examples of the different types of textural analysis techniques in 2D and 3D, including texture movie animations, are used from both plutonic and volcanic systems to highlight the roll of this approach towards a goal of true 3D textural analysis.
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NASA Astrophysics Data System (ADS)
Feng Zengzhao; Zhang Yongsheng; Jin Zhenkui
1998-06-01
Dolostones are well developed in the Ordovician Majiagou Group in the Ordos area, North China Platform. These dolostones can be divided into four types: mud-sized to silt-sized crystalline dolostones not associated with gypsum and halite beds (type I), mud-sized to silt-sized crystalline dolostones associated with gypsum and halite beds (type II), mottled silt-sized to very fine sand-sized crystalline dolostones (fine saccharoidal dolostones) (type III), and mottled coarse silt-sized to fine sand-sized crystalline dolostones (coarse saccharoidal dolostones) (type IV). Type I dolostones consist of mud-sized to silt-sized dolomite crystals. Laminar stromatolites, ripple marks, mud cracks and birdseyes are common. Such dolostones are not associated with gypsum and halite beds, but lath-shaped pseudomorphs after gypsum are common. The ordering of dolomites averages 0.59, and molar concentration of CaCO 3 averages 51.44%. δ13C averages -0.8‰ (PDB Standard), δ18O averages -2.9‰, δCe averages 0.83. The above characteristics suggest that type I dolostones result from penecontemporaneous dolomitization of lime mud on supratidal flat environments by hypersaline sea water. Type II dolostones mainly consist of mud-sized to silt-sized dolomite crystals. They are commonly well laminated but show no desiccation structures. Such dolostones are intercalated within laminated gypsum and halite beds or are intermixed with them. Such dolostones resulted from dolomitization of lime mud by hypersaline sea water in gypsum and halite precipitating lagoons. Type III dolostones consist of coarse silt-sized to very fine sand-sized dolomite crystals. They commonly underlie type I dolostones and grade downwards to dolomite-mottled limestones and pure limestones. The ordering of dolomites averages 0.63, and molar concentration of CaCO 3 averages 55.64%. δ13C averages -0.2‰, δ18O averages -3.3‰, δCe averages 1.24. Such dolostones resulted from reflux dolomitization by hypersaline sea water. Type IV dolostones consist of coarse-silt-sized to fine-sand-sized dolomite crystals. In such dolostones, stylolites are cut by dolomite crystals. Fluid inclusions are present, and the homogenization temperature commonly ranges from 104°C to 203°C. The ordering of dolomites averages 0.85, and molar concentration of CaCO 3 averages 50.65%. δ13C averages 0.6‰, δ18O averages -7.4‰, and δCe averages 1.16. Such dolostones resulted from deep burial dolomitization. In the Ordos area, type I and II dolostones modified by palaeokarstification are the major gas reservoir rocks of the Ordos Gas Field at present. Type IV dolostones show good reservoir characteristics and may also be potential reservoir rocks.
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Growth of urea crystals by physical vapor transport
NASA Technical Reports Server (NTRS)
Feigelson, R. S.; Route, R. K.; Kao, T.-M.
1985-01-01
This work demonstrates that high optical quality crystals of urea can be grown by the physical vapor transport method. The unique features of this method are compared with growth from methanol/water solutions. High growth rates, exceeding 2.5 mm/day, were achieved, and cm-size optical quality single crystals were obtained. Details of the growth technique and the physical properties of the crystals are presented.
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NASA Astrophysics Data System (ADS)
Jiang, Jingkun; Chen, Da-Ren; Biswas, Pratim
2007-07-01
A flame aerosol reactor (FLAR) was developed to synthesize nanoparticles with desired properties (crystal phase and size) that could be independently controlled. The methodology was demonstrated for TiO2 nanoparticles, and this is the first time that large sets of samples with the same size but different crystal phases (six different ratios of anatase to rutile in this work) were synthesized. The degree of TiO2 nanoparticle agglomeration was determined by comparing the primary particle size distribution measured by scanning electron microscopy (SEM) to the mobility-based particle size distribution measured by online scanning mobility particle spectrometry (SMPS). By controlling the flame aerosol reactor conditions, both spherical unagglomerated particles and highly agglomerated particles were produced. To produce monodisperse nanoparticles, a high throughput multi-stage differential mobility analyser (MDMA) was used in series with the flame aerosol reactor. Nearly monodisperse nanoparticles (geometric standard deviation less than 1.05) could be collected in sufficient mass quantities (of the order of 10 mg) in reasonable time (1 h) that could be used in other studies such as determination of functionality or biological effects as a function of size.
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Exploring growth conditions and Eu2+ concentration effects for KSr2I5:Eu scintillator crystals
NASA Astrophysics Data System (ADS)
Stand, L.; Zhuravleva, M.; Camarda, G.; Lindsey, A.; Johnson, J.; Hobbs, C.; Melcher, C. L.
2016-04-01
Our current research is focused on understanding dopant optimization, growth rate, homogeneity and their impact on the overall performance of KSr2I5:Eu2+ single crystal scintillators. In this work we have investigated the effects of Eu2+ concentration in the potassium strontium iodide matrix, and we found that the concentration needed to maximize the light yield was 4 mol%. In order to assess the effects of the pulling rate, we grew single crystals at 12, 24 and 120 mm/day via the vertical Bridgman technique. For the sample sizes measured (5×5×5 mm3), we found that the crystal grown at the fastest rate of 120 mm/day showed a light yield within ~7% of the more slowly grown boules, and no significant change was observed in the energy resolution. Therefore, light yields from 88,000 to 96,000 ph/MeV and energy resolutions from 2.4 to 3.0% (at 662 keV) were measured for KSr2I5:Eu 4% over a relatively wide range of growth conditions. In order to assess the homogeneity of KSr2I5:Eu 4%, a newly developed micro-resolution X-ray technique was used to map the light yield as a function of excitation position. In the crystals that we studied, we did not observe any significant inhomogeneity other than a smooth gradient due to light collection and self absorption effects.
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Cyclic deformation leads to defect healing and strengthening of small-volume metal crystals
Wang, Zhang-Jie; Li, Qing-Jie; Cui, Yi-Nan; ...
2015-10-19
When microscopic and macroscopic specimens of metals are subjected to cyclic loading, the creation, interaction, and accumulation of defects lead to damage, cracking, and failure. We demonstrate that when aluminum single crystals of submicrometer dimensions are subjected to low-amplitude cyclic deformation at room temperature, the density of preexisting dislocation lines and loops can be dramatically reduced with virtually no change of the overall sample geometry and essentially no permanent plastic strain. Furthermore, this “cyclic healing” of the metal crystal leads to significant strengthening through dramatic reductions in dislocation density, in distinct contrast to conventional cyclic strain hardening mechanisms arising frommore » increases in dislocation density and interactions among defects in microcrystalline and macrocrystalline metals and alloys. Our real-time, in situ transmission electron microscopy observations of tensile tests reveal that pinned dislocation lines undergo shakedown during cyclic straining, with the extent of dislocation unpinning dependent on the amplitude, sequence, and number of strain cycles. Those unpinned mobile dislocations moving close enough to the free surface of the thin specimens as a result of such repeated straining are then further attracted to the surface by image forces that facilitate their egress from the crystal. Our results point to a versatile pathway for controlled mechanical annealing and defect engineering in submicrometer-sized metal crystals, thereby obviating the need for thermal annealing or significant plastic deformation that could cause change in shape and/or dimensions of the specimen.« less
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Cyclic deformation leads to defect healing and strengthening of small-volume metal crystals
Wang, Zhang-Jie; Li, Qing-Jie; Cui, Yi-Nan; Liu, Zhan-Li; Ma, Evan; Li, Ju; Sun, Jun; Zhuang, Zhuo; Dao, Ming; Shan, Zhi-Wei; Suresh, Subra
2015-01-01
When microscopic and macroscopic specimens of metals are subjected to cyclic loading, the creation, interaction, and accumulation of defects lead to damage, cracking, and failure. Here we demonstrate that when aluminum single crystals of submicrometer dimensions are subjected to low-amplitude cyclic deformation at room temperature, the density of preexisting dislocation lines and loops can be dramatically reduced with virtually no change of the overall sample geometry and essentially no permanent plastic strain. This “cyclic healing” of the metal crystal leads to significant strengthening through dramatic reductions in dislocation density, in distinct contrast to conventional cyclic strain hardening mechanisms arising from increases in dislocation density and interactions among defects in microcrystalline and macrocrystalline metals and alloys. Our real-time, in situ transmission electron microscopy observations of tensile tests reveal that pinned dislocation lines undergo shakedown during cyclic straining, with the extent of dislocation unpinning dependent on the amplitude, sequence, and number of strain cycles. Those unpinned mobile dislocations moving close enough to the free surface of the thin specimens as a result of such repeated straining are then further attracted to the surface by image forces that facilitate their egress from the crystal. These results point to a versatile pathway for controlled mechanical annealing and defect engineering in submicrometer-sized metal crystals, thereby obviating the need for thermal annealing or significant plastic deformation that could cause change in shape and/or dimensions of the specimen. PMID:26483463
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NASA Astrophysics Data System (ADS)
Kumar, Dinesh; Verma, Narendra Kumar; Singh, Chandra Bhal; Singh, Akhilesh Kumar
2018-04-01
The nanocrystalline Sr-doped LaMnO3 (La0.7Sr0.3MnO3 = LSMO) perovskite manganites having different crystallite size were synthesized using the nitrate-glycine auto-combustion method. The phase purity of the manganites was checked by X-ray diffraction (XRD) measurement. The XRD patterns of the sample reveal that La0.7S0.3MnO3 crystallizes into rhombohedral crystal structure with space group R-3c. The size-dependence of structural lattice parameters have been investigated with the help of Rietveld refinement. The structural parameters increase as a function of crystallite size. The crystallite-size and internal strain as a function of crystallite-size have been calculated using Williamson-Hall plot.
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NASA Technical Reports Server (NTRS)
Ackerman, A.; Jensen, E.; Stevens, D.; Wang, D.; Heymsfield, A.; Miloshevich, L.; Twohy, C.; Poellot, M.; VanReken, T.; Fridland, Ann
2003-01-01
NASA's 2002 CRYSTAL-FACE field experiment focused on the formation and evolution of tropical cirrus cloud systems in southern Florida. Multiple aircraft extensively sampled cumulonimbus dynamical and microphysical properties, as well as characterizing ambient aerosol populations both inside and outside the full depth of the convective column. On July 18, unique measurements were taken when a powerful updraft was traversed directly by aircraft, providing a window into the primary source region of cumulonimbus anvil crystals. Observations of the updraft, entered at approximately l0 km altitude and -34 C, indicated more than 200 cloud particles per mL at vertical velocities exceeding 20 m/s and the presence of significant condensation nuclei and liquid water within the core. In this work, aerosol and cloud phase observations are integrated by simulating the updraft conditions using a large-eddy resolving model with 3 explicit multiphase microphysics, including treatment of size-resolved aerosol fields, aerosol activation and freezing, and evaporation of cloud particles back to the aerosol phase. Simulations were initialized with observed thermodynamic and aerosol size distributions profiles and convection was driven by surface fluxes assimilated from the ARPS forecast model. Model results are consistent with the conclusions that most crystals are homogeneously frozen droplets and that entrained free tropospheric aerosols may contribute a significant fraction of the crystals. Thus most anvil crystals appear to be formed aloft in updraft cores, well above cloud base. These conclusions are supported by observations of hydrometeor size distribution made while traversing the dore, as well as aerosol and cloud particle size distributions generally observed by aircraft below 4km and crystal properties generally observed by aircraft above 12km.
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Random lasing in dye-doped polymer dispersed liquid crystal film
NASA Astrophysics Data System (ADS)
Wu, Rina; Shi, Rui-xin; Wu, Xiaojiao; Wu, Jie; Dai, Qin
2016-09-01
A dye-doped polymer-dispersed liquid crystal film was designed and fabricated, and random lasing action was studied. A mixture of laser dye, nematic liquid crystal, chiral dopant, and PVA was used to prepare the dye-doped polymer-dispersed liquid crystal film by means of microcapsules. Scanning electron microscopy analysis showed that most liquid crystal droplets in the polymer matrix ranged from 30 μm to 40 μm, the size of the liquid crystal droplets was small. Under frequency doubled 532 nm Nd:YAG laser-pumped optical excitation, a plurality of discrete and sharp random laser radiation peaks could be measured in the range of 575-590 nm. The line-width of the lasing peak was 0.2 nm and the threshold of the random lasing was 9 mJ. Under heating, the emission peaks of random lasing disappeared. By detecting the emission light spot energy distribution, the mechanism of radiation was found to be random lasing. The random lasing radiation mechanism was then analyzed and discussed. Experimental results indicated that the size of the liquid crystal droplets is the decisive factor that influences the lasing mechanism. The surface anchor role can be ignored when the size of the liquid crystal droplets in the polymer matrix is small, which is beneficial to form multiple scattering. The transmission path of photons is similar to that in a ring cavity, providing feedback to obtain random lasing output. Project supported by the National Natural Science Foundation of China (Grant No. 61378042), the Colleges and Universities in Liaoning Province Outstanding Young Scholars Growth Plans, China (Grant No. LJQ2015093), and Shenyang Ligong University Laser and Optical Information of Liaoning Province Key Laboratory Open Funds, China.
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Tian, Tian; Cai, Bin; Sugihara, Okihiro
2016-12-07
A substrate-supported rapid evaporation crystallization (SSREC) method was used to develop a highly nonlinear optical material, 4-N,N-dimethylamino-4'-N'-methyl-stilbazolium tosylate (DAST), which satisfies the Rayleigh scattering requirement for the fabrication of highly transparent composites. DAST nanocrystals have a second harmonic generation active crystal structure and a high signal-to-noise ratio second harmonic generation signal when excited by using a 1064 nm cw laser. The nanocrystals also possess size-dependent UV-vis absorption and fluorescence behavior which is not seen in the bulk state. SSREC offers a very convenient means of nanocrystal size control for fabricating nonlinear optical nanomaterials, and the unique properties of these DAST NCs provide potential applications in the fields of lasing, fluorescence probes, and other nonlinear optical photonics.
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Crystallinity of the epitaxial heterojunction of C60 on single crystal pentacene
NASA Astrophysics Data System (ADS)
Tsuruta, Ryohei; Mizuno, Yuta; Hosokai, Takuya; Koganezawa, Tomoyuki; Ishii, Hisao; Nakayama, Yasuo
2017-06-01
The structure of pn heterojunctions is an important subject in the field of organic semiconductor devices. In this work, the crystallinity of an epitaxial pn heterojunction of C60 on single crystal pentacene is investigated by non-contact mode atomic force microscopy and high-resolution grazing incidence x-ray diffraction. Analysis shows that the C60 molecules assemble into grains consisting of single crystallites on the pentacene single crystal surface. The in-plane mean crystallite size exceeds 0.1 μm, which is at least five time larger than the size of crystallites deposited onto polycrystalline pentacene thin films grown on SiO2. The results indicate that improvement in the crystal quality of the underlying molecular substrate leads to drastic promotion of the crystallinity at the organic semiconductor heterojunction.
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High-temperature crystallization of nanocrystals into three-dimensional superlattices
Wu, Liheng; Willis, Joshua J.; McKay, Ian Salmon; ...
2017-07-31
Crystallization of colloidal nanocrystals into superlattices represents a practical bottom-up process with which to create ordered metamaterials with emergent functionalities. With precise control over the size, shape and composition of individual nanocrystals, various single-and multi-component nanocrystal superlattices have been produced, the lattice structures and chemical compositions of which can be accurately engineered. Nanocrystal superlattices are typically prepared by carefully controlling the assembly process through solvent evaporation or destabilization or through DNA-guided crystallization. Slow solvent evaporation or cooling of nanocrystal solutions (over hours or days) is the key element for successful crystallization processes. Here we report the rapid growth (seconds) ofmore » micrometre-sized, face-centred-cubic, three-dimensional nanocrystal superlattices during colloidal synthesis at high temperatures (more than 230 degrees Celsius). Using in situ small-angle X-ray scattering, we observe continuous growth of individual nanocrystals within the lattices, which results in simultaneous lattice expansion and fine nanocrystal size control due to the superlattice templates. Thermodynamic models demonstrate that balanced attractive and repulsive interparticle interactions dictated by the ligand coverage on nanocrystal surfaces and nanocrystal core size are responsible for the crystallization process. The interparticle interactions can also be controlled to form different superlattice structures, such as hexagonal close-packed lattices. In conclusion, the rational assembly of various nanocrystal systems into novel materials is thus facilitated for both fundamental research and for practical applications in the fields of magnetics, electronics and catalysis.« less
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Botha, Sabine; Nass, Karol; Barends, Thomas R M; Kabsch, Wolfgang; Latz, Beatrice; Dworkowski, Florian; Foucar, Lutz; Panepucci, Ezequiel; Wang, Meitian; Shoeman, Robert L; Schlichting, Ilme; Doak, R Bruce
2015-02-01
Recent advances in synchrotron sources, beamline optics and detectors are driving a renaissance in room-temperature data collection. The underlying impetus is the recognition that conformational differences are observed in functionally important regions of structures determined using crystals kept at ambient as opposed to cryogenic temperature during data collection. In addition, room-temperature measurements enable time-resolved studies and eliminate the need to find suitable cryoprotectants. Since radiation damage limits the high-resolution data that can be obtained from a single crystal, especially at room temperature, data are typically collected in a serial fashion using a number of crystals to spread the total dose over the entire ensemble. Several approaches have been developed over the years to efficiently exchange crystals for room-temperature data collection. These include in situ collection in trays, chips and capillary mounts. Here, the use of a slowly flowing microscopic stream for crystal delivery is demonstrated, resulting in extremely high-throughput delivery of crystals into the X-ray beam. This free-stream technology, which was originally developed for serial femtosecond crystallography at X-ray free-electron lasers, is here adapted to serial crystallography at synchrotrons. By embedding the crystals in a high-viscosity carrier stream, high-resolution room-temperature studies can be conducted at atmospheric pressure using the unattenuated X-ray beam, thus permitting the analysis of small or weakly scattering crystals. The high-viscosity extrusion injector is described, as is its use to collect high-resolution serial data from native and heavy-atom-derivatized lysozyme crystals at the Swiss Light Source using less than half a milligram of protein crystals. The room-temperature serial data allow de novo structure determination. The crystal size used in this proof-of-principle experiment was dictated by the available flux density. However, upcoming developments in beamline optics, detectors and synchrotron sources will enable the use of true microcrystals. This high-throughput, high-dose-rate methodology provides a new route to investigating the structure and dynamics of macromolecules at ambient temperature.
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Liu, Dandan; Liu, Yunqi; Dai, Fangna; Zhao, Jinchong; Yang, Kang; Liu, Chenguang
2015-10-07
In this paper, an efficient method to fabricate Al-based metal organic framework (Al-MOF) MIL-96 crystals with controllable size and morphology, by mixing other forms of reactants to replace the coordination modulators or capping agents, is presented. The size and morphology of the MIL-96 crystals can be selectively varied by simply altering the ratio of dual reactants via their hydrolysis reaction. All the samples were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), Fourier Transform Infrared (FT-IR) spectroscopy, thermogravimetric analysis (TGA) and nitrogen sorption. Then based on the BFDH theory, a mechanism for the impact of hydrolysis of reactants on the crystal size and morphology is presented and discussed. We also evaluated the performance of these MOFs as sorbents for capturing CO2, and they all show enhanced adsorption properties compared with the bulk material, displaying high adsorption capacities on CO2 at atmospheric pressure and ambient temperature.
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Magnetic properties of GdMnO3 nanoparticles embedded in mesoporous silica
NASA Astrophysics Data System (ADS)
Tajiri, Takayuki; Mito, Masaki; Deguchi, Hiroyuki; Kohno, Atsushi
2018-05-01
Perovskite manganite GdMnO3 nanoparticles were synthesized using mesoporous silica as a template, and their magnetic properties and crystal structure were investigated. Powder X-ray diffraction data indicated successful synthesis of the GdMnO3 nanoparticles, with mean particle sizes of 13.9 and 20.9 nm. The lattice constants for the nanoparticles were slightly different from those for the bulk material and varied with the particle size. The magnetic transition temperatures for the nanoparticles were higher than those of the bulk crystal. The synthesized GdMnO3 nanoparticles exhibited superparamagnetic behaviors: The blocking temperature, coercive field, and transition temperature depended on the particle size. Magnetic measurements and crystal structure analysis suggest that the changes in the magnetic properties for GdMnO3 nanoparticles can be attributed to the modulation of the crystallographic structure.
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Ultrathin pyrolytic carbon films on a magnetic substrate
NASA Astrophysics Data System (ADS)
Umair, Ahmad; Raza, Tehseen Z.; Raza, Hassan
2016-07-01
We report the growth of ultrathin pyrolytic carbon (PyC) films on nickel substrate by using chemical vapor deposition at 1000 °C under methane ambience. We find that the ultra-fast cooling is crucial for PyC film uniformity by controlling the segregation of carbon on nickel. We characterize the in-plane crystal size of the PyC film by using Raman spectroscopy. The Raman peaks at ˜1354 and ˜1584 cm-1 wavenumbers are used to extract the D and G bands. The corresponding peak intensities are then used in an excitation energy dependent equation to calculate the in-plane crystal size. Using Raman area mapping, the mean value of in-plane crystal size over an area of 100 μm × 100 μm is about 22.9 nm with a standard deviation of about 2.4 nm.
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Analyses of Cometary Silicate Crystals: DDA Spectral Modeling of Forsterite
NASA Technical Reports Server (NTRS)
Wooden, Diane
2012-01-01
Comets are the Solar System's deep freezers of gases, ices, and particulates that were present in the outer protoplanetary disk. Where comet nuclei accreted was so cold that CO ice (approximately 50K) and other supervolatile ices like ethane (C2H2) were preserved. However, comets also accreted high temperature minerals: silicate crystals that either condensed (greater than or equal to 1400 K) or that were annealed from amorphous (glassy) silicates (greater than 850-1000 K). By their rarity in the interstellar medium, cometary crystalline silicates are thought to be grains that formed in the inner disk and were then radially transported out to the cold and ice-rich regimes near Neptune. The questions that comets can potentially address are: How fast, how far, and over what duration were crystals that formed in the inner disk transported out to the comet-forming region(s)? In comets, the mass fractions of silicates that are crystalline, f_cryst, translate to benchmarks for protoplanetary disk radial transport models. The infamous comet Hale-Bopp has crystalline fractions of over 55%. The values for cometary crystalline mass fractions, however, are derived assuming that the mineralogy assessed for the submicron to micron-sized portion of the size distribution represents the compositional makeup of all larger grains in the coma. Models for fitting cometary SEDs make this assumption because models can only fit the observed features with submicron to micron-sized discrete crystals. On the other hand, larger (0.1-100 micrometer radii) porous grains composed of amorphous silicates and amorphous carbon can be easily computed with mixed medium theory wherein vacuum mixed into a spherical particle mimics a porous aggregate. If crystalline silicates are mixed in, the models completely fail to match the observations. Moreover, models for a size distribution of discrete crystalline forsterite grains commonly employs the CDE computational method for ellipsoidal platelets (c:a:b=8.14x8.14xl in shape with geometrical factors of x:y:z=1:1:10, Fabian et al. 2001; Harker et al. 2007). Alternatively, models for forsterite employ statistical methods like the Distribution of Hollow Spheres (Min et al. 2008; Oliveira et al. 2011) or Gaussian Random Spheres (GRS) or RGF (Gielen et al. 200S). Pancakes, hollow spheres, or GRS shapes similar to wheat sheaf crystal habit (e.g., Volten et al. 2001; Veihelmann et al. 2006), however, do not have the sharp edges, flat faces, and vertices seen in images of cometary crystals in interplanetary dust particles (IDPs) or in Stardust samples. Cometary forsterite crystals often have equant or tabular crystal habit (J. Bradley). To simulate cometary crystals, we have computed absorption efficiencies of forsterite using the Discrete Dipole Approximation (DDA) DDSCAT code on NAS supercomputers. We compute thermal models that employ a size distribution of discrete irregularly shaped forsterite crystals (nonspherical shapes with faces and vertices) to explore how crystal shape affects the shape and wavelength positions of the forsterite spectral features and to explore whether cometary crystal shapes support either condensation or annealing scenarios (Lindsay et al. 2012a, b). We find forsterite crystal shapes that best-fit comet Hale-Bopp are tetrahedron, bricks or brick platelets, essentially equant or tabular (Lindsay et al. 2012a,b), commensurate with high temperature condensation experiments (Kobatake et al. 2008). We also have computed porous aggregates with crystal monomers and find that the crystal resonances are amplified. i.e., the crystalline fraction is lower in the aggregate than is derived by fitting a linear mix of spectral features from discrete subcomponents, and the crystal resonances 'appear' to be from larger crystals (Wooden et al. 2012). These results may indicate that the crystalline mass fraction in comets with comae dominated by aggregates may be lower than deduced by popular methods that only emoy ensembles of discrete crystals.
