Finding the "true" age: ways to read high-precision U-Pb zircon dates

NASA Astrophysics Data System (ADS)

Schaltegger, U.; Schoene, B.; Ovtcharova, M.; Sell, B. K.; Broderick, C. A.; Wotzlaw, J.

2011-12-01

Refined U-Pb dating techniques, applying an empirical chemical abrasion treatment prior to analysis [1], and using a precisely calibrated double isotope Pb, U EARTHTIME tracer solution, have led to an unprecedented <0.1% precision and accuracy of obtained 206Pb/238U dates of single zircon crystals or fragments. Results very often range over 10e4 to 10e6 years and cannot be treated as statistically singular age populations. The interpretation of precise zircon U-Pb ages is biased by two problems: (A) Post-crystallization Pb loss from decay damaged areas is considered to be mitigated by applying chemical abrasion techniques. The success of such treatment can, however, not be assumed a priori. The following examples demonstrate that youngest zircons are not biased by lead loss but represent close-to-youngest zircon growth: (i) coincidence of youngest zircon dates with co-magmatic titanite in tonalite; (ii) coincidence with statistically equivalent clusters of 206Pb/238U dates from zircon in residual melts of cogenetic mafic magmas; (iii) youngest zircons in ash beds of sedimentary sequences do not violate the stratigraphic superposition, whereas conventional statistical interpretation (mean or median values) does; (iv) results of published inter-laboratory cross-calibration tests using chemical abrasion on natural zircon crystals of the same sample arrive at the same 206Pb/238U result within <0.1% (e.g., [2]); (v) Youngest crystals coincide in age with the astronomical age of hosting cyclic sediments. Residual lead loss may, however, still be identified in the case of single, significantly younger dates (>3 sigma), and are common in many pre-Triassic and hydrothermally altered rocks. (B) Pre-eruptive/pre-intrusive growth is found to be the main reason for scattered zircon ages in igneous rocks. Zircons crystallizing from the final magma batch are called autocrystic [3]. Autocrystic growth will happen in a moving or stagnant magma shortly before or after the rheological lockup by the crystals. Last crystallizing zircons in the interstitial melt may therefore postdate emplacement of the magma. The range of 206Pb/238U ages may yield a time frame for the cooling of a given magma batch, which could be added to quantitative thermal models of magma emplacement and cooling. Hf isotopes and trace elements of the dated zircon are used to trace the nature of the dated grains [4], specifically for identification of crystals that form earlier at lower crustal levels (antecrysts). Autocrystic zircons typically show, e.g., distinctly different (higher or lower) Th/U ratios. Cautiously interpreted high-precision U-Pb data of chemically abraded zircons may resolve the evolution of a magmatic system from its roots to final emplacement or eruption, trace fractional crystallization of zircon and other accessory and major phases in a magma batch, and add quantitative temporal constraints to thermal models. The proposed interpretation scheme thus adds significant information compared to conventional statistics. [1] Mattinson J., 2005, Chem. Geol. 200, 47-66; ; [2] Slama et al., 2008, Chem. Geol. 249, 1-35; [3] Miller et al., 2007, J. Volc. Geotherm. Res. 167, 282-299; [4] Schoene et al., 2010, Geochim. Cosmochim. Acta 74, 7144-7159

Estimation of the growth kinetics for the cooling crystallisation of paracetamol and ethanol solutions

NASA Astrophysics Data System (ADS)

Mitchell, Niall A.; Ó'Ciardhá, Clifford T.; Frawley, Patrick J.

2011-08-01

This work details the estimation of the growth kinetics of paracetamol in ethanol solutions for cooling crystallisation processes, by means of isothermal seeded batch experiments. The growth kinetics of paracetamol crystals were evaluated in isolation, with the growth rate assumed to be size independent. Prior knowledge of the Metastable Zone Width (MSZW) was required, so that supersaturation ratios of 1.7-1.1 could be induced in solution without the occurrence of nucleation. The technique involved the utilisation of two in-situ Process Analytical Techniques (PATs), with a Focused Beam Reflectance Measurement (FBRM ®) utilised to ensure that negligible nucleation occurred and an Attenuated Total Reflectance-Fourier Transform Infrared (ATR-FTIR) probe employed for online monitoring of solute concentration. Initial Particle Size Distributions (PSDs) were used in conjunction with desupersaturation profiles to determine the growth rate as a function of temperature and supersaturation. Furthermore, the effects of seed loading and size on the crystal growth rate were investigated. A numerical model, incorporating the population balance equation and the method of moments, was utilised to describe the crystal growth process. Experimental parameters were compared to the model simulation, with the accuracy of the model validated by means of the final product PSDs and solute concentration.

Batch crystallization of rhodopsin for structural dynamics using an X-ray free-electron laser

DOE PAGES

Wu, Wenting; Nogly, Przemyslaw; Rheinberger, Jan; ...

2015-06-27

Rhodopsin is a membrane protein from the G protein-coupled receptor family. Together with its ligand retinal, it forms the visual pigment responsible for night vision. In order to perform ultrafast dynamics studies, a time-resolved serial femtosecond crystallography method is required owing to the nonreversible activation of rhodopsin. In such an approach, microcrystals in suspension are delivered into the X-ray pulses of an X-ray free-electron laser (XFEL) after a precise photoactivation delay. Here in this study, a millilitre batch production of high-density microcrystals was developed by four methodical conversion steps starting from known vapour-diffusion crystallization protocols: (i) screening the low-salt crystallizationmore » conditions preferred for serial crystallography by vapour diffusion, (ii) optimization of batch crystallization, (iii) testing the crystal size and quality using second-harmonic generation (SHG) imaging and X-ray powder diffraction and (iv) production of millilitres of rhodopsin crystal suspension in batches for serial crystallography tests; these crystals diffracted at an XFEL at the Linac Coherent Light Source using a liquid-jet setup.« less

Gypsum crystal size distribution in four continuous flow stirred slurry boric acid reactors in series compared with the batch

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.

Effects of cooling interval and MnO2, TiO2, CdO, NiO additions on spheluritic willemite crystals

NASA Astrophysics Data System (ADS)

Coşkun, Nihal Derin; Uz, Veli; Issi, Ali; Genç, Soner; Çakı, Münevver

2017-01-01

Macro crystal production in crystal glaze systems is a very important topic in ceramic art and science. In this study, crystal growth was obtained in two different firing regimes. Recipes were prepared by adding MnO, TiO, NiO and CdO into the frit. The first firing regime, which is used in artistic ceramics, has a 100 °C cooling temperature interval. The second regime that has a 580 °C cooling temperature interval, was determined by DTA analysis. Then, the development of crystals was compared between these two firing regimes. According to the results, spheluritic willemite crystals up to three cm in the glazes doped MnO2 have been obtained by cooling it in a wide cooling interval. Larger willemite crystals were not formed in the narrow cooling temperature interval. It was determined that larger crystals can be produced by cooling at wide cooling temperature intervals and holding at lower temperature which involves nucleating the temperature of the crystal.

Effect of Cooling Rates on Shape and Crystal Size Distributions of Mefenamic Acid Polymorph in Ethyl Acetate

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.

Protein Crystals and their Growth

NASA Technical Reports Server (NTRS)

Chernov, A. A.

2004-01-01

Recent results on binding between protein molecules in crystal lattice, crystal-solution surface energy, elastic properties and strength and spontaneous crystal cracking are reviewed and discussed in the first half of this paper (Sea 2-4). In the second par&, some basic approaches to solubility of proteins are followed by overview on crystal nucleation and growth (Sec 5). It is argued that variability of mixing in batch crystallization may be a source for scattering of crystal number ultimately appearing in the batch. Frequency at which new molecules join crystal lattice is measured by kinetic coefficient and related to the observable crystal growth rate. Numerical criteria to discriminate diffusion and kinetic limited growth are discussed on this basis in Sec 7. In Sec 8, creation of defects is discussed with the emphasis on the role of impurities and convection on macromolecular crystal I;erfection.

A green preparation method of battery grade α-PbO based on Pb-O2 fuel cell

NASA Astrophysics Data System (ADS)

Wang, Pingyuan; Pan, Junqing; Gong, Shumin; Sun, Yanzhi

2017-08-01

In order to solve the problem of high pollution and high energy consumption of the current lead oxide (PbO) preparation processes, a new clean and energy saving preparation method for high purity α-PbO via discharge of a Pb-O2 fuel cell is reported. The fuel cell with metallic lead anode, oxygen cathode, and 30% NaOH electrolyte can provide a discharge voltage of 0.66-0.38 V corresponding to discharge current range of 5-50 mA cm-2. PbO is precipitated from the NaHPbO2-containing electrolyte through a cooling crystallization process after discharge process, and the XRD patterns indicate the structure is pure α-PbO. The mother liquid after crystallization can be recycled for the next batch. The obtained PbO mixed with 60% Shimadzu PbO is superior to the pure Shimadzu PbO in discharge capacity and cycle ability.

High density protein crystal growth

NASA Technical Reports Server (NTRS)

Rouleau, Robyn (Inventor); Hedden, Douglas Keith (Inventor); Delucas, Lawrence (Inventor)

2004-01-01

A protein crystal growth assembly including a crystal growth cell and further including a cell body having a top side and a bottom side and a first aperture defined therethrough, the cell body having opposing first and second sides and a second aperture defined therethrough. A cell barrel is disposed within the cell body, the cell barrel defining a cavity alignable with the first aperture of the cell body, the cell barrel being rotatable within the second aperture. A reservoir is coupled to the bottom side of the cell body and a cap having a top side is disposed on the top side of the cell body. The protein crystal growth assembly may be employed in methods including vapor diffusion crystallization, liquid to liquid crystallization, batch crystallization, and temperature induction batch mode crystallization.

Improving crystal size distribution by internal seeding combined cooling/antisolvent crystallization with a cooling/heating cycle

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.

Stacking with stochastic cooling

NASA Astrophysics Data System (ADS)

Caspers, Fritz; Möhl, Dieter

2004-10-01

Accumulation of large stacks of antiprotons or ions with the aid of stochastic cooling is more delicate than cooling a constant intensity beam. Basically the difficulty stems from the fact that the optimized gain and the cooling rate are inversely proportional to the number of particles 'seen' by the cooling system. Therefore, to maintain fast stacking, the newly injected batch has to be strongly 'protected' from the Schottky noise of the stack. Vice versa the stack has to be efficiently 'shielded' against the high gain cooling system for the injected beam. In the antiproton accumulators with stacking ratios up to 105 the problem is solved by radial separation of the injection and the stack orbits in a region of large dispersion. An array of several tapered cooling systems with a matched gain profile provides a continuous particle flux towards the high-density stack core. Shielding of the different systems from each other is obtained both through the spatial separation and via the revolution frequencies (filters). In the 'old AA', where the antiproton collection and stacking was done in one single ring, the injected beam was further shielded during cooling by means of a movable shutter. The complexity of these systems is very high. For more modest stacking ratios, one might use azimuthal rather than radial separation of stack and injected beam. Schematically half of the circumference would be used to accept and cool new beam and the remainder to house the stack. Fast gating is then required between the high gain cooling of the injected beam and the low gain stack cooling. RF-gymnastics are used to merge the pre-cooled batch with the stack, to re-create free space for the next injection, and to capture the new batch. This scheme is less demanding for the storage ring lattice, but at the expense of some reduction in stacking rate. The talk reviews the 'radial' separation schemes and also gives some considerations to the 'azimuthal' schemes.

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.

Crystallization history of lunar picritic basalt sample 12002 - Phase-equilibria and cooling-rate studies

NASA Technical Reports Server (NTRS)

Walker, D.; Kirkpatrick, R. J.; Longhi, J.; Hays, J. F.

1976-01-01

Experimental crystallization of a lunar picrite composition (sample 12002) at controlled linear cooling rates produces systematic changes in the temperature at which crystalline phases appear, in the texture, and in crystal morphology as a function of cooling rate. Phases crystallize in the order olivine, chromium spinel, pyroxene, plagioclase, and ilmenite during equilibrium crystallization, but ilmenite and plagioclase reverse their order of appearance and silica crystallizes in the groundmass during controlled cooling experiments. The partition of iron and magnesium between olivine and liquid is independent of cooling rate, temperature, and pressure. Comparison of the olivine nucleation densities in the lunar sample and in the experiments indicates that the sample began cooling at about 1 deg C/hr. Pyroxene size, chemistry, and growth instability spacings, as well as groundmass coarseness, all suggest that the cooling rate subsequently decreased by as much as a factor of 10 or more. The porphyritic texture of this sample, then, is produced at a decreasing, rather than a discontinuously increasing, cooling rate.

Investigation of the operating conditions to morphology evolution of β-L-glutamic acid during seeded cooling crystallization

NASA Astrophysics Data System (ADS)

Zhang, Fangkun; Liu, Tao; Huo, Yan; Guan, Runduo; Wang, Xue Z.

2017-07-01

In this paper the effects of operating conditions including cooling rate, initial supersaturation, and seeding temperature were investigated on the morphology evolution of β-L-glutamic acid (β-LGA) during seeded cooling crystallization. Based on the results of in-situ image acquisition of the crystal morphology evolution during the crystallization process, it was found that the crystal products tend to be plate-like or short rod-like under a slow cooling rate, low initial supersaturation, and low seeding temperature. In the opposite, the operating conditions of a faster cooling rate, higher initial supersaturation, and higher seeding temperature tend to produce long rod-like or needle-like crystals, and meanwhile, the length and width of crystal products will be increased together with a wider crystal size distribution (CSD). The aspect ratio of crystals, defined by the crystal length over width measured from in-situ or sample images, was taken as a shape index to analyze the crystal morphologies. Based on comparative analysis of the experimental results, guidelines on these operating conditions were given for obtaining the desired crystal shapes, along with the strategies for obtaining a narrower CSD for better product quality. Experimental verifications were performed to illustrate the proposed guidelines on the operating conditions for seeded cooling crystallization of LGA solution.

Crystal Engineering for Low Defect Density and High Efficiency Hybrid Chemical Vapor Deposition Grown Perovskite Solar Cells.

PubMed

Ng, Annie; Ren, Zhiwei; Shen, Qian; Cheung, Sin Hang; Gokkaya, Huseyin Cem; So, Shu Kong; Djurišić, Aleksandra B; Wan, Yangyang; Wu, Xiaojun; Surya, Charles

2016-12-07

Synthesis of high quality perovskite absorber is a key factor in determining the performance of the solar cells. We demonstrate that hybrid chemical vapor deposition (HCVD) growth technique can provide high level of versatility and repeatability to ensure the optimal conditions for the growth of the perovskite films as well as potential for batch processing. It is found that the growth ambient and degree of crystallization of CH 3 NH 3 PbI 3 (MAPI) have strong impact on the defect density of MAPI. We demonstrate that HCVD process with slow postdeposition cooling rate can significantly reduce the density of shallow and deep traps in the MAPI due to enhanced material crystallization, while a mixed O 2 /N 2 carrier gas is effective in passivating both shallow and deep traps. By careful control of the perovskite growth process, a champion device with power conversion efficiency of 17.6% is achieved. Our work complements the existing theoretical studies on different types of trap states in MAPI and fills the gap on the theoretical analysis of the interaction between deep levels and oxygen. The experimental results are consistent with the theoretical predictions.

Gas-liquid reactive crystallization kinetics of 2,4,6-triamino-1,3,5-trinitrobenzene in the semi-batch procedure

NASA Astrophysics Data System (ADS)

Liu, Ruqin; Huang, Ming; Yao, Xiaolu; Chen, Shuang; Wang, Shucun; Suo, Zhirong

2018-06-01

2,4,6-Triamino-1,3,5-trinitrobenzene is the attractive insensitive high energetic material used extensively in the military and civil fields. Combined with the double-films theory, the global gas-liquid chemical reaction kinetics of 2,4,6-triamino-1,3,5-trinitrobenzene was developed by means of the infinitesimal material balance calculation. The raw material concentration and reactive temperature effects on the crystallization of 2,4,6-triamino-1,3,5-trinitrobenzene were investigated by the batch experiments. The reactive crystallization kinetics associated ammonia feeding rate of 2,4,6-triamino-1,3,5-trinitrobenzene, including nucleation as well as crystal growth, was systematically investigated in the heterogonous semi-batch procedure. The nucleation and crystal growth kinetic exponents were estimated by the linear least-squares method. The crystallization kinetic results indicated that nucleation rate strongly increased but liner growth rate decreased with the increasing of ammonia feeding rate. In terms of manufacturing coarse 2,4,6-triamino-1,3,5-trinitrobenzene, it was found that a slow ammonia feeding rate and a low raw material concentration were feasible under the present experimental conditions.

Computing Cooling Flows in Turbines

NASA Technical Reports Server (NTRS)

Gauntner, J.

1986-01-01

Algorithm developed for calculating both quantity of compressor bleed flow required to cool turbine and resulting decrease in efficiency due to cooling air injected into gas stream. Program intended for use with axial-flow, air-breathing, jet-propulsion engines with variety of airfoil-cooling configurations. Algorithm results compared extremely well with figures given by major engine manufacturers for given bulk-metal temperatures and cooling configurations. Program written in FORTRAN IV for batch execution.

A Differential Scanning Calorimetry Method for Construction of Continuous Cooling Transformation Diagram of Blast Furnace Slag

NASA Astrophysics Data System (ADS)

Gan, Lei; Zhang, Chunxia; Shangguan, Fangqin; Li, Xiuping

2012-06-01

The continuous cooling crystallization of a blast furnace slag was studied by the application of the differential scanning calorimetry (DSC) method. A kinetic model describing the correlation between the evolution of the degree of crystallization with time was obtained. Bulk cooling experiments of the molten slag coupled with numerical simulation of heat transfer were conducted to validate the results of the DSC methods. The degrees of crystallization of the samples from the bulk cooling experiments were estimated by means of the X-ray diffraction (XRD) and the DSC method. It was found that the results from the DSC cooling and bulk cooling experiments are in good agreement. The continuous cooling transformation (CCT) diagram of the blast furnace slag was constructed according to crystallization kinetic model and experimental data. The obtained CCT diagram characterizes with two crystallization noses at different temperature ranges.

Process Analytical Technology in Freeze-Drying: Detection of the Secondary Solute + Water Crystallization with Heat Flux Sensors.

PubMed

Wang, Qiming; Shalaev, Evgenyi

2018-04-01

In situ and non-invasive detection of solute crystallization during freeze-drying would facilitate cycle optimization and scale-up from the laboratory to commercial manufacturing scale. The objective of the study is to evaluate heat flux sensor (HFS) as a tool for monitoring solute crystallization and other first-order phase transitions (e.g., onset of freezing). HFS is a thin-film differential thermopile, which acts as a transducer to generate an electrical signal proportional to the total heat applied to its surface. In this study, HFS is used to detect both primary (ice formation) and secondary (also known as eutectic) solute + water crystallization during cooling and heating of solutions in a freeze-dryer. Binary water-solute mixtures with typical excipients concentrations (e.g., 0.9% of NaCl and 5% mannitol) and fill volumes (1 to 3 ml/vial) are studied. Secondary crystallization is detected by the HFS during cooling in all experiments with NaCl solutions, whereas timing of mannitol crystallization depends on the cooling conditions. In particular, mannitol crystallization takes place during cooling, if the cooling rate is lower than the critical value. On the other hand, if the cooling rate exceeds the critical cooling rate, mannitol crystallization during cooling is prevented, and crystallization occurs during subsequent warming or annealing. It is also observed that, while controlled ice nucleation allows initiation of the primary freezing event in different vials simultaneously, there is a noticeable vial-to-vial difference in the timing of secondary crystallization. The HFS could be a valuable process monitoring tool for non-invasive detection of various crystallization events during freeze-drying manufacturing.

Solid state optical refrigeration using stark manifold resonances in crystals

DOEpatents

Seletskiy, Denis V.; Epstein, Richard; Hehlen, Markus P.; Sheik-Bahae, Mansoor

2017-02-21

A method and device for cooling electronics is disclosed. The device includes a doped crystal configured to resonate at a Stark manifold resonance capable of cooling the crystal to a temperature of from about 110K to about 170K. The crystal host resonates in response to input from an excitation laser tuned to exploit the Stark manifold resonance corresponding to the cooling of the crystal.

FUGITIVE EMISSION SOURCES AND BATCH OPERATIONS IN SYNTHETIC ORGANIC CHEMICAL PRODUCTION

EPA Science Inventory

This survey report was developed for the EPA for use in assessing the potential magnitude of fugitive volatile organic compound (VOC) emissions from agitator seals, cooling towers and batch operations in the production of 378 designated chemicals. The information presented in thi...

Physical and Structural Studies on the Cryo-cooling of Insulin Crystals

NASA Technical Reports Server (NTRS)

Lovelace, J.; Bellamy, H.; Snell, E. H.; Borgstahl, G.

2003-01-01

Reflection profiles were analyzed from microgravity-(mg) and earth-grown insulin crystals to measure mosaicity (h) and to reveal mosaic domain structure and composition. The effects of cryocooling on single and multi-domain crystals were compared. The effects of cryocooling on insulin structure were also re-examined. Microgravity crystals were larger, more homogeneous, and more perfect than earth crystals. Several mg crystals contained primarily a single mosaic domain with havg of 0.005deg. The earth crystals varied in quality and all contained multiple domains with havg of 0.031deg. Cryocooling caused a 43-fold increase in h for mg crystals (havg=0.217deg) and an %fold increase for earth crystals (havg=0.246deg). These results indicate that very well-ordered crystals are not completely protected from the stresses associated with cryocooling, especially when structural perturbations occur. However, there were differences in the reflection profiles. For multi-mosaic domain crystals, each domain individually broadened and separated from the other domains upon cryo-cooling. Cryo-cooling did not cause an increase in the number of domains. A crystal composed of a single domain retained this domain structure and the reflection profiles simply broadened. Therefore, an improved signal-to-noise ratio for each reflection was measured from cryo-cooled single domain crystals relative to cryo-cooled multi-domain crystals. This improved signal, along with the increase in crystal size, facilitated the measurement of the weaker high- resolution reflections. The observed broadening of reflection profiles indicates increased variation in unit cell dimensions which may be linked to cryo-cooling-associated structural changes and disorder.

A Few Good Crystals Please

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.

Extruded ceramic honeycomb and method

DOEpatents

Day, J. Paul

1995-04-04

Extruded low-expansion ceramic honeycombs comprising beta-spodumene solid solution as the principal crystal phase and with less than 7 weight percent of included mullite are produced by compounding an extrusion batch comprising a lithium aluminosilicate glass powder and a clay additive, extruding a green honeycomb body from the batch, and drying and firing the green extruded cellular honeycomb to crystallize the glass and clay into a low-expansion spodumene ceramic honeycomb body.

Rapid crystallization of externally produced ions in a Penning trap

NASA Astrophysics Data System (ADS)

Murböck, T.; Schmidt, S.; Birkl, G.; Nörtershäuser, W.; Thompson, R. C.; Vogel, M.

2016-10-01

We have studied the cooling dynamics, formation process, and geometric structure of mesoscopic crystals of externally produced magnesium ions in a Penning trap. We present a cooling model and measurements for a combination of buffer gas cooling and laser cooling which has been found to reduce the ion kinetic energy by eight orders of magnitude from several hundreds of eV to μ eV and below within seconds. With ion numbers of the order of 1 ×103 to 1 ×105 , such cooling leads to the formation of ion Coulomb crystals which display a characteristic shell structure in agreement with the theory of non-neutral plasmas. We show the production and characterization of two-species ion crystals as a means of sympathetic cooling of ions lacking a suitable laser-cooling transition.

Long-term stability of crystal-stabilized water-in-oil emulsions.

PubMed

Ghosh, Supratim; Pradhan, Mamata; Patel, Tejas; Haj-Shafiei, Samira; Rousseau, Dérick

2015-12-15

The impact of cooling rate and mixing on the long-term kinetic stability of wax-stabilized water-in-oil emulsions was investigated. Four cooling/mixing protocols were investigated: cooling from 45°C to either 25°C or 4°C with/without stirring and two cooling rates - slow (1°C/min) and fast (5°C/min). The sedimentation behaviour of the emulsions was significantly affected by cooling protocol. Stirring was critical to the stability of all emulsions, with statically-cooled (no stirring) emulsions suffering from extensive aqueous phase separation. Emulsions stirred while cooling showed sedimentation of a waxy emulsion layer leaving a clear oil layer at the top, with a smaller separation and droplet size distribution at 4°C compared to 25°C, indicating the importance of the amount of crystallized wax on emulsion stability. Light microscopy revealed that crystallized wax appeared both on the droplet surface and in the continuous phase, suggesting that stirring ensured dispersibility of the water droplets during cooling as the wax was crystallizing. Wax crystallization on the droplet surface provided stability against droplet coalescence while continuous phase wax crystals minimized inter-droplet collisions. The key novel aspect of this research is in the simplicity to tailor the spatial distribution of wax crystals, i.e., either at the droplet surface or in the continuous phase via use of a surfactant and judicious stirring and/or cooling. Knowledge gained from this research can be applied to develop strategies for long-term storage stability of crystal-stabilized W/O emulsions. Copyright © 2015 Elsevier Inc. All rights reserved.

Do thermal donors reduce the lifetimes of Czochralski-grown silicon crystals?

NASA Astrophysics Data System (ADS)

Miyamura, Y.; Harada, H.; Nakano, S.; Nishizawa, S.; Kakimoto, K.

2018-05-01

High-performance electronics require long carrier lifetimes within their silicon crystals. This paper reports the effects of thermal donors on the lifetimes of carriers in as-grown n-type silicon crystals grown by the Czochralski method. We grew silicon crystals with two different concentrations of thermal donors using the following two cooling processes: one was cooled with a 4-h halt after detaching the crystal from the melt, and the other was cooled continuously. The crystal grown with the cooling halt contained higher concentrations of thermal donors of the order of 1 × 1013 cm-3, while the crystal without the halt had no thermal donors. The measured bulk lifetimes were in the range of 15-18 ms. We concluded that thermal donors in Czochralski-grown silicon crystals do not act to reduce their lifetimes.

Control of heat transfer in continuous-feeding Czochralski-silicon crystal growth with a water-cooled jacket

NASA Astrophysics Data System (ADS)

Zhao, Wenhan; Liu, Lijun

2017-01-01

The continuous-feeding Czochralski method is an effective method to reduce the cost of single crystal silicon. By promoting the crystal growth rate, the cost can be reduced further. However, more latent heat will be released at the melt-crystal interface under a high crystal growth rate. In this study, a water-cooled jacket was applied to enhance the heat transfer at the melt-crystal interface. Quasi-steady-state numerical calculation was employed to investigate the impact of the water-cooled jacket on the heat transfer at the melt-crystal interface. Latent heat released during the crystal growth process at the melt-crystal interface and absorbed during feedstock melting at the feeding zone was modeled in the simulations. The results show that, by using the water-cooled jacket, heat transfer in the growing crystal is enhanced significantly. Melt-crystal interface deflection and thermal stress increase simultaneously due to the increase of radial temperature at the melt-crystal interface. With a modified heat shield design, heat transfer at the melt-crystal interface is well controlled. The crystal growth rate can be increased by 20%.

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.

Indomethacin nanocrystals prepared by different laboratory scale methods: effect on crystalline form and dissolution behavior

NASA Astrophysics Data System (ADS)

Martena, Valentina; Censi, Roberta; Hoti, Ela; Malaj, Ledjan; Di Martino, Piera

2012-12-01

The objective of this study is to select very simple and well-known laboratory scale methods able to reduce particle size of indomethacin until the nanometric scale. The effect on the crystalline form and the dissolution behavior of the different samples was deliberately evaluated in absence of any surfactants as stabilizers. Nanocrystals of indomethacin (native crystals are in the γ form) (IDM) were obtained by three laboratory scale methods: A (Batch A: crystallization by solvent evaporation in a nano-spray dryer), B (Batch B-15 and B-30: wet milling and lyophilization), and C (Batch C-20-N and C-40-N: Cryo-milling in the presence of liquid nitrogen). Nanocrystals obtained by the method A (Batch A) crystallized into a mixture of α and γ polymorphic forms. IDM obtained by the two other methods remained in the γ form and a different attitude to the crystallinity decrease were observed, with a more considerable decrease in crystalline degree for IDM milled for 40 min in the presence of liquid nitrogen. The intrinsic dissolution rate (IDR) revealed a higher dissolution rate for Batches A and C-40-N, due to the higher IDR of α form than γ form for the Batch A, and the lower crystallinity degree for both the Batches A and C-40-N. These factors, as well as the decrease in particle size, influenced the IDM dissolution rate from the particle samples. Modifications in the solid physical state that may occur using different particle size reduction treatments have to be taken into consideration during the scale up and industrial development of new solid dosage forms.

Rheology of the 2006 eruption at Tungurahua volcano, Ecuador

NASA Astrophysics Data System (ADS)

Hanson, J. B.; Lavallée, Y.; Hess, K.-U.; von Aulock, F. W.; Dingwell, D. B.

2009-04-01

During August 16th to 18th 2006, the eruptive crisis at Tungurahua volcano (Ecuador) culminated in VEI 2 eruption with tens of pyroclastic flows and the extrusion of a lava flow. The nearly simultaneous occurrence of a lava flow and a pyroclastic flow from a single vent deserves attention. Generally, the rheology is a chief determinant of eruption style. Specifically, magmas are ductile (effusive) at low strain rates whereas they are brittle (explosive) at high strain rates. Although this distinction has been extensively described for single-phase magmas, there remain many questions as to the rheological implications of crystals and bubbles present in magmas. Here we present preliminary characterizations of the complex rheology of the magma involved in the 2006 eruption at Tungurahua volcano. The magma present in this eruption was andesitic with an interstitial melt composition averaging ~58 wt.% SiO2. The bombs present in the pyroclastic deposit show an open porosity ranging from 15 to 35 vol.% and a crystallinity generally greater than ~30 vol.% and occasionally up to 60 vol.% in samples affected by microlite growth. Petrographic analyses revealed magma batches with different crystallization histories. In high-porosity samples containing microlites, a recrystallization rim around clinopyroxene and resorption of the plagioclase were observed. In contrast, the dense samples show pristine, euhedral crystals and a near absence of microlites. The heterogeneous petrographic structures suggest the possibilities of mingling in the conduit or of magma batches with different decompression rates. Dilatometric analyses suggest glass transition temperatures (Tg) of ~974 °C for the dense material (porosity~15 vol.%) and as high as ~1060 °C for the high-porosity bombs (porosity~35 vol.%). Successive series of heating and cooling of the glass reveal an increase of Tg by as much as 60 °C indicative of significant water left in the melt. Preliminary analyses of images obtained via high-resolution neutron tomography also suggest the remnant of water in the bombs. This work in progress suggests that the large eruptive event in mid-August 2006 were caused by recharge in the magma reservoir or possibly in the conduit. Subsequently, both magma batches ascended through the pipe-like conduit, but rheological differences and possibly different ascent rates impeded complete mixing. This distinction may also explain the simultaneous occurrence of a lava flow and pyroclastic flows.

Hot zone design for controlled growth to mitigate cracking in laser crystal growth

NASA Astrophysics Data System (ADS)

Zhang, Hui; Zheng, Lili; Fang, Haisheng

2011-03-01

Cracking is a major problem during large diameter crystal growth. The objective of this work is to design an effective hot zone for a controlled growth of Yb:S-FAP [Yb3+:Sr5(PO4)3F] laser crystal by the Czochralski technology and effective cooling that can reduce stress. Theoretical and numerical analyses are performed to study the causes of cracking, mitigate the major cracking, as well as reduce cooling time. In the current system, three locations in the crystal are prone to crack, such as the top shoulder of the crystal, the middle portion above the crucible edge, and the bottom tail portion. Based on numerical simulations, we propose a new hot zone design and cooling procedure to grow and cool large diameter crystal without cracking.

Kinetic Controls on Formation of Textures in Rapidly Cooled Rocks

NASA Technical Reports Server (NTRS)

Lofgren, Gary E.

2006-01-01

The crystallization of silicate melts is a complex process involving melts usually produced by partial melting and cooling environments that are rapid in volcanic lavas or so slow as to be auto-metamorphic in plutonic regimes. The volcanic lavas are amenable to laboratory study as are chondrules that comprise the bulk of chondritic meteorites. Dynamic crystallization studies of basalt and chondrule melts have shown that nucleation has a more profound effect on the final texture than the cooling or crystal growth rates. The sequence of crystal shapes grown at increasing degrees of supercooling (DELTA T) or cooling rate demonstrates the effect of increasing growth rate. Equant or euhedral crystals become skeletal, then dendritic and ultimately spherulitic indicating the nucleation temperature and the DELTA T when growth began. Because crystals cannot grow until they nucleate, cooling rate does not always correlate with crystal growth rate and thus crystal shape. Silicate melts cooled at the same rate can have drastically different textures depending on the temperature of nucleation. A dynamic crystallization study of basaltic rocks shows that basaltic lavas must erupt with sufficient crystals present in the melt to act as nuclei and foster growth. With nuclei present, growth will begin when the temperature drops below the liquidus temperature and typical basaltic textures such as intersertal, intergranular or subophitic will form. If nuclei are not present, crystallization will not begin immediately and the DELTA T will increase until embryos in the melts become nuclei. The DELTA T present when grow begins dictates the growth rate and the crystal shapes and thus the rock texture. If nucleation is delayed, growth will take place at high DELTA T and the crystals will favor skeletal or dendritic shapes. Chondrules are usually considered crystallized melt droplets and clearly some are, but most are not. Most chondrules have porphyritic textures that cannot develop from totally melted droplets because nucleation is delayed during cooling and growth occurs at high DELTA T and the resulting textures are dendritic or spherulitic. The porphyritic textures will develop only if the chondrule is partially molten and begins to crystallize immediately upon cooling. Chondrule compositions are close to komatiites and these studies bear on the origin of their textures as well.

Physical and chemical microstructural damage in pressed CL-20 explosives

NASA Astrophysics Data System (ADS)

Demol, Gauthier; Sandusky, Harold W.

2000-04-01

The ultimate utility of CL-20 as an ingredient in explosive and propellant formulations will depend upon the ability to understand the factors that are responsible for batch-to-batch variability with respect to sensitivity, and also to control the sensitivity in formulations within acceptable limits. We used light microscopy of cold-mounted, polished samples to characterize CL-20 at various stages in its life cycle. The evolution of damage from the initial neat crystals of CL-20 to the ready-to-use pressed pellets shows that processing seriously damages the crystals. These crystals are very brittle, and several explanations are proposed.

Evaluation of the Crystallization Tendency of Commercially Available Amorphous Tacrolimus Formulations Exposed to Different Stress Conditions.

PubMed

Trasi, Niraj S; Purohit, Hitesh S; Taylor, Lynne S

2017-10-01

Tacrolimus, an immunosuppressant, is a poorly water soluble compound whereby the commercially available capsule formulations contain the drug in amorphous form. The goal of this study was to evaluate the robustness of the innovator product and five generic formulations to crystallization following storage at stress conditions. Products were purchased from a pharmacy and stored at 40°C/75% relative humidity (RH), open dish conditions. Crystallinity was determined using X-ray diffraction. The quantity of the ingredients in the formulations were determined using different approaches and the various factors that might cause instability in the formulations were studied. After 4 weeks of open dish storage at 40°C/75% RH, one of the generic formulations showed evidence of tacrolimus crystallization. Further investigations revealed batch-to-batch variations in crystallization tendency with the extent of crystallinity varying between 50 and 100% for different batches. Crystallization was also observed at lower storage temperatures (30°C) when the RH was maintained at 75%. It was found that crystallization could be induced in a model formulation by wet granulating an ethanolic solution of the drug with lactose and drying at 60-70°C followed by exposure to stress conditions. It seems probable that the generic that was susceptible to crystallization contains amorphous drug physically mixed with polymeric excipients, rather than as an amorphous solid dispersion. This study highlights the importance of considering the manufacturing process on the stability of the resultant amorphous product.

Optimization of the cooling profile to achieve crack-free Yb:S-FAP crystals

NASA Astrophysics Data System (ADS)

Fang, H. S.; Qiu, S. R.; Zheng, L. L.; Schaffers, K. I.; Tassano, J. B.; Caird, J. A.; Zhang, H.

2008-08-01

Yb:S-FAP [Yb 3+:Sr 5(PO 4) 3F] crystals are an important gain medium for diode-pumped laser applications. Growth of 7.0 cm diameter Yb:S-FAP crystals utilizing the Czochralski (CZ) method from SrF 2-rich melts often encounters cracks during the post-growth cool-down stage. To suppress cracking during cool-down, a numerical simulation of the growth system was used to understand the correlation between the furnace power during cool-down and the radial temperature differences within the crystal. The critical radial temperature difference, above which the crystal cracks, has been determined by benchmarking the simulation results against experimental observations. Based on this comparison, an optimal three-stage ramp-down profile was implemented, which produced high-quality, crack-free Yb:S-FAP crystals.

Modeling of the non-isothermal crystallization kinetics of polyamide 6 composites during thermoforming

NASA Astrophysics Data System (ADS)

Kugele, Daniel; Dörr, Dominik; Wittemann, Florian; Hangs, Benjamin; Rausch, Julius; Kärger, Luise; Henning, Frank

2017-10-01

The combination of thermoforming processes of continuous-fiber reinforced thermoplastics and injection molding offers a high potential for cost-effective use in automobile mass production. During manufacturing, the thermoplastic laminates are initially heated up to a temperature above the melting point. This is followed by continuous cooling of the material during the forming process, which leads to crystallization under non-isothermal conditions. To account for phase change effects in thermoforming simulation, an accurate modeling of the crystallization kinetics is required. In this context, it is important to consider the wide range of cooling rates, which are observed during processing. Consequently, this paper deals with the experimental investigation of the crystallization at cooling rates varying from 0.16 K/s to 100 K/s using standard differential scanning calorimetry (DSC) and fast scanning calorimetry (Flash DSC). Two different modeling approaches (Nakamura model, modified Nakamura-Ziabicki model) for predicting crystallization kinetics are parameterized according to DSC measurements. It turns out that only the modified Nakamura-Ziabicki model is capable of predicting crystallization kinetics for all investigated cooling rates. Finally, the modified Nakamura-Ziabicki model is validated by cooling experiments using PA6-CF laminates with embedded temperature sensors. It is shown that the modified Nakamura-Ziabicki model predicts crystallization at non-isothermal conditions and varying cooling rates with a good accuracy. Thus, the study contributes to a deeper understanding of the non-isothermal crystallization and presents an overall method for modeling crystallization under process conditions.

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.

Crystal-field effects in fluoride crystals for optical refrigeration

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hehlen, Markus P

2010-01-01

The field of optical refrigeration of rare-earth-doped solids has recently seen an important breakthrough. The cooling of a YLiF{sub 4} (YLF) crystal doped with 5 mol% Yb3+ to 155 K by Seletskiy et al [NPhot] has surpassed the lowest temperatures ({approx}170 K for {approx}100 mW cooling capacity) that are practical with commercial multi-stage thermoelectric coolers (TEC) [Glaister]. This record performance has advanced laser cooling into an application relevant regime and has put first practical optical cryocoolers within reach. The result is also relevant from a material perspective since for the first time, an Yb3+-doped crystal has outperformed an Yb3+-doped glass.more » The record temperature of 208 K was held by the Yb3+-doped fluorozirconate glass ZBLAN. Advanced purification and glass fabrication methods currently under development are expected to also advance ZBLAN:Yb3+ to sub-TEC temperatures. However, recent achievements with YLF:Yb3+ illustrate that crystalline materials may have two potentially game-changing advantajes over glassy materials. First, the crystalline environment reduces the inhomogeneous broadening of the Yb3+ electronic transitions as compared to a glassy matrix. The respective sharpening of the crystal-field transitions increases the peak absorption cross section at the laser excitation wavelength and allows for more efficient pumping of the Yb3+ ions, particularly at low temperatures. Second, many detrimental impurities present in the starting materials tend to be excluded from the crystal during its slow growth process, in contrast to a glass where all impurities present in the starting materials are included in the glass when it is formed by temperature quenching a melt. The ultra high purity required for laser cooling materials [PRB] therefore may be easier to realize in crystals than in glasses. Laser cooling occurs by laser excitation of a rare-earth ion followed by anti-Stokes luminescence. Each such laser-cooling cycle extracts thermal energy from the solid and carries it away as high-entropy light, thereby cooling the material. In the ideal case, the respective laser-cooling power is given by the pump wavelength ({lambda}{sub p}), the mean fluorescence wavelength ({bar {lambda}}{sub L}), and the absorption coefficient (a{sub r}) of the pumped transition. These quantities are solely determined by crystal field interactions. On one hand, a large crystal-field splitting offers a favorably large difference of {lambda}{sub p} - {bar {lambda}}{sub L} and thus a high cooling efficiency {eta}{sub cool} = ({lambda}{sub p} - {bar {lambda}}{sub L})/{bar {lambda}}{sub L}. On the other hand, a small crystal-field splitting offers a high thermal population (n{sub i}) of the initial state of the pumped transition, giving a high pump absorption coefficient and thus high laser cooling power, particularly at low temperatures. A quantitative description of crystal-field interactions is therefore critical to the understanding and optimization of optical refrigeration. In the case of Yb3+ as the laser cooling ion, however, development of a crystal-field model is met with substantial difficulties. First, Yb3+ has only two 4/multiplets, {sup 2}F{sub 7/2} and {sup 2}F{sub 5/2}, which lead to at most 7 crystal-field levels. This makes it difficult, and in some cases impossible, to evaluate the crystal-field Hamiltonian, which has at least 4 parameters for any Yb3+ point symmety lower than cubic. Second, {sup 2}F{sub 7/2}{leftrightarrow}{sup 2}F{sub 5/2} transitions exhibit an exceptionally strong electron-phonon coupling compared to 4f transitions of other rare earths. This makes it difficult to distinguish electronic from vibronic transitions in the absorption and luminescence spectra and to reliably identify the crystal-field levels. Yb3+ crystal-field splittings reported in the literature should thus generally be viewed with caution. This paper explores the effects of crystal-field interactions on the laser cooling performance of Yb3+-doped fluoride crystals. It is shown that the total crystal-field splitting of the {sup 2}F{sub 7/2} and {sup 2}F{sub 5/2} multiplets of Yb3+ can be estimated from crystal-field splittings of other rare-earth-doped fluoride crystals. This approach takes advantage of an extensive body of experimental work from which Yb3+ doped fluoride crystals with favorable laser cooling properties might be identified. Section 2 reviews the crystal-field splitting of the 4f electronic states and introduces the crystal-field strength as a means to predict the total crystal-field splitting of the {sup 2}F{sub 7/2} and {sup 2}F{sub 5/2} multiplets. Section 3 illustrates the effect of the total {sup 2}F{sub 7/2} crystal field splitting on the laser cooling power. Finally, Section 4 compiles literature data on crystal-field splittings in fluoride crystals from which the {sup 2}F{sub 7/2} splitting is predicted.« less

Fate of a perched crystal layer in a magma ocean

NASA Technical Reports Server (NTRS)

Morse, S. A.

1992-01-01

The pressure gradients and liquid compressibilities of deep magma oceans should sustain the internal flotation of native crystals owing to a density crossover between crystal and liquid. Olivine at upper mantle depths near 250 km is considered. The behavior of a perched crystal layer is part of the general question concerning the fate of any transient crystal carried away from a cooling surface, whether this be a planetary surface or the roof of an intrusive magma body. For magma bodies thicker than a few hundred meters at modest crustal depths, the major cooling surface is the roof even when most solidification occurs at the floor. Importation of cool surroundings must also be invoked for the generation of a perched crystal layer in a magma ocean, but in this case the perched layer is deeply embedded in the hot part of the magma body, and far away from any cooling surface. Other aspects of this study are presented.

Ice nucleation in the upper troposphere: Sensitivity to aerosol number density, temperature, and cooling rate

NASA Technical Reports Server (NTRS)

Jensen, E. J.; Toon, O. B.

1994-01-01

We have investigated the processes that control ice crystal nucleation in the upper troposphere using a numerical model. Nucleation of ice resulting from cooling was simulated for a range of aerosol number densities, initial temperatures, and cooling rates. In contrast to observations of stratus clouds, we find that the number of ice crystals that nucleate in cirrus is relatively insensitive to the number of aerosols present. The ice crystal size distribution at the end of the nucleation process is unaffected by the assumed initial aerosol number density. Essentially, nucleation continues until enough ice crystals are present such that their deposition growth rapidly depletes the vapor and shuts off any further nucleation. However, the number of ice crystals nucleated increases rapidly with decreasing initial temperature and increasing cooling rate. This temperature dependence alone could explain the large ice crystal number density observed in very cold tropical cirrus.

Optimization of the cooling profile to achieve crack-free Yb:S-FAP crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fang, H; Qiu, S; Kheng, L

Yb:S-FAP [Yb{sup 3+}:Sr{sub 5}(PO{sub 4}){sub 3}F] crystals are an important gain medium for diode-pumped laser applications. Growth of 7.0 cm diameter Yb:S-FAP crystals utilizing the Czochralski (CZ) method from SrF{sub 2}-rich melts often encounter cracks during the post growth cool down stage. To suppress cracking during cool down, a numerical simulation of the growth system was used to understand the correlation between the furnace power during cool down and the radial temperature differences within the crystal. The critical radial temperature difference, above which the crystal cracks, has been determined by benchmarking the simulation results against experimental observations. Based on thismore » comparison, an optimal three-stage ramp-down profile was implemented and produced high quality, crack-free Yb:S-FAP crystals.« less

Influence of pH and method of crystallization on the solid physical form of indomethacin.

PubMed

Dubbini, Alessandra; Censi, Roberta; Martena, Valentina; Hoti, Ela; Ricciutelli, Massimo; Malaj, Ledjan; Di Martino, Piera

2014-10-01

The purpose of this study was to investigate the effect of pH and method of crystallization on the solid physical form of indomethacin (IDM). IDM, a non steroidal anti-inflammatory drug poorly soluble in water, underwent two different crystallization methods: crystallization by solvent evaporation under reduced pressure at 50.0°C (method A), and crystallization by cooling of solution from 50.0 to 5.0°C (method B). In both cases, several aqueous ethanolic solutions of IDM of different pHs were prepared. pHs were adjusted by adding acidic solutions (HCl 2M) or alkali (NaOH or NH4OH 2M) to an aqueous ethanolic solution of IDM. Thus, several batches were recovered after crystallization. The chemical stability of IDM was verified through (1)H NMR and mass spectroscopy (FIA-ESI-MS), that revealed that IDM degraded in strong alkali media (pH ≥ 12). Crystals obtained under different crystallization conditions at pHs of 1.0, 4.5, 7.0, 8.0, 10.0 and chemically stable were thus characterized for crystal habit by scanning electron microscopy, for thermal behaviour by differential scanning calorimetry, and thermogravimetry, and for solid state by X-ray powder diffractometry. Under the Method A, IDM always crystallized into pure metastable alpha form when solutions were acidified or alkalized respectively with HCl and NH4OH. On the contrary, in presence of NaOH, IDM crystallized under a mixture of alpha and sodium trihydrate form, because the presence of the sodium counter ion orientates the crystallization towards the formation of the trihydrate salt. Under the method B, at pH of 1.0, IDM crystallized under the alpha form; at pH 4.5, IDM crystallized under the form alpha in presence of some nuclei of gamma form; at pH 7.0, 8.0, and 10.0 for NH4OH, IDM crystallized under the most stable polymorph gamma form, whereas in presence of NaOH, a mix of alpha, and salt forms was formed whatever the pH of the solution. Copyright © 2014 Elsevier B.V. All rights reserved.

Thermal deformation of cryogenically cooled silicon crystals under intense X-ray beams: measurement and finite-element predictions of the surface shape

PubMed Central

Zhang, Lin; Sánchez del Río, Manuel; Monaco, Giulio; Detlefs, Carsten; Roth, Thomas; Chumakov, Aleksandr I.; Glatzel, Pieter

2013-01-01

X-ray crystal monochromators exposed to white-beam X-rays in third-generation synchrotron light sources are subject to thermal deformations that must be minimized using an adequate cooling system. A new approach was used to measure the crystal shape profile and slope of several cryogenically cooled (liquid nitrogen) silicon monochromators as a function of beam power in situ and under heat load. The method utilizes multiple angular scans across the Bragg peak (rocking curve) at various vertical positions of a narrow-gap slit downstream from the monochromator. When increasing the beam power, the surface of the liquid-nitrogen-cooled silicon crystal deforms from a concave shape at low heat load to a convex shape at high heat load, passing through an approximately flat shape at intermediate heat load. Finite-element analysis is used to calculate the crystal thermal deformations. The simulated crystal profiles and slopes are in excellent agreement with experiments. The parameters used in simulations, such as material properties, absorbed power distribution on the crystal and cooling boundary conditions, are described in detail as they are fundamental for obtaining accurate results. PMID:23765298

History dependent crystallization of Zr41Ti14Cu12Ni10Be23 melts

NASA Astrophysics Data System (ADS)

Schroers, Jan; Johnson, William L.

2000-07-01

The crystallization of Zr41Ti14Cu12Ni10Be23 (Vit 1) melts during constant heating is investigated. (Vit 1) melts are cooled with different rates into the amorphous state and the crystallization temperature upon subsequent heating is studied. In addition, Vit 1 melts are cooled using a constant rate to different temperatures and subsequently heated from this temperature with a constant rate. We investigate the influence of the temperature to which the melt was cooled on the crystallization temperature measured upon heating. In both cases the onset temperature of crystallization shows strong history dependence. This can be explained by an accumulating process during cooling and heating. An attempt is made to consider this process in a simple model by steady state nucleation and subsequent growth of the nuclei which results in different crystallization kinetics during cooling or heating. Calculations show qualitative agreement with the experimental results. However, calculated and experimental results differ quantitatively. This difference can be explained by a decomposition process leading to a nonsteady nucleation rate which continuously increases with decreasing temperature.

Liquid encapsulated crystal growth

NASA Technical Reports Server (NTRS)

Morrison, Andrew D. (Inventor)

1989-01-01

Low-defect crystals are grown in a closed ampoule under a layer of encapsulant. After crystal growth, the crystal is separated from the melt and moved into the layer of encapsulant and cooled to a first temperature at which crystal growth stops. The crystal is then moved into the inert gas ambient in the ampoule and further cooled. The crystal can be separated from the melt by decanting the melt into an adjacent reservoir or by rotating the ampoule to rotate the crystal into the encapsulant layer.

Liquid encapsulated crystal growth

NASA Technical Reports Server (NTRS)

Morrison, Andrew D. (Inventor)

1987-01-01

Low-defect crystals are grown in a closed ampoule under a layer of encapsulant. After crystal growth, the crystal is separated from the melt and moved into the layer of encapsulant and cooled to a first temperature at which crystal growth stops. The crystal is then moved into the inert gas ambient in the ampoule and further cooled. The crystal can be separated from the melt by decanting the melt into and adjacent reservoir or by rotating the ampoule to rotate the crystal into the encapsulant layer.

An experimental study of pyroxene crystallization during rapid cooling in a thermal gradient; applications to komatiites and chondrites

NASA Astrophysics Data System (ADS)

Bouquain, S.; Arndt, N. T.; Faure, F.; Libourel, G.

2013-03-01

To investigate the crystallization of pyroxene in spinifex-textured komatiites and in chondrites we undertook a series of experiments in which compositions in the CMAS system were cooling rapidly in a thermal gradient. Cooling rates were generally between 5 to 10 °C h-1 but some runs were made at 100-200 °C h-1; thermal gradients were between 10 and 20 °C cm-1. These conditions reproduced those at various levels in the crust of komatiitic lava flow. The starting composition was chosen to have pigeonite on the liquidus and a majority of the experiments crystallized zoned pigeonite-diopside crystals like those in komatiite lavas. A~conspicuous aspect of the experimental results was their lack of reproduceability. Some experiments crystallized forsterite whereas others that were run under similar conditions crystallized two pyroxenes and no forsterite; some experiments were totally glassy but others totally crystallized to pyroxene. The degree of supercooling at the onset of pyroxene crystallization was variable, from less than 25 °C to more than 110 °C. We attribute these results to the difficulty of nucleation of pyroxene. In some cases forsterite crystallized metastably and modified the liquid composition to inhibit pyroxene crystallization; in others no nucleation took place until a large degree of supercooling was achieved, then pyroxene crystallized rapidly. Pigeonite crystallized under a wide range of conditions, at cooling rates from 3 to 100 °C h-1. The notion that this mineral only forms at low cooling rates is not correct.

Demonstration of Crystal Structure.

ERIC Educational Resources Information Center

Neville, Joseph P.

1985-01-01

Describes an experiment where equal parts of copper and aluminum are heated then cooled to show extremely large crystals. Suggestions are given for changing the orientation of crystals by varying cooling rates. Students are more receptive to concepts of microstructure after seeing this experiment. (DH)

Astigmatic Herriott cell for optical refrigeration

NASA Astrophysics Data System (ADS)

Gragossian, Aram; Meng, Junwei; Ghasemkhani, Mohammadreza; Albrecht, Alexander R.; Sheik-Bahae, Mansoor

2017-01-01

Cooling rare-earth-doped crystals to the lowest temperature possible requires enhanced resonant absorption and high-purity crystals. Since resonant absorption decreases as the crystal is cooled, the only path forward is to increase the number of roundtrips that the laser makes inside the crystal. To achieve even lower temperatures than previously reported, we have employed an astigmatic Herriott cell to improve laser absorption at low temperatures. Preliminary results indicate improvement over previous designs. This cavity potentially enables us to use unpolarized high-power fiber lasers, and to achieve much higher cooling power for practical applications.

Progressing batch hydrolysis process

DOEpatents

Wright, J.D.