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Determination of struvite crystallization mechanisms in urine using turbidity measurement.
Triger, Aurélien; Pic, Jean-Stéphane; Cabassud, Corinne
2012-11-15
Sanitation improvement in developing countries could be achieved through wastewater treatment processes. Nowadays alternative concepts such as urine separate collection are being developed. These processes would be an efficient way to reduce pollution of wastewater while recovering nutrients, especially phosphorus, which are lost in current wastewater treatment methods. The precipitation of struvite (MgNH(4)PO(4)∙6H(2)O) from urine is an efficient process yielding more than 98% phosphorus recovery with very high reaction rates. The work presented here aims to determine the kinetics and mechanisms of struvite precipitation in order to supply data for the design of efficient urine treatment processes. A methodology coupling the resolution of the population balance equation to turbidity measurement was developed, and batch experiments with synthetic and real urine were performed. The main mechanisms of struvite crystallization were identified as crystal growth and nucleation. A satisfactory approximation of the volumetric crystal size distribution was obtained. The study has shown the low influence on the crystallization process of natural organic matter contained in real urine. It has also highlighted the impact of operational parameters. Mixing conditions can create segregation and attrition which influence the nucleation rate, resulting in a change in crystals number, size, and thus final crystal size distribution (CSD). Moreover urine storage conditions can impact urea hydrolysis and lead to spontaneous struvite precipitation in the stock solution also influencing the final CSD. A few limits of the applied methodology and of the proposed modelling, due to these phenomena and to the turbidity measurement, are also discussed. Copyright © 2012 Elsevier Ltd. All rights reserved.
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Particle engineering using sonocrystallization: salbutamol sulphate for pulmonary delivery.
Dhumal, Ravindra S; Biradar, Shailesh V; Paradkar, Anant R; York, Peter
2009-02-23
The aim of present work was to produce fine elongated crystals of salbutamol sulphate (SS) by sonocrystallization for pulmonary delivery and compare with micronized and spray dried SS (SDSS) for in vitro aerosolization behavior. Application of ultrasound during anti-solvent crystallization resulted in fine elongated crystals (sonocrystallized SS; SCSS) compared to aggregates of large irregular crystals obtained without sonication. Higher sonication amplitude, time, concentration and lower processing temperatures favored formation of smaller crystals with narrow particle size distribution (PSD). SCSS was separated from dispersion by spray drying in the form of loose aggregates (SD-SCSS). The fine particle fraction (FPF) of formulations with coarse lactose carrier in cascade impactor increased from 16.66% for micronized SS to 31.12% for SDSS (obtained by spray drying aqueous SS solution) and 44.21% for SD-SCSS, due to reduced cohesive/adhesive forces and aerodynamic size by virtue of elongated shape of crystals. SD-SCSS was stable without any change in crystallinity and aerodynamic behavior for 3 months at 40 degrees C/75% RH, but amorphous SDSS showed recrystallization with poor aerosolization performance on storage. Sonocrystallization, a rapid and simple technique is reported for production of SS crystals suitable for inhalation delivery.
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NASA Astrophysics Data System (ADS)
Sathyamoorthy, K.; Vinothkumar, P.; Irshad Ahamed, J.; Murali Manohar, P.; Priya, M.; Liu, Jinghe
2018-04-01
Single crystals of organometallic (DL)-trithioureatartrato-O1,O2,O3-cadmium(II) (TUDLC) have been grown from methanol solution by using the slow evaporation of solvent growth technique. The lattice structure and crystalline perfection have been determined by carrying out single crystal X-ray diffraction and high resolution X-ray diffraction measurements. The grown crystal was characterized thermally and mechanically by carrying out thermo-gravimetric and micro hardness measurements. The linear and nonlinear optical characterizations were made by carrying out optical transmittance, surface laser damage threshold, particle size-dependent second harmonic generation (SHG) efficiency and photo conductivity measurements. The grown crystal was electrically characterized by carrying out frequency-dependent dielectric measurements. Chemical etching study was also carried out and the dislocation density was estimated. Results obtained in the present study indicate that the grown TUDLC crystal is optically transparent with lower cut-off wavelength 304 nm, mechanically soft, thermally stable up to 101 °C and NLO active with SHG efficiency 2.13 (in KDP unit). The grown crystal is found to have considerably large size, good crystalline perfection, large specific heat capacity, higher surface laser damage threshold and negative photoconductivity.
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Effect of binder liquid type on spherical crystallization.
Maghsoodi, Maryam; Hajipour, Ali
2014-11-01
Spherical crystallization is a process of formation of agglomerates of crystals held together by binder liquid. This research focused on understanding the effect of type of solvents used as binder liquid on the agglomeration of crystals. Carbamazepine and ethanol/water were used respectively as a model drug and crystallization system. Eight solvents as binder liquid including chloroform, dichloromethane, isopropyl acetate, ethyl acetate, n-hexane, dimethyl aniline, benzene and toluene were examined to better understand the relationship between the physical properties of the binder liquid and its ability to bring about the formation of the agglomerates. Moreover, the agglomerates obtained from effective solvents as binder liquid were evaluated in term of size, apparent particle density and compressive strength. In this study the clear trend was observed experimentally in the agglomerate formation as a function of physical properties of the binder liquid such as miscibility with crystallization system. Furthermore, the properties of obtained agglomerates such as size, apparent particle density and compressive strength were directly related to physical properties of effective binder liquids. RESULTS of this study offer a useful starting point for a conceptual framework to guide the selection of solvent systems for spherical crystallization.
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NASA Technical Reports Server (NTRS)
Han, Qingyuan; Rossow, William B.; Chou, Joyce; Welch, Ronald M.
1997-01-01
Cloud microphysical parameterizations have attracted a great deal of attention in recent years due to their effect on cloud radiative properties and cloud-related hydrological processes in large-scale models. The parameterization of cirrus particle size has been demonstrated as an indispensable component in the climate feedback analysis. Therefore, global-scale, long-term observations of cirrus particle sizes are required both as a basis of and as a validation of parameterizations for climate models. While there is a global scale, long-term survey of water cloud droplet sizes (Han et al. 1994), there is no comparable study for cirrus ice crystals. In this paper a near-global survey of cirrus ice crystal sizes is conducted using ISCCP satellite data analysis. The retrieval scheme uses phase functions based upon hexagonal crystals calculated by a ray tracing technique. The results show that global mean values of D(e) are about 60 micro-m. This study also investigates the possible reasons for the significant difference between satellite retrieved effective radii (approx. 60 micro-m) and aircraft measured particle sizes (approx. 200 micro-m) during the FIRE I IFO experiment. They are (1) vertical inhomogeneity of cirrus particle sizes; (2) lower limit of the instrument used in aircraft measurements; (3) different definitions of effective particle sizes; and (4) possible inappropriate phase functions used in satellite retrieval.
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Birone, Claire; Brown, Maria; Hernandez, Jesus; Neff, Sherry; Williams, Daniel; Allaire, Marc; Orville, Allen M.; Sweet, Robert M.; Soares, Alexei S.
2014-01-01
High throughput screening technologies such as acoustic droplet ejection (ADE) greatly increase the rate at which X-ray diffraction data can be acquired from crystals. One promising high throughput screening application of ADE is to rapidly combine protein crystals with fragment libraries. In this approach, each fragment soaks into a protein crystal either directly on data collection media or on a moving conveyor belt which then delivers the crystals to the X-ray beam. By simultaneously handling multiple crystals combined with fragment specimens, these techniques relax the automounter duty-cycle bottleneck that currently prevents optimal exploitation of third generation synchrotrons. Two factors limit the speed and scope of projects that are suitable for fragment screening using techniques such as ADE. Firstly, in applications where the high throughput screening apparatus is located inside the X-ray station (such as the conveyor belt system described above), the speed of data acquisition is limited by the time required for each fragment to soak into its protein crystal. Secondly, in applications where crystals are combined with fragments directly on data acquisition media (including both of the ADE methods described above), the maximum time that fragments have to soak into crystals is limited by evaporative dehydration of the protein crystals during the fragment soak. Here we demonstrate that both of these problems can be minimized by using small crystals, because the soak time required for a fragment hit to attain high occupancy depends approximately linearly on crystal size. PMID:24988328
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Cole, Krystal; Roessler, Christian G; Mulé, Elizabeth A; Benson-Xu, Emma J; Mullen, Jeffrey D; Le, Benjamin A; Tieman, Alanna M; Birone, Claire; Brown, Maria; Hernandez, Jesus; Neff, Sherry; Williams, Daniel; Allaire, Marc; Orville, Allen M; Sweet, Robert M; Soares, Alexei S
2014-01-01
High throughput screening technologies such as acoustic droplet ejection (ADE) greatly increase the rate at which X-ray diffraction data can be acquired from crystals. One promising high throughput screening application of ADE is to rapidly combine protein crystals with fragment libraries. In this approach, each fragment soaks into a protein crystal either directly on data collection media or on a moving conveyor belt which then delivers the crystals to the X-ray beam. By simultaneously handling multiple crystals combined with fragment specimens, these techniques relax the automounter duty-cycle bottleneck that currently prevents optimal exploitation of third generation synchrotrons. Two factors limit the speed and scope of projects that are suitable for fragment screening using techniques such as ADE. Firstly, in applications where the high throughput screening apparatus is located inside the X-ray station (such as the conveyor belt system described above), the speed of data acquisition is limited by the time required for each fragment to soak into its protein crystal. Secondly, in applications where crystals are combined with fragments directly on data acquisition media (including both of the ADE methods described above), the maximum time that fragments have to soak into crystals is limited by evaporative dehydration of the protein crystals during the fragment soak. Here we demonstrate that both of these problems can be minimized by using small crystals, because the soak time required for a fragment hit to attain high occupancy depends approximately linearly on crystal size.
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Predictions of Crystal Structures from First Principles
2007-06-01
RDX crystal in hoped that the problem could be resolved by the molecular dynamics simulations . The fully ab initio development of density functional... Molecular Dynamics Simulations of RDX i.e., without any use of experimental results (except that Crystal the geometry of monomers was derived from X-ray...applied in molecular dynamics simulations of the RDX system, due to its size, is intractable by any high-level ab crystal. We performed isothermal
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Ice Fog and Light Snow Measurements Using a High-Resolution Camera System
NASA Astrophysics Data System (ADS)
Kuhn, Thomas; Gultepe, Ismail
2016-09-01
Ice fog, diamond dust, and light snow usually form over extremely cold weather conditions, and they affect both visibility and Earth's radiative energy budget. Prediction of these hydrometeors using models is difficult because of limited knowledge of the microphysical properties at the small size ranges due to measurement issues. These phenomena need to be better represented in forecast and climate models; therefore, in addition to remote sensing accurate measurements using ground-based instrumentation are required. An imaging instrument, aimed at measuring ice fog and light snow particles, has been built and is presented here. The ice crystal imaging (ICI) probe samples ice particles into a vertical, tapered inlet with an inlet flow rate of 11 L min-1. A laser beam across the vertical air flow containing the ice crystals allows for their detection by a photodetector collecting the scattered light. Detected particles are then imaged with high optical resolution. An illuminating LED flash and image capturing are triggered by the photodetector. In this work, ICI measurements collected during the fog remote sensing and modeling (FRAM) project, which took place during Winter of 2010-2011 in Yellowknife, NWT, Canada, are summarized and challenges related to measuring small ice particles are described. The majority of ice particles during the 2-month-long campaign had sizes between 300 and 800 μm. During ice fog events the size distribution measured had a lower mode diameter of 300 μm compared to the overall campaign average with mode at 500 μm.
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Hosokawa, Akihiro; Kato, Yoshiteru
2011-08-01
The purpose of this article is to study factors affecting color strength of printing on film-coated tablets by ultraviolet (UV) laser irradiation: particle size, crystal structure, or concentration of titanium dioxide (TiO2) in film, and irradiated UV laser power. Hydroxypropylmethylcellulose films containing 4.0% of TiO2, of which BET particle sizes were ranging from 126.1 to 219.8 nm, were irradiated 3.14W of UV laser at a wavelength 355 nm to study effects of TiO2 particle size and crystal structure on the printing. The films containing TiO2 concentration ranging from 1.0 to 7.7% were irradiated 3.14 or 5.39W of the UV laser to study effect of TiO2 concentration on the printing. The film containing 4.0% of TiO2, was irradiated the UV laser up to 6.42W to study effect of the UV laser power on the printing. The color strength of the printed films was estimated by a spectrophotometer as total color difference (dE). Particle size, crystal structure, and concentration of TiO2 in the films did not affect the printing. In the relationship between the irradiated UV laser power and dE, there found an inflection point (1.6W). When the UV laser power was below 1.6W, the films were not printed. When it was beyond the point, total color difference increased linearly in proportion with the irradiated laser power. The color strength of the printing on film was not changed by TiO2 particle size, crystal structure, and concentration, but could be controlled by regulating the irradiated UV laser power beyond the inflection point.
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High resolution electron microscopy study of crystal growth mechanisms in chicken bone composites
NASA Astrophysics Data System (ADS)
Cuisinier, F. J. G.; Steuer, P.; Brisson, A.; Voegel, J. C.
1995-12-01
The present study describes the early stages of chicken bone crystal growth, followed by high resolution electron microscopy (HREM). We have developed an original analysis procedure to determine the crystal structure. Images were first digitalized and selected areas were fast Fourier transformed. Numerical masks were selected around the most intense spots and the filtered signal was retransformed back to real space. The filtered images were then compared to computer calculated images to identify the inorganic mineral phase. Nanometer-sized particles were observed on amorphous areas. These particles have a structure loosely related to hydroxyapatite (HA) and a specific orientation. In a more advanced situation, the nanoparticles appeared to grow in two dimensions and to form plate-like crystals. These crystals seem, in a last growth step, to fuse by their (100) faces. These experimental observations allowed us to propose a four-step model for the development and growth of chicken bone crystals. The two initial stages are the ionic adsorption onto the organic substrate followed by the nucleation of nanometer-sized particles. The two following steps, i.e. two-dimensional growth of the nanoparticles leading to the formation of needle-like crystals, and the lateral fusion of these crystals by their (100) faces, are controlled only by spatial constraints inside the extracellular organic matrix.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Tian, Bingtao; Wang, Xiaodong, E-mail: xiaodong-wang@tongji.edu.cn; Niu, Yanyan
2016-04-15
Lithium triborate (LiB{sub 3}O{sub 5}, LBO) crystal is now one of the most useful nonlinear optical materials for frequency conversion of high power lasers. The use of the crystal, however, has been hampered by the unavailability of antireflective (AR) coatings with high laser damage resistance. In this work, a “point contact” dip-coating method is developed to prepare sol–gel SiO{sub 2} AR coatings on small-size LBO crystals. Using this approach, we obtain a homogenous coating surface on an 8 mm×8 mm×3 mm LBO crystal. The stress measurements show that the stresses in sol–gel SiO{sub 2} coatings vary with the time ofmore » natural drying, which is beyond our expectation. The anisotropic Young’s modulus of the LBO crystal and the different evolution tendency of the stress in the different SiO{sub 2} coating layers are found to be responsible for the crack of the double-layer AR coatings on anisotropic LBO crystal. Meanwhile, the resulting coatings on LBO crystal achieve a LIDT of over 15 J/cm{sup 2} (532 nm, 3ns) and the coated LBO is expected to have a transmittance of over 99% at 800 nm.« less
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NASA Astrophysics Data System (ADS)
Fridlind, A. M.; Atlas, R.; van Diedenhoven, B.; Ackerman, A. S.; Rind, D. H.; Harrington, J. Y.; McFarquhar, G. M.; Um, J.; Jackson, R.; Lawson, P.
2017-12-01
It has recently been suggested that seeding synoptic cirrus could have desirable characteristics as a geoengineering approach, but surprisingly large uncertainties remain in the fundamental parameters that govern cirrus properties, such as mass accommodation coefficient, ice crystal physical properties, aggregation efficiency, and ice nucleation rate from typical upper tropospheric aerosol. Only one synoptic cirrus model intercomparison study has been published to date, and studies that compare the shapes of observed and simulated ice size distributions remain sparse. Here we amend a recent model intercomparison setup using observations during two 2010 SPARTICUS campaign flights. We take a quasi-Lagrangian column approach and introduce an ensemble of gravity wave scenarios derived from collocated Doppler cloud radar retrievals of vertical wind speed. We use ice crystal properties derived from in situ cloud particle images, for the first time allowing smoothly varying and internally consistent treatments of nonspherical ice capacitance, fall speed, gravitational collection, and optical properties over all particle sizes in our model. We test two new parameterizations for mass accommodation coefficient as a function of size, temperature and water vapor supersaturation, and several ice nucleation scenarios. Comparison of results with in situ ice particle size distribution data, corrected using state-of-the-art algorithms to remove shattering artifacts, indicate that poorly constrained uncertainties in the number concentration of crystals smaller than 100 µm in maximum dimension still prohibit distinguishing which parameter combinations are more realistic. When projected area is concentrated at such sizes, the only parameter combination that reproduces observed size distribution properties uses a fixed mass accommodation coefficient of 0.01, on the low end of recently reported values. No simulations reproduce the observed abundance of such small crystals when the projected area is concentrated at larger sizes. Simulations across the parameter space are also compared with MODIS collection 6 retrievals and forward simulations of cloud radar reflectivity and mean Doppler velocity. Results motivate further in situ and laboratory measurements to narrow parameter uncertainties in models.
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Determining the Molecular Growth Mechanisms of Protein Crystal Faces by Atomic Force Microscopy
NASA Technical Reports Server (NTRS)
Nadarajah, Arunan; Li, Huayu; Pusey, Marc L.
1999-01-01
A high resolution atomic force microscopy (AFM) study had shown that the molecular packing on the tetragonal lysozyme (110) face corresponded to only one of two possible packing arrangements, suggesting that growth layers on this face were of bimolecular height. Theoretical analyses of the packing also indicated that growth of this face should proceed by the addition of growth units of at least tetramer size corresponding to the 43 helices in the crystal. In this study an AFM linescan technique was devised to measure the dimensions of individual growth units on protein crystal faces as they were being incorporated into the lattice. Images of individual growth events on the (110) face of tetragonal lysozyme crystals were observed, shown by jump discontinuities in the growth step in the linescan images as shown in the figure. The growth unit dimension in the scanned direction was obtained from these images. A large number of scans in two directions on the (110) face were performed and the distribution of lysozyme growth unit sizes were obtained. A variety of unit sizes corresponding to 43 helices, were shown to participate in the growth process, with the 43 tetramer being the minimum observed size. This technique represents a new application for AFM allowing time resolved studies of molecular process to be carried out.
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Bustamante, Eugenia L; Fernández, José L; Zamaro, Juan M
2014-06-15
The effect of the solvent on the synthesis process and on the nanocrystal characteristics of the zeolitic imidazolate framework-8 (ZIF-8) was investigated. A synthesis protocol at room temperature employing a series of aliphatic alcohols, water, dimethylformamide and acetone was employed. The results show that the solvent modifies the evolution of the reaction, altering the crystallization rates and nanocrystal sizes. Its hydrogen bond donation ability is the main factor that governs this effect. More precisely, the solvent modulates the formation of ZIF-8 nanocrystals with sizes in the range between 15 and 42 nm. When synthesized in alcohol and acetone, these nanocrystals form globular aggregates with sizes between 130 and 420 nm. In contrast, under the same synthesis conditions, when using water or dimethylformamide the ZIF phase is not developed. In alcohols other than methanol, the crystals develop pill-shaped morphologies with poorly defined facets. Moreover, a markedly fast growing kinetics is verified in these alcohols, leading to an ultra-fast crystallization of ZIF-8 in about 60s. These findings provide new information about the role of the solvent in the synthesis process of nanoZIF-8, which can be useful for controlling the crystallization rates and nanocrystal sizes of this material. Copyright © 2014 Elsevier Inc. All rights reserved.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Sornadurai, D.; Ravindran, T. R.; Paul, V. Thomas
Synthesis parameters are optimized in order to grow single crystals of multiferroic BiFeO{sub 3}. 2 to 3 mm size pyramid (tetrahedron) shaped single crystals were successfully obtained by solvothermal method. Scanning electron microscopy with EDAX confirmed the phase formation. Raman scattering spectra of bulk BiFeO3 single crystals have been measured which match well with reported spectra.
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Carbonate crystals precipitated by freshwater bacteria and their use as a limestone consolidant.
Zamarreño, Dania V; Inkpen, Robert; May, Eric
2009-09-01
Bacterial carbonate precipitation is known to be a natural phenomenon associated with a wide range of bacterial species. Recently, the ability of bacteria to produce carbonates has been studied for its value in the conservation of limestone monuments and concrete. This paper describes investigations of carbonate crystals precipitated by freshwater bacteria by means of histological (Loeffler's methylene blue and alcian blue-periodic acid-Schiff stain) and fluorescence (CTC [5-cyano-2,3-ditolyl tetrazolium chloride]) stains, determination of cell viability inside carbonate crystals, and pore size reduction in limestone by image analysis. Carbonate crystals were found to be composed of bacteria embedded in a matrix of neutral and acid polysaccharides. Cell viability inside the carbonate crystals decreased with time. On stone, bacteria were found to form carbonate crystals, with only a few bacteria remaining as isolated cells or as cell aggregates. Pore size was reduced by about 50%, but no blockage was detected. Taken together, the results of this research provide some reassurance to conservators that biocalcification by bacteria could be a safe consolidation tool in a restoration strategy for building stone conservation.
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Carbonate Crystals Precipitated by Freshwater Bacteria and Their Use as a Limestone Consolidant▿
Zamarreño, Dania V.; Inkpen, Robert; May, Eric
2009-01-01
Bacterial carbonate precipitation is known to be a natural phenomenon associated with a wide range of bacterial species. Recently, the ability of bacteria to produce carbonates has been studied for its value in the conservation of limestone monuments and concrete. This paper describes investigations of carbonate crystals precipitated by freshwater bacteria by means of histological (Loeffler's methylene blue and alcian blue-periodic acid-Schiff stain) and fluorescence (CTC [5-cyano-2,3-ditolyl tetrazolium chloride]) stains, determination of cell viability inside carbonate crystals, and pore size reduction in limestone by image analysis. Carbonate crystals were found to be composed of bacteria embedded in a matrix of neutral and acid polysaccharides. Cell viability inside the carbonate crystals decreased with time. On stone, bacteria were found to form carbonate crystals, with only a few bacteria remaining as isolated cells or as cell aggregates. Pore size was reduced by about 50%, but no blockage was detected. Taken together, the results of this research provide some reassurance to conservators that biocalcification by bacteria could be a safe consolidation tool in a restoration strategy for building stone conservation. PMID:19617383
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Gao, Lan, E-mail: lgao@pppl.gov; Hill, K. W.; Bitter, M.
A high spatial resolution of a few μm is often required for probing small-scale high-energy-density plasmas using high resolution x-ray imaging spectroscopy. This resolution can be achieved by adjusting system magnification to overcome the inherent limitation of the detector pixel size. Laboratory experiments on investigating the relation between spatial resolution and system magnification for a spherical crystal spectrometer are presented. Tungsten Lβ{sub 2} rays from a tungsten-target micro-focus x-ray tube were diffracted by a Ge 440 crystal, which was spherically bent to a radius of 223 mm, and imaged onto an x-ray CCD with 13-μm pixel size. The source-to-crystal (p)more » and crystal-to-detector (q) distances were varied to produce spatial magnifications (M = q/p) ranging from 2 to 10. The inferred instrumental spatial width reduces with increasing system magnification M. However, the experimental measurement at each M is larger than the theoretical value of pixel size divided by M. Future work will focus on investigating possible broadening mechanisms that limit the spatial resolution.« less
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Spatial resolution of a spherical x-ray crystal spectrometer at various magnifications
Gao, Lan; Hill, K. W.; Bitter, M.; ...
2016-08-23
Here, a high spatial resolution of a few μm is often required for probing small-scale high-energy-density plasmas using high resolution x-ray imaging spectroscopy. This resolution can be achieved by adjusting system magnification to overcome the inherent limitation of the detector pixel size. Laboratory experiments on investigating the relation between spatial resolution and system magnification for a spherical crystal spectrometer are presented. Tungsten Lβ 2 rays from a tungsten-target micro-focus x-ray tube were diffracted by a Ge 440 crystal, which was spherically bent to a radius of 223 mm, and imaged onto an x-ray CCD with 13-μm pixel size. The source-to-crystalmore » (p) and crystal-to-detector (q) distances were varied to produce spatial magnifications ( M = q/p) ranging from 2 to 10. The inferred instrumental spatial width reduces with increasing system magnification M. However, the experimental measurement at each M is larger than the theoretical value of pixel size divided by M. Future work will focus on investigating possible broadening mechanisms that limit the spatial resolution.« less
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Tahara, Kohei; Nishikawa, Masahiro; Matsui, Ko; Hisazumi, Koji; Onodera, Risako; Tozuka, Yuichi; Takeuchi, Hirofumi
2016-09-01
The aim of this study was to enhance the dissolution and oral absorption of poorly water-soluble active pharmaceutical ingredients (APIs) using nanoparticle suspensions prepared with a PureNano™ continuous crystallizer (PCC). Nanoparticle suspensions were prepared with a PCC, which is based on microfluidics reaction technology and solvent-antisolvent crystallization. Phenytoin, bezafibrate, flurbiprofen, and miconazole were used as model APIs. These APIs were dissolved in ethanol and precipitated by the addition of water and polyvinyl alcohol. Batch crystallization (BC) using a beaker was also performed to prepare the suspensions. Both PCC and BC formulations were freeze-dried before being characterized in vitro and in vivo. The particle sizes of the nanoparticle suspensions prepared with the PCC were smaller than those prepared by BC. The dissolution rate of each API in vitro significantly increased after crystallization. Reducing the particle size of either the BC or PCC formulation led to increased API flux across Caco-2 cell monolayers. PCC preparations showed higher plasma concentrations after oral administration, demonstrating the advantages of a fast dissolution rate and increased interaction with the gastrointestinal tract owing to the smaller particle size. PCC can continuously produce nanoparticle APIs and is an efficient approach for improving their oral bioavailability.
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NASA Astrophysics Data System (ADS)
Lubenets, S. V.; Rusakova, A. V.; Fomenko, L. S.; Moskalenko, V. A.
2018-01-01
The anisotropy of microhardness of pure α-Ti single crystals, indentation size effect in single-crystal, course grained (CG) pure and nanocrystalline (NC) VT1-0 titanium, as well as the temperature dependences of the microhardness of single-crystal and CG Ti in the temperature range 77-300 K were studied. The minimum value of hardness was obtained when indenting into the basal plane (0001). The indentation size effect (ISE) was clearly observed in the indentation of soft high-purity single-crystal iodide titanium while it was the least pronounced in a sample of nanocrystalline VT1-0 titanium. It has been demonstrated that the ISE can be described within the model of geometrically necessary dislocations (GND), which follows from the theory of strain gradient plasticity. The true hardness and others parameters of the GND model were determined for all materials. The temperature dependence of the microhardness is in agreement with the idea of the governing role of Peierls relief in the dislocation thermally-activated plastic deformation of pure titanium as has been earlier established and justified in macroscopic tensile investigations at low temperatures. The activation energy and activation volume of dislocation motion in the strained region under the indenter were estimated.
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Lin, Pao-Chung; Huang, Cheng-Wei; Hsiao, Ching-Ta; Teng, Hsisheng
2008-04-15
Magnesium hydroxide extracted from magnesium-bearing minerals is considered a promising agent for binding CO2 as a carbonate mineral in a gas-solid reaction. An efficient extraction route consisting of hydrothermal treatment on serpentine in HCl followed by NaOH titration for Mg(OH)2 precipitation was demonstrated. The extracted Mg(OH)2 powder had a mean crystal domain size as small as 12 nm and an apparent surface area of 54 m2/g. Under one atmosphere of 10 vol% CO2/N2, carbonation of the serpentine-derived Mg(OH)2 to 26% of the stoichiometric limit was achieved at 325 degrees C in 2 h; while carbonation of a commercially available Mg(OH)2, with a mean crystal domain size of 33 nm and an apparent surface area of 3.5 m2/g, reached only 9% of the stoichiometric limit. The amount of CO2 fixation was found to be inversely proportional to the crystal domain size of the Mg(OH)2 specimens. The experimental data strongly suggested that only a monolayer of carbonates was formed on the crystal domain boundary in the gas-solid reaction, with little penetration of the carbonates into the crystal domain.
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Desgranges, Caroline; Delhommelle, Jerome
2018-06-18
Using molecular dynamics simulation, we study the impact of the degree of supercooling on the crystal nucleation of ultra-soft particles, modeled with the Gaussian core potential. Focusing on systems with a high number density, our simulations reveal dramatically different behaviors as the degree of supercooling is varied. In the moderate supercooling regime, crystal nucleation proceeds as expected from classical nucleation theory, with a decrease in the free energy of nucleation, as well as in the size of the critical nucleus, as supercooling is increased. On the other hand, in the large supercooling regime, we observe an unusual reversal of behavior with an increase in the free energy of nucleation and in the critical size, as supercooling is increased. This unexpected result is analyzed in terms of the interplay between the glass transition and the crystal nucleation process. Specifically, medium range order crystal-like domains, with structural features different from that of the crystal nucleus, are found to form throughout the system when the supercooling is very large. These, in turn, play a pivotal role in the increase in the free energy of nucleation, as well as in the critical size, as the temperature gets closer to the glass transition.
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Femtosecond X-ray protein nanocrystallography.
Chapman, Henry N; Fromme, Petra; Barty, Anton; White, Thomas A; Kirian, Richard A; Aquila, Andrew; Hunter, Mark S; Schulz, Joachim; DePonte, Daniel P; Weierstall, Uwe; Doak, R Bruce; Maia, Filipe R N C; Martin, Andrew V; Schlichting, Ilme; Lomb, Lukas; Coppola, Nicola; Shoeman, Robert L; Epp, Sascha W; Hartmann, Robert; Rolles, Daniel; Rudenko, Artem; Foucar, Lutz; Kimmel, Nils; Weidenspointner, Georg; Holl, Peter; Liang, Mengning; Barthelmess, Miriam; Caleman, Carl; Boutet, Sébastien; Bogan, Michael J; Krzywinski, Jacek; Bostedt, Christoph; Bajt, Saša; Gumprecht, Lars; Rudek, Benedikt; Erk, Benjamin; Schmidt, Carlo; Hömke, André; Reich, Christian; Pietschner, Daniel; Strüder, Lothar; Hauser, Günter; Gorke, Hubert; Ullrich, Joachim; Herrmann, Sven; Schaller, Gerhard; Schopper, Florian; Soltau, Heike; Kühnel, Kai-Uwe; Messerschmidt, Marc; Bozek, John D; Hau-Riege, Stefan P; Frank, Matthias; Hampton, Christina Y; Sierra, Raymond G; Starodub, Dmitri; Williams, Garth J; Hajdu, Janos; Timneanu, Nicusor; Seibert, M Marvin; Andreasson, Jakob; Rocker, Andrea; Jönsson, Olof; Svenda, Martin; Stern, Stephan; Nass, Karol; Andritschke, Robert; Schröter, Claus-Dieter; Krasniqi, Faton; Bott, Mario; Schmidt, Kevin E; Wang, Xiaoyu; Grotjohann, Ingo; Holton, James M; Barends, Thomas R M; Neutze, Richard; Marchesini, Stefano; Fromme, Raimund; Schorb, Sebastian; Rupp, Daniela; Adolph, Marcus; Gorkhover, Tais; Andersson, Inger; Hirsemann, Helmut; Potdevin, Guillaume; Graafsma, Heinz; Nilsson, Björn; Spence, John C H
2011-02-03
X-ray crystallography provides the vast majority of macromolecular structures, but the success of the method relies on growing crystals of sufficient size. In conventional measurements, the necessary increase in X-ray dose to record data from crystals that are too small leads to extensive damage before a diffraction signal can be recorded. It is particularly challenging to obtain large, well-diffracting crystals of membrane proteins, for which fewer than 300 unique structures have been determined despite their importance in all living cells. Here we present a method for structure determination where single-crystal X-ray diffraction 'snapshots' are collected from a fully hydrated stream of nanocrystals using femtosecond pulses from a hard-X-ray free-electron laser, the Linac Coherent Light Source. We prove this concept with nanocrystals of photosystem I, one of the largest membrane protein complexes. More than 3,000,000 diffraction patterns were collected in this study, and a three-dimensional data set was assembled from individual photosystem I nanocrystals (∼200 nm to 2 μm in size). We mitigate the problem of radiation damage in crystallography by using pulses briefer than the timescale of most damage processes. This offers a new approach to structure determination of macromolecules that do not yield crystals of sufficient size for studies using conventional radiation sources or are particularly sensitive to radiation damage.
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2017-01-01
Lycaenid butterflies from the genera Callophrys, Cyanophrys and Thecla have evolved remarkable biophotonic gyroid nanostructures within their wing scales that have only recently been replicated by nanoscale additive manufacturing. These nanostructures selectively reflect parts of the visible spectrum to give their characteristic non-iridescent, matte-green appearance, despite a distinct blue–green–yellow iridescence predicted for individual crystals from theory. It has been hypothesized that the organism must achieve its uniform appearance by growing crystals with some restrictions on the possible distribution of orientations, yet preferential orientation observed in Callophrys rubi confirms that this distribution need not be uniform. By analysing scanning electron microscope and optical images of 912 crystals in three wing scales, we find no preference for their rotational alignment in the plane of the scales. However, crystal orientation normal to the scale was highly correlated to their colour at low (conical) angles of view and illumination. This correlation enabled the use of optical images, each containing up to 104–105 crystals, for concluding the preferential alignment seen along the at the level of single scales, appears ubiquitous. By contrast, orientations were found to occur at no greater rate than that expected by chance. Above a critical cone angle, all crystals reflected bright green light indicating the dominant light scattering is due to the predicted band gap along the direction, independent of the domain orientation. Together with the natural variation in scale and wing shapes, we can readily understand the detailed mechanism of uniform colour production and iridescence suppression in these butterflies. It appears that the combination of preferential alignment normal to the wing scale, and uniform distribution within the plane is a near optimal solution for homogenizing the angular distribution of the band gap relative to the wings. Finally, the distributions of orientations, shapes, sizes and degree of order of crystals within single scales provide useful insights for understanding the mechanisms at play in the formation of these biophotonic nanostructures. PMID:28630678
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Di Martino, Piera; Joiris, Etienne; Martelli, Sante
2004-09-01
The aim of this study is to assess an experimental approach for technological development of a direct compression formulation. A simple formula was considered composed by an active ingredient, a diluent and a lubricant. The active ingredient and diluent were selected as an example according to their typical densification mechanism: the nitrofurantoine, a fragmenting material, and the cellulose microcrystalline (Vivapur), which is a typical visco-elastic material, equally displaying good bind and disintegrant properties. For each ingredient, samples of different particle size distribution were selected. Initially, tabletability of pure materials was studied by a rotary press without magnesium stearate. Vivapur tabletability decreases with increase in particle size. The addition of magnesium stearate as lubricant decreases tabletability of Vivapur of greater particle size, while it kept unmodified that of Vivapur of lower particle size. Differences in tabletability can be related to differences in particle-particle interactions; for Vivapur of higher particle size (Vivapur 200, 102 and 101), the lower surface area develops lower surface available for bonds, while for Vivapur of lower particle size (99 and 105) the greater surface area allows high particle proximity favouring particle cohesivity. Nitrofurantoine shows great differences in compression behaviour according to its particle size distribution. Large crystals show poorer tabletability than fine crystals, further decreased by lubricant addition. The large crystals poor tabletability is due to their poor compactibility, in spite of high compressibility and plastic intrinsic deformability; in fact, in spite of the high densification tendency, the nature of the involved bonds is very weak. Nitrofurantoine samples were then mixed with Vivapurs in different proportions. Compression behaviour of binary mixes (tabletability and compressibility) was then evaluated according to diluents proportion in the mixes. The mix of either nitrofurantoine large crystals or fine crystals with cellulose microcrystalline showed a negative interaction in all proportions, whatever particle sizes. The lubricant addition induced a positive interaction with Vivapur of greater particle size distribution (200, 102 and 101) favouring higher particle adhesivity, while it maintained unaltered that of Vivapurs of lower particle size (105 and 99). Definitely, when cohesive forces are predominant (Vivapur 105 and 99), the establishment of adhesive bonds between nitrofurantoine and Vivapur remain unnoticed; on the contrary, when cohesion bonds between microcrystalline cellulose particles are weakened by the presence of magnesium stearate, the existence of adhesion bonds between particles of different nature is in evidence, leading to a positive interaction.
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The Backscatter Cloudprobe with Polarization Detection: A New Aircraft Ice Water Detector
NASA Astrophysics Data System (ADS)
Freer, M.; Baumgardner, D.; Axisa, D.
2017-12-01
The differentiation of liquid water and ice crystals smaller than 100 um in mixed phase clouds continues to challenge the cloud measurement community. In situ imaging probes now have pixel resolution down to about 5 um, but at least 10 pixels are needed to accurately distinguish a water droplet from an ice crystal. This presents a major obstacle for the understanding of cloud glaciation in general, and the formation and evolution of cloud ice in particular. A new sensor has recently been developed that can detect and quantify supercooled liquid droplets and ice crystals. The Backscatter Cloudprobe with Polarization Detection (BCPD) is a very lightweight, compact and low power optical spectrometer that has already undergone laboratory, wind tunnel and flight tests that have validated its capabilities. The BCPD employs the optical approach with single particles that has been used for years in remote sensing to distinguish liquid water from ice crystals in ensembles of cloud particles. The sensor is mounted inside an aircraft and projects a linearly polarized laser beam to the outside through a heated window. Particles that pass through the sample volume of the laser scatter light and the photons scattered in the back direction pass through another heated window where they are collected and focused onto a beam splitter that directs them onto two photodetectors. The P-detector senses the light with polarization parallel to that of the incident light and the S-Detector measures the light that is perpendicular to that of the laser. The polarization ratio, S/P, is sensitive to the asphericity of a particle and is used to identify liquid water and ice crystals. The BCPD has now been exercised in an icing wind tunnel where it was compared with other cloud spectrometers. It has also been flown on the NCAR C-130 and on a commercial Citation, making measurements in all water, all ice and mixed phase clouds. Results from these three applications clearly show that the BCPD can be employed successfully to derive ice fraction in mixed phase clouds at sizes less than 50 um, a size range that has previously been inaccessible to cloud researchers.
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NASA Astrophysics Data System (ADS)
Lin, Ruei-Fong; O'C. Starr, David; Demott, Paul J.; Cotton, Richard; Sassen, Kenneth; Jensen, Eric; Kärcher, Bernd; Liu, Xiaohong
2002-08-01
The Cirrus Parcel Model Comparison Project, a project of the GCSS [Global Energy and Water Cycle Experiment (GEWEX) Cloud System Studies] Working Group on Cirrus Cloud Systems, involves the systematic comparison of current models of ice crystal nucleation and growth for specified, typical, cirrus cloud environments. In Phase 1 of the project reported here, simulated cirrus cloud microphysical properties from seven models are compared for `warm' (40°C) and `cold' (60°C) cirrus, each subject to updrafts of 0.04, 0.2, and 1 m s1. The models employ explicit microphysical schemes wherein the size distribution of each class of particles (aerosols and ice crystals) is resolved into bins or the evolution of each individual particle is traced. Simulations are made including both homogeneous and heterogeneous ice nucleation mechanisms (all-mode simulations). A single initial aerosol population of sulfuric acid particles is prescribed for all simulations. Heterogeneous nucleation is disabled for a second parallel set of simulations in order to isolate the treatment of the homogeneous freezing (of haze droplets) nucleation process. Analysis of these latter simulations is the primary focus of this paper.Qualitative agreement is found for the homogeneous-nucleation-only simulations; for example, the number density of nucleated ice crystals increases with the strength of the prescribed updraft. However, significant quantitative differences are found. Detailed analysis reveals that the homogeneous nucleation rate, haze particle solution concentration, and water vapor uptake rate by ice crystal growth (particularly as controlled by the deposition coefficient) are critical components that lead to differences in the predicted microphysics.Systematic differences exist between results based on a modified classical theory approach and models using an effective freezing temperature approach to the treatment of nucleation. Each method is constrained by critical freezing data from laboratory studies, but each includes assumptions that can only be justified by further laboratory research. Consequently, it is not yet clear if the two approaches can be made consistent. Large haze particles may deviate considerably from equilibrium size in moderate to strong updrafts (0.2-1 m s1) at 60°C. The equilibrium assumption is commonly invoked in cirrus parcel models. The resulting difference in particle-size-dependent solution concentration of haze particles may significantly affect the ice particle formation rate during the initial nucleation interval. The uptake rate for water vapor excess by ice crystals is another key component regulating the total number of nucleated ice crystals. This rate, the product of particle number concentration and ice crystal diffusional growth rate, which is particularly sensitive to the deposition coefficient when ice particles are small, modulates the peak particle formation rate achieved in an air parcel and the duration of the active nucleation time period. The consequent differences in cloud microphysical properties, and thus cloud optical properties, between state-of-the-art models of ice crystal initiation are significant.Intermodel differences in the case of all-mode simulations are correspondingly greater than in the case of homogeneous nucleation acting alone. Definitive laboratory and atmospheric benchmark data are needed to improve the treatment of heterogeneous nucleation processes.
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Nikfarjam, Ali; Shokoohi, Mostafa; Shahesmaeili, Armita; Haghdoost, Ali Akbar; Baneshi, Mohammad Reza; Haji-Maghsoudi, Saiedeh; Rastegari, Azam; Nasehi, Abbas Ali; Memaryan, Nadereh; Tarjoman, Termeh
2016-05-01
For a better understanding of the current situation of drug use in Iran, we utilized the network scale-up approach to estimate the prevalence of illicit drug use in the entire country. We implemented a self-administered, street-based questionnaire to 7535 passersby from the general public over 18 years of age by street based random walk quota sampling (based on gender, age and socio-economic status) from 31 provinces in Iran. The sample size in each province was approximately 400, ranging from 200 to 1000. In each province 75% of sample was recruited from the capital and the remaining 25% was recruited from one of the large cities of that province through stratified sampling. The questionnaire comprised questions on demographic information as well as questions to measure the total network size of participants as well as the network size in each of seven drug use groups including Opium, Shire (combination of Opium residue and pure opium), Crystal Methamphetamine, heroin/crack (which in Iranian context is a cocaine-free drug that mostly contains heroin, codeine, morphine and caffeine with or without other drugs), Hashish, Methamphetamine/LSD/ecstasy, and injecting drugs. The estimated size for each group was adjusted for transmission and barrier ratios. The most common type of illicit drug used was opium with the prevalence of 1500 per 100,000 population followed by shire (660), crystal methamphetamine (590), hashish (470), heroin/crack (350), methamphetamine, LSD and ecstasy (300) and injecting drugs (280). All types of substances were more common among men than women. The use of opium, shire and injecting drugs was more common in individuals over 30 whereas the use of stimulants and hashish was largest among individuals between 18 and 30 years of age. It seems that younger individuals and women are more desired to use new synthetic drugs such as crystal methamphetamine. Extending the preventive programs especially in youth as like as scaling up harm reduction services would be the main priorities in prevention and control of substance use in Iran. Because of poor service coverage and high stigma in women, more targeted programs in this affected population are needed. Copyright © 2016 Elsevier B.V. All rights reserved.
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NASA Astrophysics Data System (ADS)
Avery, Patrick; Zurek, Eva
2017-04-01
A new algorithm, RANDSPG, that can be used to generate trial crystal structures with specific space groups and compositions is described. The program has been designed for systems where the atoms are independent of one another, and it is therefore primarily suited towards inorganic systems. The structures that are generated adhere to user-defined constraints such as: the lattice shape and size, stoichiometry, set of space groups to be generated, and factors that influence the minimum interatomic separations. In addition, the user can optionally specify if the most general Wyckoff position is to be occupied or constrain select atoms to specific Wyckoff positions. Extensive testing indicates that the algorithm is efficient and reliable. The library is lightweight, portable, dependency-free and is published under a license recognized by the Open Source Initiative. A web interface for the algorithm is publicly accessible at http://xtalopt.openmolecules.net/randSpg/randSpg.html. RANDSPG has also been interfaced with the XTALOPT evolutionary algorithm for crystal structure prediction, and it is illustrated that the use of symmetric lattices in the first generation of randomly created individuals decreases the number of structures that need to be optimized to find the global energy minimum.
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Control of solvent evaporation in hen egg white lysozyme crystallization
NASA Technical Reports Server (NTRS)
Wilson, L. J.; Suddath, F. L.
1992-01-01
An investigation of the role of solvent evaporation in tetragonal lysozyme crystallization was preformed with a device that employs N2(g) to control the evaporation of solvent from a micro-volume crystallization hanging drop. The number of crystals was found to vary with the rate at which the final supersaturation level was achieved. It was found that the more rapid the approach to supersaturation the larger the number of crystals. Accordingly, the crystals reached a smaller terminal size. Elongation of the (110) face parallel to the four-fold axis was observed with the slower evaporation rates.
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Leulliot, Nicolas; Trésaugues, Lionel; Bremang, Michael; Sorel, Isabelle; Ulryck, Nathalie; Graille, Marc; Aboulfath, Ilham; Poupon, Anne; Liger, Dominique; Quevillon-Cheruel, Sophie; Janin, Joël; van Tilbeurgh, Herman
2005-06-01
Crystallization has long been regarded as one of the major bottlenecks in high-throughput structural determination by X-ray crystallography. Structural genomics projects have addressed this issue by using robots to set up automated crystal screens using nanodrop technology. This has moved the bottleneck from obtaining the first crystal hit to obtaining diffraction-quality crystals, as crystal optimization is a notoriously slow process that is difficult to automatize. This article describes the high-throughput optimization strategies used in the Yeast Structural Genomics project, with selected successful examples.
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Aerosol Route Synthesis and Applications of Doped Nanostructured Materials
NASA Astrophysics Data System (ADS)
Sahu, Manoranjan
Nanotechnology presents an attractive opportunity to address various challenges in air and water purification, energy, and other environment issues. Thus, the development of new nanoscale materials in low-cost scalable synthesis processes is important. Furthermore, the ability to independently manipulate the material properties as well as characterize the material at different steps along the synthesis route will aide in product optimization. In addition, to ensure safe and sustainable development of nanotechnology applications, potential impacts need to be evaluated. In this study, nanomaterial synthesis in a single-step gas phase reactor to continuously produce doped metal oxides was demonstrated. Copper-doped TiO2 nanomaterial properties (composition, size, and crystal phase) were independently controlled based on nanoparticle formation and growth mechanisms dictated by process control parameters. Copper dopant found to significantly affect TiO2 properties such as particle size, crystal phase, stability in the suspension, and absorption spectrum (shift from UV to visible light absorption). The in-situ charge distribution characterization of the synthesized nanomaterials was carried out by integrating a tandem differential mobility analyzer (TDMA) set up with the flame reactor synthesis system. Both singly- and doubly- charged nanoparticles were measured, with the charged fractions dependent on particle mobility and dopant concentration. A theoretical calculation was conducted to evaluate the relative importance of the two charging mechanisms, diffusion and thermo-ionization, in the flame. Nanoparticle exposure characterization was conducted during synthesis as a function of operating condition, product recovery and handling technique, and during maintenance of the reactors. Strategies were then indentified to minimize the exposure risk. The nanoparticle exposure potential varied depending on the operating conditions such as precursor feed rate, working conditions of the fume hood, ventilation system, and distance from the reactors. Nanoparticle exposure varied during product recovery and handling depending on the quantity of nanomaterial handled. Most nanomaterial applications require nanomaterials to be in solution. Thus, the role of nanomaterial physio-chemical properties (size, crystal phase, dopant types and concentrations) on dispersion properties was investigated based on hydrodynamic size and surface charge. Dopant type and concentration were found to significantly affect iso-electric point (IEP)-shifting the IEP to a high or lower pH value compared to pristine TiO2 based on the oxidation state of the dopant. The microbial inactivation effectiveness of as-synthesized nanomaterials was investigated under different light irradiation conditions. Microbial inactivation was found to strongly depend on the light irradiation condition as well as on material properties such chemical composition, crystal phase, and particle size. The potential interaction mechanisms of copper-doped TiO2 nanomaterial with microbes were also explored. The studies conducted as part of this dissertation addressed issues in nanomaterial synthesis, characterization and their potential environmental applications.