1985-01-10

A progressive batch hydrolysis process is disclosed for producing sugar from a lignocellulosic feedstock. It comprises passing a stream of dilute acid serially through a plurality of percolation hydrolysis reactors charged with feed stock, at a flow rate, temperature and pressure sufficient to substantially convert all the cellulose component of the feed stock to glucose. The cooled dilute acid stream containing glucose, after exiting the last percolation hydrolysis reactor, serially fed through a plurality of pre-hydrolysis percolation reactors, charged with said feedstock, at a flow rate, temperature and pressure sufficient to substantially convert all the hemicellulose component of said feedstock to glucose. The dilute acid stream containing glucose is cooled after it exits the last prehydrolysis reactor.

Progressing batch hydrolysis process

DOEpatents

Wright, John D.

1986-01-01

A progressive batch hydrolysis process for producing sugar from a lignocellulosic feedstock, comprising passing a stream of dilute acid serially through a plurality of percolation hydrolysis reactors charged with said feedstock, at a flow rate, temperature and pressure sufficient to substantially convert all the cellulose component of the feedstock to glucose; cooling said dilute acid stream containing glucose, after exiting the last percolation hydrolysis reactor, then feeding said dilute acid stream serially through a plurality of prehydrolysis percolation reactors, charged with said feedstock, at a flow rate, temperature and pressure sufficient to substantially convert all the hemicellulose component of said feedstock to glucose; and cooling the dilute acid stream containing glucose after it exits the last prehydrolysis reactor.

SEPARATION OF TIN FROM ALLOYS

DOEpatents

Kattner, W.T.

1959-08-11

A process is described for recovering tin from bronze comprising melting the bronze; slowly cooling the melted metal to from 280 to 240 deg C whereby eta- phase bronze crystallizes; separating the eta-bronze crystals from the liquid metal by mechanical means; melting the separated crystals; slowly cooling the melted eta-crystals to a temperature from 520 to 420 deg C whereby crystals of epsilonbronze precipitate; removing said epsilon-crystals from the remaining molten metal; and reintroducing the remaining molten metal into the process for eta-crystallization.

Sideband cooling of small ion Coulomb crystals in a Penning trap

NASA Astrophysics Data System (ADS)

Stutter, G.; Hrmo, P.; Jarlaud, V.; Joshi, M. K.; Goodwin, J. F.; Thompson, R. C.

2018-03-01

We have recently demonstrated the laser cooling of a single ? ion to the motional ground state in a Penning trap using the resolved-sideband cooling technique on the electric quadrupole transition S? D?. Here we report on the extension of this technique to small ion Coulomb crystals made of two or three ? ions. Efficient cooling of the axial motion is achieved outside the Lamb-Dicke regime on a two-ion string along the magnetic field axis as well as on two- and three-ion planar crystals. Complex sideband cooling sequences are required in order to cool both axial degrees of freedom simultaneously. We measure a mean excitation after cooling of ? for the centre of mass (COM) mode and ? for the breathing mode of the two-ion string with corresponding heating rates of 11(2) ? and ? at a trap frequency of 162 kHz. The occupation of the ground state of the axial modes (?) is above 75% for the two-ion planar crystal and the associated heating rates 0.8(5) ? at a trap frequency of 355 kHz.

Measurement and analysis of the mannitol partition coefficient in sucrose crystallization under simulated industrial conditions

USDA-ARS?s Scientific Manuscript database

Mannitol is a major deterioration product of Leuconstoc mesenteroides bacterial deterioration of both sugarcane and sugar beet. The effect of crystallization conditions on the mannitol partition coefficient (Keff) between impure sucrose syrup and crystal has been investigated in a batch laboratory c...

An experimental study of pyroxene crystallization during rapid cooling in a thermal gradient: application to komatiites

NASA Astrophysics Data System (ADS)

Bouquain, S.; Arndt, N. T.; Faure, F.; Libourel, G.

2014-07-01

To investigate the crystallization of pyroxene in spinifex-textured komatiites, we undertook a series of experiments in which compositions in the CaO-MgO-Al2O3-SiO2 CMAS system were cooled rapidly in a thermal gradient. Cooling rates were generally between 5 and 10 °C h-1, but some runs were made at 100-200 °C h-1; thermal gradients were between 10 and 20 °C cm-1. These conditions reproduced those at various depths in the crust of komatiite lava flow. The starting composition was chosen to have pigeonite on the liquidus, and most of the experimental charges crystallized zoned pigeonite-diopside crystals like those in komatiite lavas. An intriguing aspect of the experimental results was their lack of reproducibility. Some experiments crystallized forsterite, whereas others that were run under similar conditions crystallized two pyroxenes and no forsterite; some experiments were totally glassy, but others crystallized entirely to pyroxene. The degree of supercooling at the onset of pyroxene crystallization was variable, from less than 25 °C to more than 110 °C. We attribute these results to the difficulty of nucleation of pyroxene under the conditions of the experiments. In some cases forsterite crystallized metastably and modified the liquid composition to inhibit pyroxene crystallization; in others no nucleation took place until a large degree of supercooling was achieved, and then pyroxene crystallized rapidly. Pigeonite crystallized under a wide range of conditions, at cooling rates from 3 to 100 °C h-1. The notion that this mineral only forms at low cooling rates is not correct.

Comparative study on ATR-FTIR calibration models for monitoring solution concentration in cooling crystallization

NASA Astrophysics Data System (ADS)

Zhang, Fangkun; Liu, Tao; Wang, Xue Z.; Liu, Jingxiang; Jiang, Xiaobin

2017-02-01

In this paper calibration model building based on using an ATR-FTIR spectroscopy is investigated for in-situ measurement of the solution concentration during a cooling crystallization process. The cooling crystallization of L-glutamic Acid (LGA) as a case is studied here. It was found that using the metastable zone (MSZ) data for model calibration can guarantee the prediction accuracy for monitoring the operating window of cooling crystallization, compared to the usage of undersaturated zone (USZ) spectra for model building as traditionally practiced. Calibration experiments were made for LGA solution under different concentrations. Four candidate calibration models were established using different zone data for comparison, by using a multivariate partial least-squares (PLS) regression algorithm for the collected spectra together with the corresponding temperature values. Experiments under different process conditions including the changes of solution concentration and operating temperature were conducted. The results indicate that using the MSZ spectra for model calibration can give more accurate prediction of the solution concentration during the crystallization process, while maintaining accuracy in changing the operating temperature. The primary reason of prediction error was clarified as spectral nonlinearity for in-situ measurement between USZ and MSZ. In addition, an LGA cooling crystallization experiment was performed to verify the sensitivity of these calibration models for monitoring the crystal growth process.

Forward to cryogenic temperature: laser cooling of Yb: LuLiF crystal

NASA Astrophysics Data System (ADS)

Zhong, Biao; Luo, Hao; Lei, Yongqing; Shi, Yanling; Yin, Jianping

2017-06-01

The high quality Yb-doped fluoride crystals have broad prospects for optical refrigeration. We have laser cooled the Yb:LuLiF crystal to a temperature below the limit of current thermoelectric coolers ( 180 K). The 5% Yb:LuLiF crystal sample has a geometry of 2 mm×2 mm×5 mm and was supported by two fibers of 200 μm in diameter. They were placed in a 2×10-4 Pa vacuum chamber with an environment temperature of 294.5 K. The 1019 nm CW laser of power 38.7 W was adopted to irradiate the sample. The temperature of the sample was measured utilizing the DLT methods. After 20 minutes of laser irradiation, the 5% Yb:LuLiF crystal sample was cooled down to 182.4 K. By further optimizing experimental conditions and increasing the doped Yb concentration, the Yb:LuLiF crystal might be optically cooled below the cryogenic temperature of 123K in the near future.

Process of making cryogenically cooled high thermal performance crystal optics

DOEpatents

Kuzay, Tuncer M.

1992-01-01

A method for constructing a cooled optic wherein one or more cavities are milled, drilled or formed using casting or ultrasound laser machining techniques in a single crystal base and filled with porous material having high thermal conductivity at cryogenic temperatures. A non-machined strain-free single crystal can be bonded to the base to produce superior optics. During operation of the cooled optic, N.sub.2 is pumped through the porous material at a sub-cooled cryogenic inlet temperature and with sufficient system pressure to prevent the fluid bulk temperature from reaching saturation.

Process of making cryogenically cooled high thermal performance crystal optics

DOEpatents

Kuzay, T.M.

1992-06-23

A method is disclosed for constructing a cooled optic wherein one or more cavities are milled, drilled or formed using casting or ultrasound laser machining techniques in a single crystal base and filled with porous material having high thermal conductivity at cryogenic temperatures. A non-machined strain-free single crystal can be bonded to the base to produce superior optics. During operation of the cooled optic, N[sub 2] is pumped through the porous material at a sub-cooled cryogenic inlet temperature and with sufficient system pressure to prevent the fluid bulk temperature from reaching saturation. 7 figs.

History dependent crystallization of Zr{sub 41}Ti{sub 14}Cu{sub 12}Ni{sub 10}Be{sub 23} melts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schroers, Jan; Johnson, William L.

The crystallization of Zr{sub 41}Ti{sub 14}Cu{sub 12}Ni{sub 10}Be{sub 23} (Vit 1) melts during constant heating is investigated. (Vit 1) melts are cooled with different rates into the amorphous state and the crystallization temperature upon subsequent heating is studied. In addition, Vit 1 melts are cooled using a constant rate to different temperatures and subsequently heated from this temperature with a constant rate. We investigate the influence of the temperature to which the melt was cooled on the crystallization temperature measured upon heating. In both cases the onset temperature of crystallization shows strong history dependence. This can be explained by anmore » accumulating process during cooling and heating. An attempt is made to consider this process in a simple model by steady state nucleation and subsequent growth of the nuclei which results in different crystallization kinetics during cooling or heating. Calculations show qualitative agreement with the experimental results. However, calculated and experimental results differ quantitatively. This difference can be explained by a decomposition process leading to a nonsteady nucleation rate which continuously increases with decreasing temperature. (c) 2000 American Institute of Physics.« less

Linking rapid magma reservoir assembly and eruption trigger mechanisms at evolved Yellowstone-type supervolcanoes

USGS Publications Warehouse

Wotzlaw, J.F.; Bindeman, I.N.; Watts, Kathryn E.; Schmitt, A.K.; Caricchi, L.; Schaltegger, U.

2014-01-01

The geological record contains evidence of volcanic eruptions that were as much as two orders of magnitude larger than the most voluminous eruption experienced by modern civilizations, the A.D. 1815 Tambora (Indonesia) eruption. Perhaps nowhere on Earth are deposits of such supereruptions more prominent than in the Snake River Plain–Yellowstone Plateau (SRP-YP) volcanic province (northwest United States). While magmatic activity at Yellowstone is still ongoing, the Heise volcanic field in eastern Idaho represents the youngest complete caldera cycle in the SRP-YP, and thus is particularly instructive for current and future volcanic activity at Yellowstone. The Heise caldera cycle culminated 4.5 Ma ago in the eruption of the ∼1800 km3 Kilgore Tuff. Accessory zircons in the Kilgore Tuff display significant intercrystalline and intracrystalline oxygen isotopic heterogeneity, and the vast majority are 18O depleted. This suggests that zircons crystallized from isotopically distinct magma batches that were generated by remelting of subcaldera silicic rocks previously altered by low-δ18O meteoric-hydrothermal fluids. Prior to eruption these magma batches were assembled and homogenized into a single voluminous reservoir. U-Pb geochronology of isotopically diverse zircons using chemical abrasion–isotope dilution–thermal ionization mass spectrometry yielded indistinguishable crystallization ages with a weighted mean 206Pb/238U date of 4.4876 ± 0.0023 Ma (MSWD = 1.5; n = 24). These zircon crystallization ages are also indistinguishable from the sanidine 40Ar/39Ar dates, and thus zircons crystallized close to eruption. This requires that shallow crustal melting, assembly of isolated batches into a supervolcanic magma reservoir, homogenization, and eruption occurred extremely rapidly, within the resolution of our geochronology (103–104 yr). The crystal-scale image of the reservoir configuration, with several isolated magma batches, is very similar to the reservoir configurations inferred from seismic data at active supervolcanoes. The connection of magma batches vertically distributed over several kilometers in the upper crust would cause a substantial increase of buoyancy overpressure, providing an eruption trigger mechanism that is the direct consequence of the reservoir assembly process.

Crystallization Behavior of the CaO-Al2O3-MgO System Studied with a Confocal Laser Scanning Microscope

NASA Astrophysics Data System (ADS)

Jung, Sung Suk; Sohn, Il

2012-12-01

The crystallization behavior of a calcium-aluminate system with various MgO content from 2.5 to 7.5 wt pct and CaO/Al2O3 ratios between 0.8 and 1.2 has been examined using a confocal laser scanning microscope (CLSM). CCT (continuous cooling transformation) and time temperature transformation (TTT) diagrams were constructed to identify the primary crystal phase of slag at different compositions and at cooling rates between 25 and 800 K/minutes. In the slag at a CaO/Al2O3 ratio of 1.0, crystallization temperature increased during isothermal and continuous cooling with higher MgO content, and the shortest incubation time was observed at 5 wt pct MgO. When MgO content was fixed to be 5 wt pct, crystallization temperature increased with lower CaO/Al2O3 ratio. According to the slag composition, cooling rates and temperature, the primary phase could be CA, or C5A3, or C3A, or C3MA2, or MgO, and the crystal morphology changes from dendrites to faceted crystals to columnar crystals in this composition range.

Challenges in Physics of Biocrystals and Biocrystallization

NASA Technical Reports Server (NTRS)

Chernov, Alexander A.

2004-01-01

Selected problems in biocrystal mechanics(1), nucleation(2) and growth(3) will be addressed. (1) Elastic moduli of protein crystals found from triple bonding, rod vibrations, ultrasound speed and Brillion light scattering vary in a wide range of 0.3 - 3 GPa. This diversity comes from behaviour of intracrystalline liquid. Namely, liquid flow through the narrow intermolecular channels between compressed and expanded regions within an inhomogeneously deformed crystal was considered. The deformation comes from bending or ultrasound wave propagation. (2) Wide scattering in the number of crystals nucleated in the batch technique may come from liquid flow turbulence associated with pipetting; the Reynolds number these injections reaches 10(exp 3). (3) Poor reproducibility in crystal size and, probably, perfection is supposed to come from a variety of growth conditions in the same batch. Growth in a kinetic growth mode in laminar flow, e.g., in a microfluidic device, would allow to better understand growth kinetics and defect formation.

Investigation of Artificial Forced Cooling in the Bridgman Crystal Growth of Cadmium Zinc Telluride

NASA Astrophysics Data System (ADS)

Liu, Juncheng; Li, Jiao; Zhang, Guodong; Li, Changxing; Lennon, Craig; Sivananthan, Siva

2007-08-01

The effects of artificial forced cooling on the solid liquid interface and on solute segregation were investigated by modeling the vertical Bridgman method for the single-crystal growth of CdZnTe, taking into consideration effects such as increasing the axial outward heat flux from the crucible bottom, the radial outward heat flux from the crucible wall, and the carbon film thickness on the crucible inner wall. Axial artificially forced cooling noticeably increases convection and the temperature gradient in the melt next to the solid liquid interface, and substantially reduces interface concavity at the initial solidification stage. Interface concavity increases a little when the solidification proceeds further, however. Axial artificially forced cooling reduces radial solute segregation of the initial segment of the grown crystal and slightly increases the solute iso-concentration segment. Radial artificially forced cooling enhances melt convection substantially, affects solid liquid interface concavity only slightly, and hardly affects solute segregation in the grown crystal. Doubling the carbon film thickness weakens convection of the melt in front of the interface, substantially increases interface concavity, and hardly affects solute segregation in the grown crystal.

The synthesis of cadmium sulfide nanoplatelets using a novel continuous flow sonochemical reactor

DOE PAGES

Palanisamy, Barath; Paul, Brian; Chang, Chih -hung

2015-01-21

A continuous flow sonochemical reactor was developed capable of producing metastable cadmium sulfide (CdS) nanoplatelets with thicknesses at or below 10 nm. The continuous flow sonochemical reactor included the passive in-line micromixing of reagents prior to sonochemical reaction. Synthesis results were compared with those from reactors involving batch conventional heating and batch ultrasound-induced heating. The continuous sonochemical synthesis was found to result in high aspect ratio hexagonal platelets of CdS possessing cubic crystal structures with thicknesses well below 10 nm. The unique shape and crystal structure of the nanoplatelets are suggestive of high localized temperatures within the sonochemical process. Asmore » a result, the particle size uniformity and product throughput are much higher for the continuous sonochemical process in comparison to the batch sonochemical process and conventional synthesis processes.« less

Probing polymer crystallization at processing-relevant cooling rates with synchrotron radiation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cavallo, Dario, E-mail: Dario.cavallo@unige.it; Portale, Giuseppe; Androsch, René

2015-12-17

Processing of polymeric materials to produce any kind of goods, from films to complex objects, involves application of flow fields on the polymer melt, accompanied or followed by its rapid cooling. Typically, polymers solidify at cooling rates which span over a wide range, from a few to hundreds of °C/s. A novel method to probe polymer crystallization at processing-relevant cooling rates is proposed. Using a custom-built quenching device, thin polymer films are ballistically cooled from the melt at rates between approximately 10 and 200 °C/s. Thanks to highly brilliant synchrotron radiation and to state-of-the-art X-ray detectors, the crystallization process ismore » followed in real-time, recording about 20 wide angle X-ray diffraction patterns per second while monitoring the instantaneous sample temperature. The method is applied to a series of industrially relevant polymers, such as isotactic polypropylene, its copolymers and virgin and nucleated polyamide-6. Their crystallization behaviour during rapid cooling is discussed, with particular attention to the occurrence of polymorphism, which deeply impact material’s properties.« less

Specific Features of the Domain Structure of BaTiO3 Crystals during Thermal Heating and Cooling

NASA Astrophysics Data System (ADS)

Kiselev, D. A.; Ilina, T. S.; Malinkovich, M. D.; Sergeeva, O. N.; Bolshakova, N. N.; Semenova, E. M.; Kuznetsova, Yu. V.

2018-04-01

This paper presents the results of the study of the domain structure of barium titanate crystals in a wide temperature range including the Curie point ( T C) using the polarization-optical method in the reflected light and the force microscopy of the piezoelectric response. It is shown that a new a-c domain structure forms during cyclic heating of the crystal above T C and subsequent cooling to the ferroelectric phase. The role of uncompensated charges appeared on the crystal surface during the phase transition and their influence on the formation of the domain structure during cooling are discussed.

Phase equilibrium modelling of granite magma petrogenesis: B. An evaluation of the magma compositions that result from fractional crystallization

NASA Astrophysics Data System (ADS)

Garcia-Arias, Marcos; Stevens, Gary

2017-04-01

Several fractional crystallization processes (flow segregation, gravitational settling, filter-pressing), as well as batch crystallization, have been investigated in this study using thermodynamic modelling (pseudosections) to test whether they are able to reproduce the compositional trends shown by S-type granites. Three starting compositions comprising a pure melt phase and variable amounts of entrained minerals (0, 20 and 40 wt.% of the total magma) have been used to study a wide range of likely S-type magma compositions. The evolution of these magmas was investigated from the segregation from their sources at 0.8 GPa until emplacement at 0.3 GPa in an adiabatic path, followed by isobaric cooling until the solidus was crossed, in a closed-system scenario. The modelled magmas and the fractionated mineral assemblages are compared to the S-type granites of the Peninsula pluton, Cape Granite Suite, South Africa, which have a composition very similar to most of the S-type granites. The adiabatic ascent of the magmas digests partially the entrained mineral assemblage of the magmas, but unless this entrained assemblage represents less than 1 wt.% of the original magma, part of the mineral fraction survives the ascent up to the chosen pressure of emplacement. At the level of emplacement, batch crystallization produces magmas that only plot within the composition of the granites of the Peninsula pluton if the bulk composition of the original magmas already matched that of the granites. Flow segregation of crystals during the ascent and gravitational settling fractional crystallization produce bodies that are generally more mafic than the most mafic granites of the pluton and the residual melts have an almost haplogranitic composition, producing a bimodal compositional distribution not observed in the granites. Consequently, these two processes are ruled out. Filter-pressing fractional crystallization produces bodies in an onion-layer structure that become more felsic with increasing crystallization, culminating in a haplogranitic melt, and is able to reproduce the compositional trends of the granites, but only if the original magmas already had the composition of the granites. Filter-pressing fractionation produces a mineral assemblage that is 1.5 times more mafic than the magma fraction from which it is derived. However, the mineral assemblages produced by crystallization of an originally pure melt phase are still too felsic to account for the bulk of the granites of the Peninsula pluton. For filter-pressing to produce the most mafic granites of the pluton, the original magmas must already contain an entrained mafic mineral assemblage and have the same composition of the granites, otherwise the modelled trends do not match the maficity (FeO + MgO) or the slope against maficity of the granites. Crystallization of the magma in filter-pressing releases a free water phase, whose amount depends on the amount of water of the original magma, and whose behaviour may be controlled by a water-saturation front. In summary, the main control in the composition of S-type granites is the amount and nature of the entrained mineral assemblage, and filter-pressing fractional crystallization can only modify slightly the compositions of the granitic bodies derived from these magmas.

Spectroscopic and laser cooling results on Yb3+-doped BaY2F8 single crystal

NASA Astrophysics Data System (ADS)

Bigotta, Stefano; Parisi, Daniela; Bonelli, Lucia; Toncelli, Alessandra; Tonelli, Mauro; Di Lieto, Alberto

2006-07-01

Anti-Stokes cooling has been observed in an Yb3+-doped BaY2F8 single crystal. Single crystals have been grown by the Czochralski technique. The absorption spectra and the emission properties have been measured at room temperature and at 10K. The energy positions of the Stark sublevels of the ground and the excited state manifolds have been determined and separated from the vibronic substructure. The intrinsic decay time of the F5/22 level has been measured taking care of avoiding the effect of multiple reabsorption processes. The theoretical and experimental cooling efficiencies of Yb:BaY2F8 are evaluated and compared with respect to those of the most frequently investigated materials for laser cooling. A temperature drop of almost 4K was measured by pumping the crystal with 3W of laser radiation at ˜1025nm in single pass configuration with a cooling efficiency of ˜3%.

Laboratory duplication of comb layering in the Rhum pluton. [igneous rocks with comb layered texture

NASA Technical Reports Server (NTRS)

Donaldson, C. H.

1977-01-01

A description is provided of the texture of harrisite comb layers, taking into account the results of crystallization experiments at controlled cooling rates, which have reproduced the textural change from 'cumulate' to comb-layered harrisite. Melted samples of harrisite were used in the dynamic crystallization experiments considered. The differentiation of a cooling rate run with respect to olivine grain size and shape is shown and three possible origins of hopper olivine in differentiated crystallization runs are considered. It is found that olivine nucleation occurred throughout cooling, except for the incubation period during early cooling. The elongate combed olivines in harrisite apparently grew as the magma locally supercooled to at least 30 C. It is suggested that the branching crystals in most comb layers, including comb-layered harrisite, probably grew along thermal gradients.

Crystallization of Synthetic Blast Furnace Slags Pertaining to Heat Recovery

NASA Astrophysics Data System (ADS)

Esfahani, Shaghayegh

Heat recovery from blast furnace slags is often contradicted by another requirement, to generate amorphous slag for its use in cement production. As both the rate and extent of heat recovery and slag structure are determined by its cooling rate, a relation between the crystallization kinetics and the cooling conditions is highly desired. In this study, CaO-SiO2-Al2O3-MgO (CSAM) slags with different basicities were studied by Single Hot Thermocouple Technique (SHTT) during isothermal treatment and non-isothermal cooling. Their time-temperature-transformation (TTT) and continuous-cooling-transformation (CCT) diagrams were plotted and compared with each other. Furthermore, kinetic parameters such as the Avrami exponent (n), rate coefficient (K) and effective activation energy of crystallization (EA) were found by analysis of data obtained from in-situ observation of glassy to crystalline transformation and image analysis. Also, the dependence of nucleation and growth rates of crystalline phases were quantified as a function of time, temperature, and slag basicity. Together with the observations of crystallization front, they facilitated establishing the dominant mechanisms of crystallization. In addition to the experimental work, a mathematical model was developed and validated that predicts the amount of crystallization during cooling. A second mathematical model that calculates temperature history of slag during its cooling was coupled with the above model, to allow studying the effect of parameters such as the slag/air ratio and granule size on the heat recovery and glass content of slag.

Phase determinations and crystal growth of Pb 2KNb 5O 15 (PKN)

NASA Astrophysics Data System (ADS)

Kramer, W. E.; Roland, G. W.

1982-07-01

Two problems must be addressed before good quality crystals of Pb 2KNb 5O 15 (PKN) can be grown: first, the compound does not melt congruently and therefore growth must be slow to avoid inclusions in the crystal; and second, cracking of crystals occurs during cooling due to anisotropic behavior of the thermal expansion coefficients at the Curie temperature. Extremely slow cooling in a uniform temperature gradient is necessary to get good quality, uncracked crystals.

Raw material variability of an active pharmaceutical ingredient and its relevance for processability in secondary continuous pharmaceutical manufacturing.

PubMed

Stauffer, F; Vanhoorne, V; Pilcer, G; Chavez, P-F; Rome, S; Schubert, M A; Aerts, L; De Beer, T

2018-06-01

Active Pharmaceutical Ingredients (API) raw material variability is not always thoroughly considered during pharmaceutical process development, mainly due to low quantities of drug substance available. However, synthesis, crystallization routes and production sites evolve during product development and product life cycle leading to changes in physical material attributes which can potentially affect their processability. Recent literature highlights the need for a global approach to understand the link between material synthesis, material variability, process and product quality. The study described in this article aims at explaining the raw material variability of an API using extensive material characterization on a restricted number of representative batches using multivariate data analysis. It is part of a larger investigation trying to link the API drug substance manufacturing process, the resulting physical API raw material attributes and the drug product continuous manufacturing process. Eight API batches produced using different synthetic routes, crystallization, drying, delumping processes and processing equipment were characterized, extensively. Seventeen properties from seven characterization techniques were retained for further analysis using Principal Component Analysis (PCA). Three principal components (PCs) were sufficient to explain 92.9% of the API raw material variability. The first PC was related to crystal length, agglomerate size and fraction, flowability and electrostatic charging. The second PC was driven by the span of the particle size distribution and the agglomerates strength. The third PC was related to surface energy. Additionally, the PCA allowed to summarize the API batch-to-batch variability in only three PCs which can be used in future drug product development studies to quantitatively evaluate the impact of the API raw material variability upon the drug product process. The approach described in this article could be applied to any other compound which is prone to batch-to-batch variability. Copyright © 2018 Elsevier B.V. All rights reserved.

19. RW Meyer Sugar: 18761889. Cooling Shed Interior, 1881. View: ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

19. RW Meyer Sugar: 1876-1889. Cooling Shed Interior, 1881. View: Looking toward west end of cooling shed. After the concentrated syrup flowed out of the sorghum pan it cooled and crystallized in large sugar coolers. The humidity and vapors caused by the sorghum pan would have retarded the crystallizing and cooling of the sugar in the boiling house. In 1881 this shed was constructed to house the coolers and the sugar before it was dried in the centrifugals. - R. W. Meyer Sugar Mill, State Route 47, Kualapuu, Maui County, HI

First demonstration of an all-solid-state optical cryocooler

DOE PAGES

Hehlen, Markus P.; Meng, Junwei; Albrecht, Alexander R.; ...