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Synthesis and Exfoliation of Discotic Zirconium Phosphates to Obtain Colloidal Liquid Crystals
Yu, Yi-Hsien; Wang, Xuezhen; Shinde, Abhijeet; Cheng, Zhengdong
2016-01-01
Due to their abundance in natural clay and potential applications in advanced materials, discotic nanoparticles are of interest to scientists and engineers. Growth of such anisotropic nanocrystals through a simple chemical method is a challenging task. In this study, we fabricate discotic nanodisks of zirconium phosphate [Zr(HPO4)2·H2O] as a model material using hydrothermal, reflux and microwave-assisted methods. Growth of crystals is controlled by duration time, temperature, and concentration of reacting species. The novelty of the adopted methods is that discotic crystals of size ranging from hundred nanometers to few micrometers can be obtained while keeping the polydispersity well within control. The layered discotic crystals are converted to monolayers by exfoliation with tetra-(n)-butyl ammonium hydroxide [(C4H9)4NOH, TBAOH]. Exfoliated disks show isotropic and nematic liquid crystal phases. Size and polydispersity of disk suspensions is highly important in deciding their phase behavior. PMID:27284765
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Othman, Rahimah; Vladisavljević, Goran T; Simone, Elena; Nagy, Zoltan K; Holdich, Richard G
2017-12-06
Microcrystals of piroxicam (PRX) monohydrate with a narrow size distribution were prepared from acetone/PRX solutions by antisolvent crystallization via metallic membranes with ordered pore arrays. Crystallization was achieved by controlled addition of the feed solution through the membrane pores into a well-stirred antisolvent. A complete transformation of an anhydrous form I into a monohydrate form of PRX was confirmed by Raman spectroscopy and differential scanning calorimetry. The size of the crystals was 7-34 μm and was controlled by the PRX concentration in the feed solution (15-25 g L -1 ), antisolvent/solvent volume ratio (5-30), and type of antisolvent (Milli-Q water or 0.1-0.5 wt % aqueous solutions of hydroxypropyl methyl cellulose (HPMC), poly(vinyl alcohol) or Pluronic P-123). The smallest crystals were obtained by injecting 25 g L -1 PRX solution through a stainless-steel membrane with a pore size of 10 μm into a 0.06 wt % HPMC solution stirred at 1500 rpm using an antisolvent/solvent ratio of 20. HPMC provided better steric stabilization of microcrystals against agglomeration than poly(vinyl alcohol) and Pluronic P-123, due to hydrogen bonding interactions with PRX and water. A continuous production of large PRX monohydrate microcrystals with a volume-weighted mean diameter above 75 μm was achieved in a continuous stirred membrane crystallizer. Rapid pouring of Milli-Q water into the feed solution resulted in a mixture of highly polydispersed prism-shaped and needle-shaped crystals.
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NASA Astrophysics Data System (ADS)
Wada, Y.; Kobayashi, T.; Matsumoto, M.; Onoe, K.
2017-10-01
To develop the technique for the control of the crystal composition and properties such as size distribution and morphology utilizing the contact reaction field around the minute droplets in atmospheric pressure plasma, fine spherical particles of hydroxyapatite ((Ca10(PO4)6(OH)2); HAp) were synthesized by a new plasma crystallization method. In this work, to elucidate the effects of the production region and crystal properties of hydroxyapatite for the liquid source composition, Ca2+ concentration and the Ca/P molar ratio in minute droplets were varied. The following results were obtained: (1) fine spherical HAp particles can be produced by the introduction of minute droplets with the initial Ca2+ concentration ((CCa)0) of 0.50 mol/l and the Ca/P molar ratio of 1.67. (2) When the (CCa)0 is set in the range higher than 1.00 mol/l at the constant Ca/P molar ratio of 1.67, fine spherical particles of β-TCP and HAp mixture are crystallized. (3) For the Ca/P molar ratio below 1.67, α-TCP and HAp co-precipitated. (4) The composition of the produced particles depends on both the reactant concentration and Ca/P molar ratio in the HAp source solution. (5) The dependence of the reactant concentration on the average size of the produced HAp particles is large compared with droplet size.
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High-energy x-ray diffraction from surfaces and nanoparticles
NASA Astrophysics Data System (ADS)
Hejral, U.; Müller, P.; Shipilin, M.; Gustafson, J.; Franz, D.; Shayduk, R.; Rütt, U.; Zhang, C.; Merte, L. R.; Lundgren, E.; Vonk, V.; Stierle, A.
2017-11-01
High-energy surface-sensitive x-ray diffraction (HESXRD) is a powerful high-energy photon technique (E > 70 keV) that has in recent years proven to allow a fast data acquisition for the 3D structure determination of surfaces and nanoparticles under in situ and operando conditions. The use of a large-area detector facilitates the direct collection of nearly distortion-free diffraction patterns over a wide q range, including crystal truncation rods perpendicular to the surface and large-area reciprocal space maps from epitaxial nanoparticles, which is not possible in the conventional low-photon energy approach (E =10 -20 keV ). Here, we present a comprehensive mathematical approach, explaining the working principle of HESXRD for both single-crystal surfaces and epitaxial nanostructures on single-crystal supports. The angular calculations used in conventional crystal truncation rod measurements at low-photon energies are adopted for the high-photon-energy regime, illustrating why and to which extent large reciprocal-space areas can be probed in stationary geometry with fixed sample rotation. We discuss how imperfections such as mosaicity and finite domain size aid in sampling a substantial part of reciprocal space without the need of rotating the sample. An exact account is given of the area probed in reciprocal space using such a stationary mode, which is essential for in situ or operando time-resolved experiments on surfaces and nanostructures.
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LOR-interleaving image reconstruction for PET imaging with fractional-crystal collimation
NASA Astrophysics Data System (ADS)
Li, Yusheng; Matej, Samuel; Karp, Joel S.; Metzler, Scott D.
2015-01-01
Positron emission tomography (PET) has become an important modality in medical and molecular imaging. However, in most PET applications, the resolution is still mainly limited by the physical crystal sizes or the detector’s intrinsic spatial resolution. To achieve images with better spatial resolution in a central region of interest (ROI), we have previously proposed using collimation in PET scanners. The collimator is designed to partially mask detector crystals to detect lines of response (LORs) within fractional crystals. A sequence of collimator-encoded LORs is measured with different collimation configurations. This novel collimated scanner geometry makes the reconstruction problem challenging, as both detector and collimator effects need to be modeled to reconstruct high-resolution images from collimated LORs. In this paper, we present a LOR-interleaving (LORI) algorithm, which incorporates these effects and has the advantage of reusing existing reconstruction software, to reconstruct high-resolution images for PET with fractional-crystal collimation. We also develop a 3D ray-tracing model incorporating both the collimator and crystal penetration for simulations and reconstructions of the collimated PET. By registering the collimator-encoded LORs with the collimator configurations, high-resolution LORs are restored based on the modeled transfer matrices using the non-negative least-squares method and EM algorithm. The resolution-enhanced images are then reconstructed from the high-resolution LORs using the MLEM or OSEM algorithm. For validation, we applied the LORI method to a small-animal PET scanner, A-PET, with a specially designed collimator. We demonstrate through simulated reconstructions with a hot-rod phantom and MOBY phantom that the LORI reconstructions can substantially improve spatial resolution and quantification compared to the uncollimated reconstructions. The LORI algorithm is crucial to improve overall image quality of collimated PET, which can have significant implications in preclinical and clinical ROI imaging applications.
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Solvothermal synthesis and surface chemistry to control the size and morphology of nanoquartz
Sochalski-Kolbus, Lindsay M.; Wang, Hsiu-Wen; Rondinone, Adam Justin; ...
2015-09-29
In this paper, we report a solvothermal synthesis method that allows the crystallization of quartz to occur at a relatively low temperature of 300°C in the form of isolated nanosized euhedral crystals. Transmission electron microscopy (TEM) and small area electron diffraction (SAED) were used to confirm the phases present and their particle sizes, morphologies, and crystallinity of the products. In conclusion, the results show that it is possible to control the size and morphology of the nanoquartz from rough nanospheres to nanorods using fluoride, which templates the nanocrystals and moderates growth.
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NASA Astrophysics Data System (ADS)
Bacon, Neil Julian
2001-12-01
I describe experiments to investigate the properties of microscopic ice particles. The goal of the work was to measure parameters that are important in cloud processes and radiative transfer, using a novel technique that avoids the use of substrates. The experiments were conducted in two separate electrodynamic balance chambers. Single, charged ice particles were formed from frost particles or from droplets frozen either homogeneously or heteroge neously with a bionucleant. The particles were trapped at temperatures between -38°C and -4°C and grown or sublimated according to the temperature gradient in the cham ber. I describe observations of breakup of sublimating frost particles, measurements of light scattering by hexagonal crystals, and observations of the morphology of ice particles grown from frozen water droplets and frost particles. The breaking strength of frost particles was an order of magnitude less than that of bulk ice. Light scattering features not previously observed were analyzed and related to crystal dimension. Initial results from a computer model failed to reproduce these features. The widths of scattering peaks suggest that surface roughness may play a role in determining the angular distribution of scattered light. Ice particle mass evolution was found to be consistent with diffusion- limited growth. Crystals grown slowly from frozen droplets adopted isometric habits, while faster growth resulted in thin side-planes, although there was not an exact correspondence between growth conditions and particle morphology. From the morphological transition, I infer lower limits for the critical supersaturation for layer nucleation on the prism face of 2.4% at -15°C, 4.4% at -20°C, and 3.1% at -25°C. Analytic expressions for the size dependence of facet stability are developed, indicating a strong dependence of stability on both crystal size and surface kinetics, and compared with data. I discuss the role of complex particle morphologies in radiative transfer and highlight the need for further measurements.
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Nanomechanics of cellulose crystals and cellulose-based polymer composites
NASA Astrophysics Data System (ADS)
Pakzad, Anahita
Cellulose-polymer composites have potential applications in aerospace and transportation areas where lightweight materials with high mechanical properties are needed. In addition, these economical and biodegradable composites have been shown to be useful as polymer electrolytes, packaging structures, optoelectronic devices, and medical implants such as wound dressing and bone scaffolds. In spite of the above mentioned advantages and potential applications, due to the difficulties associated with synthesis and processing techniques, application of cellulose crystals (micro and nano sized) for preparation of new composite systems is limited. Cellulose is hydrophilic and polar as opposed to most of common thermoplastics, which are non-polar. This results in complications in addition of cellulose crystals to polymer matrices, and as a result in achieving sufficient dispersion levels, which directly affects the mechanical properties of the composites. As in other composite materials, the properties of cellulose-polymer composites depend on the volume fraction and the properties of individual phases (the reinforcement and the polymer matrix), the dispersion quality of the reinforcement through the matrix and the interaction between CNCs themselves and CNC and the matrix (interphase). In order to develop economical cellulose-polymer composites with superior qualities, the properties of individual cellulose crystals, as well as the effect of dispersion of reinforcements and the interphase on the properties of the final composites should be understood. In this research, the mechanical properties of CNC polymer composites were characterized at the macro and nano scales. A direct correlation was made between: - Dispersion quality and macro-mechanical properties - Nanomechanical properties at the surface and tensile properties - CNC diameter and interphase thickness. Lastly, individual CNCs from different sources were characterized and for the first time size-scale effect on their nanomechanical properties were reported. Then the effect of CNC surface modification on the mechanical properties was studied and correlated to the crystalline structure of these materials.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Chen, K.; Meng, W. J.; Mei, F.
2011-02-01
A single crystal Al specimen was molded at room temperature with long, rectangular, strip diamond punches. Quantitative molding response curves were obtained at a series of punch widths, ranging from 5 {micro}m to 550 nm. A significant size effect was observed, manifesting itself in terms of significantly increasing characteristic molding pressure as the punch width decreases to 1.5 {micro}m and below. A detailed comparison of the present strip punch molding results was made with Berkovich pyramidal indentation on the same single crystal Al specimen. The comparison reveals distinctly different dependence of the characteristic pressure on corresponding characteristic length. The presentmore » results show the feasibility of micro-/nano-scale compression molding as a micro-/nano-fabrication technique, and offer an experimental test case for size-dependent plasticity theories.« less
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NASA Astrophysics Data System (ADS)
Tahrin, Rabiatul Addawiyah Azwa; Azma, Nur Syafiqa; Kassim, Syara; Harun, Noor Aniza
2017-09-01
3-dimensional (3D) photonic crystals have been extended use in wide research and application from material to sensor. Nanoparticles of poly (methyl methacrylate) (PMMA) latex beads have been successfully prepared by green-chemistry approach where no surfactant, linking agent and solvent were involved. Regardless of the effect of initiator in polymerization reaction, this study presents the effect of temperature, monomer concentration, stirring speed and reaction period in order to tune the particle size. Its morphology of uniformity sized-tuned was confirming by using particle size analyzer (PSA) and scanning electron microscopy (SEM). The fabrication of 3D photonic crystals film by using self-assembly method to pattern the desired PMMA layers which is the most feasible, low cost method are also presented. The detailed properties of PMMA nanoparticles from this experimental study will be discussed and its potential used in photonic application will be explained.
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Morikawa, Satoshi; Inamoto, Takuya; Takashiri, Masayuki
2018-02-16
The effect of crystal grain size on the thermoelectric properties of nanocrystalline antimony telluride (Sb 2 Te 3 ) thin films was investigated by experiments and first-principles studies using a developed relaxation time approximation. The Sb 2 Te 3 thin films were deposited on glass substrates using radio-frequency magnetron sputtering. To change the crystal grain size of the Sb 2 Te 3 thin films, thermal annealing was performed at different temperatures. The crystal grain size, lattice parameter, and crystal orientation of the thin films were estimated using XRD patterns. The carrier concentration and in-plane thermoelectric properties of the thin films were measured at room temperature. A theoretical analysis was performed using a first-principles study based on density functional theory. The electronic band structures of Sb 2 Te 3 were calculated using different lattice parameters, and the thermoelectric properties were predicted based on the semi-classical Boltzmann transport equation in the relaxation time approximation. In particular, we introduced the effect of carrier scattering at the grain boundaries into the relaxation time approximation by estimating the group velocities from the electronic band structures. Finally, the experimentally measured thermoelectric properties were compared with those obtained by calculation. As a result, the calculated thermoelectric properties were found to be in good agreement with the experimental results. Therefore, we can conclude that introducing the effect of carrier scattering at the grain boundaries into the relaxation time approximation contributes to enhance the accuracy of a first-principles calculation relating to nanocrystalline materials.
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NASA Astrophysics Data System (ADS)
Morikawa, Satoshi; Inamoto, Takuya; Takashiri, Masayuki
2018-02-01
The effect of crystal grain size on the thermoelectric properties of nanocrystalline antimony telluride (Sb2Te3) thin films was investigated by experiments and first-principles studies using a developed relaxation time approximation. The Sb2Te3 thin films were deposited on glass substrates using radio-frequency magnetron sputtering. To change the crystal grain size of the Sb2Te3 thin films, thermal annealing was performed at different temperatures. The crystal grain size, lattice parameter, and crystal orientation of the thin films were estimated using XRD patterns. The carrier concentration and in-plane thermoelectric properties of the thin films were measured at room temperature. A theoretical analysis was performed using a first-principles study based on density functional theory. The electronic band structures of Sb2Te3 were calculated using different lattice parameters, and the thermoelectric properties were predicted based on the semi-classical Boltzmann transport equation in the relaxation time approximation. In particular, we introduced the effect of carrier scattering at the grain boundaries into the relaxation time approximation by estimating the group velocities from the electronic band structures. Finally, the experimentally measured thermoelectric properties were compared with those obtained by calculation. As a result, the calculated thermoelectric properties were found to be in good agreement with the experimental results. Therefore, we can conclude that introducing the effect of carrier scattering at the grain boundaries into the relaxation time approximation contributes to enhance the accuracy of a first-principles calculation relating to nanocrystalline materials.
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Size dependence of nanoscale wear of silicon carbide
Chaiyapat Tangpatjaroen; David Grierson; Steve Shannon; Joseph E. Jakes; Izabela Szlufarska
2017-01-01
Nanoscale, single-asperity wear of single-crystal silicon carbide (sc- SiC) and nanocrystalline silicon carbide (nc-SiC) is investigated using single-crystal diamond nanoindenter tips and nanocrystalline diamond atomic force microscopy (AFM) tips under dry conditions, and the wear behavior is compared to that of single-crystal silicon with both thin and thick native...
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Crystal growth and annealing method and apparatus
Gianoulakis, Steven E.; Sparrow, Robert
2001-01-01
A method and apparatus for producing crystals that minimizes birefringence even at large crystal sizes, and is suitable for production of CaF.sub.2 crystals. The method of the present invention comprises annealing a crystal by maintaining a minimal temperature gradient in the crystal while slowly reducing the bulk temperature of the crystal. An apparatus according to the present invention includes a thermal control system added to a crystal growth and annealing apparatus, wherein the thermal control system allows a temperature gradient during crystal growth but minimizes the temperature gradient during crystal annealing. An embodiment of the present invention comprises a secondary heater incorporated into a conventional crystal growth and annealing apparatus. The secondary heater supplies heat to minimize the temperature gradients in the crystal during the annealing process. The secondary heater can mount near the bottom of the crucible to effectively maintain appropriate temperature gradients.
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Comparative analysis of anti-polyglutamine Fab crystals grown on Earth and in microgravity.
Owens, Gwen E; New, Danielle M; Olvera, Alejandra I; Manzella, Julia Ashlyn; Macon, Brittney L; Dunn, Joshua C; Cooper, David A; Rouleau, Robyn L; Connor, Daniel S; Bjorkman, Pamela J
2016-10-01
Huntington's disease is one of nine neurodegenerative diseases caused by a polyglutamine (polyQ)-repeat expansion. An anti-polyQ antigen-binding fragment, MW1 Fab, was crystallized both on Earth and on the International Space Station, a microgravity environment where convection is limited. Once the crystals returned to Earth, the number, size and morphology of all crystals were recorded, and X-ray data were collected from representative crystals. The results generally agreed with previous microgravity crystallization studies. On average, microgravity-grown crystals were 20% larger than control crystals grown on Earth, and microgravity-grown crystals had a slightly improved mosaicity (decreased by 0.03°) and diffraction resolution (decreased by 0.2 Å) compared with control crystals grown on Earth. However, the highest resolution and lowest mosaicity crystals were formed on Earth, and the highest-quality crystal overall was formed on Earth after return from microgravity.
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Comparative analysis of anti-polyglutamine Fab crystals grown on Earth and in microgravity
Owens, Gwen E.; New, Danielle M.; Olvera, Alejandra I.; Manzella, Julia Ashlyn; Macon, Brittney L.; Dunn, Joshua C.; Cooper, David A.; Rouleau, Robyn L.; Connor, Daniel S.; Bjorkman, Pamela J.
2016-01-01
Huntington’s disease is one of nine neurodegenerative diseases caused by a polyglutamine (polyQ)-repeat expansion. An anti-polyQ antigen-binding fragment, MW1 Fab, was crystallized both on Earth and on the International Space Station, a microgravity environment where convection is limited. Once the crystals returned to Earth, the number, size and morphology of all crystals were recorded, and X-ray data were collected from representative crystals. The results generally agreed with previous microgravity crystallization studies. On average, microgravity-grown crystals were 20% larger than control crystals grown on Earth, and microgravity-grown crystals had a slightly improved mosaicity (decreased by 0.03°) and diffraction resolution (decreased by 0.2 Å) compared with control crystals grown on Earth. However, the highest resolution and lowest mosaicity crystals were formed on Earth, and the highest-quality crystal overall was formed on Earth after return from microgravity. PMID:27710941
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Crystalline heterogeneities and instabilities in thermally convecting magma chamber
NASA Astrophysics Data System (ADS)
Culha, C.; Suckale, J.; Qin, Z.
2016-12-01
A volcanic vent can supply different densities of crystals over an eruption time period. This has been seen in Hawai'i's Kilauea Iki 1959 eruption; however it is not common for all Kilauea or basaltic eruptions. We ask the question: Under what conditions can homogenous magma chamber cultivate crystalline heterogeneities? In some laboratory experiments and numerical simulations, a horizontal variation is observed. The region where crystals reside is identified as a retention zone: convection velocity balances settling velocity. Simulations and experiments that observe retention zones assume crystals do not alter the convection in the fluid. However, a comparison of experiments and simulations of convecting magma with crystals suggest that large crystal volume densities and crystal sizes alter fluid flow considerably. We introduce a computational method that fully resolves the crystalline phase. To simulate basaltic magma chambers in thermal convection, we built a numerical solver of the Navier-Stoke's equation, continuity equation, and energy equation. The modeled magma is assumed to be a viscous, incompressible fluid with a liquid and solid phase. Crystals are spherical, rigid bodies. We create Rayleigh-Taylor instability through a cool top layer and hot bottom layer and update magma density while keeping crystal temperature and size constant. Our method provides a detailed picture of magma chambers, which we compare to other models and experiments to identify when and how crystals alter magma chamber convection. Alterations include stratification, differential settling and instabilities. These characteristics are dependent on viscosity, convection vigor, crystal volume density and crystal characteristics. We reveal that a volumetric crystal density variation may occur over an eruption time period, if right conditions are met to form stratifications and instabilities in magma chambers. These conditions are realistic for Kilauea Iki's 1959 eruption.
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Scale effects in crystal plasticity
NASA Astrophysics Data System (ADS)
Padubidri Janardhanachar, Guruprasad
The goal of this research work is to further the understanding of crystal plasticity, particularly at reduced structural and material length scales. Fundamental understanding of plasticity is central to various challenges facing design and manufacturing of materials for structural and electronic device applications. The development of microstructurally tailored advanced metallic materials with enhanced mechanical properties that can withstand extremes in stress, strain, and temperature, will aid in increasing the efficiency of power generating systems by allowing them to work at higher temperatures and pressures. High specific strength materials can lead to low fuel consumption in transport vehicles. Experiments have shown that enhanced mechanical properties can be obtained in materials by constraining their size, microstructure (e.g. grain size), or both for various applications. For the successful design of these materials, it is necessary to have a thorough understanding of the influence of different length scales and evolving microstructure on the overall behavior. In this study, distinction is made between the effect of structural and material length scale on the mechanical behavior of materials. A length scale associated with an underlying physical mechanism influencing the mechanical behavior can overlap with either structural length scales or material length scales. If it overlaps with structural length scales, then the material is said to be dimensionally constrained. On the other hand, if it overlaps with material length scales, for example grain size, then the material is said to be microstructurally constrained. The objectives of this research work are: (1) to investigate scale and size effects due to dimensional constraints; (2) to investigate size effects due to microstructural constraints; and (3) to develop a size dependent hardening model through coarse graining of dislocation dynamics. A discrete dislocation dynamics (DDD) framework where the scale of analysis is intermediate between a fully discretized (e.g. atomistic) and fully continuum is used for this study. This mesoscale tool allows to address all the stated objectives of this study within a single framework. Within this framework, the effect of structural and the material length scales are naturally accounted for in the simulations and need not be specified in an ad hoc manner, as in some continuum models. It holds the promise of connecting the evolution of the defect microstructure to the effective response of the crystal. Further, it provides useful information to develop physically motivated continuum models to model size effects in materials. The contributions of this study are: (a) provides a new interpretation of mechanical size effect due to only dimensional constraint using DDD; (b) a development of an experimentally validated DDD simulation methodology to model Cu micropillars; (c) a coarse graining technique using DDD to develop a phenomenological model to capture size effect on strain hardening; and (d) a development of a DDD framework for polycrystals to investigate grain size effect on yield strength and strain hardening.
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NASA Technical Reports Server (NTRS)
1986-01-01
The report gives the results of feasibility studies and a cost analysis done on GaAs solar battery cells for space stations. The studies and their results are as follows: (1) Cell size - The 2 x 4 cm cell size was found superior to the 4 x 4 cm cell; (2) Manufacturing technology - Overall, LPE crystal growth was found more suitable than MO-CVD. Current technology for post-growth processes and applying large-area cover glass can be used with few or no modifications; (3) Cell assemblies - Tests for mechanical and thermal stresses encountered from assembly through operation are recommended; (4) Procuring materials - Steps should be taken to avoid sharp price increases due to a speculative gallium market. There are no problems with arsenic materials; (5) Production facilities - The capital investment needed remains to be determined, but a working area of 4000 m2 will be required; (6) Cell costs to be determined; (7) Cell development-supply plan - Two-year lead time will be needed to develop the necessary technology and prepare for production.
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Stephens, Michael; Weber, Erica; Barrett, Steven F
2006-01-01
An assistive technology (AT) device was originally created for a young child who has difficulty communicating. The child is not able to talk and is not old enough to read yet. This rules out conventional communication devices that this child could use to communicate. A device was requested by the child's educator that would talk for the child. Originally it needed to be wristwatch size and able to visually cue the child so that the child would know what was going to be said. The project's first prototype was built by a senior design student. Although the basic features of the prototype functioned properly, it was not practical for day to day use. Originally a rebuild was requested by the educator but after further investigation it was decided that a new design was needed so that it could better cue the child. A new device was built using a high resolution graphic liquid crystal display (LCD), a voice recording chip and a microcontroller. The wristwatch size requirement was changed to meet available technology and the device was packaged to be used on a lanyard.
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On melt solutions for the growth of CaTiO3 crystals
NASA Astrophysics Data System (ADS)
Klimm, Detlef; Schmidt, Max; Wolff, Nora; Guguschev, Christo; Ganschow, Steffen
2018-03-01
When calcium titanate crystals are grown from stoichiometric melts, they crystallize in the cubic perovskite structure. Upon cooling to room temperature they undergo subsequent phase transitions to tetragonal and orthorhombic modifications. These phase transitions are disruptive and result in severely damaged crystals. This paper presents differential thermal analysis data for several prospective solvents, with the aim to identify a system offering the possibility to perform crystal growth of undistorted CaTiO3 crystals by crystallizing them significantly below the melting point directly in the low temperature modification. From mixtures CaF2:TiO2:CaTiO3 = 3:1:1 (molar ratio) the growth of undistorted, at least millimeter-sized CaTiO3 crystals is possible.
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Linear, non-linear and thermal properties of single crystal of LHMHCl
NASA Astrophysics Data System (ADS)
Kulshrestha, Shobha; Shrivastava, A. K.
2018-05-01
The single crystal of amino acid of L-histidine monohydrochloride was grown by slow evaporation technique at room temperature. High optical quality and appropriate size of crystals were grown under optimized growth conditions. The grown crystals were transparent. Crystals are characterized with different characterizations such as Solubility test, UV-Visible, optical band gap (Eg). With the help of optical data to be calculate absorption coefficient (α), extinction coefficient (k), refractive index (n), dielectric constant (ɛ). These optical constants are shows favorable conditions for photonics devices. Second harmonic generation (NLO) test show the green light emission which is confirm that crystal have properties for laser application. Thermal stability of grown crystal is confirmed by TG/DTA.
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Wang, Lei; Bock, David C.; Li, Jing; ...
2018-02-20
Here, a series of one-dimensional CuFe 2O 4 nano/sub-micron wires possessing different diameters, crystal phases, and crystal sizes have been successfully generated using a facile template-assisted co precipitation reaction at room temperature, followed by a short post-annealing process. The diameter and the crystal structure of the resulting CuFe 2O4 (CFO) wires were judiciously tuned by varying the pore size of the template and the post-annealing temperature, respectively. Carbon nanotubes (CNTs) were incorporated to generate CFO-CNT binder-free anodes, and multiple characterization techniques were employed with the goal of delineating the relationships between electrochemical behavior and the properties of both the CFOmore » wires (crystal phase, wire diameter, crystal size) and the electrode architecture (binder-free vs. conventionally prepared approaches). The study reveals several notable findings. First, the crystal phase (cubic or tetragonal) did not influence the electrochemical behavior in this CFO system. Second, regarding crystallite size and wire diameter, CFO wires with larger crystallite sizes exhibit improved cycling stability, while wires possessing smaller diameters exhibiting higher capacities. Finally, the electrochemical behavior is strongly influenced by the electrode architecture, with CFO-CNT binder-free electrodes demonstrating significantly higher capacities and cycling stability compared to conventionally prepared coatings. The mechanism(s) associated with the high capacities under low current density but limited electrochemical reversibility of CFO electrodes under high current density were probed via x-ray absorption spectroscopy (XAS) mapping with sub-micron spatial resolution for the first time. Results suggest that the capacity of the binder-free electrodes under high rate is limited by the irreversible formation of Cu 0, as well as limited reduction of Fe 3+, to Fe 2+ not Fe 0. The results (1) shed fundamental insight into the reversibility of CuFe 2O 4 materials cycled at high current density and (2) demonstrate that a synergistic effort to control both active material morphology and electrode architecture is an effective strategy for optimizing electrochemical behavior.« less
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Wang, Lei; Bock, David C.; Li, Jing
Here, a series of one-dimensional CuFe 2O 4 nano/sub-micron wires possessing different diameters, crystal phases, and crystal sizes have been successfully generated using a facile template-assisted co precipitation reaction at room temperature, followed by a short post-annealing process. The diameter and the crystal structure of the resulting CuFe 2O4 (CFO) wires were judiciously tuned by varying the pore size of the template and the post-annealing temperature, respectively. Carbon nanotubes (CNTs) were incorporated to generate CFO-CNT binder-free anodes, and multiple characterization techniques were employed with the goal of delineating the relationships between electrochemical behavior and the properties of both the CFOmore » wires (crystal phase, wire diameter, crystal size) and the electrode architecture (binder-free vs. conventionally prepared approaches). The study reveals several notable findings. First, the crystal phase (cubic or tetragonal) did not influence the electrochemical behavior in this CFO system. Second, regarding crystallite size and wire diameter, CFO wires with larger crystallite sizes exhibit improved cycling stability, while wires possessing smaller diameters exhibiting higher capacities. Finally, the electrochemical behavior is strongly influenced by the electrode architecture, with CFO-CNT binder-free electrodes demonstrating significantly higher capacities and cycling stability compared to conventionally prepared coatings. The mechanism(s) associated with the high capacities under low current density but limited electrochemical reversibility of CFO electrodes under high current density were probed via x-ray absorption spectroscopy (XAS) mapping with sub-micron spatial resolution for the first time. Results suggest that the capacity of the binder-free electrodes under high rate is limited by the irreversible formation of Cu 0, as well as limited reduction of Fe 3+, to Fe 2+ not Fe 0. The results (1) shed fundamental insight into the reversibility of CuFe 2O 4 materials cycled at high current density and (2) demonstrate that a synergistic effort to control both active material morphology and electrode architecture is an effective strategy for optimizing electrochemical behavior.« less
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Synergistic Measurement of Ice Cloud Microphysics using C- and Ka-Band Radars
NASA Astrophysics Data System (ADS)
Ewald, F.; Gross, S.; Hagen, M.; Li, Q.; Zinner, T.
2017-12-01
Ice clouds play an essential role in the climate system since they have a large effect on the Earth's radiation budget. Uncertainties associated with their spatial and temporal distribution as well as their optical and microphysical properties still account for large uncertainties in climate change predictions. Substantial improvement of our understanding of ice clouds was achieved with the advent of cloud radars into the field of ice cloud remote sensing. Here, highly variable ice crystal size distributions are one of the key issues remaining to be resolved. With radar reflectivity scaling with the sixth moment of the particle size, the assumed ice crystal size distribution has a large impact on the results of microphysical retrievals. Different ice crystal sizes distributions can, however, be distinguished, when cloud radars of different wavelength are used simultaneously.For this study, synchronous RHI scans were performed for a common measurement range of about 30 km between two radar instruments using different wavelengths: the dual-polarization C-band radar POLDIRAD operated at DLR and the Mira-36 Ka-band cloud radar operated at the University of Munich. For a measurement period over several months, the overlapping region for ice clouds turned out to be quite large. This gives evidence on the presence of moderate-sized ice crystals for which the backscatter is sufficient high to be visible in the C-band as well. In the range between -10 to +10 dBz, reflectivity measurements from both radars agreed quite well indicating the absence of large ice crystals. For reflectivities above +10 dBz, we observed differences with smaller values at the Ka-band due to Mie scattering effects at larger ice crystals.In this presentation, we will show how this differential reflectivity can be used to gain insight into ice cloud microphysics on the basis of electromagnetic scattering calculations. We will further explore ice cloud microphysics using the full polarization agility of the C-band radar and compare the results to simultaneous linear depolarization measurements with the Ka-band radar. In summary, we will explore if the scientific understanding of ice cloud microphysics can be advanced by the combination of C- and Ka-band radars.
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Reentrant equilibrium disordering in nanoparticle–polymer mixtures
Meng, Dong; Kumar, Sanat K.; Grest, Gary S.; ...
2017-01-31
A large body of experimental work has established that athermal colloid/polymer mixtures undergo a sequence of transitions from a disordered fluid state to a colloidal crystal to a second disordered phase with increasing polymer concentration. These transitions are driven by polymer-mediated interparticle attraction, which is a function of both the polymer density and size. It has been posited that the disordered state at high polymer density is a consequence of strong interparticle attractions that kinetically inhibit the formation of the colloidal crystal, i.e., the formation of a non-equilibrium gel phase interferes with crystallization. Here we use molecular dynamics simulations andmore » density functional theory on polymers and nanoparticles (NPs) of comparable size and show that the crystal-disordered phase coexistence at high polymer density for sufficiently long chains corresponds to an equilibrium thermodynamic phase transition. While the crystal is, indeed, stabilized at intermediate polymer density by polymer-induced intercolloid attractions, it is destabilized at higher densities because long chains lose significant configurational entropy when they are forced to occupy all of the crystal voids. Finally, our results are in quantitative agreement with existing experimental data and show that, at least in the nanoparticle limit of sufficiently small colloidal particles, the crystal phase only has a modest range of thermodynamic stability.« less
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Crystallization of glass-forming liquids: Specific surface energy
DOE Office of Scientific and Technical Information (OSTI.GOV)
Schmelzer, Jürn W. P., E-mail: juern-w.schmelzer@uni-rostock.de; Abyzov, Alexander S.
2016-08-14
A generalization of the Stefan-Skapski-Turnbull relation for the melt-crystal specific interfacial energy is developed in terms of the generalized Gibbs approach extending its standard formulation to thermodynamic non-equilibrium states. With respect to crystal nucleation, this relation is required in order to determine the parameters of the critical crystal clusters being a prerequisite for the computation of the work of critical cluster formation. As one of its consequences, a relation for the dependence of the specific surface energy of critical clusters on temperature and pressure is derived applicable for small and moderate deviations from liquid-crystal macroscopic equilibrium states. Employing the Stefan-Skapski-Turnbullmore » relation, general expressions for the size and the work of formation of critical crystal clusters are formulated. The resulting expressions are much more complex as compared to the respective relations obtained via the classical Gibbs theory. Latter relations are retained as limiting cases of these more general expressions for moderate undercoolings. By this reason, the formulated, here, general relations for the specification of the critical cluster size and the work of critical cluster formation give a key for an appropriate interpretation of a variety of crystallization phenomena occurring at large undercoolings which cannot be understood in terms of the Gibbs’ classical treatment.« less
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NASA Astrophysics Data System (ADS)
Tanaka, Kyoko K.; Diemand, Jürg; Tanaka, Hidekazu; Angélil, Raymond
2017-08-01
In this paper, we present multistep homogeneous nucleations in vapor-to-solid transitions as revealed by molecular dynamics simulations on Lennard-Jones molecules, where liquidlike clusters are created and crystallized. During a long, direct N V E (constant volume, energy, and number of molecules) involving the integration of (1.9 -15 )× 106 molecules in up to 200 million steps (=4.3 μ s ), crystallization in many large, supercooled nanoclusters is observed once the liquid clusters grow to a certain size (˜800 molecules for the case of T ≃0.5 ɛ /k ). In the simulations, we discovered an interesting process associated with crystallization: the solid clusters lost 2-5 % of their mass during crystallization at low temperatures below their melting temperatures. Although the crystallized clusters were heated by latent heat, they were stabilized by cooling due to evaporation. The clusters crystallized quickly and completely except at surface layers. However, they did not have stable crystal structures, rather they had metastable structures such as icosahedral, decahedral, face-centered-cubic-rich (fcc-rich), and hexagonal-close-packed-rich (hcp-rich). Several kinds of cluster structures coexisted in the same size range of ˜1000 -5000 molecules. Our results imply that multistep nucleation is a common first stage of condensation from vapor to solid.
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NASA Technical Reports Server (NTRS)
2003-01-01
In order to rapidly and efficiently grow crystals, tools were needed to automatically identify and analyze the growing process of protein crystals. To meet this need, Diversified Scientific, Inc. (DSI), with the support of a Small Business Innovation Research (SBIR) contract from NASA s Marshall Space Flight Center, developed CrystalScore(trademark), the first automated image acquisition, analysis, and archiving system designed specifically for the macromolecular crystal growing community. It offers automated hardware control, image and data archiving, image processing, a searchable database, and surface plotting of experimental data. CrystalScore is currently being used by numerous pharmaceutical companies and academic and nonprofit research centers. DSI, located in Birmingham, Alabama, was awarded the patent Method for acquiring, storing, and analyzing crystal images on March 4, 2003. Another DSI product made possible by Marshall SBIR funding is VaporPro(trademark), a unique, comprehensive system that allows for the automated control of vapor diffusion for crystallization experiments.
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NASA Astrophysics Data System (ADS)
Zhou, Wei; Shijimaya, Chiko; Takahashi, Mari; Miyata, Masanobu; Mott, Derrick; Koyano, Mikio; Ohta, Michihiro; Akatsuka, Takeo; Ono, Hironobu; Maenosono, Shinya
2017-12-01
Uniform Cu2Sn1-xZnxS3 (x = 0-0.2) nanoparticles (NPs) with a characteristic size of about 40 nm were chemically synthesized. The primary crystal phase of the NPs was wurtzite (WZ) with a mean crystalline size of about 20 nm. The NPs were sintered to form nanostructured pellets with different compositions preserving the composition and grain size of the original NPs by the pulse electric current sintering technique. The pellets had a zinc blende (ZB) structure with a residual WZ phase, and the mean crystalline size was found to remain virtually unchanged for all pellets. Among all samples, the pellets of Cu2Sn0.95Zn0.05S3 and Cu2Sn0.85Zn0.15S3 exhibited the highest ZT value (0.37 at 670 K) which is 10 times higher than that of a non-nanostructured Cu2SnS3 bulk crystal thanks to effective phonon scattering by nanograins, the phase-pure ZB crystal structure, and the increase in hole carrier density by Zn doping.
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NASA Astrophysics Data System (ADS)
Arienti, Marco; Geier, Manfred; Yang, Xiaoyuan; Orcutt, John; Zenker, Jake; Brooks, Sarah D.
2018-05-01
We investigate the optical properties of ice crystals nucleated on atmospheric black carbon (BC). The parameters examined in this study are the shape of the ice crystal, the volume fraction of the BC inclusion, and its location inside the crystal. We report on new spectrometer measurements of forward scattering and backward polarization from ice crystals nucleated on BC particles and grown under laboratory-controlled conditions. Data from the Cloud and Aerosol Spectrometer with Polarization (CASPOL) are used for direct comparison with single-particle calculations of the scattering phase matrix. Geometrical optics and discrete dipole approximation techniques are jointly used to provide the best compromise of flexibility and accuracy over a broad range of size parameters. Together with the interpretation of the trends revealed by the CASPOL measurements, the numerical results confirm previous reports on absorption cross-section magnification in the visible light range. Even taking into account effects of crystal shape and inclusion position, the ratio between absorption cross-section of the compound particle and the absorption cross-section of the BC inclusion alone (the absorption magnification) has a lower bound of 1.5; this value increases to 1.7 if the inclusion is centered with respect to the crystal. The simple model of BC-ice particle presented here also offers new insights on the effect of the relative position of the BC inclusion with respect to the crystal's outer surfaces, the shape of the crystal, and its size.
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Granular crystals: Nonlinear dynamics meets materials engineering
Porter, Mason A.; Kevrekidis, Panayotis G.; Daraio, Chiara
2015-11-01
In this article, the freedom to choose the size, stiffness, and spatial distribution of macroscopic particles in a lattice makes granular crystals easily tailored building blocks for shock-absorbing materials, sound-focusing devices, acoustic switches, and other exotica.
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Temperature lowering program for homogeneous doping in flux growth
NASA Astrophysics Data System (ADS)
Qiwei, Wang; Shouquan, Jia
1989-10-01
Based on the mass conservation law and the Burton-Prim-Slichter equation, the temperature program for homogeneous doping in flux growth by slow cooling was derived. The effect of various factors, such as initial supersaturation, solution volume, growth kinetic coefficient and degree of mixing in the solution on growth rate, crystal size and temperature program is discussed in detail. Theoretical analysis shows that there is a critical crystal size above which homogeneous doping is impossible.
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NASA Astrophysics Data System (ADS)
Wang, Junfeng; Xiong, Rui; Yi, Fan; Yin, Di; Ke, Manzhu; Li, Changzhen; Liu, Zhengyou; Shi, Jing
2005-05-01
High quality and large-sized Rb 0.3MoO 3 single crystals were synthesized by molten salt electrolysis method. X-ray diffraction (XRD) patterns and rocking curves, as well as the white beam Laue diffraction of X-ray images show the crystals grown by this method have high quality. The lattice constants evaluated from XRD patterns are a0=1.87 nm, b0=0.75 nm, c0=1.00 nm, β=118.83∘. The in situ selected area electron diffraction (SAED) patterns along the [101¯], [11¯1¯] and [103¯] zone axes at room temperature indicate that the Rb 0.3MoO 3 crystal possess perfect C-centered symmetry. Temperature dependence of the resistivity shows this compound undergoes a metal to semiconductor transition at 183 K.
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Controlling the Topological Sector of Magnetic Solitons in Exfoliated Cr 1 / 3 NbS 2 Crystals
DOE Office of Scientific and Technical Information (OSTI.GOV)
Wang, Lin; Chepiga, N.; Ki, D. -K.
Here, we investigate manifestations of topological order in monoaxial helimagnet Cr 1/3NbS 2 by performing transport measurements on ultrathin crystals. Upon sweeping the magnetic field perpendicularly to the helical axis, crystals thicker than one helix pitch (48 nm) but much thinner than the magnetic domain size (similar to 1 mu m) are found to exhibit sharp and hysteretic resistance jumps. We also show that these phenomena originate from transitions between topological sectors with a different number of magnetic solitons. This is confirmed by measurements on crystals thinner than 48 nm-in which the topological sector cannot change-that do not exhibit anymore » jump or hysteresis. These results show the ability to deterministically control the topological sector of finite-size Cr 1/3NbS 2 and to detect intersector transitions by transport measurements.« less
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Controlling the Topological Sector of Magnetic Solitons in Exfoliated Cr 1 / 3 NbS 2 Crystals
Wang, Lin; Chepiga, N.; Ki, D. -K.; ...
2017-06-23
Here, we investigate manifestations of topological order in monoaxial helimagnet Cr 1/3NbS 2 by performing transport measurements on ultrathin crystals. Upon sweeping the magnetic field perpendicularly to the helical axis, crystals thicker than one helix pitch (48 nm) but much thinner than the magnetic domain size (similar to 1 mu m) are found to exhibit sharp and hysteretic resistance jumps. We also show that these phenomena originate from transitions between topological sectors with a different number of magnetic solitons. This is confirmed by measurements on crystals thinner than 48 nm-in which the topological sector cannot change-that do not exhibit anymore » jump or hysteresis. These results show the ability to deterministically control the topological sector of finite-size Cr 1/3NbS 2 and to detect intersector transitions by transport measurements.« less
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Polarized spectral properties and potential application of large-size Nd3+:Ba3Gd2(BO3)4 crystal
NASA Astrophysics Data System (ADS)
Gao, S. F.; Lv, S. Z.; Zhu, Z. J.; Wang, Y.; You, Z. Y.; Li, J. F.; Xu, J. L.; Wang, H. Y.; Tu, C. Y.
2014-06-01
The Nd3+-doped Ba3Gd2(BO3)4 crystal with high optical quality and large size is reported in this paper. The growing processes and characteristics of Nd3+:Ba3Gd2(BO3)4 crystal are discussed. The absorption and luminescence spectra of Nd3+ in Ba3Gd2(BO3)4 crystal were measured at room temperature. The luminescence decay curve in correspondence with the 4F3/2 →4I11/2 transition centered at 1062 nm was also measured. The JO intensity parameters Ωt (t = 2,4,6) were calculated to be Ω2 = 1.263, Ω4 = 2.496, Ω6 = 3.606. The radiative lifetime τr and fluorescence lifetime τf are 317.771 and 115 μs respectively, and the fluorescence quantum efficiency is 37.1%.
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Somlai-Schweiger, I; Ziegler, S I
2015-04-01
A new concept for a depth-of-interaction (DOI) capable time-of-flight (TOF) PET detector is defined, based only on the detection of Cherenkov photons. The proposed "CHERENCUBE" consists of a cubic Cherenkov radiator with position-sensitive photodetectors covering each crystal face. By means of the spatial distribution of the detected photons and their time of arrival, the point of interaction of the gamma-ray in the crystal can be determined. This study analyzes through theoretical calculations and Monte Carlo simulations the potential advantages of the concept toward reaching a Cherenkov-only detector for TOF-PET with DOI capability. Furthermore, an algorithm for the DOI estimation is presented and the requirements for a practical implementation of the proposed concept are defined. The Monte Carlo simulations consisted of a cubic crystal with one photodetector coupled to each one of the faces of the cube. The sensitive area of the detector matched exactly the crystal size, which was varied in 1 mm steps between 1 × 1 × 1 mm(3) and 10 × 10 × 10 mm(3). For each size, five independent simulations of ten thousand 511 keV gamma-rays were triggered at a fixed distance of 10 mm. The crystal chosen was PbWO4. Its scintillation properties were simulated, but only Cherenkov photons were analyzed. Photodetectors were simulated having perfect photodetection efficiency and infinite time resolution. For every generated particle, the analysis considered its creation process, parent and daughter particles, energy, origin coordinates, trajectory, and time and position of detection. The DOI determination is based on the distribution of the emission time of all photons per event. These values are calculated as a function of the coordinates of detection and origin for every photon. The common origin is estimated by finding the distribution with the most similar emission time-points. Detection efficiency increases with crystal size from 8.2% (1 × 1 × 1 mm(3)) to 58.6% (10 × 10 × 10 mm(3)) and decreases applying a photon detection threshold of 5/10/20 photons to 6.3%/4.3%/0.7% and 49.3%/30.4%/2.8%, respectively. The detection rate in the six photodetectors is uniform due to the nearly isotropic cone emission. Most cones originated after a photoelectric effect interaction, with two dominating peaks for the kinetic energy of the electron at 422.99 and 441.47 keV. The detection distance between same-event photons defines the spatial resolution of the detector required for individual photon recognition, with 20% of the detected photons having their closest neighbor within a distance of 5% of the length of the cube. Same-event photons are detected within a time window whose width is determined by the crystal size, with values of 30 and 150 ps for a 1 × 1 × 1 mm(3) and a 10 × 10 × 10 mm(3) cube, respectively. The DOI reconstruction has an accuracy of approximately 23% of the length of the cube, with an average value of 2.2 mm for a 10 × 10 × 10 mm(3) CHERENCUBE. The proposed concept requires a detector with high photodetection efficiency. The structure of the sensitive surface of the detector should be a two dimensional array of microcells, able to provide individual detection coordinates and time stamps. The microcell size determines the ability to recognize individual photons, influencing detection efficiency. The 3D DOI recognition relies on the accuracy of the time stamps and detection coordinates, without the need for a recognition of the projected patterns of photons. The refractive index of the material defines a detector intrinsic energy-based rejection of scattered PET events at the cost of reduced sensitivity.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Somlai-Schweiger, I., E-mail: ian.somlai@tum.de; Ziegler, S. I.