2018-06-06

Solid-state optical refrigeration uses anti-Stokes fluorescence to cool macroscopic objects to cryogenic temperatures without vibrations. Crystals such as Yb 3+-doped YLiF 4 (YLF:Yb) have previously been laser-cooled to 91 K. In this study, we show for the first time laser cooling of a payload connected to a cooling crystal. A YLF:Yb crystal was placed inside a Herriott cell and pumped with a 1020-nm laser (47 W) to cool a HgCdTe sensor that is part of a working Fourier Transform Infrared (FTIR) spectrometer to 135 K. This first demonstration of an all-solid-state optical cryocooler was enabled by careful control of themore » various desired and undesired heat flows. Fluorescence heating of the payload was minimized by using a single-kink YLF thermal link between the YLF:Yb cooling crystal and the copper coldfinger that held the HgCdTe sensor. The adhesive-free bond between YLF and YLF:Yb showed excellent thermal reliability. This laser-cooled assembly was then supported by silica aerogel cylinders inside a vacuum clamshell to minimize undesired conductive and radiative heat loads from the warm surroundings. Our structure can serve as a baseline for future optical cryocooler devices.« less

First demonstration of an all-solid-state optical cryocooler

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hehlen, Markus P.; Meng, Junwei; Albrecht, Alexander R.

Solid-state optical refrigeration uses anti-Stokes fluorescence to cool macroscopic objects to cryogenic temperatures without vibrations. Crystals such as Yb 3+-doped YLiF 4 (YLF:Yb) have previously been laser-cooled to 91 K. In this study, we show for the first time laser cooling of a payload connected to a cooling crystal. A YLF:Yb crystal was placed inside a Herriott cell and pumped with a 1020-nm laser (47 W) to cool a HgCdTe sensor that is part of a working Fourier Transform Infrared (FTIR) spectrometer to 135 K. This first demonstration of an all-solid-state optical cryocooler was enabled by careful control of themore » various desired and undesired heat flows. Fluorescence heating of the payload was minimized by using a single-kink YLF thermal link between the YLF:Yb cooling crystal and the copper coldfinger that held the HgCdTe sensor. The adhesive-free bond between YLF and YLF:Yb showed excellent thermal reliability. This laser-cooled assembly was then supported by silica aerogel cylinders inside a vacuum clamshell to minimize undesired conductive and radiative heat loads from the warm surroundings. Our structure can serve as a baseline for future optical cryocooler devices.« less

Kinetic study on the isothermal and nonisothermal crystallization of monoglyceride organogels.

PubMed

Meng, Zong; Yang, Lijun; Geng, Wenxin; Yao, Yubo; Wang, Xingguo; Liu, Yuanfa

2014-01-01

The isothermal and nonisothermal crystallization kinetics of monoglyceride (MAG) organogels were studied by pulsed nuclear magnetic resonance (pNMR) and differential scanning calorimetry (DSC), respectively. The Avrami equation was used to describe the isothermal crystallization kinetics and experimental data fitted the equation fairly well. Results showed that the crystal growth of MAG organogels was a rod-like growth of instantaneous nuclei at higher degrees of supercooling and a plate-like form with high nucleation rate at lower degrees of supercooling. The exothermic peak in nonisothermal DSC curves for the MAG organogels became wider and shifted to lower temperature when the cooling rate increased, and nonisothermal crystallization was analyzed by Mo equation. Results indicated that at the same crystallization time, to get a higher degree of relative crystallinity, a higher cooling rate was necessary. The activation energy of nonisothermal crystallization was calculated as 739.59 kJ/mol according to the Kissinger method. Therefore, as the results of the isothermal and nonisothermal crystallization kinetics for the MAG organogels obtained, the crystallization rate, crystal nucleation, and growth during the crystallization process could be preliminarily monitored through temperature and cooling rate regulation, which laid the foundation for the real industrial manufacture and application of the MAG organogels.

Heat load studies of a water-cooled minichannel monochromator for synchrotron x-ray beams

NASA Astrophysics Data System (ADS)

Freund, Andreas K.; Arthur, John R.; Zhang, Lin

1997-12-01

We fabricated a water-cooled silicon monochromator crystal with small channels for the special case of a double-crystal fixed-exit monochromator design where the beam walks across the crystal when the x-ray energy is changed. The two parts of the cooled device were assembled using a new technique based on low melting point solder. The bending of the system produced by this technique could be perfectly compensated by mechanical counter-bending. Heat load tests of the monochromator in a synchrotron beam of 75 W total power, 3 mm high and 15 mm wide, generated by a multipole wiggler at SSRL, showed that the thermal slope error of the crystal is 1 arcsec/40 W power, in full agreement with finite element analysis. The cooling scheme is adequate for bending magnet beamlines at the ESRF and present wiggler beamlines at the SSRL.

Effect of Cooling Rate and Oxygen Fugacity on the Crystallization of the Queen Alexandra Range 94201 Martian Melt Composition

NASA Technical Reports Server (NTRS)

Koizumi, E.; Mikouchi, T.; McKay, G.; Schwandt, C.; Monkawa, A.; Miyamoto, M.

2002-01-01

Although many basaltic shergottites have been recently found in north African deserts, QUE94201 basaltic shergottite (QUE) is still important because of its particular mineralogical and petrological features. This meteorite is thought to represent its parent melt composition [1 -3] and to crystallize under most reduced condition in this group [1,4]. We performed experimental study by using the synthetic glass that has the same composition as the bulk of QUE. After homogenization for 48 hours at 1300 C, isothermal and cooling experiments were done under various conditions (e.g. temperature, cooling rates, and redox states). Our goals are (1) to verify that QUE really represents its parent melt composition, (2) to estimate a cooling rate of this meteorite, (3) to clarify the crystallization sequences of present minerals, and (4) to verity that this meteorite really crystallized under reduced condition.

Use of Plastic Capillaries for Macromolecular Crystallization

NASA Technical Reports Server (NTRS)

Potter, Rachel R.; Hong, Young-Soo; Ciszak, Ewa M.

2003-01-01

Methods of crystallization of biomolecules in plastic capillaries (Nalgene 870 PFA tubing) are presented. These crystallization methods used batch, free-interface liquid- liquid diffusion alone, or a combination with vapor diffusion. Results demonstrated growth of crystals of test proteins such as thaumatin and glucose isomerase, as well as protein studied in our laboratory such dihydrolipoamide dehydrogenase. Once the solutions were loaded in capillaries, they were stored in the tubes in frozen state at cryogenic temperatures until the desired time of activation of crystallization experiments.

Adsorption of saturated fatty acid in urea complexation: Kinetics and equilibrium studies

NASA Astrophysics Data System (ADS)

Setyawardhani, Dwi Ardiana; Sulistyo, Hary; Sediawan, Wahyudi Budi; Fahrurrozi, Mohammad

2018-02-01

Urea complexation is fractionation process for concentrating poly-unsaturated fatty acids (PUFAs) from vegetable oil or animal fats. For process design and optimization in commercial industries, it is necessary to provide kinetics and equilibrium data. Urea inclusion compounds (UICs) as the product is a unique complex form which one molecule (guest) is enclosed within another molecule (host). In urea complexation, the guest-host bonding exists between saturated fatty acids (SFAs) and crystalline urea. This research studied the complexation is analogous to an adsorption process. The Batch adsorption process was developed to obtain the experimental data. The ethanolic urea solution was mixed with SFA in certain compositions and adsorption times. The mixture was heated until it formed homogenous and clear solution, then it cooled very slowly until the first numerous crystal appeared. Adsorption times for the kinetic data were determined since the crystal formed. The temperature was maintained constant at room temperature. Experimental sets of data were observed with adsorption kinetics and equilibrium models. High concentration of saturated fatty acid (SFA) was used to represent adsorption kinetics and equilibrium parameters. Kinetic data were examined with pseudo first-order, pseudo second-order and intra particle diffusion models. Linier, Freundlich and Langmuir isotherm were used to study the equilibrium model of this adsorption. The experimental data showed that SFA adsorption in urea crystal followed pseudo second-order model. The compatibility of the data with Langmuir isotherm showed that urea complexation was a monolayer adsorption.

A Novel Compact Pyroelectric X-Ray and Neutron Source

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yaron Danon

2007-08-31

This research was focused on the utilization of pyroelectric crystals for generation of radiation. When in constant temperature pyroelectric crystals are spontaneously polarized. The polarization causes internal charges to accumulate near the crystal faces and masking charges from the environment are attracted to the crystal faces and neutralize the charge. When a pyroelectric crystal is heated or cooled it becomes depolarized and the surface charges become available. If the heating or cooling is done on a crystal in vacuum where no masking charges are available, the crystal becomes a charged capacitor and because of its small capacitance large potential developsmore » across the faces of the crystal.« less

Three-Dimensional Microstructure of Biological Tissues during Freezing and Thawing

NASA Astrophysics Data System (ADS)

Ishiguro, Hiroshi; Horimizu, Takashi; Kataori, Akinobu; Kajigaya, Hiroshi

Three-dimensional behavior of ice crystals and cells during the freezing and thawing of biological tissues was investigated microscopically in real time by using a confocal laser scanning microscope(CLSM) and a fluorescent dye, acridine orange (AO). Fresh tender meat (2nd pectoral muscles) of chicken was stained with the AO in physiological saline to distinguish ice crystals and cells by their different colors, and then frozen and thawed under two different thermal protocols: a) slow-cooling and rapid-warming and b) rapid-cooling and rapid-warming. The CLSM noninvasively produced optical tomograms of the tissues to clarify the pattern of freezing, morphology of ice crystals in the tissues, and the interaction between ice crystals and cells. Also, the tissues were morphologically investigated by pathological means after the freezing and thawing. Typical freezing pattern during the slow-cooling was extracellular-freezing, and those during the rapid-cooling were extracellular-freezing and intracellular freezing with a lot of fine ice crystals in the cells. Cracks caused by the extracellular and intracellular ice crystals remained in the muscle tissues after the thawing. The results obtained by using the CLSM/dye method were consistent with pathologically morphological changes in the tissues through freezing and thawing.

An Investigation into the Polymorphism and Crystallization of Levetiracetam and the Stability of its Solid Form.

PubMed

Xu, Kailin; Xiong, Xinnuo; Guo, Liuqi; Wang, Lili; Li, Shanshan; Tang, Peixiao; Yan, Jin; Wu, Di; Li, Hui

2015-12-01

Levetiracetam (LEV) crystals were prepared using different solvents at different temperatures. The LEV crystals were systematically characterized by X-ray powder diffraction (XRPD) and morphological analysis. The results indicated that many kinds of crystal habits exist in a solid form of LEV. To investigate the effects of LEV concentration, crystallization temperature, and crystallization type on crystallization and solid phase transformation of LEV, multiple methods were performed for LEV aqueous solution to determine if a new solid form exists in solid-state LEV. However, XRPD data demonstrate that the LEV solid forms possess same spatial arrangements that are similar to the original solid form. This result indicates that the LEV concentration, crystallization temperature, and crystallization type in aqueous solution have no influence on the crystallization and solid phase transformation of LEV. Moreover, crystallization by sublimation, melt cooling, and quench cooling, as well as mechanical effect, did not result in the formation of new LEV solid state. During melt cooling, the transformation of solid form LEV is a direct process from melting amorphous phase to the original LEV crystal phase, and the conversion rate is very quick. In addition, stability investigation manifested that LEV solid state is very stable under various conditions. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

Cooling and crystallization of lava in open channels, and the transition of Pāhoehoe Lava to 'A'ā

NASA Astrophysics Data System (ADS)

Cashman, Katharine V.; Thornber, Carl; Kauahikaua, James P.

Samples collected from a lava channel active at Kīlauea Volcano during May 1997 are used to constrain rates of lava cooling and crystallization during early stages of flow. Lava erupted at near-liquidus temperatures ( 1150 °C) cooled and crystallized rapidly in upper parts of the channel. Glass geothermometry indicates cooling by 12-14 °C over the first 2km of transport. At flow velocities of 1-2m/s, this translates to cooling rates of 22-50 °C/h. Cooling rates this high can be explained by radiative cooling of a well-stirred flow, consistent with observations of non-steady flow in proximal regions of the channel. Crystallization of plagioclase and pyroxene microlites occurred in response to cooling, with crystallization rates of 20-50% per hour. Crystallization proceeded primarily by nucleation of new crystals, and nucleation rates of 104/cm3s are similar to those measured in the 1984 open channel flow from Mauna Loa Volcano. There is no evidence for the large nucleation delays commonly assumed for plagioclase crystallization in basaltic melts, possibly a reflection of enhanced nucleation due to stirring of the flow. The transition of the flow surface morphology from pāhoehoe to 'a'ā occurred at a distance of 1.9km from the vent. At this point, the flow was thermally stratified, with an interior temperature of 1137 °C and crystallinity of 15%, and a flow surface temperature of 1100 °C and crystallinity of 45%. 'A'ā formation initiated along channel margins, where crust was continuously disrupted, and involved tearing and clotting of the flow surface. Both observations suggest that the transition involved crossing of a rheological threshold. We suggest this threshold to be the development of a lava yield strength sufficient to prevent viscous flow of lava at the channel margin. We use this concept to propose that 'a'ā formation in open channels requires both sufficiently high strain rates for continued disruption of surface crusts and sufficient groundmass crystallinity to generate a yield strength equivalent to the imposed stress. In Hawai'i, where lava is typically microlite poor on eruption, these combined requirements help to explain two common observations on 'a'ā formation: (a) 'a'ā flow fields are generated when effusion rates are high (thus promoting crustal disruption); and (b) under most eruption conditions, lava issues from the vent as pāhoehoe and changes to 'a'ā only after flowing some distance, thus permitting sufficient crystallization.

Magnetism out of antisite disorder in the J =0 compound Ba2YIrO6

NASA Astrophysics Data System (ADS)

Chen, Q.; Svoboda, C.; Zheng, Q.; Sales, B. C.; Mandrus, D. G.; Zhou, H. D.; Zhou, J.-S.; McComb, D.; Randeria, M.; Trivedi, N.; Yan, J.-Q.

2017-10-01

We systematically investigate the magnetic properties and local structure of Ba2YIrO6 to demonstrate that Y and Ir lattice defects in the form of antiphase boundary or clusters of antisite disorder affect the magnetism observed in this 5 d4 compound. The experimental investigation involved comparison of the magnetic properties and atomic imaging of (1) a slow-cooled crystal, (2) a crystal quenched from 900°C after growth, and (3) a crystal grown using a faster cooling rate during growth than the slow-cooled one. Atomic-scale imaging by scanning transmission electron microscopy (STEM) shows that quenching from 900°C introduces Ir-rich antiphase boundaries in the crystals, and a faster cooling rate during crystal growth leads to clusters of Y and Ir antisite disorder. Compared to the slow-cooled crystals, Ba2YIrO6 crystals with clusters of antisite defects have a larger effective moment and a larger saturation moment, while quenched crystals with Ir-rich antiphase boundary show a slightly suppressed moment. Our DFT and model magnetic Hamiltonian calculations suggest magnetic condensation is unlikely, as the energy to be gained from superexchange is small compared to the spin-orbit gap. However, once Y is replaced by Ir in the antisite disordered region, the picture of local nonmagnetic singlets breaks down and magnetism can be induced. This is because of (a) enhanced interactions due to increased orbital overlap and (b) increased number of orbitals mediating the interactions. Our work highlights the importance of lattice defects in understanding the experimentally observed magnetism in Ba2YIrO6 and other J =0 systems.

Magnetism out of antisite disorder in the J = 0 compound Ba 2 YIrO 6

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Qiang; Svoboda, Chris; Zheng, Qiang

Here, we systematically investigate the magnetic properties and local structure of Ba 2YIrO 6 to demonstrate that Y and Ir lattice defects in the form of antiphase boundary or clusters of antisite disorder affect the magnetism observed in this 5d 4 compound. The experimental investigation involved comparison of the magnetic properties and atomic imaging of (1) a slow-cooled crystal, (2) a crystal quenched from 900°C after growth, and (3) a crystal grown using a faster cooling rate during growth than the slow-cooled one. Atomic-scale imaging by scanning transmission electron microscopy (STEM) shows that quenching from 900°C introduces Ir-rich antiphase boundariesmore » in the crystals, and a faster cooling rate during crystal growth leads to clusters of Y and Ir antisite disorder. Compared to the slow-cooled crystals, Ba 2YIrO 6 crystals with clusters of antisite defects have a larger effective moment and a larger saturation moment, while quenched crystals with Ir-rich antiphase boundary show a slightly suppressed moment. Our DFT and model magnetic Hamiltonian calculations suggest magnetic condensation is unlikely, as the energy to be gained from superexchange is small compared to the spin-orbit gap. However, once Y is replaced by Ir in the antisite disordered region, the picture of local nonmagnetic singlets breaks down and magnetism can be induced. This is because of (a) enhanced interactions due to increased orbital overlap and (b) increased number of orbitals mediating the interactions. Our work highlights the importance of lattice defects in understanding the experimentally observed magnetism in Ba 2YIrO 6 and other J = 0 systems.« less

Magnetism out of antisite disorder in the J = 0 compound Ba 2 YIrO 6

DOE PAGES

Chen, Qiang; Svoboda, Chris; Zheng, Qiang; ...

2017-10-18

Here, we systematically investigate the magnetic properties and local structure of Ba 2YIrO 6 to demonstrate that Y and Ir lattice defects in the form of antiphase boundary or clusters of antisite disorder affect the magnetism observed in this 5d 4 compound. The experimental investigation involved comparison of the magnetic properties and atomic imaging of (1) a slow-cooled crystal, (2) a crystal quenched from 900°C after growth, and (3) a crystal grown using a faster cooling rate during growth than the slow-cooled one. Atomic-scale imaging by scanning transmission electron microscopy (STEM) shows that quenching from 900°C introduces Ir-rich antiphase boundariesmore » in the crystals, and a faster cooling rate during crystal growth leads to clusters of Y and Ir antisite disorder. Compared to the slow-cooled crystals, Ba 2YIrO 6 crystals with clusters of antisite defects have a larger effective moment and a larger saturation moment, while quenched crystals with Ir-rich antiphase boundary show a slightly suppressed moment. Our DFT and model magnetic Hamiltonian calculations suggest magnetic condensation is unlikely, as the energy to be gained from superexchange is small compared to the spin-orbit gap. However, once Y is replaced by Ir in the antisite disordered region, the picture of local nonmagnetic singlets breaks down and magnetism can be induced. This is because of (a) enhanced interactions due to increased orbital overlap and (b) increased number of orbitals mediating the interactions. Our work highlights the importance of lattice defects in understanding the experimentally observed magnetism in Ba 2YIrO 6 and other J = 0 systems.« less

The Effect of the Wall Contact and Post-Growth C001-Down on Defects in CdTe Crystals Grown by Contactless PVT

NASA Technical Reports Server (NTRS)

Palosz, W.; Grasza, K.; Dudley, M.; Raghothamachar, B.; Cai, L.; Durose, K.; Halliday, D.; Boyall, N. M.; Rose, M. Franklin (Technical Monitor)

2001-01-01

In crystal growth, the quality of the final material may depend, among other factors, on its interaction with the walls of the ampoule during and after the growth, and on the rate of the crystal cool-down at the end of ate the process. To investigate the above phenomena, a series of CdTe crystal growth processes was carried out, The crystals were grown by physical vapor transport without contact with the side walls of the silica glass ampoules, applying the Low Supersaturation Nucleation technique. The source temperature was 930 C, the undercooling was a few degrees. The crystals, having the diameter of 25 mm, grew at the rate of a few mm per day. The post-growth cool-down to the room temperature was conducted at different rates, and lasted from a few minutes to four days. The crystals were characterized using chemical etching low temperature luminescence, and Synchrotron White Beam X-ray Topography techniques. The dislocation (etch pit) density was measured and its distribution was analyzed by comparison with Poisson curves and with the Normalized Radial Distribution Correlation Function. It was found that the contact of the crystal with silica leads to a strain field and high (in the 105 sq cm range) dislocation (etch pit) density. Similar defect concentrations were found in crystals subjected to fast post-growth cool-down. Typical EPD values for lower cool-down rates and in regions not affected by wall interactions are in the lower 10(exp 4) sq cm range. In some areas the actual dislocation density was about 10(exp 3) sq cm or even less. No apparent effect of the cool-down rate on polygonization was observed. A fine structure could be discerned in low-temperature PL spectra of crystals with low dislocation density.

Thin-Film Evaporative Cooling for Side-Pumped Laser

NASA Technical Reports Server (NTRS)

Stewart, Brian K. (Inventor)

2010-01-01

A system and method are provided for cooling a crystal rod of a side-pumped laser. A transparent housing receives the crystal rod therethrough so that an annular gap is defined between the housing and the radial surface of the crystal rod. A fluid coolant is injected into the annular gap such the annular gap is partially filled with the fluid coolant while the radial surface of the crystal rod is wetted as a thin film all along the axial length thereof.

Practical macromolecular cryocrystallography

PubMed Central

Pflugrath, J. W.

2015-01-01

Cryocrystallography is an indispensable technique that is routinely used for single-crystal X-ray diffraction data collection at temperatures near 100 K, where radiation damage is mitigated. Modern procedures and tools to cryoprotect and rapidly cool macromolecular crystals with a significant solvent fraction to below the glass-transition phase of water are reviewed. Reagents and methods to help prevent the stresses that damage crystals when flash-cooling are described. A method of using isopentane to assess whether cryogenic temperatures have been preserved when dismounting screened crystals is also presented. PMID:26057787

Kinetic Study on the Isothermal and Nonisothermal Crystallization of Monoglyceride Organogels

PubMed Central

Meng, Zong; Yang, Lijun; Geng, Wenxin; Yao, Yubo; Wang, Xingguo; Liu, Yuanfa

2014-01-01

The isothermal and nonisothermal crystallization kinetics of monoglyceride (MAG) organogels were studied by pulsed nuclear magnetic resonance (pNMR) and differential scanning calorimetry (DSC), respectively. The Avrami equation was used to describe the isothermal crystallization kinetics and experimental data fitted the equation fairly well. Results showed that the crystal growth of MAG organogels was a rod-like growth of instantaneous nuclei at higher degrees of supercooling and a plate-like form with high nucleation rate at lower degrees of supercooling. The exothermic peak in nonisothermal DSC curves for the MAG organogels became wider and shifted to lower temperature when the cooling rate increased, and nonisothermal crystallization was analyzed by Mo equation. Results indicated that at the same crystallization time, to get a higher degree of relative crystallinity, a higher cooling rate was necessary. The activation energy of nonisothermal crystallization was calculated as 739.59 kJ/mol according to the Kissinger method. Therefore, as the results of the isothermal and nonisothermal crystallization kinetics for the MAG organogels obtained, the crystallization rate, crystal nucleation, and growth during the crystallization process could be preliminarily monitored through temperature and cooling rate regulation, which laid the foundation for the real industrial manufacture and application of the MAG organogels. PMID:24701138

Rutilated quartz: combining Ti-in-quartz thermometry and lattice diffusion

NASA Astrophysics Data System (ADS)

Tailby, N.; Towbin, H.; Ackerson, M. R.

2017-12-01

The Ti content of quartz can be used to evaluate crystallization temperatures in silicic magmas like the S-type Jillamatong granodiorite of the Lachlan Fold Belt. Additionally, the presence of crystallographically-aligned exsolved rutile needles in quartz from this granodiorite suggests that post-crystallization modification of Ti in quartz can be used to assess magmatic cooling rates. In this study we report Ti-in-quartz temperatures that indicate crystallization between 600-700 °C at this location (i.e., 25-60 ppmw Ti, P = 5 kbar, aTiO2= 0.46-0.66). After crystallization, Ti in quartz can be reset via lattice diffusion, a process that can be quantified or evaluated from experimentally-determined values [Cherniak et al., 2007; where DTi = 7x10-8exp (-273±12kJmol-1/RT) m2sec-1)]. The slow diffusivity of Ti through the quartz lattice is one factor that contributes to the general use of quartz thermometry - this is to say that unrealistically long time periods are required in order for a cooling quartz crystal to re-equilibrate with the new thermal regime. This is particularly true of crystal cores (generally on the mm scale), where the diffusive length scale from the core to rim of the crystal could be used to suggest core retention is likely in even the slowest cooling granitic systems. In the Jillamatong pluton - as we predict is possible in a significant body of granitoids - coupling of slow diffusion and decreasing Ti solubility in quartz upon cooling can lead to a situation where a quartz crystal becomes saturated in Ti (i.e., aTiO2=1) and rutile exsolutions develop. The radius ( 0.6 microns) and distribution of these needles, coupled with the diffusive draw down well ( 11 microns) around these exsolutions, can be used to evaluate the cooling history of the pluton, thus providing a comprehensive time-integrated crystallization and cooling history of plutonic rocks. ReferencesCherniak et al., 2007. Chem. Geol. 236, 65-74 Thomas et al., 2010. Contrib. Mineral. Petr. 160, 743-759

A Kinetic Study of the Effect of Basicity on the Mold Fluxes Crystallization

NASA Astrophysics Data System (ADS)

Zhou, Lejun; Wang, Wanlin; Ma, Fanjun; Li, Jin; Wei, Juan; Matsuura, Hiroyuki; Tsukihashi, Fumitaka

2012-04-01

The effect of basicity on the mold fluxes crystallization was investigated in this article. The time-temperature-transformation (TTT) diagrams and continuous-cooling-transformation (CCT) diagrams of mold fluxes with different basicity were constructed by using single, hot thermocouple technology (SHTT). The results showed that with the increase of basicity, the incubation time of isothermal crystallization became shorter, the crystallization temperature was getting higher, and the critical cooling rate of continuous cooling crystallization became faster. The X-ray diffraction analysis suggested that calcium silicate (CaO·SiO2) was precipitated at the upper part of the TTT diagram and cuspidine (Ca4Si2O7F2) was formed at the lower part, when the basicity of mold fluxes was within 1.0 to 1.2. However, when basicity was 0.8, only the cuspidine phase was formed. A kinetic study of isothermal crystallization process indicated that the increase of the basicity tended to enhance the mold flux crystallization, and the crystallization activation energy became smaller. The crystallization mechanism of cupsidine was changing from one-dimensional growth to three-dimensional growth with a constant number of nuclei, when the basicity of mold fluxes varied from 0.8 to 1.2.

Reversible thermosalience of 4-aminobenzonitrile.

PubMed

Alimi, Lukman O; van Heerden, Dewald P; Lama, Prem; Smith, Vincent J; Barbour, Leonard J

2018-05-31

Crystals of 4-aminobenzonitrile grown by sublimation undergo reversible thermosalient phase changes during cooling and subsequent heating. Single-crystal diffraction studies have been carried out at 20 K intervals during cooling from 300 to 100 K in order to explain the structural change that occurs.

Film-Cooling Heat-Transfer Measurements Using Liquid Crystals

NASA Technical Reports Server (NTRS)

Hippensteele, Steven A.