Purpose: A new concept for a depth-of-interaction (DOI) capable time-of-flight (TOF) PET detector is defined, based only on the detection of Cherenkov photons. The proposed “CHERENCUBE” consists of a cubic Cherenkov radiator with position-sensitive photodetectors covering each crystal face. By means of the spatial distribution of the detected photons and their time of arrival, the point of interaction of the gamma-ray in the crystal can be determined. This study analyzes through theoretical calculations and Monte Carlo simulations the potential advantages of the concept toward reaching a Cherenkov-only detector for TOF-PET with DOI capability. Furthermore, an algorithm for the DOI estimationmore » is presented and the requirements for a practical implementation of the proposed concept are defined. Methods: The Monte Carlo simulations consisted of a cubic crystal with one photodetector coupled to each one of the faces of the cube. The sensitive area of the detector matched exactly the crystal size, which was varied in 1 mm steps between 1 × 1 × 1 mm{sup 3} and 10 × 10 × 10 mm{sup 3}. For each size, five independent simulations of ten thousand 511 keV gamma-rays were triggered at a fixed distance of 10 mm. The crystal chosen was PbWO{sub 4}. Its scintillation properties were simulated, but only Cherenkov photons were analyzed. Photodetectors were simulated having perfect photodetection efficiency and infinite time resolution. For every generated particle, the analysis considered its creation process, parent and daughter particles, energy, origin coordinates, trajectory, and time and position of detection. The DOI determination is based on the distribution of the emission time of all photons per event. These values are calculated as a function of the coordinates of detection and origin for every photon. The common origin is estimated by finding the distribution with the most similar emission time-points. Results: Detection efficiency increases with crystal size from 8.2% (1 × 1 × 1 mm{sup 3}) to 58.6% (10 × 10 × 10 mm{sup 3}) and decreases applying a photon detection threshold of 5/10/20 photons to 6.3%/4.3%/0.7% and 49.3%/30.4%/2.8%, respectively. The detection rate in the six photodetectors is uniform due to the nearly isotropic cone emission. Most cones originated after a photoelectric effect interaction, with two dominating peaks for the kinetic energy of the electron at 422.99 and 441.47 keV. The detection distance between same-event photons defines the spatial resolution of the detector required for individual photon recognition, with 20% of the detected photons having their closest neighbor within a distance of 5% of the length of the cube. Same-event photons are detected within a time window whose width is determined by the crystal size, with values of 30 and 150 ps for a 1 × 1 × 1 mm{sup 3} and a 10 × 10 × 10 mm{sup 3} cube, respectively. The DOI reconstruction has an accuracy of approximately 23% of the length of the cube, with an average value of 2.2 mm for a 10 × 10 × 10 mm{sup 3} CHERENCUBE. Conclusions: The proposed concept requires a detector with high photodetection efficiency. The structure of the sensitive surface of the detector should be a two dimensional array of microcells, able to provide individual detection coordinates and time stamps. The microcell size determines the ability to recognize individual photons, influencing detection efficiency. The 3D DOI recognition relies on the accuracy of the time stamps and detection coordinates, without the need for a recognition of the projected patterns of photons. The refractive index of the material defines a detector intrinsic energy-based rejection of scattered PET events at the cost of reduced sensitivity.« less
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NASA Astrophysics Data System (ADS)
Luo, Zhilong; Cui, Yingdan; Dong, Weibing; Xu, Qipeng; Zou, Gaoxing; Kang, Chao; Hou, Baohong; Chen, Song; Gong, Junbo
2017-12-01
Nitroguanidine (NQ) is a commonly used explosive, which has been widely used for both civilian and military explosive applications. However, the weak flowability and mechanical performance limit its application. In this work, mechanical performance and thermodynamic stability of NQ crystals were improved by controlling crystal morphologies in the crystallization process. Typical NQ crystals with multiple morphologies and single crystal form were obtained in the presence of additives during the cooling crystallization. The morphology controlled NQ crystals showed higher density, unimodal crystal size distribution and enhanced flowability. The additives showed the inhibitory effect on the nucleation of NQ crystals by in-situ FBRM and PVM determination, and the mechanism was analyzed by means of morphological prediction and molecular simulation. Furthermore, the morphology controlled NQ crystals suggested higher thermodynamic stability according to the calculation of entropy, enthalpy, Gibbs free energy and apparent activation energy on the basis of DSC results.
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Maghsoodi, Maryam
2015-01-01
Crystallization is often used for manufacturing drug substances. Advances of crystallization have achieved control over drug identity and purity, but control over the physical form remains poor. This review discusses the influence of solvents used in crystallization process on crystal habit and agglomeration of crystals with potential implication for dissolution. According to literature it has been known that habit modification of crystals by use of proper solvents may enhance the dissolution properties by changing the size, number and the nature of crystal faces exposed to the dissolution medium. Also, the faster dissolution rate of drug from the agglomerates of crystals compared with the single crystals may be related to porous structure of the agglomerates and consequently their better wettability. It is concluded from this review that in-depth understanding of role of the solvents in crystallization process can be applied to engineering of crystal habit or crystal agglomeration, and predictably dissolution improvement in poorly soluble drugs. PMID:25789214
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Protein Crystals Grown in Space
NASA Technical Reports Server (NTRS)
2000-01-01
A collage of protein and virus crystals, many of which were grown on the U.S. Space Shuttle or Russian Space Station, Mir. The crystals include the proteins canavalin; mouse monoclonal antibody; a sweet protein, thaumatin; and a fungal protease. Viruses are represented here by crystals of turnip yellow mosaic virus and satellite tobacco mosaic virus. The crystals are photographed under polarized light (thus causing the colors) and range in size from a few hundred microns in edge length up to more than a millimeter. All the crystals are grown from aqueous solutions and are useful for X-ray diffraction analysis. Credit: Dr. Alex McPherson, University of California, Irvine.
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Laser furnace and method for zone refining of semiconductor wafers
NASA Technical Reports Server (NTRS)
Griner, Donald B. (Inventor); zur Burg, Frederick W. (Inventor); Penn, Wayne M. (Inventor)
1988-01-01
A method of zone refining a crystal wafer (116 FIG. 1) comprising the steps of focusing a laser beam to a small spot (120) of selectable size on the surface of the crystal wafer (116) to melt a spot on the crystal wafer, scanning the small laser beam spot back and forth across the surface of the crystal wafer (116) at a constant velocity, and moving the scanning laser beam across a predetermined zone of the surface of the crystal wafer (116) in a direction normal to the laser beam scanning direction and at a selectible velocity to melt and refine the entire crystal wafer (116).
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An investigation of the optical properties of cholesterol crystals in human synovial fluid
NASA Astrophysics Data System (ADS)
Zakharova, M. M.; Nasonova, V. A.; Konstantinova, A. F.; Chudakov, V. S.; Gaĭnutdinov, R. V.
2009-05-01
The synovial fluid of patients with rheumatoid diseases has been investigated. The presence of cholesterol crystals in the synovial fluid is revealed by polarization microscopy. A comparative analysis of the composition and properties of synovial fluid and the optical properties of cholesterol crystals is performed. It is established that the size, number, and growth of cholesterol crystals are interrelated to the synovial fluid composition. It is shown that rheumatoid diseases can be accompanied by the formation of cholesterol crystals in the synovial fluid from different joints and in rheumatic nodules. It is shown that all investigated crystals have a significant birefringence.
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Munjal, Bhushan; Bansal, Arvind K
2015-01-01
The effect of tert-butyl alcohol (TBA) on isothermal crystallization kinetics of gemcitabine hydrochloride (GHCl) in frozen aqueous solutions was assessed by cold-stage microscopy. Addition of TBA (0%-5%, w/w) increased the value of Johnson-Mehl-Avrami rate constant (1.3-33.3 h⁻¹) and reduced the Avrami exponent (2.5-1.0). Thermodynamic parameters [enthalpy (ΔH(‡)), entropy (ΔS(‡)), and free energy (ΔG(‡)) of activation], calculated using Arrhenius and Eyring-Polanyi equations, established that TBA (2%, w/w) accelerated GHCl crystallization by reducing its ΔH(‡) (53.9 cf. 96.5 kJ/mol⁻¹) and ΔG(‡) (68.5 cf. 74.9 kJ/mol⁻¹). Further, to explore insights into the effect of TBA on nucleation and crystal growth of GHCl, crystallization kinetics data were deconvolved using Finke-Watzky model. This revealed that addition of TBA decreased ΔH(‡) of nucleation and increased ΔS(‡) of crystal growth, thereby reducing ΔG(‡) of nucleation and crystal growth by 11.7% and 4.2%, respectively. Finkey-Watzky model also predicted a reduction in the crystal size upon TBA addition, which was confirmed by comparing particle size of GHCl lyophilized in the presence and absence of TBA. In conclusion, TBA reduces ΔG(‡) of nucleation and crystal growth in a differential manner, thereby enhancing the crystallization kinetics of GHCl and affecting its morphological features. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.
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Crystal growth and electronic structure of low-temperature phase SrMgF{sub 4}
DOE Office of Scientific and Technical Information (OSTI.GOV)
Atuchin, Victor V.; Functional Electronics Laboratory, Tomsk State University, Tomsk 634050; Laboratory of Semiconductor and Dielectric Materials, Novosibirsk State University, Novosibirsk 630090
2016-04-15
Using the vertical Bridgman method, the single crystal of low temperature phase SrMgF{sub 4} is obtained. The crystal is in a very good optical quality with the size of 10×7×5 mm{sup 3}. Detailed photoemission spectra of the element core levels are determined by a monochromatic AlKa (1486.6 eV) X-ray source. Moreover, the first-principles calculations are performed to investigate the electronic structure of SrMgF{sub 4}. A good agreement between experimental and calculated results is achieved. It is demonstrated that almost all the electronic orbitals are strongly localized and the hybridization with the others is very small, but the Mg–F bonds covalencymore » is relatively stronger than that of Sr–F bonds. - Graphical abstract: Large size of low-temperature phase SrMgF{sub 4} crystal was obtained (right) and its electronic structure was investigated by X-ray photoelectron spectroscopy and first-principles calculation (left). - Highlights: • Large size single crystal of low-temperature phase SrMgF{sub 4} is obtained. • Electronic structure of SrMgF{sub 4} is measured by X-ray photoelectron spectroscopy. • Partial densities of states are determined by first-principles calculation. • Good agreement between experimental and calculated results is achieved. • Strong ionic characteristics of chemical bonds are exhibited in SrMgF{sub 4}.« less
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Righettoni, Marco; Pratsinis, Sotiris E., E-mail: sotiris.pratsinis@ptl.mavt.ethz.ch
Highlights: • Flame-made WO{sub 3} nanoparticles with closely controlled crystal and grain size. • Dynamic phase transition of annealing of pure and Si-doped WO{sub 3} by in situ XRD. • Irreversible evolution of WO{sub 3} crystallinity by heating/cooling during its annealing. • Si-doping alters the WO{sub 3} crystallinity dynamics and stabilizes nanosized WO{sub 3}. • Flame-made nano-WO{sub 3} can sense NO at the ppb level. - Abstract: Tungsten trioxide is a semiconductor with distinct applications in gas sensors, catalysis, batteries and pigments. As such the transition between its different crystal structures during its annealing are of interest, especially for sensormore » applications. Here, WO{sub 3} nanoparticles with closely controlled crystal and grain size (9–15 nm) and phase composition are made by flame spray pyrolysis and the formation of different WO{sub 3} phases during annealing is investigated. Most notably, the dynamic phase transition and crystal size evolution of WO{sub 3} during heating and cooling is monitored by in situ X-ray diffraction revealing how metastable WO{sub 3} phases can be captured stably. The effect of Si-doping is studied since it is used in practise to control crystal growth and phase transition during metal oxide synthesis and processing. Finally the influence of annealing on the WO{sub 3} sensing performance of NO, a lung inflammation tracer in the human breath, is explored at the ppb-level.« less
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Single-crystal growth, structure refinement and the properties of Bis(glycine) Strontium Chloride
NASA Astrophysics Data System (ADS)
Balaji, S. R.; Balu, T.; Rajasekaran, T. R.
2018-02-01
Single crystals of Bis (glycine) Strontium Chloride (BGSC) were grown by means of slow evaporation process by using analar grade Glycine and Strontium Chloride Hexahydrate as a parent compound from its aqueous solution at room temperature. The final chemical composition, [{{Sr}}{({{{C}}}2{{{H}}}5{{{NO}}}2)}2{{{Cl}}}2].{{{H}}}4{{{O}}}3+{{{H}}}8{{{O}}}3, formed were metallic light colorless block, about the size of 28 mm × 9 mm × 8 mm. A single-crystal x-ray diffraction study revealed an ordered superstructure with orthorhombic symmetry that could be assigned to the space group Pbcn. The structure in BGSC, revealed in the electron density distribution was analyzed by the direct methods (SHELXS-2014) and refined by least squares full matrix method (SHELXL-2014). The crystal structure, including anisotropic atomic displacement parameters for each atom and isotropic atomic displacement parameters for hydrogen atom, was refined to R1 = 0.0395, wR2 = 0.0776 using 1097 independent reflections. The FTIR spectrum of BGSC confirms the protonation of amino groups and the different molecular groups present in BGSC vibrate in different modes. Reverse Indentation Size Effect (RISE) was revealed in BGSC in the micro-hardness analysis using Vicker’s micro-hardness analysis. DTA and DSC results ruled out the possibility of structural change independent of mass change. The AFM studies shows fine nano size fiber like structure of the grown crystals.
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Kim, Byeongsoo; Gil, Hyung Bae; Min, Sang-Gi; Lee, Si-Kyung; Choi, Mi-Jung
2014-01-01
This study investigates the effects of the gelatin concentration (10-40%, w/v), freezing temperatures (from -20℃ to -50℃) and freezing methods on the structural and physical properties of gelatin matrices. To freeze gelatin, the pressure-shift freezing (PSF) is being applied at 0.1 (under atmospheric control), 50 and 100 MPa, respectively. The freezing point of gelatin solutions decrease with increasing gelatin concentrations, from -0.2℃ (10% gelatin) to -6.7℃ (40% gelatin), while the extent of supercooling did not show any specific trends. The rheological properties of the gelatin indicate that both the storage (G') and loss (G") moduli were steady in the strain amplitude range of 0.1-10%. To characterize gelatin matrices formed by the various freezing methods, the ice crystal sizes which were being determined by the scanning electron microscopy (SEM) are affected by the gelatin concentrations. The ice crystal sizes are affected by gelatin concentrations and freezing temperature, while the size distributions of ice crystals depend on the freezing methods. Smaller ice crystals are being formed with PSF rather than under the atmospheric control where the freezing temperature is above -40℃. Thus, the results of this study indicate that the PSF processing at a very low freezing temperature (-50℃) offers a potential advantage over commercial atmospheric freezing points for the formation of small ice crystals. PMID:26760743
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Femtosecond X-ray protein nanocrystallography
Chapman, Henry N.; Fromme, Petra; Barty, Anton; White, Thomas A.; Kirian, Richard A.; Aquila, Andrew; Hunter, Mark S.; Schulz, Joachim; DePonte, Daniel P.; Weierstall, Uwe; Doak, R. Bruce; Maia, Filipe R. N. C.; Martin, Andrew V.; Schlichting, Ilme; Lomb, Lukas; Coppola, Nicola; Shoeman, Robert L.; Epp, Sascha W.; Hartmann, Robert; Rolles, Daniel; Rudenko, Artem; Foucar, Lutz; Kimmel, Nils; Weidenspointner, Georg; Holl, Peter; Liang, Mengning; Barthelmess, Miriam; Caleman, Carl; Boutet, Sébastien; Bogan, Michael J.; Krzywinski, Jacek; Bostedt, Christoph; Bajt, Saša; Gumprecht, Lars; Rudek, Benedikt; Erk, Benjamin; Schmidt, Carlo; Hömke, André; Reich, Christian; Pietschner, Daniel; Strüder, Lothar; Hauser, Günter; Gorke, Hubert; Ullrich, Joachim; Herrmann, Sven; Schaller, Gerhard; Schopper, Florian; Soltau, Heike; Kühnel, Kai-Uwe; Messerschmidt, Marc; Bozek, John D.; Hau-Riege, Stefan P.; Frank, Matthias; Hampton, Christina Y.; Sierra, Raymond G.; Starodub, Dmitri; Williams, Garth J.; Hajdu, Janos; Timneanu, Nicusor; Seibert, M. Marvin; Andreasson, Jakob; Rocker, Andrea; Jönsson, Olof; Svenda, Martin; Stern, Stephan; Nass, Karol; Andritschke, Robert; Schröter, Claus-Dieter; Krasniqi, Faton; Bott, Mario; Schmidt, Kevin E.; Wang, Xiaoyu; Grotjohann, Ingo; Holton, James M.; Barends, Thomas R. M.; Neutze, Richard; Marchesini, Stefano; Fromme, Raimund; Schorb, Sebastian; Rupp, Daniela; Adolph, Marcus; Gorkhover, Tais; Andersson, Inger; Hirsemann, Helmut; Potdevin, Guillaume; Graafsma, Heinz; Nilsson, Björn; Spence, John C. H.
2012-01-01
X-ray crystallography provides the vast majority of macromolecular structures, but the success of the method relies on growing crystals of sufficient size. In conventional measurements, the necessary increase in X-ray dose to record data from crystals that are too small leads to extensive damage before a diffraction signal can be recorded1-3. It is particularly challenging to obtain large, well-diffracting crystals of membrane proteins, for which fewer than 300 unique structures have been determined despite their importance in all living cells. Here we present a method for structure determination where single-crystal X-ray diffraction ‘snapshots’ are collected from a fully hydrated stream of nanocrystals using femtosecond pulses from a hard-X-ray free-electron laser, the Linac Coherent Light Source4. We prove this concept with nanocrystals of photosystem I, one of the largest membrane protein complexes5. More than 3,000,000 diffraction patterns were collected in this study, and a three-dimensional data set was assembled from individual photosystem I nanocrystals (~200 nm to 2 μm in size). We mitigate the problem of radiation damage in crystallography by using pulses briefer than the timescale of most damage processes6. This offers a new approach to structure determination of macromolecules that do not yield crystals of sufficient size for studies using conventional radiation sources or are particularly sensitive to radiation damage. PMID:21293373
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Zakharov, Boris; Fisyuk, Alexander; Fitch, Andy; Watier, Yves; Kostyuchenko, Anastasia; Varshney, Dushyant; Sztucki, Michael; Boldyreva, Elena; Shalaev, Evgenyi
2016-07-01
Ice formation and recrystallization is a key phenomenon in freezing and freeze-drying of pharmaceuticals and biopharmaceuticals. In this investigation, high-resolution synchrotron X-ray diffraction is used to quantify the extent of disorder of ice crystals in binary aqueous solutions of a cryoprotectant (sorbitol) and a protein, bovine serum albumin. Ice crystals in more dilute (10 wt%) solutions have lower level of microstrain and larger crystal domain size than these in more concentrated (40 wt%) solutions. Warming the sorbitol-water mixtures from 100 to 228 K resulted in partial ice melting, with simultaneous reduction in the microstrain and increase in crystallite size, that is, recrystallization. In contrast to sorbitol solutions, ice crystals in the BSA solutions preserved both the microstrain and smaller crystallite size on partial melting, demonstrating that BSA inhibits ice recrystallization. The results are consistent with BSA partitioning into quasi-liquid layer on ice crystals but not with a direct protein-ice interaction and protein sorption on ice surface. The study shows for the first time that a common (i.e., not-antifreeze) protein can have a major impact on ice recrystallization and also presents synchrotron X-ray diffraction as a unique tool for quantification of crystallinity and disorder in frozen aqueous systems. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.
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Crystal Engineering; How molecules build solids
NASA Astrophysics Data System (ADS)
Williams, Jeffrey H.
2017-09-01
There are more than 20 million chemicals in the literature, with new materials being synthesized each week. Most of these molecules are stable, and the 3-dimensional arrangement of the atoms in the molecules, in the various solids may be determined by routine x-ray crystallography. When this is done, it is found that this vast range of molecules, with varying sizes and shapes can be accommodated by only a handful of solid structures. This limited number of architectures for the packing of molecules of all shapes and sizes, to maximize attractive intermolecular forces and minimizing repulsive intermolecular forces, allows us to develop simple models of what holds the molecules together in the solid. In this volume we look at the origin of the molecular architecture of crystals; a topic that is becoming increasingly important and is often termed, crystal engineering. Such studies are a means of predicting crystal structures, and of designing crystals with particular properties by manipulating the structure and interaction of large molecules. That is, creating new crystal architectures with desired physical characteristics in which the molecules pack together in particular architectures; a subject of particular interest to the pharmaceutical industry.
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Fabrication of large binary colloidal crystals with a NaCl structure
Vermolen, E. C. M.; Kuijk, A.; Filion, L. C.; Hermes, M.; Thijssen, J. H. J.; Dijkstra, M.; van Blaaderen, A.
2009-01-01
Binary colloidal crystals offer great potential for tuning material properties for applications in, for example, photonics, semiconductors and spintronics, because they allow the positioning of particles with quite different characteristics on one lattice. For micrometer-sized colloids, it is believed that gravity and slow crystallization rates hinder the formation of high-quality binary crystals. Here, we present methods for growing binary colloidal crystals with a NaCl structure from relatively heavy, hard-sphere-like, micrometer-sized silica particles by exploring the following external fields: electric, gravitational, and dielectrophoretic fields and a structured surface (colloidal epitaxy). Our simulations show that the free-energy difference between the NaCl and NiAs structures, which differ in their stacking of the hexagonal planes of the larger spheres, is very small (≈0.002 kBT). However, we demonstrate that the fcc stacking of the large spheres, which is crucial for obtaining the pure NaCl structure, can be favored by using a combination of the above-mentioned external fields. In this way, we have successfully fabricated large, 3D, oriented single crystals having a NaCl structure without stacking disorder. PMID:19805259
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Modeling the Crystallization of Proteins
NASA Astrophysics Data System (ADS)
Liu, Hongjun; Kumar, Sanat; Garde, Shekhar
2007-03-01
We have used molecular dynamics and monte carlo simulations to understand the pathway to protein crystallization. We find that models which ignore the patchy nature of protein-protein interactions only crystallize inside the metastable gas-lqiuid coexistence region. In this regime they crystallize through the formation of a critical nucleus. In contrast, when patchiness is introduced we find that there is no need to be inside this metastable gas-liquid boundary. Rather, crystallization occurs through an intermediate which is composed of disordered aggregates. These are formed by patchy interactions. Further, there appears to be no need for the formation of a critical nucleus. Thus the pathways for crystallization are strongly controlled by the nature of protein-protein interactions, in good agreement with current experiments.
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NASA Astrophysics Data System (ADS)
Yilmaz, Hulusi
A comprehensive density functional theory study of atomic and the electronic properties of wurtzite gallium nitride (GaN) nanostructures with different sizes and shapes is presented and the effect of external electric field on these properties is examined. We show that the atomic and electronic properties of [101¯0] facet single-crystal GaN nanotubes (quasi-1D), nanowires (1D) and nanolayers (2D) are mainly determined by the surface to volume ratio. The shape dependent quantum confinement and strain effects on the atomic and electronic properties of these GaN nanostructures are found to be negligible. Based on this similarity between the atomic and electronic properties of the small size GaN nanostructures, we calculated the atomic and electronic properties of the practical size (28.1 A wall thickness) single-crystal GaN nanotubes through computational much economical GaN nanoslabs (nanolayers). Our results show that, regardless of diameter, hydrogen saturated single-crystal GaN tubes with the wall thickness of 28.1 A are energetically stable and they have a noticeably larger band gap with respect to the band gap of bulk GaN. The band gap of unsaturated single-crystal GaN tubes, on the other hand, is always smaller than the band gap of the wurtzite bulk GaN. In a separate study, we show that a transverse electric field induces a homojunction across the diameter of initially semiconducting GaN single-crystal nanotubes and nanowires. The homojunction arises due to the decreased energy of the electronic states in the higher potential region with respect to the energy of those states in the lower potential region under the transverse electric field. Calculations on single-crystal GaN nanotubes and nanowires of different diameter and wall thickness show that the threshold electric field required for the semiconductor-homojunction induction increases with increasing wall thickness and decreases significantly with increasing diameter.