1997-01-01

The following topics are discussed: (1) The Transient Liquid-Crystal Heat-Transfer Technique; (2) 2-D Film-Cooling Heat-Transfer on an AlliedSignal Vane; and (3) Effects of Tab Vortex Generators on Surface Heat Transfer. Downstream of a Jet in Crossflow.

An unusual type of polymorphism in a liquid crystal

DOE PAGES

Li, Lin; Salamonczyk, Miroslaw; Shadpour, Sasan; ...

2018-02-19

Polymorphism is a remarkable concept in chemistry, materials science, computer science, and biology. Whether it is the ability of a material to exist in two or more crystal structures, a single interface connecting to two different entities, or alternative phenotypes of an organism, polymorphism determines function and properties. In materials science, polymorphism can be found in an impressively wide range of materials, including crystalline materials, minerals, metals, alloys, and polymers. Here in this paper we report on polymorphism in a liquid crystal. A bent-core liquid crystal with a single chiral side chain forms two structurally and morphologically significantly different liquidmore » crystal phases solely depending on the cooling rate from the isotropic liquid state. On slow cooling, the thermodynamically more stable oblique columnar phase forms, and on rapid cooling, a not heretofore reported helical microfilament phase. Since structure determines function and properties, the structural color for these phases also differs.« less

An unusual type of polymorphism in a liquid crystal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Lin; Salamonczyk, Miroslaw; Shadpour, Sasan

Polymorphism is a remarkable concept in chemistry, materials science, computer science, and biology. Whether it is the ability of a material to exist in two or more crystal structures, a single interface connecting to two different entities, or alternative phenotypes of an organism, polymorphism determines function and properties. In materials science, polymorphism can be found in an impressively wide range of materials, including crystalline materials, minerals, metals, alloys, and polymers. Here in this paper we report on polymorphism in a liquid crystal. A bent-core liquid crystal with a single chiral side chain forms two structurally and morphologically significantly different liquidmore » crystal phases solely depending on the cooling rate from the isotropic liquid state. On slow cooling, the thermodynamically more stable oblique columnar phase forms, and on rapid cooling, a not heretofore reported helical microfilament phase. Since structure determines function and properties, the structural color for these phases also differs.« less

Magma oceanography. II - Chemical evolution and crustal formation. [lunar crustal rock fractional crystallization model

NASA Technical Reports Server (NTRS)

Longhi, J.

1977-01-01

A description is presented of an empirical model of fractional crystallization which predicts that slightly modified versions of certain of the proposed whole moon compositions can reproduce the major-element chemistry and mineralogy of most of the primitive highland rocks through equilibrium and fractional crystallization processes combined with accumulation of crystals and trapping of residual liquids. These compositions contain sufficient Al to form a plagioclase-rich crust 60 km thick on top of a magma ocean that was initially no deeper than about 300 km. Implicit in the model are the assumptions that all cooling and crystallization take place at low pressure and that there are no compositional or thermal gradients in the liquid. Discussions of the cooling and crystallization of the proposed magma ocean show these assumptions to be disturbingly naive when applied to the ocean as a whole. However, the model need not be applied to the whole ocean, but only to layers of cooling liquid near the surface.

Temperature distribution of laser crystal in end-pumped DPSSL

NASA Astrophysics Data System (ADS)

Zheng, Yibo; Jia, Liping; Zhang, Lei; Wen, Jihua; Kang, Junjian

2009-11-01

The temperature distribution in different cooling system was studied. A thermal distribution model of laser crystal was established. Based on the calculation, the temperature distribution and deformation of ND:YVO4 crystal in different cooling system were obtained. When the pumping power is 2 W and the radius of pumping beams is 320μm, the temperature distribution and end face distortion of the laser crystal are lowest by using side directly hydrocooling method. The study shows that, the side directly hydrocooling method is a more efficient method to control the crystal temperature distribution and reduce the thermal effect.

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.

Heterogeneous-nucleation and glass-formation studies of 56Ga2O3-44CaO

NASA Technical Reports Server (NTRS)

Ethridge, Edwin C.; Curreri, Peter A.; Pline, David

1987-01-01

Glass formation and heterogeneous crystallization are described for the reluctant-glass-forming 56Ga2O3-44CaO eutectic composition. The times and temperatures for nucleation at various cooling rates and experimental conditions were measured and empirical continuous-cooling-crystallization boundaries were constructed for various heterogeneous nucleation processes. A definition for an empirical critical cooling rate to form a glass from reluctant borderline glass formers is proposed, i.e., the cooling rate that results in glass formation in 95 percent of the quenching experiments.

The Effect of the Wall Contact and Post-Growth, Cool-Down on Defects in CdTe Crystals Grown By 'Contactless' PVT

NASA Technical Reports Server (NTRS)

Palosz, W.; Grasza, K.; Dudley, M.; Raghothamachar, B.; Cai, L.; Dunrose, K.; Halliday, D.; Boyall, N. M.; Rose, M. Franklin (Technical Monitor)

2001-01-01

To take a maximum advantage of materials processing in microgravity for understanding the effects of gravity, gravity-independent effects should be minimized. In crystal growth, the quality of the grown crystals may depend, among other factors, on their interaction with the walls of the processing container during and after growth, and on the rate of the crystal cool-down at the end of the process. To investigate the above phenomena, a series of CdTe crystal growth processes was carried out. The crystals were grown by physical vapor transport without contact with the side walls of the silica glass ampoules. To eliminate the effect of the seed quality, and to reduce the number of nuclei and related crystal grains, the Low Supersaturation Nucleation technique was applied. The source temperature was 930 C, the undercooling was a few degrees. The crystals, having the diameter of 25 mm, grew at the rate of a few mm per day. The post-growth cool-down to the room temperature was conducted at different rates, and lasted from a few minutes to four days. The crystals were characterized using chemical etching, low temperature luminescence, and Synchrotron White Beam X-ray Topography techniques. The dislocation (etch pit) density was measured and its distribution was analyzed by comparison with Poisson curves and with the Normalized Radial Distribution Correlation Function. In the regions where the crystal is in contact with silica, the materials show a considerable strain field which extends for a few mm or more from the silica-crystal interface. In the reference crystal grown with contact with the ampoule walls, and when the crystals are cooled at the highest rates, the etch pit/dislocation density is in the high 10(exp 5) per square centimeter region. Typical EPD values for lower cool-down rates are in the lower 10(exp 4) per square centimeter region. In some areas the actual dislocation density was about 10(exp 3) per square centimeter or even less. No apparent effect of the cool-down rate on polygonization was observed. Low temperature PL spectra show, that the dominant peak is (D(sup 0), h) and (A(sup 0), e) for samples with low and high dislocation densities, respectively. For low EPD crystals a peak at 1.45 eV with 21 meV phonon replicas was observed and attributed to donor-acceptor pair to neutral copper-acceptor transition. In high EPD crystals this PL structure was not observed, apparently due to the masking effect of the strong contribution from the dislocation band.

Influence of water quench cooling on degassing and aroma stability of roasted coffee.

PubMed

Baggenstoss, Juerg; Poisson, Luigi; Luethi, Regina; Perren, Rainer; Escher, Felix

2007-08-08

Coffee roasting experiments with air cooling versus water quench cooling were carried out on laboratory scale with a fluidized-bed hot air roasting system (200 g batch size) and on production scale with a rotating bowl roaster (320 kg batch size). Two series of coffees with different water contents resulted, which were stored at 25 degrees C under normal atmospheric conditions. Carbon dioxide desorption was followed and stability of selected aroma compounds was tested with headspace solid-phase microextraction-gas chromatography-mass spectrometry (SPME-GC-MS) and stable isotope labeled compounds as internal standards. Degassing is faster in water-quenched coffees with higher moisture content, but pore size distribution in the different coffee samples did not correlate with degassing behavior. Bean firmness, which increases with increasing moisture content, might have an influence on degassing. Air- and water-quenched coffees exhibit similar stability of most aroma compounds despite different degassing behavior. However, evolution of dimethyl trisulfide was different in coffees with increased water content. This suggests higher thiol oxidation rates, a factor that is cited to be related to a faster loss of freshness attributes.

Heat transfer analysis of catheters used for localized tissue cooling to attenuate reperfusion injury.

PubMed

Merrill, Thomas L; Mitchell, Jennifer E; Merrill, Denise R

2016-08-01

Recent revascularization success for ischemic stroke patients using stentrievers has created a new opportunity for therapeutic hypothermia. By using short term localized tissue cooling interventional catheters can be used to reduce reperfusion injury and improve neurological outcomes. Using experimental testing and a well-established heat exchanger design approach, the ɛ-NTU method, this paper examines the cooling performance of commercially available catheters as function of four practical parameters: (1) infusion flow rate, (2) catheter location in the body, (3) catheter configuration and design, and (4) cooling approach. While saline batch cooling outperformed closed-loop autologous blood cooling at all equivalent flow rates in terms of lower delivered temperatures and cooling capacity, hemodilution, systemic and local, remains a concern. For clinicians and engineers this paper provides insights for the selection, design, and operation of commercially available catheters used for localized tissue cooling. Copyright © 2016 IPEM. Published by Elsevier Ltd. All rights reserved.

Examining the role of canister cooling conditions on the formation of nepheline from nuclear waste glasses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Christian, J. H.

2015-09-01

Nepheline (NaAlSiO₄) crystals can form during slow cooling of high-level waste (HLW) glass after it has been poured into a waste canister. Formation of these crystals can adversely affect the chemical durability of the glass. The tendency for nepheline crystallization to form in a HLW glass increases with increasing concentrations of Al₂O₃ and Na₂O.

Cryo-cooling in macromolecular crystallography: advantages, disadvantages and optimization.

PubMed

Juers, Douglas H; Matthews, Brian W

2004-05-01

The flash-cooling of crystals in macromolecular crystallography has become commonplace. The procedure makes it possible to collect data from much smaller specimens than was the case in the past Also, flash-cooled crystals are much less prone to radiation damage than their room-temperature counterparts, allowing data to be accumulated over extended periods of time. Notwithstanding the attractiveness of the technique, it does have potential disadvantages. First, better methods need to be developed to prevent damage to crystals on freezing. There is also a risk that structures determined at low temperature may suggest conclusions based on aspects of the structure that are not necessarily relevant at room temperature.

Numerical investigation on the batch characteristics of liquid encapsulated vertical Bridgman crystal growth

NASA Astrophysics Data System (ADS)

Lan, C. W.; Ting, C. C.

1995-04-01

Since the liquid encapsulated vertical Bridgman (LEVB) crystal growth is a batch process, it is time dependent in nature. A numerical simulation is conducted to study the unsteady features of the process, including the dynamic evolution of heat flow, growth rate, and interface morphology during crystal growth. The numerical model, which is governed by time-dependent equations for momentum and energy transport, and the conditions for evolution of melt/crystal and melt/encapsulant interfaces, is approximated by a body-fitted coordinate finite-volume method. The resulting differential/algebraic equations are then solved by the ILU (0) preconditioned DASPK code. Sample calculations are mainly conducted for GaAs. Dynamic effects of some process parameters, such as the growth speed, the ambient temperature profile, and ampoule design, are illustrated through calculated results. Due to the heat of fusion release and time-dependent end effects, in some cases a near steady-state operation is not possible. The control of growth front by modifying the ambient temperature profile is also demonstrated. Calculations are also performed for a 4.8 cm diameter InP crystal. The calculated melt/seed interface shape is compared with the measured one from Matsumoto et al. [J. Crystal Growth 132 (1993) 348] and they are in good agreement.

Phosphorus removal characteristics in hydroxyapatite crystallization using converter slag.

PubMed

Kim, Eung-Ho; Hwang, Hwan-Kook; Yim, Soo-Bin

2006-01-01

This study was performed to investigate the phosphorus removal characteristics in hydroxyapatite (HAP) crystallization using converter slag as a seed crystal and the usefulness of a slag column reactor system. The effects of alkalinity, and the isomorphic-substitutable presence of ionic magnesium, fluoride, and iron on HAP crystallization seeded with converter slag, were examined using a batch reactor system. The phosphorus removal efficiencies of the batch reactor system were found to increase with increases in the iron and fluoride ion concentrations, and to decrease with increases in the alkalinity and magnesium ion concentration. A column reactor system for HAP crystallization using converter slag was found to achieve high, stable levels of phosphorus elimination: the average PO4-P removal efficiency over 414 days of operation was 90.4%, in which the effluent phosphorus concentration was maintained at less than 0.5 mg/L under the appropriate phosphorus crystallization conditions. The X-ray diffraction (XRD) patterns and Fourier transform infrared (FTIR) spectra of the crystalline material deposited on the seed particles exhibited peaks consistent with HAP. Scanning electron micrograph (SEM) images showed that finely distributed crystalline material was formed on the surfaces of the seed particles. Energy dispersive X-ray spectroscopy (EDS) mapping analysis revealed that the molar Ca/P composition ratio of the crystalline material was 1.72.

Growth of triglycine sulfate (TGS) crystals by solution technique

NASA Technical Reports Server (NTRS)

Lal, R. B.; Kroes, R. L.; Wilcox, W. R.

1982-01-01

The growth of crystals from solution is greatly influenced by buoyancy driven convection. In a low-g environment, convection is greatly suppressed and diffusion becomes the predominant mechanism for thermal and mass transport. An experiment to grow TGS crystals by solution technique during the orbital Spacelab III mission has been designed. Crystals are grown by a new and unique technique of extracting heat from the crystal through a sting. The cooling at the sting tip is responsible for the desired supersaturation near the growing crystal. Calculations indicate that the cooled sting technique for solution crystal growth is necessary in low-g to maintain a maximum growth rate of 1 mm/day. Results of groundbased work in support of the flight experiment are discussed.

On thermal conditions and properties of thallium bromide single crystals grown by the Electro Dynamic Gradient method

NASA Astrophysics Data System (ADS)

Zheng, Zhiping; Yu, Yongtao; Gong, Shuping; Fu, Qiuyun; Zhou, Dongxiang

2013-05-01

The Electro Dynamic Gradient (EDG) method has been proved to be a feasible way to grow TlBr crystals in our previous work. In this research, the influence of thermal conditions such as cooling rate during growth process on the crystal performance was investigated. Crystals of approximately 12 mm diameter were obtained by the EDG method at different cooling rates during the growth process, and the quality of the crystals was routinely evaluated by X-ray diffraction (XRD), infrared (IR) and ultraviolet (UV) transmission, I-V measurement and energy response spectrum. The results proved that thermal conditions during growth had a profound influence on the characteristics of the crystals.

Monoclinic MB phase and phase instability in [110] field cooled Pb(Zn1/3Nb2/3)O3-4.5%PbTiO3 single crystals

NASA Astrophysics Data System (ADS)

Yao, Jianjun; Cao, Hu; Ge, Wenwei; Li, Jiefang; Viehland, D.

2009-08-01

We report the finding of a monoclinic MB phase in Pb(Zn1/3Nb2/3)O3-4.5%PbTiO3 single crystals. High precision x-ray diffraction investigations of [110] field cooled crystals have shown a transformation sequence of cubic(C)→tetragonal(T)→orthorhombic(O)→monoclinic(MB), which is different from that previously reported [A.-E. Renault et al., J. Appl. Phys. 97, 044105 (2005)]. Beginning in the zero-field-cooled condition at 383 K, a rhombohedral (R)→MB→O sequence was observed with increasing field. Coexisting MB and O phases were then found upon removal of field, which fully transformed to MB on cooling to room temperature.

Improved thermoelectrically cooled quartz crystal microbalance

NASA Technical Reports Server (NTRS)

Mckeown, W. E.; Corbin, W. E., Jr.; Fox, M. G.

1974-01-01

Design changes in the thermoelectrically-cooled quartz microbalance, which is used to monitor surface contamination in space simulation chambers, is described in terms of its extended temperature range, increased temperature control, mass sensitivity, and cooling power. The mass sensor uses 20 MHz quartz crystals having a sensitivity of 8.8 x 10 to the minus tenth power g/sq cm - Hz. The crystals are optically polished, metal plated, and overplated with magnesium fluoride to simulate an optical surface. The microbalance temperature circuitry is designed to readout and control surface temperature between 100 C and minus 59 C to plus or minus 0.5 C, and readout only temperature between minus 60 C and minus 199 C using auxiliary liquid nitrogen cooling. Data is included on the measurement of oil contamination of surfaces as a function of temperature in space simulation chambers.

Show Me the Mush! - Constraints From Voluminous Rhyolitic Ignimbrites of Bimodal and Calc-alkaline Settings on the Applicability of a Mush Model

NASA Astrophysics Data System (ADS)

Streck, M. J.

2012-12-01

Mush models have been popular in explaining crystal-poor rhyolites of a variety of settings. The classical mush model requires an abundance of very crystal-rich (>50%), intermediate (dacitic) magmas that upon compaction expel their interstitial liquids that erupt to give rise to rhyolitic lava flows and ignimbrites. In volcanic systems, a critical part in evaluating a mush model rests on providing evidence for the existence of suitable crystal-rich intermediate magmas that are consistent with the petrology of the erupted rhyolites. In my evaluation, I focus on providing constraints of whether or not suitable crystal mushes are likely to have existed and were instrumental in the production of a select series of voluminous (>100 km3) rhyolitic ignimbrites. Furthermore, the volcanic framework of each selected ignimbrite is used for assessing questions of "eruptibility" of magma types. The three main evaluated units representing 'hot-dry-reduced' rhyolites of bimodal settings are the 16-15.4 Ma Dinner Creek Tuff, the 9.7 Ma Devine Canyon Tuff, and 7.1 Ma Rattlesnake Tuff. All three tuffs erupted in eastern Oregon within a basalt-rhyolite suite. The key feature that makes them particularly valuable for this discussion is that each of the tuffs erupted a co-magmatic component that tracks the intermediate to mafic underpinnings to the rhyolitic magma. This allows a direct assessment of what intermediate magmas residing in close spatial proximity to the rhyolites looked like. On the other hand, other characteristics such as degree of chemical zoning, element trends, single or multiple cooling units, etc., vary considerably among the three tuffs thus covering a wide spectrum of rhyolites from bimodal settings. As representative of 'cool-wet-oxidized' rhyolites, I test applicability of the mush model on the tuffs and associated lavas of the Oligocene San Luis caldera system. This system represents strongly confocal and voluminous eruptions that are closely spaced in time at the end of the activity period of the Central Caldera Cluster of the Oligocene San Juan volcanic field, Colorado. Compositional intermediate underpinnings of each of the 'hot-dry-reduced' rhyolites fail geochemical requirements to represent suitable intermediate magmas. In addition, these underpinnings are crystal-poor and this is inconsistent with the required high crystallinity of magma mushes. Remelting scenarios to reduce crystallinities in intermediate magmas are excluded - again on geochemical grounds. Other complications with a model of voluminous crystal mushes beneath such rhyolites are the production of strong trace-element chemical gradation within single magma batches as well as multi-cyclic eruptions of crystal-poor rhyolites from the same system. For the system of 'cold-wet-oxidized' rhyolites, one of the challenges for a mush model is that interstitial melts of crystal-rich intermediate magmas compositionally deviate from erupted rhyolites when abundant amphibole (±sphene) is present, yet both phases are commonly expected phenocrystic phases at crystallinities when extraction of rhyolite from mush can take place.

Enhanced electrocaloric cooling in ferroelectric single crystals by electric field reversal

NASA Astrophysics Data System (ADS)

Ma, Yang-Bin; Novak, Nikola; Koruza, Jurij; Yang, Tongqing; Albe, Karsten; Xu, Bai-Xiang

2016-09-01

An improved thermodynamic cycle is validated in ferroelectric single crystals, where the cooling effect of an electrocaloric refrigerant is enhanced by applying a reversed electric field. In contrast to the conventional adiabatic heating or cooling by on-off cycles of the external electric field, applying a reversed field is significantly improving the cooling efficiency, since the variation in configurational entropy is increased. By comparing results from computer simulations using Monte Carlo algorithms and experiments using direct electrocaloric measurements, we show that the electrocaloric cooling efficiency can be enhanced by more than 20% in standard ferroelectrics and also relaxor ferroelectrics, like Pb (Mg1 /3 /Nb2 /3)0.71Ti0.29O3 .

HgCdTe liquid phase epitaxy - An overview

NASA Astrophysics Data System (ADS)

Castro, C. A.; Korenstein, R.

1982-08-01

Techniques and results of using liquid phase epitaxy (LPE) to form crystalline thin HgCdTe films for industrial-scale applications in IR detectors and focal plane arrays are discussed. Varying the mole fraction of CdTe in HgCdTe is noted to permit control of the bandwidth. LPE-grown films are noted to have a low carrier concentration, on the order of 4 x 10 to the 14th to 5 x 10 to the 15th/cu cm, a good surface morphology and be amenable to production scale-up. Details of the isothermal, equilibrium cooling, and supersaturation cooling LPE growth modes are reviewed, noting the necessity of developing a reliable method for determining the liquidus temperature for all modes to maintain uniformity of film growth from batch to batch. Mechanical steps can be either dipping the substrate into the melt or the slider boat approach, which is used in the production of compound semiconductors.

Tuning the functional properties of PMN-PT single crystals via doping and thermoelectrical treatments

NASA Astrophysics Data System (ADS)

Luo, Laihui; Dietze, Matthias; Solterbeck, Claus-Henning; Luo, Haosu; Es-Souni, Mohammed

2013-12-01

Single crystals based on solid solutions of lead-magnesium-niobate (PMN) and lead titanate (PT) have emerged as highly promising multifunctional systems combining piezoelectric, pyroelectric, and electro-optic properties that surpass by far those of the best known lead-zirkonium-titanate ceramics. In this paper we present new findings on how the phase transition temperature and the dielectric and ferroelectric properties can be tuned depending on crystal composition, orientation, and thermoelectrical treatment. Mn-doped and pure 0.72PbMg1/3Nb2/3O3-0.28PbTiO3 (0.72PMN-0.28PT) single crystals with ⟨111⟩ and ⟨001⟩ orientations were investigated. A special attention was devoted to field cooling (FC), i.e., cooling under electric field from different temperatures. The results illustrate different findings that were not reported before: the Curie temperature, i.e., ferroelectric-paraelectric transition temperature, is enhanced after field cooling of the Mn-doped, ⟨001⟩-oriented crystal while such a shift is not observed in the ⟨111⟩-oriented and the non-doped crystals. In addition, substantial polarization suppression occurs in the Mn-doped crystals upon FC from high temperature regardless of orientation. Based on piezoforce microscopy of the domain structure that shows suppression of domain growth following field cooling from 200 °C, we propose a mechanism for polarization suppression based on domain pinning by charged defects. The practical importance of our results lies in showing the opportunity offered by a proper choice of crystal composition and poling conditions for tuning the functional properties of PMN-PT single crystals for a specific application. This should contribute to the understanding of their properties towards advanced sensor and transducers devices.

Lead magnesium niobate actuator for micropositioning

DOEpatents

Swift, Charles D.; Bergum, John W.

1994-01-01

An improved lead magnesium niobate actuator is disclosed comprising a cylindrical lead magnesium niobate crystal stack mounted in a cylindrical casing wherein a bias means, such as one or more belleville washers, is located between one end of the crystal stack and a partially closed end of the casing; and adjustment means are provided which bear against the opposite end of the crystal stack, whereby an adjustable compressive force is constantly applied against the crystal stack, whether the crystal stack is actuated in an extended position, or is in an unactuated contracted position. In a preferred embodiment, cooling ports are provided for the circulation of coolant in the actuator to cool the crystal stack, and provision is made for removal and replacement of the crystal stack without disconnecting the actuator from the external device being actuated.

Supersaturation Control using Analytical Crystal Size Distribution Estimator for Temperature Dependent in Nucleation and Crystal Growth Phenomena

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.

Thermal Stability of RP-2 for Hydrocarbon Boost Regenerative Cooling

NASA Technical Reports Server (NTRS)

Kleinhenz, Julie E.; Deans, Matthew C.; Stiegemeier, Benjamin R.; Psaras, Peter M.

2013-01-01

A series of tests were performed in the NASA Glenn Research Centers Heated Tube Facility to study the heat transfer and thermal stability behavior of RP-2 under conditions similar to those found in rocket engine cooling channels. It has long been known that hydrocarbon fuels, such as RP-2, can decompose at high temperature to form deposits (coke) which can adversely impact rocket engine cooling channel performance. The heated tube facility provides a simple means to study these effects. Using resistively heated copper tubes in a vacuum chamber, flowing RP-2 was heated to explore thermal effects at a range of test conditions. Wall temperature (850-1050F) and bulk fluid temperature (300-500F) were varied to define thermal decomposition and stability at each condition. Flow velocity and pressure were fixed at 75 fts and 1000 psia, respectively. Additionally, five different batches of RP-2 were tested at identical conditions to examine any thermal stability differences resulting from batch to batch compositional variation. Among these tests was one with a potential coke reducing additive known as 1,2,3,4-Tetrahydroquinoline (THQ). While copper tubes were used for the majority of tests, two exploratory tests were performed with a copper alloy known as GRCop-42. Each tube was instrumented with 15 thermocouples to examine the temperature profile, and carbon deposition at each thermocouple location was determined post-test in an oxidation furnace. In many tests, intermittent local temperature increases were observed visually and in the thermocouple data. These hot spots did not appear to correspond with a higher carbon deposition.

Crystallization of calcia-gallia-silica glasses

NASA Technical Reports Server (NTRS)

Ray, C. S.; Day, D. E.

1984-01-01

A thermal image furance is presently used to study the critical cooling rate for glass formation, and the kinetics of crystallization, of the compositions 18.4CaO-(81.6-X)Ga2O3-XSiO2, where X = 3, 6, 9, and 13.8. Crystallization was studied nonisothermally, and the data were analyzed in light of the Avrami (1939) equation. Critical cooling rate and crystallization activation energy are both found to decrease with increasing silica content, and the results obtained by the present technique are noted to agree with those obtained on the basis of differential thermal analysis measurements.

Influence of metronidazole particle properties on granules prepared in a high-shear mixer-granulator.

PubMed

Di Martino, Piera; Censi, Roberta; Malaj, Ledjan; Martelli, Sante; Joiris, Etienne; Barthélémy, Christine

2007-02-01

Metronidazole is a good example of high-dose drug substance with poor granulating and tableting properties. Tablets are generally produced by liquid granulation; however, the technological process failure is quite frequent. In order to verify how the metronidazole particle characteristics can influence granule properties, three metronidazole batches differing for crystal habit, mean particle size, BET surface area and wettability were selected, primarily designed according to their different elongation ratio: needle-shaped, stick-shaped, and isodimensional. In the presence of lactose monohydrate and pregelatinized maize starch, respectively as diluent and binder, they were included in a formula for wet granulation in a high-shear mixer-granulator. In order to render the process comparable as far as possible, all parameters and experimental conditions were maintained constant. Four granule batches were obtained: granules from placebo (G-placebo), granules from needle-shaped crystals (G-needle-shaped), granules from stick-shaped crystals (G-stick-shaped), and granules from isodimensional crystals (G-isodimensional). Different granule properties were considered, in particular concerning porosity, friability, loss on drying (LOD), and flowability. In order to study their tabletability and compressibility, the different granules obtained were then compressed in a rotary press. The best tabletability was obtained with the isodimensional batch, while the poorest was exhibited by the stick-shaped one. Differences in tabletability are in good accordance with compressibility results: to a better tabletability corresponds an important granule ability to undergo a volume reduction as a result of an applied pressure. In particular, it was proposed that the greatest compressibility of the G-isodimensional must be related to the greatest granule porosity percentage.

40 CFR 63.1335 - General recordkeeping and reporting provisions.

Code of Federal Regulations, 2012 CFR

2012-07-01

..., on paper, microfilm, computer, floppy disk, magnetic tape, or microfiche. (2) If an owner or operator... subject to § 63.1316, § 63.1327 for batch process vents, § 63.1329 for process contact cooling towers, and...

40 CFR 63.1335 - General recordkeeping and reporting provisions.

Code of Federal Regulations, 2011 CFR

2011-07-01

..., on paper, microfilm, computer, floppy disk, magnetic tape, or microfiche. (2) If an owner or operator... subject to § 63.1316, § 63.1327 for batch process vents, § 63.1329 for process contact cooling towers, and...

Method for harvesting rare earth barium copper oxide single crystals

DOEpatents

Todt, V.R.; Sengupta, S.; Shi, D.

1996-04-02

A method of preparing high temperature superconductor single crystals is disclosed. The method of preparation involves preparing precursor materials of a particular composition, heating the precursor material to achieve a peritectic mixture of peritectic liquid and crystals of the high temperature superconductor, cooling the peritectic mixture to quench directly the mixture on a porous, wettable inert substrate to wick off the peritectic liquid, leaving single crystals of the high temperature superconductor on the porous substrate. Alternatively, the peritectic mixture can be cooled to a solid mass and reheated on a porous, inert substrate to melt the matrix of peritectic fluid while leaving the crystals melted, allowing the wicking away of the peritectic liquid. 2 figs.

Method for harvesting rare earth barium copper oxide single crystals

DOEpatents

Todt, Volker R.; Sengupta, Suvankar; Shi, Donglu

1996-01-01

A method of preparing high temperature superconductor single crystals. The method of preparation involves preparing precursor materials of a particular composition, heating the precursor material to achieve a peritectic mixture of peritectic liquid and crystals of the high temperature superconductor, cooling the peritectic mixture to quench directly the mixture on a porous, wettable inert substrate to wick off the peritectic liquid, leaving single crystals of the high temperature superconductor on the porous substrate. Alternatively, the peritectic mixture can be cooled to a solid mass and reheated on a porous, inert substrate to melt the matrix of peritectic fluid while leaving the crystals melted, allowing the wicking away of the peritectic liquid.

Cooling rates and crystallization dynamics of shallow level pegmatite-aplite dikes, San Diego County, California

USGS Publications Warehouse

Webber, Karen L.; Simmons, William B.; Falster, Alexander U.; Foord, Eugene E.

1999-01-01

Pegmatites of the Pala and Mesa Grande Pegmatite Districts, San Diego County, California are typically thin, sheet-like composite pegmatite-aplite dikes. Aplitic portions of many dikes display pronounced mineralogical layering referred to as "line rock," characterized by fine-grained, garnet-rich bands alternating with albite- and quartz-rich bands. Thermal modeling was performed for four dikes in San Diego County including the 1 m thick Himalaya dike, the 2 m thick Mission dike, the 8 m thick George Ashley dike, and the 25 m thick Stewart dike. Calculations were based on conductive cooling equations accounting for latent heat of crystallization, a melt emplacement temperature of 650 °C into 150 °C fractured, gabbroic country rock at a depth of 5 km, and an estimated 3 wt% initial H2O content in the melt. Cooling to -5 cm/s. Crystal size distribution (CSD) studies of garnet from layered aplites suggest growth rates of about 10-6 cm/s. These results indicate that the dikes cooled and crystallized rapidly, with variable nucleation rates but high overall crystal-growth rates. Initial high nucleation rates coincident with emplacement and strong undercooling can account for the millimeter-size aplite grains. Lower nucleation rates coupled with high growth rates can explain the decimeter-size minerals in the hanging walls, cores, and miarolitic cavities of the pegmatites. The presence of tourmaline and/or lepidolite throughout these dikes suggests that although the melts were initially H2O-undersaturated, high melt concentrations of incompatible (or fluxing) components such as B, F, and Li (±H2O), aided in the development of large pegmatitic crystals that grew rapidly in the short times suggested by the conductive cooling models.

Protein crystals and their growth

NASA Technical Reports Server (NTRS)

Chernov, Alexander A.

2003-01-01

Recent results on the associations between protein molecules in crystal lattices, crystal-solution surface energy, elastic properties, strength, and spontaneous crystal cracking are reviewed and discussed. In addition, some basic approaches to understanding the solubility of proteins are followed by an overview of crystal nucleation and growth. It is argued that variability of mixing in batch crystallization may be a source of the variation in the number of crystals ultimately appearing in the sample. The frequency at which new molecules join a crystal lattice is measured by the kinetic coefficient and is related to the observed crystal growth rate. Numerical criteria used to discriminate diffusion- and kinetic-limited growth are discussed on this basis. Finally, the creation of defects is discussed with an emphasis on the role of impurities and convection on macromolecular crystal perfection.

Efficient rotational cooling of Coulomb-crystallized molecular ions by a helium buffer gas.

PubMed

Hansen, A K; Versolato, O O; Kłosowski, L; Kristensen, S B; Gingell, A; Schwarz, M; Windberger, A; Ullrich, J; López-Urrutia, J R Crespo; Drewsen, M

2014-04-03

The preparation of cold molecules is of great importance in many contexts, such as fundamental physics investigations, high-resolution spectroscopy of complex molecules, cold chemistry and astrochemistry. One versatile and widely applied method to cool molecules is helium buffer-gas cooling in either a supersonic beam expansion or a cryogenic trap environment. Another more recent method applicable to trapped molecular ions relies on sympathetic translational cooling, through collisional interactions with co-trapped, laser-cooled atomic ions, into spatially ordered structures called Coulomb crystals, combined with laser-controlled internal-state preparation. Here we present experimental results on helium buffer-gas cooling of the rotational degrees of freedom of MgH(+) molecular ions, which have been trapped and sympathetically cooled in a cryogenic linear radio-frequency quadrupole trap. With helium collision rates of only about ten per second--that is, four to five orders of magnitude lower than in typical buffer-gas cooling settings--we have cooled a single molecular ion to a rotational temperature of 7.5(+0.9)(-0.7) kelvin, the lowest such temperature so far measured. In addition, by varying the shape of, or the number of atomic and molecular ions in, larger Coulomb crystals, or both, we have tuned the effective rotational temperature from about 7 kelvin to about 60 kelvin by changing the translational micromotion energy of the ions. The extremely low helium collision rate may allow for sympathetic sideband cooling of single molecular ions, and eventually make quantum-logic spectroscopy of buffer-gas-cooled molecular ions feasible. Furthermore, application of the present cooling scheme to complex molecular ions should enable single- or few-state manipulations of individual molecules of biological interest.

Towards establishing a combined rate law of nucleation and crystal growth - The case study of gypsum precipitation

NASA Astrophysics Data System (ADS)

Rendel, Pedro M.; Gavrieli, Ittai; Wolff-Boenisch, Domenik; Ganor, Jiwchar

2018-03-01

The main obstacle in the formulation of a quantitative rate-model for mineral precipitation is the absence of a rigorous method for coupling nucleation and growth processes. In order to link both processes, we conducted a series of batch experiments in which gypsum nucleation was followed by crystal growth. Experiments were carried out using various stirring methods in several batch vessels made of different materials. In the experiments, the initial degree of supersaturation of the solution with respect to gypsum (Ωgyp) was set between 1.58 and 1.82. Under these conditions, heterogeneous nucleation is the dominant nucleation mode. Based on changes in SO42- concentration with time, the induction time of gypsum nucleation and the following rate of crystal growth were calculated for each experiment. The induction time (6-104 h) was found to be a function of the vessel material, while the rates of crystal growth, which varied over three orders of magnitude, were strongly affected by the stirring speed and its mode (i.e. rocking, shaking, magnetic stirrer, and magnetic impeller). The SO42- concentration data were then used to formulate a forward model that couples the simple rate laws for nucleation and crystal growth of gypsum into a single kinetic model. Accordingly, the obtained rate law is based on classical nucleation theory and heterogeneous crystal growth.

Incorporation of cooling-induced crystallization into a 2-dimensional axisymmetric conduit heat flow model

NASA Astrophysics Data System (ADS)

Heptinstall, David; Bouvet de Maisonneuve, Caroline; Neuberg, Jurgen; Taisne, Benoit; Collinson, Amy

2016-04-01

Heat flow models can bring new insights into the thermal and rheological evolution of volcanic 3 systems. We shall investigate the thermal processes and timescales in a crystallizing, static 4 magma column, with a heat flow model of Soufriere Hills Volcano (SHV), Montserrat. The latent heat of crystallization is initially computed with MELTS, as a function of pressure and temperature for an andesitic melt (SHV groundmass starting composition). Three fractional crystallization simulations are performed; two with initial pressures of 34MPa (runs 1 & 2) and one of 25MPa (run 3). Decompression rate was varied between 0.1MPa/° C (runs 1 & 3) and 0.2MPa/° C (run 2). Natural and experimental matrix glass compositions are accurately reproduced by all MELTS runs. The cumulative latent heat released for runs 1, 2 and 3 differs by less than 9% (8.69E5 J/kg*K, 9.32E5 J/kg*K, and 9.49E5 J/kg*K respectively). The 2D axisymmetric conductive cooling simulations consider a 30m-diameter conduit that extends from the surface to a depth of 1500m (34MPa). The temporal evolution of temperature is closely tracked at depths of 10m, 750m and 1400m in the centre of the conduit, at the conduit walls, and 20m from the walls into the host rock. Following initial cooling by 7-15oC at 10m depth inside the conduit, the magma temperature rebounds through latent heat release by 32-35oC over 85-123 days to a maximum temperature of 1002-1005oC. At 10m depth, it takes 4.1-9.2 years for the magma column to cool by 108-131oC and crystallize to 75wt%, at which point it cannot be easily remobilized. It takes 11-31.5 years to reach the same crystallinity at 750-1400m depth. We find a wide range in cooling timescales, particularly at depths of 750m or greater, attributed to the initial run pressure and the dominant latent heat producing crystallizing phase, Albite-rich Plagioclase Feldspar. Run 1 is shown to cool fastest and run 3 cool the slowest, with surface emissivity having the strongest cooling influence in the upper tens of meters of the conduit in all runs.

Mathematical modeling of static layer crystallization for propellant grade hydrogen peroxide

NASA Astrophysics Data System (ADS)

Hao, Lin; Chen, Xinghua; Sun, Yaozhou; Liu, Yangyang; Li, Shuai; Zhang, Mengqian

2017-07-01

Hydrogen peroxide (H2O2) is an important raw material widely used in many fields. In this work a mathematical model of heat conduction with a moving boundary was proposed to study the melt crystallization process of hydrogen peroxide which was carried out outside a cylindrical crystallizer. Considering the effects of the temperature of the cooling fluid on the thermal conductivity of crude crystal, the model is an improvement of Guardani's research and can be solved by analytic iteration method. An experiment was designed to measure the thickness of crystal layer with time under different conditions. A series of analysis, including the effects of different refrigerant temperature on crystal growth rate, the effects of different cooling rates on crystal layer growth rate, the effects of crystallization temperature on heat transfer and the model's application scope were conducted based on the comparison between experimental results and simulation results of the model.

Lead magnesium niobate actuator for micropositioning

DOEpatents

Swift, C.D.; Bergum, J.W.

1994-10-25

An improved lead magnesium niobate actuator is disclosed comprising a cylindrical lead magnesium niobate crystal stack mounted in a cylindrical casing wherein a bias means, such as one or more belleville washers, is located between one end of the crystal stack and a partially closed end of the casing; and adjustment means are provided which bear against the opposite end of the crystal stack, whereby an adjustable compressive force is constantly applied against the crystal stack, whether the crystal stack is actuated in an extended position, or is in an unactuated contracted position. In a preferred embodiment, cooling ports are provided for the circulation of coolant in the actuator to cool the crystal stack, and provision is made for removal and replacement of the crystal stack without disconnecting the actuator from the external device being actuated. 3 figs.

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.

Specific features of the structural and magnetic states of a Zn1 - x Ni x Se crystal ( x = 0.0025) at low temperatures

NASA Astrophysics Data System (ADS)

Dubinin, S. F.; Sokolov, V. I.; Parkhomenko, V. D.; Teploukhov, S. G.; Gruzdev, N. B.

2008-12-01

The magnetic state and the structure of a Zn1 - x Ni x Se ( x = 0.0025) bulk crystal were studied at low temperatures. It is revealed that the magnetic and crystal structures below T ≅ 15 K are dependent on the cooling rate of this dilute semiconductor. For example, on fast cooling to 4.2 K, about 10% hexagonal ferromagnetic phase is formed in the crystal. During heating, the phase disappears at T ≅ 15 K. The results obtained are discussed with allowance for the specific features of the Jahn-Teller distortions in this compound.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sundaramurthi, Prakash; Patapoff, Thomas W.; Suryanarayanan, Raj

To study the crystallization of trehalose in frozen solutions and to understand the phase transitions during the entire freeze-drying cycle. Aqueous trehalose solution was cooled to -40 C in a custom-designed sample holder. The frozen solution was warmed to -18 C and annealed, and then dried in the sample chamber of the diffractometer. XRD patterns were continuously collected during cooling, annealing and drying. After cooling, hexagonal ice was the only crystalline phase observed. However, upon annealing, crystallization of trehalose dihydrate was evident. Seeding the frozen solution accelerated the solute crystallization. Thus, phase separation of the lyoprotectant was observed in frozenmore » solutions. During drying, dehydration of trehalose dihydrate yielded a substantially amorphous anhydrous trehalose. Crystallization of trehalose, as trehalose dihydrate, was observed in frozen solutions. The dehydration of the crystalline trehalose dihydrate to substantially amorphous anhydrate occurred during drying. Therefore, analyzing the final lyophile will not reveal crystallization of the lyoprotectant during freeze-drying. The lyoprotectant crystallization can only become evident by continuous monitoring of the system during the entire freeze-drying cycle. In light of the phase separation of trehalose in frozen solutions, its ability to serve as a lyoprotectant warrants further investigation.« less

Inter-Batch Variation and the Effect of Casting Vacuum on Ballistic and Mechanical Properties of a High Performing Cast Composite Rocket Propellant

DTIC Science & Technology

2014-12-01

premature dewetting of crystal surfaces. This is a similar phenomenon to that described by Gocmez, et al. [7] for coarse/fine ratios of AP. That is...they postulated that a greater force is required to dewet fine AP crystals due to a larger surface area/volume ratio and therefore a larger overall...tensile strength. Dewetting of AP crystals from binder during the application of stress creates vacuoles which contribute to total specimen elongation

Diffusion-Cooled Tantalum Hot-Electron Bolometer Mixers

NASA Technical Reports Server (NTRS)

Skalare, Anders; McGrath, William; Bumble, Bruce; LeDuc, Henry

2004-01-01

A batch of experimental diffusion-cooled hot-electron bolometers (HEBs), suitable for use as mixers having input frequencies in the terahertz range and output frequencies up to about a gigahertz, exploit the superconducting/normal-conducting transition in a thin strip of tantalum. The design and operation of these HEB mixers are based on mostly the same principles as those of a prior HEB mixer that exploited the superconducting/normal- conducting transition in a thin strip of niobium and that was described elsewhere.

Cation ordering in orthopyroxenes and cooling rates of meteorites: Low temperature cooling rates of Estherville, Bondoc and Shaw

NASA Technical Reports Server (NTRS)

Ganguly, J.; Yang, H.; Ghose, S.

1993-01-01

The cooling rates of meteorites provide important constraints on the size of their parent bodies, and their accretionary and evolutionary histories. However, the cooling rates obtained so far from the commonly used metallographic, radiometric and fission-track methods have been sometimes quite controversial, such as in the case of the mesosiderites and the meteorite Shaw. We have undertaken a systematic study of the cooling rates of meteorites using a different approach, which involves single crystal x-ray determination of Fe(2+)-Mg ordering in orthopyroxenes (OP(x)) in meteorites, subject to bulk compositional constraints, and numerical simulation of the evolution of the ordering state as a function of cooling rate, within the framework of the thermodynamic and kinetic principles governing cation ordering. We report the results obtained for OP(x) crystals from Shaw and two mesosiderites, Estherville and Bondoc.

DKDP crystal growth controlled by cooling rate

NASA Astrophysics Data System (ADS)

Xie, Xiaoyi; Qi, Hongji; Shao, Jianda

2017-08-01

The performance of deuterated potassium dihydrogen phosphate (DKDP) crystal directly affects beam quality, energy and conversion efficiency in the Inertial Confinement Fusion（ICF）facility, which is related with the initial saturation temperature of solution and the real-time supersaturation during the crystal growth. However, traditional method to measure the saturation temperature is neither efficient nor accurate enough. Besides, the supersaturation is often controlled by experience, which yields the higher error and leads to the instability during the crystal growth. In this paper, DKDP solution with 78% deuteration concentration is crystallized in different temperatures. We study the relation between solubility and temperature of DKDP and fit a theoretical curve with a parabola model. With the model, the measurement of saturation temperature is simplified and the control precision of the cooling rate is improved during the crystal growth, which is beneficial for optimizing the crystal growth process.

Solid-state transformations in the β-form of chlorpropamide on cooling to 100 K.

PubMed

Drebushchak, Tatiana N; Drebushchak, Valeri A; Boldyreva, Elena V

2011-04-01

A single-crystal X-ray diffraction study of the effect of cooling down to 100 K on the β-form of chlorpropamide, 4-chloro-N-(propylaminocarbonyl)benzenesulfonamide, has revealed reversible phase transitions at ∼257 K and between 150 and 125 K: β (Pbcn, Z' = 1) ⇔ β(II) (P2/c, Z' = 2) ⇔ β(III) (P2/n, a' = 2a, Z' = 4); the sequence corresponds to cooling. Despite changes in the space group and number of symmetry-independent molecules, the volume per molecule changes continuously in the temperature range 100-300 K. The phase transition at ∼257 K is accompanied by non-merohedral twinning, which is preserved on further cooling and through the second phase transition, but the original single crystal does not crack. DSC (differential scanning calorimetry) and X-ray powder diffraction investigations confirm the phase transitions. Twinning disappears on heating as the reverse transformations take place. The second phase transition is related to a change in conformation of the alkyl tail from trans to gauche in 1/4 of the molecules, regularly distributed in the space. Possible reasons for the increase in Z' upon cooling are discussed in comparison to other reported examples of processes (crystallization, phase transitions) in which organic crystals with Z' > 1 have been formed. Implications for pharmaceutical applications are discussed. © 2011 International Union of Crystallography

Influence of other rare earth ions on the optical refrigeration efficiency in Yb:YLF crystals.

PubMed

Di Lieto, Alberto; Sottile, Alberto; Volpi, Azzurra; Zhang, Zhonghan; Seletskiy, Denis V; Tonelli, Mauro

2014-11-17

We investigated the effect of rare earth impurities on the cooling efficiency of Yb³⁺:LiYF₄ (Yb:YLF). The refrigeration performance of two single crystals, doped with 5%-at. Yb and with identical history but with different amount of contaminations, have been compared by measuring the cooling efficiency curves. Spectroscopic and elemental analyses of the samples have been carried out to identify the contaminants, to quantify their concentrations and to understand their effect on the cooling efficiencies. A model of energy transfer processes between Yb and other rare earth ions is suggested, identifying Erbium and Holmium as elements that produce a detrimental effect on the cooling performance.

Enhancement radiative cooling performance of nanoparticle crystal via oxidation

NASA Astrophysics Data System (ADS)

Jia, Zi-Xun; Shuai, Yong; Li, Meng; Guo, Yanmin; Tan, He-ping

2018-03-01

Nanoparticle-crystal is a promising candidate for large scale metamaterial fabrication. However, in radiative cooling application, the maximum blackbody radiation wavelength locates far from metal's plasmon wavelength. In this paper, it will be shown if the metallic nanoparticle crystal can be properly oxidized, the absorption performance within room temperature blackbody radiation spectrum can be improved. Magnetic polariton and surface plasmon polariton have been explained for the mechanism of absorption improvement. Three different oxidation patterns have been investigated in this paper, and the results show they share a similar enhancing mechanism.

Structured laser gain-medium by new bonding for power micro-laser

NASA Astrophysics Data System (ADS)

Kausas, Arvydas; Zheng, Lihe; Taira, Takunori

2017-02-01

In this work, we have compared the Q-switched performance of single rod crystal to a newly developed distributed face cooling structure. This structure was made by surface activated bonding technology and allowed to combine transparent heatsink to a gain crystal at room temperature. The Sapphire and Nd3+:YAG crystal plates were combined in this fashion to produce eight crystal chip which was further used to obtain Q-switch pulses with Cr4+:YAG crystal as saturable absorber. Energy of 9 mJ and pulse duration of 815 ps were achieved. Although the energy obtained with single rod system was 10 mJ, the degradation of the beam prevents such crystal to be used in further applications. This is the first demonstration of distributed face cooling system outperformed conventionally single rod system.

Treatment of TNT red water by layer melt crystallization.

PubMed

Jo, Jeong-Hyeon; Ernest, Takyi; Kim, Kwang-Joo

2014-09-15

Treatment of the red water, which is wastewater of 2,4,6- trinitrotoluene (TNT) manufacturing process has been explored using ice crystallization. This study focuses on the formation of ice crystals from the red water in a layer crystallizer under various operating conditions. Among the parameters which affect layer crystallization, attention was given to cooling rate, cooling temperature, sweating rate and concentration of the red water. The study highlights the effect of subcooling and growth rate on purity of the ice crystalline layers produced. After sweating, the COD value of crystalline ice layer was significantly reduced from 10,000 mg/L to below 20mg/L. Most organic contaminants were removed in sweating fractions of 0.5. Eventually, the red water was treated by layer crystallization combined with the sweating process. Copyright © 2014 Elsevier B.V. All rights reserved.

Crystallization phenomena in slags

NASA Astrophysics Data System (ADS)

Orrling, Carl Folke

2000-09-01

The crystallization of the mold slag affects both the heat transfer and the lubrication between the mold and the strand in continuous casting of steel. In order for mold slag design to become an engineering science rather than an empirical exercise, a fundamental understanding of the melting and solidification behavior of a slag must be developed. Thus it is necessary to be able to quantify the phenomena that occur under the thermal conditions that are found in the mold of a continuous caster. The double hot thermocouple technique (DHTT) and the Confocal Laser Scanning Microscope used in this study are two novel techniques for investigating melting and solidification phenomena of transparent slags. Results from these techniques are useful in defining the phenomena that occur when the slag film infiltrates between the mold and the shell of the casting. TTT diagrams were obtained for various slags and indicated that the onset of crystallization is a function of cooling rate and slag chemistry. Crystal morphology was found to be dependent upon the experimental temperature and four different morphologies were classified based upon the degree of melt undercooling. Continuous cooling experiments were carried out to develop CCT diagrams and it was found that the amount and appearance of the crystalline fraction greatly depends on the cooling conditions. The DHTT can also be used to mimic the cooling profile encountered by the slag in the mold of a continuous caster. In this differential cooling mode (DCT), it was found that the details of the cooling rate determine the actual response of the slag to a thermal gradient and small changes can lead to significantly different results. Crystal growth rates were measured and found to be in the range between 0.11 mum/s to 11.73 mum/s depending on temperature and slag chemistry. Alumina particles were found to be effective innoculants in oxide melts reducing the incubation time for the onset of crystallization and also extending the temperature range of observed crystallization. The effect of changing the gas atmosphere surrounding the sample has been studied. The presence of water vapor increased the nucleation rate and crystal growth rate significantly when compared to experiments carried out in a dry atmosphere. With an atmosphere of Argon and Argon-3% Hydrogen mixture, the incubation time for crystallization was increased with several minutes. The crystal growth rate in these atmospheres was also drastically reduced compared to an atmosphere of normal air. Significant numbers of bubbles were formed during the initial melting of mold slag samples and the melting rate of the slag was found to be related to the rate of bubble generation and to the rate of heat transport.

Observations on the crystallization of spodumene from aqueous solutions in a hydrothermal diamond-anvil cell

USGS Publications Warehouse

Li, Jianking; Chou, I-Ming; Yuan, Shunda; Burruss, Robert A.

2013-01-01

Crystallization experiments were conducted in a new type of hydrothermal diamond-anvil cell (HDAC; type V) using LiAlSi2O6 (S) gel and H2O (W) as starting materials. A total of 21 experiments were performed at temperatures up to 950°C and pressures up to 788 MPa. In the samples with relatively low W/S ratios, many small crystals formed in the melt phase during cooling. In those with high W/S ratios, only a few crystals with smooth surfaces crystallized from the aqueous fluid in the presence of melt droplets, which were gradually consumed during crystal growth, indicating rapid transfer of material from the melt to the crystals through the aqueous fluid. The nucleation of crystals started at 710 (±70)°C and 520 (±80) MPa, and crystal growth ended at 570 (±40)°C and 320 (±90) MPa, with the cooling P-T path within the stability field of spodumene + quartz in the S-W system. The observed linear crystal growth rates in the aqueous phase, calculated by dividing the maximum length of a single crystal by the duration of the entire growth step, were 4.7 × 10−6 and 5.7 × 10−6 cm s−1 for the cooling rates of 0.5 and 1°C min−1, respectively. However, a rapid crystal growth rate of 3.6 × 10−5 cm s−1 in the aqueous fluid was observed when the components were supplied by nearby melt droplets. Our results show that when crystals nucleate in the aqueous fluid instead of the melt phase, there are fewer nuclei formed, and they grow much faster due to the low viscosity of the aqueous fluid, which accelerates diffusion of components for the growth of crystals. Therefore, the large crystals in granitic pegmatite can crystallize directly from aqueous fluids rather than hydrosilicate melt.

Solid-state microrefrigerator

DOEpatents

Ullom, Joel N.

2003-06-24

A normal-insulator-superconductor (NIS) microrefrigerator in which a superconducting single crystal is both the substrate and the superconducting electrode of the NIS junction. The refrigerator consists of a large ultra-pure superconducting single crystal and a normal metal layer on top of the superconducting crystal, separated by a thin insulating layer. The superconducting crystal can be either cut from bulk material or grown as a thick epitaxial film. The large single superconducting crystal allows quasiparticles created in the superconducting crystal to easily diffuse away from the NIS junction through the lattice structure of the crystal to normal metal traps to prevent the quasiparticles from returning across the NIS junction. In comparison to thin film NIS refrigerators, the invention provides orders of magnitude larger cooling power than thin film microrefrigerators. The superconducting crystal can serve as the superconducting electrode for multiple NIS junctions to provide an array of microrefrigerators. The normal electrode can be extended and supported by microsupports to provide support and cooling of sensors or arrays of sensors.