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Rahaman, Md Saifur; Mavinic, Donald S; Meikleham, Alexandra; Ellis, Naoko
2014-03-15
The cost associated with the disposal of phosphate-rich sludge, the stringent regulations to limit phosphate discharge into aquatic environments, and resource shortages resulting from limited phosphorus rock reserves, have diverted attention to phosphorus recovery in the form of struvite (MAP: MgNH4PO4·6H2O) crystals, which can essentially be used as a slow release fertilizer. Fluidized-bed crystallization is one of the most efficient unit processes used in struvite crystallization from wastewater. In this study, a comprehensive mathematical model, incorporating solution thermodynamics, struvite precipitation kinetics and reactor hydrodynamics, was developed to illustrate phosphorus depletion through struvite crystal growth in a continuous, fluidized-bed crystallizer. A thermodynamic equilibrium model for struvite precipitation was linked to the fluidized-bed reactor model. While the equilibrium model provided information on supersaturation generation, the reactor model captured the dynamic behavior of the crystal growth processes, as well as the effect of the reactor hydrodynamics on the overall process performance. The model was then used for performance evaluation of the reactor, in terms of removal efficiencies of struvite constituent species (Mg, NH4 and PO4), and the average product crystal sizes. The model also determined the variation of species concentration of struvite within the crystal bed height. The species concentrations at two extreme ends (inlet and outlet) were used to evaluate the reactor performance. The model predictions provided a reasonably good fit with the experimental results for PO4-P, NH4-N and Mg removals. Predicated average crystal sizes also matched fairly well with the experimental observations. Therefore, this model can be used as a tool for performance evaluation and process optimization of struvite crystallization in a fluidized-bed reactor. Crown Copyright © 2013. Published by Elsevier Ltd. All rights reserved.
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Paulino, A S; Rauber, G; Campos, C E M; Maurício, M H P; de Avillez, R R; Capobianco, G; Cardoso, S G; Cuffini, S L
2013-05-13
Deflazacort (DFZ), a derivate of prednisolone, is a poorly soluble drug which has been proposed to have major advantages over other corticosteroids. Poorly soluble drugs present limited bioavailability due to their low solubility and dissolution rate and several strategies have been developed in order to find ways to improve them. In general, pharmaceutical laboratories use a micronized process to reduce the particle size in order to increase the dissolution of the drugs. However, this process causes changes such as polymorphic transitions, particle agglomeration and a reduction in fluidity and wettability. These solid-state properties affect the dissolution behavior and stability performance of drugs. Crystallization techniques are widely used in the pharmaceutical industry and antisolvent crystallization has been used to obtain ultrafine particles. In this study, DFZ was investigated in terms of its antisolvent crystallization in different solvents and under various preparation conditions (methanol/water ratio, stirring and evaporation rate, etc.), in order to compare the physicochemical properties between crystallized samples and raw materials available on the Brazilian market with and without micronization. Crystalline structure, morphology, and particle size, and their correlation with the Intrinsic Dissolution Rate (IDR) and dissolution profile as relevant biopharmaceutical properties were studied. Crystallization conditions were achieved which provided crystalline samples of hollow-shaped crystals with internal channels, which increased the dissolution rate of DFZ. The antisolvent crystallization process allowed the formation of hollow crystals, which demonstrated a better dissolution profile than the raw material (crystalline and micronized), making this a promising technique as a crystallization strategy for improving the dissolution and thus the bioavailability of poorly soluble drugs. Copyright © 2013 Elsevier B.V. All rights reserved.
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2017-01-01
Microcrystals of piroxicam (PRX) monohydrate with a narrow size distribution were prepared from acetone/PRX solutions by antisolvent crystallization via metallic membranes with ordered pore arrays. Crystallization was achieved by controlled addition of the feed solution through the membrane pores into a well-stirred antisolvent. A complete transformation of an anhydrous form I into a monohydrate form of PRX was confirmed by Raman spectroscopy and differential scanning calorimetry. The size of the crystals was 7–34 μm and was controlled by the PRX concentration in the feed solution (15–25 g L–1), antisolvent/solvent volume ratio (5–30), and type of antisolvent (Milli-Q water or 0.1–0.5 wt % aqueous solutions of hydroxypropyl methyl cellulose (HPMC), poly(vinyl alcohol) or Pluronic P-123). The smallest crystals were obtained by injecting 25 g L–1 PRX solution through a stainless-steel membrane with a pore size of 10 μm into a 0.06 wt % HPMC solution stirred at 1500 rpm using an antisolvent/solvent ratio of 20. HPMC provided better steric stabilization of microcrystals against agglomeration than poly(vinyl alcohol) and Pluronic P-123, due to hydrogen bonding interactions with PRX and water. A continuous production of large PRX monohydrate microcrystals with a volume-weighted mean diameter above 75 μm was achieved in a continuous stirred membrane crystallizer. Rapid pouring of Milli-Q water into the feed solution resulted in a mixture of highly polydispersed prism-shaped and needle-shaped crystals. PMID:29234241
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Jo, Sinae; Kang, Seunggu
2013-11-01
Low-melting zinc-borate glass was added to the cordierite/Al2O3 composite in order to improve the sintering facility of Al2O3 and formation of nano-sized spinel crystal of high thermal conductivity. Increasing the ZnO/B2O3 ratio in the zinc-borate glass increased the ZnAl2O4 spinel and decreased the Al4B2O9 crystal peak intensities in X-ray diffraction pattern. The XRD peak intensities of the ZnAl2O4 spinel and Al4B2O9 crystals in the specimen containing 10 wt% zinc-borate glass (10G series) are higher than that of the specimen containing 5 wt% zinc-borate glass (5G series). The microstructures of most 10G series specimens had the flower-shaped crystal which was composed of 50 nm wide and 250 nm long needle-like crystals and identified as ZnAl2O4 spinel phase. The thermal conductivity of the 10G series specimen was higher than that of the 5G series in any ZnO/B2O3 ratio due to the formation of plenty of nano-sized ZnAl2O4 spinel of high thermal conductivity. Particularly, the thermal conductivity of the cordierite/Al2O3 composite containing 10 wt% zinc-borate glass of ZnO/B2O3 weight ratio = 1.5 was 3.8 W/Km which is much higher than that of the published value (3.0 W/Km).
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Double-Diffusive Convection During Growth of Halides and Selenides
NASA Technical Reports Server (NTRS)
Singh, N. B.; Su, Ching-Hua; Duval, Walter M. B.
2015-01-01
Heavy metal halides and selenides have unique properties which make them excellent materials for chemical, biological and radiological sensors. Recently it has been shown that selenohalides are even better materials than halides or selenides for gamma-ray detection. These materials also meet the strong needs of a wide band imaging technology to cover ultra-violet (UV), midwave infrared wavelength (MWIR) to very long wavelength infrared (VLWIR) region for hyperspectral imager components such as etalon filters and acousto-optic tunable filters (AO). In fact AOTF based imagers based on these materials have some superiority than imagers based on liquid crystals, FTIR, Fabry-Perot, grating, etalon, electro-optic modulation, piezoelectric and several other concepts. For example, broadband spectral and imagers have problems of processing large amount of information during real-time observation. Acousto-Optic Tunable Filter (AOTF) imagers are being developed to fill the need of reducing processing time of data, low cost operation and key to achieving the goal of covering long-wave infrared (LWIR). At the present time spectral imaging systems are based on the use of diffraction gratings are typically used in a pushbroom or whiskbroom mode. They are mostly used in systems and acquire large amounts of hyperspectral data that is processed off-line later. In contrast, acousto-optic tunable filter spectral imagers require very little image processing, providing new strategies for object recognition and tracking. They are ideally suited for tactical situations requiring immediate real-time image processing. But the performance of these imagers depends on the quality and homogeneity of acousto-optic materials. In addition for many systems requirements are so demanding that crystals up to sizes of 10 cm length are desired. We have studied several selenides and halide crystals for laser and AO imagers for MWIR and LWIR wavelength regions. We have grown and fabricated crystals of several materials such as mercurous chloride, mercurous bromide, mercurous iodide, lead chloride lead bromide, lead iodide, thallium arsenic selenide, gallium selenide, zince sulfide zinc selenide and several crystals into devices. We have used both Bridgman and physical vapor transport (PVT) crystal growth methods. In the past have examined PVT growth numerically for conditions where the boundary of the enclosure is subjected to a nonlinear thermal profile. Since past few months we have been working on binary and ternary materials such as selenoiodides, doped zinc sulfides and mercurous chloro bromide and mercurous bromoiodides. In the doped and ternary materials thermal and solutal convection play extremely important role during the growth. Very commonly striations and banding is observed. Our experiments have indicated that even in highly purified source materials, homogeneity in 1-g environment is very difficult. Some of our previous numerical studies have indicated that gravity level less than 10-4 (?-g) helps in controlling the thermosolutal convection. We will discuss the ground based growth results of HgClxBr(1-x) and ZnSe growth results for the mm thick to large cm size crystals. These results will be compared with our microgravity experiments performed with this class of materials. For both HgCl-HgBr and ZnS-ZnSe the lattice parameters of the mixtures obey Vagard's law in the studied composition range. The study demonstrates that properties are very anisotropic with crystal orientation, and performance achievement requires extremely careful fabrication to utilize highest figure of merit. In addition, some parameters such as crystal growth fabrication, processing time, resolution, field of view and efficiency will be described based on novel solid solution materials. It was predicted that very similar to the pure compounds solid solutions also have very large anisotropy, and very precise oriented and homogeneous bulk and thin film crystals is required to achieve maximum performance of laser or imagers. Some of the parameters controlling the homogeneity such as thermos-solutal convection driven forces can be controlled in microgravity environments to utilize the benefits of these unique materials.
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NASA Astrophysics Data System (ADS)
van Sebille, M.; Fusi, A.; Xie, L.; Ali, H.; van Swaaij, R. A. C. M. M.; Leifer, K.; Zeman, M.
2016-09-01
We report the effect of hydrogen on the crystallization process of silicon nanocrystals embedded in a silicon oxide matrix. We show that hydrogen gas during annealing leads to a lower sub-band gap absorption, indicating passivation of defects created during annealing. Samples annealed in pure nitrogen show expected trends according to crystallization theory. Samples annealed in forming gas, however, deviate from this trend. Their crystallinity decreases for increased annealing time. Furthermore, we observe a decrease in the mean nanocrystal size and the size distribution broadens, indicating that hydrogen causes a size reduction of the silicon nanocrystals.
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NASA Astrophysics Data System (ADS)
Belloul, M.; Bartolo, J.-F.; Ziraoui, B.; Coldren, F.; Taly, V.; El Abed, A. I.
2013-07-01
We investigate the effect of an applied ac high voltage on a confined stable nematic liquid crystal (LC) in a microfluidic device and show that this actuation leads to the formation of highly monodisperse microdroplets with an unexpected constant mean size over a large interval of the forcing frequency F and with a droplets production frequency f ≃2F. We show also that despite the nonlinear feature of the droplets formation mechanism, droplets size, and size distribution are governed simply by the LC flow rate Qd and the forcing frequency F.
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Monte Carlo Optimization of Crystal Configuration for Pixelated Molecular SPECT Scanners
NASA Astrophysics Data System (ADS)
Mahani, Hojjat; Raisali, Gholamreza; Kamali-Asl, Alireza; Ay, Mohammad Reza
2017-02-01
Resolution-sensitivity-PDA tradeoff is the most challenging problem in design and optimization of pixelated preclinical SPECT scanners. In this work, we addressed such a challenge from a crystal point-of-view by looking for an optimal pixelated scintillator using GATE Monte Carlo simulation. Various crystal configurations have been investigated and the influence of different pixel sizes, pixel gaps, and three scintillators on tomographic resolution, sensitivity, and PDA of the camera were evaluated. The crystal configuration was then optimized using two objective functions: the weighted-sum and the figure-of-merit methods. The CsI(Na) reveals the highest sensitivity of the order of 43.47 cps/MBq in comparison to the NaI(Tl) and the YAP(Ce), for a 1.5×1.5 mm2 pixel size and 0.1 mm gap. The results show that the spatial resolution, in terms of FWHM, improves from 3.38 to 2.21 mm while the sensitivity simultaneously deteriorates from 42.39 cps/MBq to 27.81 cps/MBq when pixel size varies from 2×2 mm2 to 0.5×0.5 mm2 for a 0.2 mm gap, respectively. The PDA worsens from 0.91 to 0.42 when pixel size decreases from 0.5×0.5 mm2 to 1×1 mm2 for a 0.2 mm gap at 15° incident-angle. The two objective functions agree that the 1.5×1.5 mm2 pixel size and 0.1 mm Epoxy gap CsI(Na) configuration provides the best compromise for small-animal imaging, using the HiReSPECT scanner. Our study highlights that crystal configuration can significantly affect the performance of the camera, and thereby Monte Carlo optimization of pixelated detectors is mandatory in order to achieve an optimal quality tomogram.
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The role of particle size of glyburide crystals in improving its oral absorption.
Wang, Yongjun; Yang, Wenqian; Fu, Qiang; Guo, Zhibin; Sun, Bingjun; Liu, Wen; Liu, Yaxuan; Mu, Simeng; Guo, Mengran; Li, Jingru; Pu, Xiaohui; He, Zhonggui
2017-06-01
Currently, nanosizing is becoming increasingly prevalent as an efficient way for the improvement of oral drug absorption. This study mainly focuses on two points, namely the crystal properties, and the in vitro and in vivo characterizations of drug crystals during the nanosizing process. We used glyburide, an oral type 2 diabetes (T2D) medication, as our model drug. We sought to reduce the crystalline size of this drug and evaluate its absorption properties by comparing it with the original coarse drug because of previous reports about its gastrointestinal absorption insufficiency. Glyburide crystals, ranging from 237.6 to 4473 nm were prepared successfully by jet milling and media milling. The particle sizes and the crystal morphology were analyzed by characterization of the solid states, equilibrium solubility, and dissolution behavior. Additionally, pharmacokinetic study was performed in SD rats. The solid state results indicated a loss in crystallinity, amide-imidic acid interconversion, and partial amorphization during nanosizing. Further, in in vitro tests, nanocrystal formulations remarkably increased the solubility and dissolution of the drug (compared to microcrystals). In the in vivo test, reducing the particle size from 601.3 to 312.5 nm showed no improvement on the C max and AUC (0-36 h) values, while a profound slowing of the drug elimination occurred with reduction of particle size. Further reduction from 312.5 to 237.6 nm lead to a significant increase (p < 0.001) of the AUC (0-36 h) from 6857.8 ± 369.3 ng mL -1 h to 12,928.3 ± 1591.4 ng mL -1 h, respectively, in rats. Our present study confirmed that nanosizing has a tremendous impact on promoting the oral absorption of glyburide.
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Antireflective coating for AgBr-TlI and AgBr-TlBr0.46I0.54 solid solution crystals
NASA Astrophysics Data System (ADS)
Korsakov, Alexandr; Salimgareev, Dmitrii; Lvov, Alexandr; Zhukova, Liya
2016-12-01
We researched the process of ultraviolet (UV) irradiation for the crystals of AgBr-TlI and AgBr-TlBr0.46I0.54 systems. It was found that on the surface of irradiated crystals, the film is formed and film grain size depends on exposure time and crystal composition. This film proved to gain the transmission by reducing the reflection from its surface within the 8.0-27.0 μm range.
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McFarquhar, Greg
2011-07-25
Best estimate of cloud microphysical parameters derived using data collected by the cloud microphysical probes installed on the National Research Council (NRC) of Canada Convair-580 during ISDAC. These files contain phase, liquid and ice crystal size distributions (Nw(D) and Ni(D) respectively), liquid water content (LWC), ice water content (IWC), extinction of liquid drops (bw), extinction of ice crystals (bi), effective radius of water drops (rew) and of ice crystals (rei) and median mass diameter of liquid drops (Dmml) and of ice crystals (Dmmi) at 30 second resolution.
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NASA Astrophysics Data System (ADS)
Kuramata, Akito; Koshi, Kimiyoshi; Watanabe, Shinya; Yamaoka, Yu; Masui, Takekazu; Yamakoshi, Shigenobu
2018-02-01
This paper describes the bulk crystal growth of β-Ga2O3 using edge-defined film-fed growth (EFG) process. We first describe the method of the crystal growth and show that large-size crystal with width of up to 6 inch can be grown. Then, we discuss the way to control electrical properties. In the discussion, we give some experimental results of residual impurity measurement, intentional doping using Si and Sn for n-type doping and Fe for insulating doping.
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The Effect of Thermal Cycling on Crystal-Liquid Separation During Lunar Magma Ocean Differentiation
NASA Technical Reports Server (NTRS)
Mills, Ryan D.
2013-01-01
Differentiation of magma oceans likely involves a mixture of fractional and equilibrium crystallization [1]. The existence of: 1) large volumes of anorthosite in the lunar highlands and 2) the incompatible- rich (KREEP) reservoir suggests that fractional crystallization may have dominated during differentiation of the Moon. For this to have occurred, crystal fractionation must have been remarkably efficient. Several authors [e.g. 2, 3] have hypothesized that equilibrium crystallization would have dominated early in differentiation of magma oceans because of crystal entrainment during turbulent convection. However, recent numerical modeling [4] suggests that crystal settling could have occurred throughout the entire solidification history of the lunar magma ocean if crystals were large and crystal fraction was low. These results indicate that the crystal size distribution could have played an important role in differentiation of the lunar magma ocean. Here, I suggest that thermal cycling from tidal heating during lunar magma ocean crystallization caused crystals to coarsen, leading to efficient crystal-liquid separation.
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Light scattering by nonspherical particles: Remote sensing and climatic implications
NASA Astrophysics Data System (ADS)
Liou, K. N.; Takano, Y.
Calculations of the scattering and adsorption properties of ice crystals and aerosols, which are usually nonspherical, require specific methodologies. There is no unique theoretical solution for the scattering by nonspherical particles. Practically, all the numerical solutions for the scattering of nonspherical particles, including the exact wave equation approach, integral equation method, and discrete-dipole approximation, are applicable only to size parameters less than about 20. Thus, these methods are useful for the study of radiation problems involving nonspherical aerosols and small ice crystals in the thermal infrared wavelengths. The geometric optics approximation has been used to evaluate the scattering, absorption and polarization properties of hexagonal ice crystals whose sizes are much larger than the incident wavelength. This approximation is generally valid for hexagonal ice crystals with size parameters larger than about 30. From existing laboratory data and theoretical results, we illustrate that nonspherical particles absorb less and have a smaller asymmetry factor than the equal-projected area/volume spherical counterparts. In particular, we show that hexagonal ice crystals exhibit numerous halo and arc features that cannot be obtained from spherical particles; and that ice crystals scatter more light in the 60° to 140° scattering angle regions than the spherical counterparts. Satellite remote sensing of the optical depth and height of cirrus clouds using visible and IR channels must use appropriate phase functions for ice crystals. Use of an equivalent sphere model would lead to a significant overestimation and underestimation of the cirrus optical depth and height, respectively. Interpretation of the measurements for polarization reflected from sunlight involving cirrus clouds cannot be made without an appropriate ice crystal model. Large deviations exist for the polarization patterns between spheres and hexagonal ice crystals. Interpretation of lidar backscattering and depolarization signals must also utilize the scattering characteristics of hexagonal ice crystals. Equivalent spherical models substantially underestimate the broadband solar albedos of ice crystal clouds because of stronger forward scattering and larger absorption by spherical particles than hexagonal ice crystals. We illustrate that the net cloud radiative forcing at the top of the atmosphere involving most cirrus clouds is positive, implying that the IR greenhouse effect outweighs the solar albedo effect. If the radiative properties of equivalent spheres are used, a significant increase in cloud radiative forcing occurs. Using a one-dimensional cloud and climate model, we further demonstrate that there is sufficient model sensitivity, in terms of temperature increase, to the use of ice crystal models in radiation calculations.
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A Comparison between Airborne and Mountaintop Cloud Microphysics
NASA Astrophysics Data System (ADS)
David, R.; Lowenthal, D. H.; Hallar, A. G.; McCubbin, I.; Avallone, L. M.; Mace, G. G.; Wang, Z.
2014-12-01
Complex terrain has a large impact on cloud dynamics and microphysics. Several studies have examined the microphysical details of orographically-enhanced clouds from either an aircraft or from a mountain top location. However, further research is needed to characterize the relationships between mountain top and airborne microphysical properties. During the winter of 2011, an airborne study, the Colorado Airborne Mixed-Phase Cloud Study (CAMPS), and a ground-based field campaign, the Storm Peak Lab (SPL) Cloud Property Validation Experiment (StormVEx) were conducted in the Park Range of the Colorado Rockies. The CAMPS study utilized the University of Wyoming King Air (UWKA) to provide airborne cloud microphysical and meteorological data on 29 flights totaling 98 flight hours over the Park Range from December 15, 2010 to February 28, 2011. The UWKA was equipped with instruments that measured both cloud droplet and ice crystal size distributions, liquid water content, total water content (vapor, liquid, and ice), and 3-dimensional wind speed and direction. The Wyoming Cloud Radar and Lidar were also deployed during the campaign. These measurements are used to characterize cloud structure upwind and above the Park Range. StormVEx measured cloud droplet, ice crystal, and aerosol size distributions at SPL, located on the west summit of Mt. Werner at 3220m MSL. The observations from SPL are used to determine mountain top cloud microphysical properties at elevations lower than the UWKA was able to sample in-situ. Comparisons showed that cloud microphysics aloft and at the surface were consistent with respect to snow growth processes while small crystal concentrations were routinely higher at the surface, suggesting ice nucleation near cloud base. The effects of aerosol concentrations and upwind stability on mountain top and downwind microphysics are considered.
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Development of a Self Aligned CMOS Process for Flash Lamp Annealed Polycrystalline Silicon TFTs
NASA Astrophysics Data System (ADS)
Bischoff, Paul
The emerging active matrix liquid crystal (AMLCD) display market requires a high performing semiconductor material to meet rising standards of operation. Currently amorphous silicon (a-Si) dominates the market but it does not have the required mobility for it to be used in AMLCD manufacturing. Other materials have been developed including crystallizing a-Si into poly-silicon. A new approach to crystallization through the use of flash lamp annealing (FLA) decreases manufacturing time and greatly improves carrier mobility. Previous work on FLA silicon for the use in CMOS transistors revealed significant lateral dopant diffusion into the channel greatly increasing the minimum channel length required for a working device. This was further confounded by the gate overlap due to misalignment during lithography patterning steps. Through the use of furnace dopant activation instead of FLA dopant activation and a self aligned gate the minimum size transistor can be greatly reduced. A new lithography mask and process flow were developed for the furnace annealing and self aligned gate. Fabrication of the self aligned devices resulted in oxidation of the Molybdenum self aligned gate. Further development is needed to successfully manufacture these devices. Non-self aligned transistors were made simultaneously with self aligned devices and used the furnace activation. These devices showed an increase in sheet resistance from 250 O to 800 O and lower mobility from 380 to 40.2 V/cm2s. The lower mobility can be contributed to an increase in implanted trap density indicating furnace annealing is an inferior activation method over FLA. The minimum transistor size however was reduced from 20 to 5 mum. With improvements in the self aligned process high performing small devices can be manufactured.
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Nguyen, Duc; Zhu, Zhi-Guang; Pringle, Brian; Lyding, Joseph; Wang, Wei-Hua; Gruebele, Martin
2016-06-22
Glassy metallic alloys are richly tunable model systems for surface glassy dynamics. Here we study the correlation between atomic mobility, and the hopping rate of surface regions (clusters) that rearrange collectively on a minute to hour time scale. Increasing the proportion of low-mobility copper atoms in La-Ni-Al-Cu alloys reduces the cluster hopping rate, thus establishing a microscopic connection between atomic mobility and dynamics of collective rearrangements at a glass surface made from freshly exposed bulk glass. One composition, La60Ni15Al15Cu10, has a surface resistant to re-crystallization after three heating cycles. When thermally cycled, surface clusters grow in size from about 5 glass-forming units to about 8 glass-forming units, evidence of surface aging without crystal formation, although its bulk clearly forms larger crystalline domains. Such kinetically stable glass surfaces may be of use in applications where glassy coatings stable against heating are needed.
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The Effect of an Ultrasound Radiation on the Synthesis of 4A Zeolite from Fly Ash
NASA Astrophysics Data System (ADS)
Susanto, H.; Imani, N. A. C.; Aslamiyah, N. R.; Istirokhatun, T.; Robbani, M. H.