Improved reproducibility of unit-cell parameters in macromolecular cryocrystallography by limiting dehydration during crystal mounting.

PubMed

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.

Improved reproducibility of unit-cell parameters in macromolecular cryocrystallography by limiting dehydration during crystal mounting

PubMed Central

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

Petrographic Evidence for Rapid Heating and Cooling During Chrondrule Formation

NASA Technical Reports Server (NTRS)

Wasson, J. T.

2004-01-01

The chondrule cooling rates used in most chondrule-formation models appear to be too low. Recent petrographic evidence indicates that the amount of crystal (especially olivine) growth that occurred after the last melting event was about 30 smaller than the grain sizes simulated in order to estimate cooling rates. The smaller amount of growth leads to an upwards revision of cooling rates by about a factor of 1000. Most chondrules are porphyritic. They consist of large and small crystals of olivine and, less commonly, pyroxene immersed in a mesostasis having a plagioclase-rich composition. In the most primitive chondrites the mesostasis is often vitreous. Because the large majority of chondrules contain FeS, it is clear that the nebula had cooled below the FeS condensation temperature (ca. 650 K) before chondrule formation occurred. The high FeO/(FeO+MgO) ratios of some chondrules require still lower nebular temperatures (less than 500 K). The traditional view has been that porphyritic chondrules formed in a single heating/cooling event and many laboratory experiments have been carried out in various kinds of kinds of furnaces to try to simulate the formation of chondrules textures in a single heating/cooling cycle. These furnace experiments have been used to infer the cooling rates of chondrules during the temperature range at which olivine crystallized from the melt. Most of these inferred values are in the range 0.01-1 K per second. These low cooling rates are problematical because there is no long-term nebular environment that yields such values. In transparent regions chondrules would cool at rates orders of magnitude higher, whereas in an opaque nebular disk the cooling rates would be many orders of magnitude lower. And these latter conditions are not suitable locations for chondrule formation because such high temperatures would cause the complete evaporation of chondrules (which have melting temperatures about 600 K higher than their evaporation temperatures). During the last several years several kinds of petrographic evidence indicating rapid chondrule cooling have been recognized. These include thin overgrowths on relict grains, clusters of small crystals that grew following the most recent melting event, and fragments preserving shardlike shapes that would have been hidden had several tens of micrometers of new growth occurred following the last melting event. And there are other indications of rapid cooling including the preservation of volatiles such as FeS and one case where the modeling of O-isotopic and FeO/(FeO+MgO) gradients indicated a high cooling rate.

LD side-pumped Nd:YAG Q-switched laser without water cooling

NASA Astrophysics Data System (ADS)

Ling, Ming; Jin, Guang-yong; Tan, Xue-chun; Wu, Zhi-chao; Liang, Zhu

2009-07-01

A novel LD side-pumped Nd:YAG Q-switched solid-state laser, which made use of the special pumping strcture with conductive cooling instead of water cooling, was investigated.After selecting an appropriate length and diameter of Nd:YAG laser crystal rod and using three groups of laser diode centimeter bar which was composed by 12 laser diodes and uniformly arranged according to the angle of 120°,side-pumping structure of laser was accomplished.Adopting plano-concave resonator ,mending double end face of laser crystal and designing heat-stability resonator made the resonator steadily oscillate.Laser crystal rod which was tight fastened by copper net was conductively cooled and radiation block was furnished on the external of copper net for increasing the radiation capacity.High reflection gold film was plated on the cooling wall in the opposite way of pumping light, so that the laser crystal was uniformly pumped and the laser with low order mode output.Making the use of pillar lens focus and ray trace computing, reasonable parameters were caculated to couple pumping light to laser with high-efficiency.It was the electrooptic Q-switched which was made to be micro-integration eliminating voltage by KD*P crystal that improved the ratio between acting and unacting.Inner heat radiated from laser in good time with TE cooler and the laser ran at constant temperature with water cooling when the big external heat sink emanated a steady heat to periphery. Experiments revealed that the syetem pumping efficiency riseed by 18% and the laser threshold energy was 192 mJ under the condition of this novel pumping structure. The low mode output of 10-12ns pulse width and the maximum output energy of 98 mJ was achieved with an incident pump energy of 720 mJ in 1064nm.The optical-to-optical conversion efficiency was up to 13. 6 %,and the power instability in 24 h was better than +/-1. 7 %.

Formation of crystal-like structures and branched networks from nonionic spherical micelles

NASA Astrophysics Data System (ADS)

Cardiel, Joshua J.; Furusho, Hirotoshi; Skoglund, Ulf; Shen, Amy Q.

2015-12-01

Crystal-like structures at nano and micron scales have promise for purification and confined reactions, and as starting points for fabricating highly ordered crystals for protein engineering and drug discovery applications. However, developing controlled crystallization techniques from batch processes remain challenging. We show that neutrally charged nanoscale spherical micelles from biocompatible nonionic surfactant solutions can evolve into nano- and micro-sized branched networks and crystal-like structures. This occurs under simple combinations of temperature and flow conditions. Our findings not only suggest new opportunities for developing controlled universal crystallization and encapsulation procedures that are sensitive to ionic environments and high temperatures, but also open up new pathways for accelerating drug discovery processes, which are of tremendous interest to pharmaceutical and biotechnological industries.

The application of interference fits for overcoming limitations in clamping methodologies for cryo-cooling first crystal configurations in x-ray monochromators

NASA Astrophysics Data System (ADS)

Stimson, J.; Docker, P.; Ward, M.; Kay, J.; Chapon, L.; Diaz-Moreno, S.

2017-12-01

The work detailed here describes how a novel approach has been applied to overcome the challenging task of cryo-cooling the first monochromator crystals of many of the world’s synchrotrons’ more challenging beam lines. The beam line configuration investigated in this work requires the crystal to diffract 15 Watts of 4-34 keV X-ray wavelength and dissipate the additional 485 watts of redundant X-ray power without significant deformation of the crystal surface. In this case the beam foot print is 25 mm by 25 mm on a crystal surface measuring 38 mm by 25 mm and maintain a radius of curvature of more than 50 km. Currently the crystal is clamped between two copper heat exchangers which have LN2 flowing through them. There are two conditions that must be met simultaneously in this scenario: the crystal needs to be clamped strongly enough to prevent the thermal deformation developing whilst being loose enough not to mechanically deform the diffracting surface. An additional source of error also occurs as the configuration is assembled by hand, leading to human error in the assembly procedure. This new approach explores making the first crystal cylindrical with a sleeve heat exchanger. By manufacturing the copper sleeve to be slightly larger than the silicon crystal at room temperature the sleeve can be slid over the silicon and when cooled will form an interference fit. This has the additional advantage that the crystal and its heat exchanger become a single entity and will always perform the same way each time it is used, eliminating error due to assembly. Various fits have been explored to investigate the associated crystal surface deformations under such a regime

Heat transfer analytical models for the rapid determination of cooling time in crystalline thermoplastic injection molding and experimental validation

NASA Astrophysics Data System (ADS)

Didier, Delaunay; Baptiste, Pignon; Nicolas, Boyard; Vincent, Sobotka

2018-05-01

Heat transfer during the cooling of a thermoplastic injected part directly affects the solidification of the polymer and consequently the quality of the part in term of mechanical properties, geometric tolerance and surface aspect. This paper proposes to mold designers a methodology based on analytical models to provide quickly the time to reach the ejection temperature depending of the temperature and the position of cooling channels. The obtained cooling time is the first step of the thermal conception of the mold. The presented methodology is dedicated to the determination of solidification time of a semi-crystalline polymer slab. It allows the calculation of the crystallization time of the part and is based on the analytical solution of the Stefan problem in a semi-infinite medium. The crystallization is then considered as a phase change with an effective crystallization temperature, which is obtained from Fast Scanning Calorimetry (FSC) results. The crystallization time is then corrected to take the finite thickness of the part into account. To check the accuracy of such approach, the solidification time is calculated by solving the heat conduction equation coupled to the crystallization kinetics of the polymer. The impact of the nature of the contact between the polymer and the mold is evaluated. The thermal contact resistance (TCR) appears as significant parameter that needs to be taken into account in the cooling time calculation. The results of the simplified model including or not TCR are compared in the case of a polypropylene (PP) with experiments carried out with an instrumented mold. Then, the methodology is applied for a part made with PolyEtherEtherKetone (PEEK).

Inhomogeneities and superconductivity in poly-phase Fe-Se-Te systems

NASA Astrophysics Data System (ADS)

Hartwig, S.; Schäfer, N.; Schulze, M.; Landsgesell, S.; Abou-Ras, D.; Blum, Ch. G. F.; Wurmehl, S.; Sokolowski, A.; Büchner, B.; Prokeš, K.

2018-02-01

The impact of synthesis conditions, post-preparation heating procedure, aging and influence of pressure on the superconducting properties of FeSe0.4Te0.6 crystals is reported. Two FeSe0.4Te0.6 single crystals were used in the study, prepared from stoichiometric melt but cooled down with very different cooling rates, and investigated using magnetic bulk and electrical-resistivity methods. The fast-cooled crystal contains large inclusions of Fe3Se2.1Te1.8 and exhibits bulk superconductivity in its as-prepared state, while the other is homogeneous and shows only traces of superconductivity. AC susceptibility measurements under hydrostatic pressure show that the superconducting transition temperature of the inhomogeneous crystal increases from 12.3 K at ambient pressure to Tsc = 17.9 K at 9 kbar. On the other hand, neither pressure nor mechanically-induced stress is sufficient to induce superconductivity in the homogeneous crystal. However, an additional heat treatment at 673 K followed by fast cooling down and/or long-term aging at ambient conditions leads to the appearance of bulk superconductivity also in the latter sample. This sample remains homogeneous on a scale down to few μm but shows an additional magnetic phase transition around 130 K suggesting that it must be inhomogeneous. For comparison also Fe3Se2.1Te1.8 polycrystals have been prepared and their magnetic properties have been studied. It appears that this phase is not superconducting by itself. It is concluded that nano-scale inhomogeneities that appear in the FeSexTe1-x system due to a spinodal decomposition in the solid state are necessary for bulk superconductivity, possibly due to minor changes in the crystal structure and microstructure. Macroscopic inclusions quenched by fast cooling from high temperatures lead obviously to strain and hence variations in the lattice constants, an effect that is further supported by application of pressure/stress.

Structure, dielectric and electric properties of diisobutylammonium hydrogen sulfate crystal

NASA Astrophysics Data System (ADS)

Bednarchuk, Tamara J.; Kinzhybalo, Vasyl; Markiewicz, Ewa; Hilczer, Bożena; Pietraszko, Adam

2018-02-01

Diisobutylammonium hydrogen sulfate, a new organic-inorganic hybrid compound, was successfully synthesized and three structural phases in 298-433 K temperature range were revealed by differential scanning calorimetry and X-ray powder diffraction studies. Single crystal X-ray diffraction data were used to describe the crystal structures in each particular case. In phase III (below 336/319 K on heating/cooling) the crystal arrangement appears to be within the triclinic symmetry with P-1 space group. During heating in the 336-339 K region (and 319-337 K on cooling) the crystal exists in the phase II, characterized by monoclinic symmetry with P21/c space group. Consequently, above 339 K (during heating, and 337 K during cooling temperature sequences), i.e. in phase I the crystal exhibits orthorhombic symmetry (Cmce space group). Ferroelastic domain structure was observed in phase III. These phase boundaries (III→II and II→I) were accompanied by the presence of small anomalies, apparent in the dielectric permittivity and electric conductivity experimental data. Fast proton transport with activation energy of 0.23 eV was observed in the high temperature phase I and related to phonon assisted proton diffusion conditioned by disorder of diisobutylammonium (diba) cations, as well as by high thermal displacements of oxygen and sulfur atoms of hydrogen sulfate anion (hs).

Measurement and analysis of the mannitol partition coefficient in sucrose crystallization under simulated industrial conditions.

PubMed

Eggleston, Gillian; Yen, Jenny Wu Tiu; Alexander, Clay; Gober, Jessica

2012-07-01

Mannitol is a major deterioration product of Leuconstoc mesenteroides bacterial metabolism of sucrose and fructose from both sugarcane and sugar beet. The effect of crystallization conditions on the mannitol partition coefficient (K(eff)) between impure sucrose syrup and crystal has been investigated in a batch laboratory crystallizer and a batch pilot plant-scale vacuum pan. Laboratory crystallization was operated at 65.5°C (150°F), 60.0°C (140°F), and 51.7°C (125°F) with a 78.0 Brix (% refractometric dissolved solids) pure sucrose syrup containing 0%, 0.1%, 0.2%, 1.0%, 2.0%, 3.0%, and 10% (at 65.5°C only) mannitol on a Brix basis. Produced mother liquor and crystals were separated by centrifugation and their mannitol contents measured by ion chromatography with integrated pulsed amperometric detection (IC-IPAD). The extent of mannitol partitioning into the crystals depended strongly on the mannitol concentration in the feed syrup and, to a lesser extent, the crystallization temperature. At 65.5 and 60.0°C, the K(eff) varied from ~0.4% to 3.0% with 0.2% to 3.0% mannitol in the feed syrup, respectively. The mannitol K(eff) was lower than that reported for dextran (~9-10% K(eff)), another product of Leuconstoc deterioration, under similar sucrose crystal growth conditions. At 10% mannitol concentration in the syrup at 65.5°C, co-crystallization of mannitol with sucrose occurred and the crystal growth rate was greatly impeded. In both laboratory and pilot plant crystallizations (95.7% purity; 78.0 Brix; 65.5°C), mannitol tended to cause conglomerates to form, which became progressively worse with increased mannitol syrup concentration. At the 3% mannitol concentration, crystallization at both the laboratory and pilot plant scales was more difficult. Mannitol incorporation into the sucrose crystal results mostly from liquid syrup inclusions but adsorption onto the crystal surface may play a minor role at lower mannitol concentrations. Published by Elsevier Ltd.

Incorporation of cooling-induced crystallisation into a 2-dimensional axisymmetric conduit heat flow model

NASA Astrophysics Data System (ADS)

Heptinstall, D. A.; Neuberg, J. W.; Bouvet de Maisonneuve, C.; Collinson, A.; Taisne, B.; Morgan, D. J.

2015-12-01

Heat flow models can bring new insights into the thermal and rheological evolution of volcanic systems. We shall investigate the thermal processes and timescales in a crystallizing, static magma column, with a heat flow model of Soufriere Hills Volcano (SHV), Montserrat. The latent heat of crystallization is initially computed with MELTS, as a function of pressure and temperature for an andesitic melt (SHV groundmass starting composition). Three fractional crystallization simulations are performed; two with initial pressures of 34MPa (runs 1 & 2) and one of 25MPa (run 3). Decompression rate was varied between 0.1MPa/°C (runs 1 & 3) and 0.2MPa/°C (run 2). Natural and experimental matrix glass compositions are accurately reproduced by all MELTS runs. The cumulative latent heat released for runs 1, 2 and 3 differs by less than 9% (8.69e5 J/kg*K, 9.32e5 J/kg*K, and 9.49e5 J/kg*K respectively). The 2D axisymmetric conductive cooling simulations consider a 30m-diameter conduit that extends from the surface to a depth of 1500m (34MPa). The temporal evolution of temperature is closely tracked at depths of 10m, 750m and 1400m in the center of the conduit, at the conduit walls, and 20m from the walls into the host rock. Following initial cooling by 7-15oC at 10m depth inside the conduit, the magma temperature rebounds through latent heat release by 32-35oC over 85-123 days to a maximum temperature of 1002-1005oC. At 10 m depth, it takes 4.1-9.2 years for the magma column to cool over 108-130oC and crystallize to 75wt%, at which point it cannot be easily remobilized. It takes 11-31.5 years to reach the same crystallinity at 750-1400m depth. We find a wide range in cooling timescales, particularly at depths of 750m or greater, attributed to the initial run pressure and dominant latent heat producing crystallizing phases (Quartz), where run 1 cools fastest and run 3 cools slowest. Surface cooling by comparison has the strongest influence on the upper tens of meters in all runs.

Direct flow crystal growth system

DOEpatents

Montgomery, Kenneth E.; Milanovich, Fred P.

1992-01-01

A crystal is grown in a constantly filtered solution which is flowed directly into the growing face of a crystal. In a continuous flow system, solution at its saturation temperature is removed from a crystal growth tank, heated above its saturation temperature, filtered, cooled back to its saturation temperature, and returned to the tank.

Zircon age-temperature-compositional spectra in plutonic rocks

DOE PAGES

Samperton, Kyle M.; Bell, Elizabeth A.; Barboni, Mélanie; ...

2017-08-23

We present that geochronology can resolve dispersed zircon dates in plutonic rocks when magma cooling time scales exceed the temporal precision of individual U-Pb analyses; such age heterogeneity may indicate protracted crystallization between the temperatures of zircon saturation (T sat) and rock solidification (T solid). Diffusive growth models predict asymmetric distributions of zircon dates and crystallization temperatures in a cooling magma, with volumetrically abundant old, hot crystallization at T sat decreasing continuously to volumetrically minor young, cold crystallization at T solid. We present integrated geochronological and geochemical data from Bergell Intrusion tonalites (Central Alps, Europe) that document zircon compositional changemore » over hundreds of thousands of years at the hand-sample scale, indicating melt compositional evolution during solidification. Ti-in-zircon thermometry, crystallization simulation using MELTS software, and U-Pb dates produce zircon mass-temperature-time distributions that are in excellent agreement with zircon growth models. In conclusion, these findings provide the first quantitative validation of longstanding expectations from zircon saturation theory by direct geochronological investigation, underscoring zircon’s capacity to quantify supersolidus cooling rates in magmas and resolve dynamic differentiation histories in the plutonic rock record.« less

Zircon age-temperature-compositional spectra in plutonic rocks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Samperton, Kyle M.; Bell, Elizabeth A.; Barboni, Mélanie

We present that geochronology can resolve dispersed zircon dates in plutonic rocks when magma cooling time scales exceed the temporal precision of individual U-Pb analyses; such age heterogeneity may indicate protracted crystallization between the temperatures of zircon saturation (T sat) and rock solidification (T solid). Diffusive growth models predict asymmetric distributions of zircon dates and crystallization temperatures in a cooling magma, with volumetrically abundant old, hot crystallization at T sat decreasing continuously to volumetrically minor young, cold crystallization at T solid. We present integrated geochronological and geochemical data from Bergell Intrusion tonalites (Central Alps, Europe) that document zircon compositional changemore » over hundreds of thousands of years at the hand-sample scale, indicating melt compositional evolution during solidification. Ti-in-zircon thermometry, crystallization simulation using MELTS software, and U-Pb dates produce zircon mass-temperature-time distributions that are in excellent agreement with zircon growth models. In conclusion, these findings provide the first quantitative validation of longstanding expectations from zircon saturation theory by direct geochronological investigation, underscoring zircon’s capacity to quantify supersolidus cooling rates in magmas and resolve dynamic differentiation histories in the plutonic rock record.« less

Thermal and structural behavior of anhydrous milk fat. 3. Influence of cooling rate.

PubMed

Lopez, C; Lesieur, P; Bourgaux, C; Ollivon, M

2005-02-01

The crystallization behavior of anhydrous milk fat has been examined with a new instrument coupling time-resolved synchrotron x-ray diffraction as a function of temperature (XRDT) at both small and wide angles and high-sensitivity differential scanning calorimetry. Crystallizations were monitored at cooling rates of 3 and 1 degrees C/ min from 60 to -10 degrees C to determine the triacylglycerol organizations formed. Simultaneous thermal analysis permitted the correlation of the formation/melting of the different crystalline species monitored by XRDT to the thermal events recorded by differential scanning calorimetry. At intermediate cooling rates, milk fat triacylglycerols sequentially crystallize in 3 different lamellar structures with double-chain length of 46 and 38.5 A and a triple-chain length of 72 A stackings of alpha type, which are correlated to 2 exothermic peaks at 17.2 and 13.7 degrees C, respectively. A time-dependent slow sub-alpha <--> alpha reversible transition is observed at -10 degrees C. Subsequent heating at 2 degrees C/min has shown numerous structural rearrangements of the alpha varieties into a single beta' form before final melting. This polymorphic evolution on heating, as well as the final melting point observed (approximately 39 degrees C), confirmed that cooling at 3 degrees C/min leads to the formation of crystalline varieties that are not at equilibrium. An overall comparison of the thermal and structural properties of the crystalline species formed as a function of the cooling rate and stabilization time is presented. The influence on crystal size of the cooling rates applied in situ using temperature-controlled polarized microscopy is also determined for comparison.

Modification of defects and potential fluctuations in slow-cooled and quenched Cu2ZnSnSe4 single crystals

NASA Astrophysics Data System (ADS)

Bishop, Douglas M.; McCandless, Brian; Gershon, Talia; Lloyd, Michael A.; Haight, Richard; Birkmire, Robert

2017-02-01

Recent literature reports have shown the ability to manipulate Cu-Zn cation ordering for Cu2ZnSnSe4 (CZTSe) via low temperature treatments. Theoretical arguments suggest that one of the major roadblocks to higher VOC—significant band tailing—could be improved with increased cation order; however, few direct measurements have been reported and significant device improvements have not yet been realized. This report investigates electrical properties, defects, and devices from quenched and slow-cooled single crystals of CZTSe. The extent of disorder was characterized by Raman spectroscopy as well as x-ray diffraction, where the change in Cu-Zn order can be detected by a changing c/a ratio. Quenched samples show higher acceptor concentrations, lower hole mobilities, and a lower-energy photoluminescence (PL) peak than crystals cooled at slower rates, consistent with a reduction in the bandgap. In addition, samples quenched at the highest temperatures showed lower PL yield consistent with higher quantities of deep defects. Devices fabricated using slow-cooled CZTSe single crystals showed improved efficiencies, most notably with increased VOC; however, low temperature intensity-dependent photoluminescence measurements continue to indicate the existence of potential fluctuations. We discuss the possibility that potential fluctuations in slow-cooled samples may be related to the inability to achieve a long range order of the Cu-Zn sub-lattice resulting in local regions of high and low levels of cation order, and consequent local variations in the bandgap. The presence of significant potential fluctuations, even after the slow-cooling step, suggests the difficulty in eliminating band-tailing in this system, and thus, additional approaches may be needed for significant reduction of the VOC deficit.

Optimization of anisotropic photonic density of states for Raman cooling of solids

NASA Astrophysics Data System (ADS)

Chen, Yin-Chung; Ghosh, Indronil; Schleife, André; Carney, P. Scott; Bahl, Gaurav

2018-04-01

Optical refrigeration of solids holds tremendous promise for applications in thermal management. It can be achieved through multiple mechanisms including inelastic anti-Stokes Brillouin and Raman scattering. However, engineering of these mechanisms remains relatively unexplored. The major challenge lies in the natural unfavorable imbalance in transition rates for Stokes and anti-Stokes scattering. We consider the influence of anisotropic photonic density of states on Raman scattering and derive expressions for cooling in such photonically anisotropic systems. We demonstrate optimization of the Raman cooling figure of merit considering all possible orientations for the material crystal and two example photonic crystals. We find that the anisotropic description of the photonic density of states and the optimization process is necessary to obtain the best Raman cooling efficiency for systems having lower symmetry. This general result applies to a wide array of other laser cooling methods in the presence of anisotropy.

Science Issues Associated with the Use of a Microfluidic Chip Designed Specifically for Protein Crystallization

NASA Technical Reports Server (NTRS)

Holmes, Anna M.; Monaco, Lisa; Barnes, Cindy; Spearing, Scott; Jenkins, Andy; Johnson, Todd; Mayer, Derek; Cole, Helen

2003-01-01

The Iterative Biological Crystallization team in partnership with Caliper Technologies has produced a prototype microfluidic chip for batch crystallization that has been designed and tested. The chip is designed for the mixing and dispensing of up to five solutions with possible variation of the recipe being delivered to two growth wells. Developments that have led to the successful on-chip crystallization of a few model proteins have required investigative insight into many different areas, including fluid mixing dynamics, surface treatments, quantification and fidelity of reagent delivery. This presentation will encompass the ongoing studies and data accumulated toward these efforts.

Compositions of Mars Rocks: SNC Meteorites, Differentiates, and Soils

NASA Technical Reports Server (NTRS)

Rutherford, M. J.; Minitti, M.; Weitz, C. M.

1999-01-01

The 13 samples from Mars identified in the terrestrial meteorite collections vary from dunite to pyroxenite to microgabbro or basalt. All of these rocks appear to have formed from primitive melts with similar major element compositional characteristics; i.e., FeO-rich and Al2O3-Poor melts relative to terrestrial basalt compositions. Although all of the SNC rocks can be derived by melting of the same Al-depleted mantle, contamination of SNC's by a Rb-enriched mantle or crustal source is required to explain the different REE characteristics of SNC rocks. Thus, there are indications of an old crustal rocktype on Mars, and this rock does not appear to have been sampled. This paper focuses primarily on the composition of the SNC basalts, however, and on the compositions of rocks which could be derived from SNC basaltic melt by magmatic processes. In particular, we consider the possible compositions which could be achieved through accumulation of early-formed crystals in the SNC primitive magma. Through a set of experiments we have determined (1) melt (magma) compositions which could be produced by melt evolution as crystals are removed from batches of this magma cooling at depth, and (2) which evolved (Si02enriched, MgO-depleted) rock compositions could be produced from the SNC magma, and how these compare with the Pathfinder andesite composition. Finally, we compare the SNC magma compositions to the Mars soil composition in order to determine whether any source other than SNC is required.

Melt extraction during heating and cooling of felsic crystal mushes in shallow volcanic systems: An experimental study

NASA Astrophysics Data System (ADS)

Pistone, M.; Baumgartner, L. P.; Sisson, T. W.; Bloch, E. M.

2017-12-01

The dynamics and kinetics of melt extraction in near-solidus, rheologically stalled, felsic crystal mushes (> 50 vol.% crystals) are essential to feeding many volcanic eruptions. At shallow depths (< 15 km), most felsic crystal mushes would be volatile-saturated and may be thermally stable for long time periods (104-107 years). In absence of deformation, residual melt can segregate from the mush's crystalline framework stimulated by: 1) gas injecting from hot mafic magmas into felsic mushes (heating / partial melting scenario), and 2) gas exsolving from the crystallizing mush (cooling / crystallizing scenario). The conditions and efficiency of melt extraction from a mush in the two scenarios are not well understood. Thus, we conducted high-temperature (700 to 850 °C) and -pressure (1.1 kbar) cold seal experiments (8-day duration) on synthetic felsic mushes, composed of water-saturated (4.2 wt.%) rhyodacite melt bearing different proportions of added quartz crystals (60, 70, and 80 vol%; 68 mm average particle size). High-spatial resolution X-ray tomography of run products show: 1) in the heating scenario (> 750 °C) melt has not segregated due to coalescence of vesicles (≤ 23 vol%) and large melt connectivity (> 7 vol% glass) / low pressure gradient for melt movement up to 80 vol% crystals; 2) in the cooling scenario (≤ 750 °C) vesicle (< 11 vol%) coalescence is limited or absent and limited amount of melt (3 to 11 vol%) segregated from sample center to its outer periphery (30 to 100 mm melt-rich lenses), testifying to the efficiency of melt extraction dictated by increasing crystallinity. These results suggest that silicic melt hosted within a crystal-rich mush can accumulate rapidly due to the buildup of modest gas pressures during crystallization at temperatures near the solidus.