2018-05-01
The use of coal as a fuel source generates a lot of solid waste fly ash. Thus, efforts to reduce or utilize the amount of fly ash are urgently needed. This paper presents zeolite synthesis from fly ash. The fly ash was activated by using NaOH solution prior to fusing process with a weight ratio of 1:2 and mixing with distilled water at a weight ratio of 1:5. Thereafter, the addition of alumina with a concentration of 0.71 %, 1.42 %, 2.12 %, and 2.8 % w/v was performed. The effects of heating and ultrasound radiation on the characteristic of zeolite products were investigated. The results showed that the addition of alumina 2.8 % w/v resulted in the Si/Al ratio of zeolite 4A is ∼1. SEM images demonstrated that the presence of ultrasound wave resulted in crystals structure morphology as also supported by XRD characterization. The average crystal size for the ultrasonic treatment was 42.46 nm.
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NASA Astrophysics Data System (ADS)
Gao, Hong-Yue; Liu, Pan; Zeng, Chao; Yao, Qiu-Xiang; Zheng, Zhiqiang; Liu, Jicheng; Zheng, Huadong; Yu, Ying-Jie; Zeng, Zhen-Xiang; Sun, Tao
2016-09-01
We present holographic storage of three-dimensional (3D) images and data in a photopolymer film without any applied electric field. Its absorption and diffraction efficiency are measured, and reflective analog hologram of real object and image of digital information are recorded in the films. The photopolymer is compared with polymer dispersed liquid crystals as holographic materials. Besides holographic diffraction efficiency of the former is little lower than that of the latter, this work demonstrates that the photopolymer is more suitable for analog hologram and big data permanent storage because of its high definition and no need of high voltage electric field. Therefore, our study proposes a potential holographic storage material to apply in large size static 3D holographic displays, including analog hologram displays, digital hologram prints, and holographic disks. Project supported by the National Natural Science Foundation of China (Grant Nos. 11474194, 11004037, and 61101176) and the Natural Science Foundation of Shanghai, China (Grant No. 14ZR1415500).
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Choice and maintenance of equipment for electron crystallography.
Mills, Deryck J; Vonck, Janet
2013-01-01
The choice of equipment for an electron crystallography laboratory will ultimately be determined by the available budget; nevertheless, the ideal lab will have two electron microscopes: a dedicated 300 kV cryo-EM with a field emission gun and a smaller LaB(6) machine for screening. The high-end machine should be equipped with photographic film or a very large CCD or CMOS camera for 2D crystal data collection; the screening microscope needs a mid-size CCD for rapid evaluation of crystal samples. The microscope room installations should provide adequate space and a special environment that puts no restrictions on the collection of high-resolution data. Equipment for specimen preparation includes a carbon coater, glow discharge unit, light microscope, plunge freezer, and liquid nitrogen containers and storage dewars. When photographic film is to be used, additional requirements are a film desiccator, dark room, optical diffractometer, and a film scanner. Having the electron microscopes and ancillary equipment well maintained and always in optimum condition facilitates the production of high-quality data.
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Crystallization of bovine insulin on a flow-free droplet-based platform
NASA Astrophysics Data System (ADS)
Chen, Fengjuan; Du, Guanru; Yin, Di; Yin, Ruixue; Zhang, Hongbo; Zhang, Wenjun; Yang, Shih-Mo
2017-03-01
Crystallization is an important process in the pharmaceutical manufacturing industry. In this work, we report a study to create the zinc-free crystals of bovine insulin on a flow-free droplet-based platform we previously developed. The benefit of this platform is its promise to create a single type of crystals under a simpler and more stable environment and with a high throughput. The experimental result shows that the bovine insulin forms a rhombic dodecahedra shape and the coefficient variation (CV) in the size of crystals is less than 5%. These results are very promising for the insulin production.
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2000-05-01
A collage of protein and virus crystals, many of which were grown on the U.S. Space Shuttle or Russian Space Station, Mir. The crystals include the proteins canavalin; mouse monoclonal antibody; a sweet protein, thaumatin; and a fungal protease. Viruses are represented here by crystals of turnip yellow mosaic virus and satellite tobacco mosaic virus. The crystals are photographed under polarized light (thus causing the colors) and range in size from a few hundred microns in edge length up to more than a millimeter. All the crystals are grown from aqueous solutions and are useful for X-ray diffraction analysis. Credit: Dr. Alex McPherson, University of California, Irvine.
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On the morphological and chemical stability of vitamin C crystals
NASA Astrophysics Data System (ADS)
Halász, Susan; Bodor, Beáta
1993-03-01
Mass cooling crystallization of aqueous vitamin C solution was studied by applying different cooling rates, initial supersaturations and mixing intensity. The morphology of the products (size, habit and colour) well followed the changes of process parameters. Comparing a high purity (99.9%) standard with a yellow coloured heterodisperse product and a slowly grown single crystal, HPLC chromatography detected decreasing purity of the bigger single crystals, while X-ray and NMR analysis did not show any perceptible difference. It has been concluded that not the surface oxidation (chemical degredation), but rather the inclusions are the main sources of impurities within the crystals.
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Studies of lead tungstate crystals for the ALICE electromagnetic calorimeter PHOS
NASA Astrophysics Data System (ADS)
Ippolitov, M.; Beloglovsky, S.; Bogolubsky, M.; Burachas, S.; Erin, S.; Klovning, A.; Kuriakin, A.; Lebedev, V.; Lobanov, M.; Maeland, O.; Manko, V.; Nikulin, S.; Nyanin, A.; Odland, O. H.; Punin, V.; Sadovsky, S.; Samoilenko, V.; Sibiriak, Yu.; Skaali, B.; Tsvetkov, A.; Vinogradov, Yu.; Vasiliev, A.
2002-06-01
Full-size (22×22×180 mm 3) A LICE crystals were delivered by "North Crystals" company, Apatity, Russia. These crystals were tested with test benches, specially built for measurements of the crystals optical transmission and light yield. Beam-test results of different sets of 3×3 matrices with Hamamatsu APD light readout are presented. Data were taken at electron momenta from 600 MeV/ c up to 10 GeV/ c. Energy resolution and linearity curves are measured. The tests were carried out at the C ERN PS and SPS secondary beam-lines.
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Apparatus for detecting and recognizing analytes based on their crystallization patterns
Morozov, Victor; Bailey, Charles L.; Vsevolodov, Nikolai N.; Elliott, Adam
2010-12-14
The invention contemplates apparatuses for recognition of proteins and other biological molecules by imaging morphology, size and distribution of crystalline and amorphous dry residues in droplets (further referred to as "crystallization patterns") containing predetermined amount of certain crystal-forming organic compounds (reporters) to which protein to be analyzed is added. Changes in the crystallization patterns of a number of amino-acids can be used as a "signature" of a protein added. Also, changes in the crystallization patterns, as well as the character of such changes, can be used as recognition elements in analysis of protein molecules.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Foroughi, Leila M.; Kang, You-Na; Matzger, Adam J.
Obtaining single crystals for X-ray diffraction remains a major bottleneck in structural biology; when existing crystal growth methods fail to yield suitable crystals, often the target rather than the crystallization approach is reconsidered. Here we demonstrate that polymer-induced heteronucleation, a powerful technique that has been used for small molecule crystallization form discovery, can be applied to protein crystallization by optimizing the heteronucleant composition and crystallization formats for crystallizing a wide range of protein targets. Applying these advances to two benchmark proteins resulted in dramatically increased crystal size, enabling structure determination, for a half century old form of bovine liver catalasemore » (BLC) that had previously only been characterized by electron microscopy, and the discovery of two new forms of concanavalin A (conA) from the Jack bean and accompanying structural elucidation of one of these forms.« less
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NASA Astrophysics Data System (ADS)
Saidaminov, Makhsud I.; Abdelhady, Ahmed L.; Murali, Banavoth; Alarousu, Erkki; Burlakov, Victor M.; Peng, Wei; Dursun, Ibrahim; Wang, Lingfei; He, Yao; Maculan, Giacomo; Goriely, Alain; Wu, Tom; Mohammed, Omar F.; Bakr, Osman M.
2015-07-01
Single crystals of methylammonium lead trihalide perovskites (MAPbX3; MA=CH3NH3+, X=Br- or I-) have shown remarkably low trap density and charge transport properties; however, growth of such high-quality semiconductors is a time-consuming process. Here we present a rapid crystal growth process to obtain MAPbX3 single crystals, an order of magnitude faster than previous reports. The process is based on our observation of the substantial decrease of MAPbX3 solubility, in certain solvents, at elevated temperatures. The crystals can be both size- and shape-controlled by manipulating the different crystallization parameters. Despite the rapidity of the method, the grown crystals exhibit transport properties and trap densities comparable to the highest quality MAPbX3 reported to date. The phenomenon of inverse or retrograde solubility and its correlated inverse temperature crystallization strategy present a major step forward for advancing the field on perovskite crystallization.
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Macromolecule Crystal Quality Improvement in Microgravity: The Role of Impurities
NASA Technical Reports Server (NTRS)
Judge, Russell A.; Snell, Edward H.; Pusey, Marc L.; Sportiello, Michael G.; Todd, Paul; Bellamy, Henry; Borgstahl, Gloria E.; Pokros, Matt; Cassanto, John M.
2000-01-01
While macromolecule impurities may affect crystal size and morphology the over-riding question is; "How do macromolecule impurities effect crystal X-ray quality and diffraction resolution?" In the case of chicken egg white lysozyme, crystals can be grown in the presence of a number of impurities without affecting diffraction resolution. One impurity however, the lysozyme dimer, does negatively impact the X-ray crystal properties. Crystal quality improvement as a result of better partitioning of this impurity during crystallization in microgravity has been reported'. In our recent experimental work dimer partitioning was found to be not significantly different between the two environments. Mosaicity analysis of pure crystals showed a reduced mosaicity and increased signal to noise for the microgravity grown crystals. Dimer incorporation however, did greatly reduce the resolution limit in both ground and microgravity grown crystals. These results indicate that impurity effects in microgravity are complex and may rely on the conditions or techniques employed.
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Array integration of thousands of photonic crystal nanolasers
NASA Astrophysics Data System (ADS)
Watanabe, Takumi; Abe, Hiroshi; Nishijima, Yoshiaki; Baba, Toshihiko
2014-03-01
Photonic crystal (PC) nanolasers often consist of air-bridge PC slab, which enhances optical confinement while limiting its size to 30 × 30 μm2 due to the mechanical fragileness. This limit is broken by resin-mediated bonding of the PC slab on a host substrate. In this paper, we demonstrate a GaInAsP PC slab with a size of over 100 × 100 μm2 in which 1089, 2376, and 11 664 nanolasers showing high-yield laser operation are integrated.
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Arita, Toshihiko
2010-10-01
Commercially available unmodified ceramic nanoparticles (NPs) in dry powder state were surface-modified and dispersed in almost single-crystal size. The surface-initiated living radical polymerization after just UV-ozone soft etching enables one to graft polymers onto the surface of ceramic NPs and disperse them in solvents. Furthermore, a number of NPs were dispersed with single-crystal sizes. The technique developed here could be applied to almost all ceramic NPs including metal nitrides.
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Relating Cirrus Cloud Properties to Observed Fluxes: A Critical Assessment.
NASA Astrophysics Data System (ADS)
Vogelmann, A. M.; Ackerman, T. P.
1995-12-01
The accuracy needed in cirrus cloud scattering and microphysical properties is quantified such that the radiative effect on climate can he determined. Our ability to compute and observe these properties to within needed accuracies is assessed, with the greatest attention given to those properties that most affect the fluxes.Model calculations indicate that computing net longwave fluxes at the surface to within ±5% requires that cloud temperature be known to within as little as ±3 K in cold climates for extinction optical depths greater than two. Such accuracy could be more difficult to obtain than that needed in the values of scattering parameters. For a baseline case (defined in text), computing net shortwave fluxes at the surface to within ±5% requires accuracies in cloud ice water content that, when the optical depth is greater than 1.25, are beyond the accuracies of current measurements. Similarly, surface shortwave flux computations require accuracies in the asymmetry parameter that are beyond our current abilities when the optical depth is greater than four. Unless simplifications are discovered, the scattering properties needed to compute cirrus cloud fluxes cannot be obtained explicitly with existing scattering algorithms because the range of crystal sizes is too great and crystal shapes are too varied to be treated computationally. Thus, bulk cirrus scattering properties might be better obtained by inverting cirrus cloud fluxes and radiances. Finally, typical aircraft broadband flux measurements are not sufficiently accurate to provide a convincing validation of calculations. In light of these findings we recommend a reexamination of the methodology used in field programs such as FIRE and suggest a complementary approach.
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Magnetic Resonance Characterization of Defects in Icosahedral and Cubic Boron Arsenide Bulk Crystals
NASA Astrophysics Data System (ADS)
Glaser, E. R.; Freitas, J. A., Jr.; Cress, C. D.; Perkins, F. K.; Prokes, S. M.; Ruppalt, L. B.; Culbertson, J. C.; Whiteley, C.; Edgar, J. H.; Tian, F.; Ren, Z.; Kim, J.; Shi, L.; Naval Research Lab Team; Kansas State U. Team; U. Houston Team; U. Texas Team
Low-temperature electron spin resonance (ESR) at 9.5 GHz and optically-detected magnetic resonance (ODMR) at 24 GHz were employed to investigate point defects in icosahedral and cubic Boron Arsenide bulk crystals. These semiconductors are of interest for use in high radiation and/or high temperature environments. ESR of the (001) B12As2 (Eg = 3.47 eV) mm-size platelets revealed two distinct features of unknown origin. The first signal is characterized by Zeeman splitting g-values of g|| = 2.017, g⊥ = 2.0183 while the second with g|| = 2.0182, g⊥ = 1.9997. Most notably, the second signal was also observed from ODMR on the broad 2.4 eV ``yellow/green'' photoluminescence band previously reported for these crystals and suggests its direct involvement in this likely defect-related radiative recombination process. Preliminary ESR obtained for the 100-300 micron-size cubic BAs crystals revealed a signal with g-value of 2.018 (very similar to that found for the B12As2 crystals) and broad FWHM value of 182 G. Possible origins of these defects will be discussed.
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NASA Astrophysics Data System (ADS)
Zheng, Limei; Wang, Junjun; Liu, Xuedong; Yang, Liya; Lu, Xiaoyan; Li, Yanran; Huo, Da; Lü, Weiming; Yang, Bin; Cao, Wenwu
2017-10-01
A Li and Ta modified (K, Na)NbO3 lead-free single crystal with a large size (13 × 10 × 20 mm3) has been grown by using the top-seeded solution growth method. The large size allows us to carry out an extensive study on this tetragonal crystal. We have measured a complete set of elastic, dielectric, and piezoelectric constants for the [001]C poled crystal with the single domain state. The crystal exhibits high shear piezoelectricity with d15 = 518 pC/N and k15 = 0.733, showing excellent potential in shear electro-sonic energy transformation devices. It is found that the high shear piezoelectricity originates from the vicinity of orthorhombic-tetragonal phase transition, which favors polarization rotation greatly. The orientation dependence of longitudinal dielectric, piezoelectric, and elastic constants and electromechanical coupling factor in the 3-dimentional space were calculated based on the single domain dataset. We believe that this work is of great importance for both fundamental studies and device designs for lead-free materials.
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Finite-Difference Time-Domain Analysis of Tapered Photonic Crystal Fiber
NASA Astrophysics Data System (ADS)
Ali, M. I. Md; Sanusidin, S. N.; Yusof, M. H. M.
2018-03-01
This paper brief about the simulation of tapered photonic crystal fiber (PCF) LMA-8 single-mode type based on correlation of scattering pattern at wavelength of 1.55 μm, analyzation of transmission spectrum at wavelength over the range of 1.0 until 2.5 μm and correlation of transmission spectrum with the refractive index change in photonic crystal holes with respect to taper size of 0.1 until 1.0 using Optiwave simulation software. The main objective is to simulate using Finite-Difference Time-Domain (FDTD) technique of tapered LMA-8 PCF and for sensing application by improving the capabilities of PCF without collapsing the crystal holes. The types of FDTD techniques used are scattering pattern and transverse transmission and principal component analysis (PCA) used as a mathematical tool to model the data obtained by MathCad software. The simulation results showed that there is no obvious correlation of scattering pattern at a wavelength of 1.55 μm, a correlation obtained between taper sizes with a transverse transmission and there is a parabolic relationship between the refractive index changes inside the crystal structure.
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Investigating the Effect of Impurities on Macromolecule Crystal Growth in Microgravity
NASA Technical Reports Server (NTRS)
Snell, Edward H.; Judge, Russell A.; Crawford, Lisa; Forsythe, Elizabeth L.; Pusey, Marc L.; Sportiello, Michael; Todd, Paul; Bellamy, Henry; Lovelace, Jeff; Cassanto, John M.;
2001-01-01
Chicken egg-white lysozyme (CEWL) crystals were grown in microgravity and on the ground in the presence of various amounts of a naturally occurring lysozyme dimer impurity. No significant favorable differences in impurity incorporation between microgravity and ground crystal samples were observed. At low impurity concentration the microgravity crystals preferentially incorporated the dimer. The presence of the dimer in the crystallization solutions in microgravity reduced crystal size, increased mosaicity and reduced the signal to noise ratio of the X-ray data. Microgravity samples proved more sensitive to impurity. Accurate indexing of the reflections proved critical to the X-ray analysis. The largest crystals with the best X-ray diffraction properties were grown from pure solution in microgravity.
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Recent advances and progress in photonic crystal-based gas sensors
NASA Astrophysics Data System (ADS)
Goyal, Amit Kumar; Sankar Dutta, Hemant; Pal, Suchandan
2017-05-01
This review covers the recent progress made in the photonic crystal-based sensing technology for gas sensing applications. Photonic crystal-based sensing has tremendous potential because of its obvious advantages in sensitivity, stability, miniaturisation, portability, online use, remote monitoring etc. Several 1D and 2D photonic crystal structures including photonic crystal waveguides and cavities for gas sensing applications have been discussed in this review. For each kind of photonic crystal structure, the novelty, measurement principle and their respective gas sensing properties are presented. The reported works and the corresponding results predict the possibility to realize a commercially viable miniaturized and highly sensitive photonic crystal-based optical gas sensor having flexibility in the structure of ultra-compact size with excellent sensing properties.
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SEM-induced shrinkage and site-selective modification of single-crystal silicon nanopores
NASA Astrophysics Data System (ADS)
Chen, Qi; Wang, Yifan; Deng, Tao; Liu, Zewen
2017-07-01
Solid-state nanopores with feature sizes around 5 nm play a critical role in bio-sensing fields, especially in single molecule detection and sequencing of DNA, RNA and proteins. In this paper we present a systematic study on shrinkage and site-selective modification of single-crystal silicon nanopores with a conventional scanning electron microscope (SEM). Square nanopores with measurable sizes as small as 8 nm × 8 nm and rectangle nanopores with feature sizes (the smaller one between length and width) down to 5 nm have been obtained, using the SEM-induced shrinkage technique. The analysis of energy dispersive x-ray spectroscopy and the recovery of the pore size and morphology reveal that the grown material along with the edge of the nanopore is the result of deposition of hydrocarbon compounds, without structural damage during the shrinking process. A simplified model for pore shrinkage has been developed based on observation of the cross-sectional morphology of the shrunk nanopore. The main factors impacting on the task of controllably shrinking the nanopores, such as the accelerating voltage, spot size, scanned area of e-beam, and the initial pore size have been discussed. It is found that single-crystal silicon nanopores shrink linearly with time under localized irradiation by SEM e-beam in all cases, and the pore shrinkage rate is inversely proportional to the initial equivalent diameter of the pore under the same e-beam conditions.
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Shieh, Fa-Kuen; Wang, Shao-Chun; Yen, Chia-I; Wu, Chang-Cheng; Dutta, Saikat; Chou, Lien-Yang; Morabito, Joseph V; Hu, Pan; Hsu, Ming-Hua; Wu, Kevin C-W; Tsung, Chia-Kuang
2015-04-08
We develop a new concept to impart new functions to biocatalysts by combining enzymes and metal-organic frameworks (MOFs). The proof-of-concept design is demonstrated by embedding catalase molecules into uniformly sized ZIF-90 crystals via a de novo approach. We have carried out electron microscopy, X-ray diffraction, nitrogen sorption, electrophoresis, thermogravimetric analysis, and confocal microscopy to confirm that the ~10 nm catalase molecules are embedded in 2 μm single-crystalline ZIF-90 crystals with ~5 wt % loading. Because catalase is immobilized and sheltered by the ZIF-90 crystals, the composites show activity in hydrogen peroxide degradation even in the presence of protease proteinase K.
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NASA Astrophysics Data System (ADS)
Zheng, YinBo; Ding, Lei; Zhou, XinDa; Ba, RongSheng; Yuan, Jing; Xu, HongLei; Na, Jin; Li, YaJun; Yang, XiaoYu; Chai, Liqun; Chen, Bo; Zheng, WanGuo
2016-08-01
The investigation of polarization orientation on damage performance of type I doubler KDP crystals under different wavelengths pulses irradiation is presented in this work. Pinpoints densities (PPD) and the size distribution of pinpoints are extracted through light scattering pictures captured by microscope. The obtained results indicate that the measured PPD as a function of the fluence is both wavelength and polarization dependent, although neither fluence nor polarization have impact on the size distribution of pinpoints. We also find that the damage performances can separate into three groups depending on the wavelength, which suggests the existence of different categories of precursors and different mechanisms responsible for bulk damage initiation in SHG KDP crystals.
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Facile growth of a single-crystal pattern: a case study of HKUST-1.
Li, Shaozhou; Lu, Guang; Huang, Xiao; Li, Hai; Sun, Yinghui; Zhang, Hua; Chen, Xiaodong; Huo, Fengwei
2012-12-18
In order to fabricate metal-organic framework (MOF) based devices, it is desirable to precisely position high-quality and mono-sized MOF crystals on supports. In this work, we demonstrate a facile solution procedure for the fabrication of oriented and monodispersed single-crystal MOF pattern. We expect that such capability will expand the scope of applications of MOFs to advanced fields.
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35 GHz Measurements of CO2 Crystals for Simulating Observations of the Martian Polar Caps
NASA Technical Reports Server (NTRS)
Foster, J. L.; Chang, A. T. C.; Hall, D. K.; Tait, A. B.; Barton, J. S.
1998-01-01
In order to learn more about the Martian polar caps, it is important to compare and contrast the behavior of both frozen H2O and CO2 in different parts of the electromagnetic spectrum. Relatively little attention has been given, thus far, to observing the thermal microwave part of the spectrum. In this experiment, passive microwave radiation emanating from within a 33 cm snowpack was measured with a 35 GHz hand-held radiometer, and in addition to the natural snow measurements, the radiometer was used to measure the microwave emission and scattering from layers of manufactured CO2 (dry ice). A 1 m x 2 m plate of aluminum sheet metal was positioned beneath the natural snow so that microwave emissions from the underlying soil layers would be minimized. Compared to the natural snow crystals, results for the dry ice layers exhibit lower' microwave brightness temperatures for similar thicknesses, regardless of the incidence angle of the radiometer. For example, at 50 degree H (horizontal polarization) and with a covering of 21 cm of snow and 18 cm of dry ice, the brightness temperatures were 150 K and 76 K, respectively. When the snow depth was 33 cm, the brightness temperature was 144 K, and when the total thickness of the dry ice was 27 cm, the brightness temperature was 86 K. The lower brightness temperatures are due to a combination of the lower physical temperature and the larger crystal sizes of the commercial CO2 Crystals compared to the snow crystals. As the crystal size approaches the size of the microwave wavelength, it scatters microwave radiation more effectively, thus lowering the brightness temperature. The dry ice crystals in this experiment were about an order of magnitude larger than the snow crystals and three orders of magnitude larger than the CO2 Crystals produced in the cold stage of a scanning electron microscope. Spreading soil, approximately 2 mm in thickness, on the dry ice appeared to have no effect on the brightness temperatures.
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NASA Technical Reports Server (NTRS)
Kramer, H. G.
1981-01-01
The power needed to zone silicon crystals by radio frequency heating was analyzed. The heat loss mechanisms are examined. Curves are presented for power as a function of crystal diameter for commercial silicon zoning.