Morphological evolution of copper nanoparticles: Microemulsion reactor system versus batch reactor system

NASA Astrophysics Data System (ADS)

Xia, Ming; Tang, Zengmin; Kim, Woo-Sik; Yu, Taekyung; Park, Bum Jun

2017-07-01

In the synthesis of nanoparticles, the reaction rate is important to determine the morphology of nanoparticles. We investigated morphology evolution of Cu nanoparticles in this two different reactors, microemulsion reactor and batch reactor. In comparison with the batch reactor system, the enhanced mass and heat transfers in the emulsion system likely led to the relatively short nucleation time and the highly homogeneous environment in the reaction mixture, resulting in suppressing one or two dimensional growth of the nanoparticles. We believe that this work can offer a good model system to quantitatively understand the crystal growth mechanism that depends strongly on the local monomer concentration, the efficiency of heat transfer, and the relative contribution of the counter ions (Br- and Cl-) as capping agents.

Transient Self-assembly of Edible Lipids During Crystallization

NASA Astrophysics Data System (ADS)

Mazzanti, Gianfranco; Marangoni, Alejandro; Idziak, Stefan

2002-03-01

The effects of cooling rate and shear on the structure and crystallization behavior of two natural triglyceride melts were studied using rheology and light scattering. A transparent Couette Cell with 1 mm gap was used to perform light scattering measurements. A rheometer with concentric cylinders with 1 mm gap was used for the rheological tests. Experiments were carried out at cooling rates of 3 and 0.5 C/min from the 45 C melt down to temperatures between 17.5 C and 30 C. The shear rates imposed were 90 and 1440 s-1. Results show that the effect of shear on the onset of crystallization is especially evident at slow cooling rates. The effect of shear on crystalline phase growth is more pronounced at higher temperatures and slow cooling rates. Quasi-stationary studies were carried out in the rheometer operated in a controlled stress oscillatory mode, and strain amplitudes were less than 2experiments were performed in a petroleum analyzer and in a glass capillary. The onset of light scattering coincides with an unexpected transient increase in the amplitude of the oscillatory response.

Insights into crystal growth rates from a study of orbicular granitoids from western Australia

NASA Astrophysics Data System (ADS)

Zhang, J.; Lee, C. T.

2017-12-01

The purpose of this study is to develop new tools for constraining crystal growth rate in geologic systems. Of interest is the growth of crystals in magmatic systems because crystallization changes the rheology of a magma as well as provides surfaces on which bubbles can nucleate. To explore crystal growth in more detail, we conducted a case study of orbicular granitoids from western Australia. The orbicules occur as spheroids dispersed in a granitic matrix. Most orbicules have at least two to three concentric bands, composed of elongate and radially oriented hornblende surrounded by interstitial plagioclase. We show that mineral modes and hence bulk composition at the scale of the band is homogeneous from rim to core. Crystal number density decreases and crystal size increases from rim to core. These observations suggest that the orbicules crystallized rapidly from rim to core. We hypothesize that the orbicules are blobs of hot dioritic liquid injected into a cold granitic magma and subsequently cooled and solidified. Crystals stop growing when the mass transport rate tends to zero due to the low temperature. We estimated cooling timescales based on conductive cooling models, constraining crystal growth rates to be 10-6 to 10-5 m/s. We also show that the oscillatory banding is controlled by disequilibrium crystallization, wherein hornblende preferentially crystallizes, resulting in the diffusive growth of a chemical boundary layer enriched in plagioclase component, which in turns results in crystallization of plagioclase. We show that the correlation between the width of each crystallization couplet (band) with distance from orbicule rim is linear, with the slope corresponding to the square root of the ratio between chemical diffusivity in the growth medium and thermal diffusivity. We estimate chemical diffusivity of 2*10-7 m2/s, which is remarkably fast for silicate liquids but reasonable for diffusion in hot aqueous fluids, suggesting that crystallization occurred during water-saturated conditions. Combined with the estimate of the boundary layer thickness, we use the diffusivity to estimate the diffusive flux, arriving at crystal growth rates similar to that constrained by thermal modeling. In the presence of fluids, we show that crystal growth rates in magmatic systems may be under-estimated.

Pellet Feed for Dendritic-Web Growth

NASA Technical Reports Server (NTRS)

Duncan, C. S.; Skutch, M. E.; Mchugh, J. P.

1983-01-01

Melt replenishment system sustains continuous growth of silicon dentritic web for several days. Substantially increases size of batch, limited mainly by level of impurities and life of crucible. Silicon pellets automatically added to crucible sustain crystal growth for days.

In-situ Crystallization of Highly Volatile Commercial Mold Flux Using an Isolated Observation System in the Confocal Laser Scanning Microscope

NASA Astrophysics Data System (ADS)

Park, Jun-Yong; Ryu, Jae Wook; Sohn, Il

2014-08-01

The in situ crystallization behavior of highly volatile commercial mold fluxes for medium carbon steels was investigated using the confocal laser scanning microscope (CLSM) equipped with an optimized isolated observation system. The highly volatile compounds of the mold flux were suppressed during heating allowing direct observation in the CLSM. Cooling rates of 25, 50, 100, 400, and 800 K/min were incorporated and continuous cooling transformation (CCT) diagrams of 4 different commercial mold fluxes for medium carbon steels were developed. Identification of the crystalline phase was conducted with XRD and SEM-EDS analysis. A cuspidine crystalline was observed in all samples at various cooling rates. With higher basicity, CaF2, and NaF, the crystallization of the fluxes was enhanced according to the CCT diagram. As the slag structure becomes depolymerized, the diffusion rate of the cathodic ions seems to increase.

Protein-crystal growth experiment (planned)

NASA Technical Reports Server (NTRS)

Fujita, S.; Asano, K.; Hashitani, T.; Kitakohji, T.; Nemoto, H.; Kitamura, S.

1988-01-01

To evaluate the effectiveness of a microgravity environment on protein crystal growth, a system was developed using 5 cubic feet Get Away Special payload canister. In the experiment, protein (myoglobin) will be simultaneously crystallized from an aqueous solution in 16 crystallization units using three types of crystallization methods, i.e., batch, vapor diffusion, and free interface diffusion. Each unit has two compartments: one for the protein solution and the other for the ammonium sulfate solution. Compartments are separated by thick acrylic or thin stainless steel plates. Crystallization will be started by sliding out the plates, then will be periodically recorded up to 120 hours by a still camera. The temperature will be passively controlled by a phase transition thermal storage component and recorded in IC memory throughout the experiment. Microgravity environment can then be evaluated for protein crystal growth by comparing crystallization in space with that on Earth.

A study on ice crystal formation behavior at intracellular freezing of plant cells using a high-speed camera.

PubMed

Ninagawa, Takako; Eguchi, Akemi; Kawamura, Yukio; Konishi, Tadashi; Narumi, Akira

2016-08-01

Intracellular ice crystal formation (IIF) causes several problems to cryopreservation, and it is the key to developing improved cryopreservation techniques that can ensure the long-term preservation of living tissues. Therefore, the ability to capture clear intracellular freezing images is important for understanding both the occurrence and the IIF behavior. The authors developed a new cryomicroscopic system that was equipped with a high-speed camera for this study and successfully used this to capture clearer images of the IIF process in the epidermal tissues of strawberry geranium (Saxifraga stolonifera Curtis) leaves. This system was then used to examine patterns in the location and formation of intracellular ice crystals and to evaluate the degree of cell deformation because of ice crystals inside the cell and the growing rate and grain size of intracellular ice crystals at various cooling rates. The results showed that an increase in cooling rate influenced the formation pattern of intracellular ice crystals but had less of an effect on their location. Moreover, it reduced the degree of supercooling at the onset of intracellular freezing and the degree of cell deformation; the characteristic grain size of intracellular ice crystals was also reduced, but the growing rate of intracellular ice crystals was increased. Thus, the high-speed camera images could expose these changes in IIF behaviors with an increase in the cooling rate, and these are believed to have been caused by an increase in the degree of supercooling. Copyright © 2016 Elsevier Inc. All rights reserved.

Ejection of Coulomb Crystals from a Linear Paul Ion Trap for Ion-Molecule Reaction Studies.

PubMed

Meyer, K A E; Pollum, L L; Petralia, L S; Tauschinsky, A; Rennick, C J; Softley, T P; Heazlewood, B R

2015-12-17

Coulomb crystals are being increasingly employed as a highly localized source of cold ions for the study of ion-molecule chemical reactions. To extend the scope of reactions that can be studied in Coulomb crystals-from simple reactions involving laser-cooled atomic ions, to more complex systems where molecular reactants give rise to multiple product channels-sensitive product detection methodologies are required. The use of a digital ion trap (DIT) and a new damped cosine trap (DCT) are described, which facilitate the ejection of Coulomb-crystallized ions onto an external detector for the recording of time-of-flight (TOF) mass spectra. This enables the examination of reaction dynamics and kinetics between Coulomb-crystallized ions and neutral molecules: ionic products are typically cotrapped, thus ejecting the crystal onto an external detector reveals the masses, identities, and quantities of all ionic species at a selected point in the reaction. Two reaction systems are examined: the reaction of Ca(+) with deuterated isotopologues of water, and the charge exchange between cotrapped Xe(+) with deuterated isotopologues of ammonia. These reactions are examples of two distinct types of experiment, the first involving direct reaction of the laser-cooled ions, and the second involving reaction of sympathetically-cooled heavy ions to form a mixture of light product ions. Extensive simulations are conducted to interpret experimental results and calculate optimal operating parameters, facilitating a comparison between the DIT and DCT approaches. The simulations also demonstrate a correlation between crystal shape and image shape on the detector, suggesting a possible means for determining crystal geometry for nonfluorescing ions.

Hot Views on Cold Crystals: The Application of Thermal Imaging in Cryo-crystallography

NASA Technical Reports Server (NTRS)

Snell, E. H.; vanderWoerd, M. J.; Deacon, A.

2003-01-01

In the past we have used thermal imaging techniques to visualize the cryocooling processes of macromolecular crystals. From these images it was clear that a cold wave progresses through a crystal starting at the face closest to the origin of the cold stream and ending at the point furthest away. During these studies we used large volume crystals, which were clearly distinguished from the loop holding them. These large crystals, originally grown for neutron diffraction studies, were chosen deliberately to enhance the imaging. As an extension to this work, we present used thermal imaging to study small crystals, held in a cryo-loop, in the presence of vitrified mother liquor. The different infrared transmission and reflectance properties of the crystal in comparison to the mother liquor surrounding it are thought to be the parameter that produces the contrast that makes the crystal visible. An application of this technology may be the determination of the exact location of small crystals in a cryo-loop. Data from initial tests in support of application development was recorded for lysozyme crystals and for bFGF/dna complex crystals, which were cryo-cooled and imaged in large loops, both with visible light and with infrared radiation. The crystals were clearly distinguished from the vitrified solution in the infrared spectrum, while in the case of the bFGF/dna complex the illumination had to be carefully manipulated to make the crystal visible in the visible spectrum. These results suggest that the thermal imaging may be more sensitive than visual imaging for automated location of small crystals. However, further work on small crystals robotically mounted at SSRL did not clearly visualize those crystals. The depth of field of the camera proved to be limiting and a different cooling geometry was used, compared to the previous, successful experiments. Analysis to exploit multiple images to improve depth of field and experimental work to understand cooling geometry effects is ongoing. These results will be presented along with advantages and disadvantages of the technique and a discussion of how it might be applied.

Hot Views on Cold Crystals: The Application of Thermal Imaging in Cryocrystallography

NASA Technical Reports Server (NTRS)

Snell, Eddie H.

2003-01-01

In the past we have used thermal imaging techniques to visualize the cryocooling processes of macromolecular crystals. From these images it was clear that a cold wave progresses through a crystal starting at the face closest to the origin of the cold stream and ending at the point furthest away. During these studies we used large volume crystals, which were clearly distinguished from the loop holding them. These large crystals, originally grown for neutron diffraction studies, were chosen deliberately to enhance the imaging. As an extension to this work, we used thermal imaging to study small crystals, held in a cryo- loop, in the presence of vitrified mother liquor. The different infrared transmission and reflectance properties of the crystal in comparison to the mother liquor surrounding it are thought to be the parameter that produces the contrast that makes the crystal visible. An application of this technology may be the determination of the exact location of small crystals in a cryo-loop. Data from initial tests in support of application development was recorded for lysozyme crystals and for bFGF/dna complex crystals, which were cryo-cooled and imaged in large loops, both with visible light and with infrared radiation. The crystals were clearly distinguished from the vitrified solution in the infrared spectrum, while in the case of the bFGF/dna complex the illumination had to be carefully manipulated to make the crystal visible in the visible spectrum. These results suggest that the thermal imaging may be more sensitive than visual imaging for automated location of small crystals. However, further work on small crystals robotically mounted at SSRL did not clearly visualize those crystals. The depth of field of the camera proved to be limiting and a different cooling geometry was used, compared to the previous, successful experiments. Analysis to exploit multiple images to improve depth of field and experimental work to understand cooling geometry effects is ongoing. These results will be presented along with advantages and disadvantages of the technique and a discussion of how it might be applied .

Crystallization of Chicken Egg-White Lysozyme from Ammonium Sulfate

NASA Technical Reports Server (NTRS)

Forsythe, Elizabeth L.; Snell, Edward H.; Pusey, Marc L.

1997-01-01

Chicken egg-white lysozyme was crystallized from ammonium sulfate over the pH range 4.0-7.8, with protein concentrations from 100 to 150 mg/ml. Crystals were obtained by vapor-diffusion or batch-crystallization methods. The protein crystallized in two morphologies with an apparent morphology dependence on temperature and protein concentration. In general, tetragonal crystals could be grown by lowering the protein concentration or temperature. Increasing the temperature or protein concentration resulted in the growth of orthorhombic crystals. Representative crystals of each morphology were selected for X-ray analysis. The tetragonal crystals belonged to the P4(sub 3)2(sub 1)2 space group with crystals grown at ph 4.4 having unit-cell dimensions of a = b = 78.7 1, c=38.6 A and diffracting to beyond 2.0 A. The orthorhombic crystals, grown at pH 4.8, were of space group P2(sub 1)2(sub 1)2 and had unit-cell dimensions of a = 30.51, b = 56.51 and c = 73.62 A.

Device for isolation of seed crystals during processing of solution

DOEpatents

Montgomery, Kenneth E.; Zaitseva, Natalia P.; Deyoreo, James J.; Vital, Russell L.

1999-01-01

A device for isolation of see crystals during processing of solutions. The device enables a seed crystal to be introduced into the solution without exposing the solution to contaminants or to sources of drying and cooling. The device constitutes a seed protector which allows the seed to be present in the growth solution during filtration and overheating operations while at the same time preventing the seed from being dissolved by the under saturated solution. When the solution processing has been completed and the solution cooled to near the saturation point, the seed protector is opened, exposing the seed to the solution and allowing growth to begin.

Numerical simulation of crystal fractionation in shergottite meteorites

NASA Astrophysics Data System (ADS)

Grimm, R. E.; McSween, H. Y., Jr.

Cumulus clinopyroxenes in the Shergotty and Zagami meteorites suggest crystal fractionation occurred, possibly by gravitative settling. Numerical models of this process in a nonconvecting environment argue that the small phenocrysts can segregate only under extreme conditions of cooling time or gravitational field strength. Since textures indicate that cooling time was not excessive, a large (planetary) g is required by these models, in agreement with other suggestions that the shergottite parent body may be Mars. Other calculations indicate that it is extremely difficult to produce the observed textures in a convecting environment, unless crystal setting occurred in a quiescent zone at the bottom of the magma chamber.

Numerical simulation of crystal fractionation in shergottite meteorites

NASA Technical Reports Server (NTRS)

Grimm, R. E.; Mcsween, H. Y., Jr.

1982-01-01

Cumulus clinopyroxenes in the Shergotty and Zagami meteorites suggest crystal fractionation occurred, possibly by gravitative settling. Numerical models of this process in a nonconvecting environment argue that the small phenocrysts can segregate only under extreme conditions of cooling time or gravitational field strength. Since textures indicate that cooling time was not excessive, a large (planetary) g is required by these models, in agreement with other suggestions that the shergottite parent body may be Mars. Other calculations indicate that it is extremely difficult to produce the observed textures in a convecting environment, unless crystal setting occurred in a quiescent zone at the bottom of the magma chamber.

The Si ribbon crystal for the solar battery using the horizontal pull method

NASA Technical Reports Server (NTRS)

Norifuji, H.; Matsuo, M.; Maki, T.

1979-01-01

A method utilizing a device to spray noble gases to cool the site of silicon crystal growth is described. The salient points are: (1) soft and uniform cooling was possible, (2) the length of the boundary surface of growth along the growth direction was made long over a wide width compared to the thickness, and (3) this made it possible to effectively remove the heat produced from solification. By using forced gas spraying on the solution surface in contact with the points of crystal growth, growth at the points of growth is enhanced and the rate of growth is speeded up.

Rheology and thermal budget of lunar basalts: an experimental study and its implications for rille formation of non-Newtonian lavas on the Moon

NASA Astrophysics Data System (ADS)

Sehlke, A.; Whittington, A. G.

2015-12-01

Sinuous lava channels are a characteristic feature observed on the Moon. Their formation is assumed to be due to a combination of mechanical and thermal erosion of the lava into the substrate during emplacement as surface channels, or due to collapsed subsurface lava tubes after the lava has evacuated. The viscosity (η) of the lava plays an important role, because it controls the volume flux of the emplaced lava that governs the mechanical and thermal erosion potential of the lava flow. Thermal properties, such as heat capacity (Cp) and latent heat of crystallization (ΔHcryst) are important parameters in order for the substrate to melt and causing thermal buffering during crystallization of the flowing lava. We experimentally studied the rheological evolution of analog lavas representing the KREEP terrain and high-Ti mare basalts during cooling and crystallization. We find that the two lavas behave very differently. High-Ti mare lava begins to crystallize around 1300 ºC with a viscosity of 8.6±0.6 Pa s and crystal content around 2 vol%. On cooling to 1169 ºC, the effective viscosity of the crystal-melt suspension is increased to only 538±33 Pa s (at a strain rate of 1 s-1) due to crystallization of 14±1 vol% blocky magnetite and acicular ulvöspinel-rich magnetite. The flow behavior of these suspensions depends on the strain rate, where flow curves below strain rates of 10 s-1show shear-thinning character, but resemble Bingham behavior at greater strain rates. In contrast, the KREEP lava crystallizes rapidly over a narrow temperature interval of ~ 30 degrees. The first crystals detected were ulvospinel-rich magnetites at 1204 ºC with ~2 vol% and a viscosity of 90±2 Pa s. On cooling to 1178 ºC, anorthite and enstatite appears, so that the crystal-melt suspension has become strongly pseudoplastic at a crystal content of 22±2 vol% with a flow index (n) of 0.63 and an effective viscosity of 1600±222 Pa s at a strain rate of 1 s-1. We are currently measuring the heat capacity of crystal-bearing glasses (representing erodible solid substrate) and the heat released during lava crystallization at different cooling rates measured by differential scanning calorimetry (DSC). The rheological and thermal properties will then be integrated into thermo-mechanical models of rille formation in non-Newtonian lavas on the lunar surface.

Congruent melting of gallium nitride at 6 GPa and its application to single-crystal growth.

PubMed

Utsumi, Wataru; Saitoh, Hiroyuki; Kaneko, Hiroshi; Watanuki, Tetsu; Aoki, Katsutoshi; Shimomura, Osamu

2003-11-01

The synthesis of large single crystals of GaN (gallium nitride) is a matter of great importance in optoelectronic devices for blue-light-emitting diodes and lasers. Although high-quality bulk single crystals of GaN suitable for substrates are desired, the standard method of cooling its stoichiometric melt has been unsuccessful for GaN because it decomposes into Ga and N(2) at high temperatures before its melting point. Here we report that applying high pressure completely prevents the decomposition and allows the stoichiometric melting of GaN. At pressures above 6.0 GPa, congruent melting of GaN occurred at about 2,220 degrees C, and decreasing the temperature allowed the GaN melt to crystallize to the original structure, which was confirmed by in situ X-ray diffraction. Single crystals of GaN were formed by cooling the melt slowly under high pressures and were recovered at ambient conditions.

Effects of micro electric current load during cooling of plant tissues on intracellular ice crystal formation behavior and pH.

PubMed

Ninagawa, Takako; Kawamura, Yukio; Konishi, Tadashi; Narumi, Akira

2016-08-01

Cryopreservation techniques are expected to evolve further to preserve biomaterials and foods in a fresh state for extended periods of time. Long-term cryopreservation of living materials such as food and biological tissue is generally achieved by freezing; thus, intracellular freezing occurs. Intracellular freezing injures the cells and leads to cell death. Therefore, a dream cryopreservation technique would preserve the living materials without internal ice crystal formation at a temperature low enough to prevent bacterial activity. This study was performed to investigate the effect of micro electrical current loading during cooling as a new cryopreservation technique. The behavior of intracellular ice crystal formation in plant tissues with or without an electric current load was evaluated using the degree of supercooling, degree of cell deformation, and grain size and growing rate of intracellular ice crystal. Moreover, the transition of intracellular pH during plant tissue cooling with or without electric current loading was also examined using the fluorescence intensity ratio to comprehend cell activity at lower temperatures. The results indicated that micro electric current load did not only decrease the degree of cell deformation and grain size of intracellular ice crystal but also reduced the decline in intracellular pH due to temperature lowering, compared with tissues subjected to the same cooling rate without an electric current load. Thus, the effect of electric current load on cryopreservation and the potential of a new cryopreservation technique using electric current load were discussed based on these results. Copyright © 2016 Elsevier Inc. All rights reserved.

Two-step recrystallization of water in concentrated aqueous solution of poly(ethylene glycol).

PubMed

Gemmei-Ide, Makoto; Motonaga, Tetsuya; Kasai, Ryosuke; Kitano, Hiromi

2013-02-21

Crystallization behavior of water in a concentrated aqueous solution of poly(ethylene glycol) (PEG) with a water content of 37.5 wt % was investigated by temperature variable mid-infrared (mid-IR) spectroscopy in a temperature range of 298-170 K. The mid-IR spectrum of water at 298 K showed that a large water cluster was not formed and that most of the water molecules were associated with the PEG chain. Ice formation, however, occurred as found in previous studies by differential scanning calorimetory. Ice formations were grouped into three types: crystallization at 231 K during cooling, that at 198 K during heating, and that at 210 K during heating. The latter two were just recrystallization. These ice formations were the direct transition from hydration species to ice without condensation regardless of crystallization or recrystallization. This means that the recrystallized water in the present system was not generated from low-density amorphous solid water. At a low cooling rate, nearly complete crystallization at 231 K during cooling and no recrystallization were observed. At a high cooling rate, no crystallization and two-step recrystallization at 198 and 210 K were observed. The former and latter recrystallizations were found to be generated from water associated with the PEG chains with ttg (the sequence -O-CH(2)-CH(2)-O- having a trans (t) conformation about the -C-O- bond and a gauche (g) conformation about the -C-C- bond) and random conformations, respectively. These results indicate that recrystallizable water does not have a single specific water structure.

Molecular rotation-vibration dynamics of low-symmetric hydrate crystal in the terahertz region.

PubMed

Fu, Xiaojian; Wu, Hongya; Xi, Xiaoqing; Zhou, Ji

2014-01-16

The rotational and vibrational dynamics of molecules in copper sulfate pentahydrate crystal are investigated with terahertz dielectric spectra. It is shown that the relaxation-like dielectric dispersion in the low frequency region is related to the reorientation of water molecules under the driving of terahertz electric field, whereas the resonant dispersion can be ascribed to lattice vibration. It is also found that, due to the hydrogen-bond effect, the vibrational mode at about 1.83 THz along [-111] direction softens with decreasing temperature, that is, the crystal expands in this direction when cooled. On the contrary, the mode hardens in the direction perpendicular to [-111] during the cooling process. This contributes to the further understanding of the molecular structure and bonding features of hydrate crystals.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dong, Xiaohao, E-mail: xiaohao.dong@xfel.eu; Sinn, Harald, E-mail: harald.sinn@xfel.eu; Shu, Deming, E-mail: shu@aps.anl.gov

An artificial channel-cut crystal monochromator for the hard X-Ray beamlines of SASE 1&2, cryogenically cooled by the so-called pulse tube cooler (cryorefrigerator), is currently under development at the European XFEL ( http://www.xfel.eu/ ). The fabrication is on-going. We present here the crystal optical consideration and the novel cooling configuration, according to the X-Ray FEL pulses proprieties. The mechanical design improvements are pointed out as well to implement such kind of monochromator based on the previous similar design.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dong, Xiaohao; Shu, Deming; Sinn, Harald

An artificial channel-cut crystal monochromator for the hard X-Ray beamlines of SASE 1&2, cryogenically cooled by the so-called pulse tube cooler (cryorefrigerator), is currently under development at the European XFEL (http://www.xfel.eu/). The fabrication is on-going. We present here the crystal optical consideration and the novel cooling configuration, according to the X-Ray FEL pulses proprieties. The mechanical design improvements are pointed out as well to implement such kind of monochromator based on the previous similar design.

The Fe2(+)-Mg interdiffusion in orthopyroxene: Constraints from cation ordering and structural data and implications for cooling rates of meteorites

NASA Technical Reports Server (NTRS)

Ganguly, J.; Tazzoli, V.

1993-01-01

Orthopyroxene crystals in a number of meteorites exhibit compositional zoning of Fe and Mg, which provide important constraint on their cooling rates. However, attempts to model cooling rate of these crystals from Fe-Mg zoning profiles suffer from the lack of any measured or theoretically well constrained Fe-Mg interdiffusion data in OP(x) It has been assumed that Fe-Mg interdiffusion in OP(x) only slightly slower than that in olivine. The purpose of this paper is to (1) calculate the Fe-Mg fractionation, and (2) provide analytical formulation relating cooling rate to the length of the diffusion zone across the interface of the overgrowth of a mineral on itself with application to Mg diffusion profile across OP(x) growth on OP(x) in certain mesosiderites.

Ilchulbong tuff cone, Jeju Island, Korea, revisited: A compound monogenetic volcano involving multiple magma batches, shifting vents, and discrete eruptive phases

NASA Astrophysics Data System (ADS)

Sohn, Y.; Brenna, M.; Smith, I. E.; Nemeth, K.; White, J. D.; Murtagh, R.; Jeon, Y.; Kwon, C.; Cronin, S. J.

2010-12-01

Ilchulbong (Sunrise Peak) tuff cone is a UNESCO World Heritage site that owes its scientific importance to the outstanding coastal exposures that surround it. It is also one of the classic sites that provided the sedimentary evidence for the primary pyroclastic processes that occur during phreatomagmatic basaltic eruptions. It has been long considered, based on the cone morphology, that this classic cone was produced via eruption from a single vent site. Reanalysis of the detailed sedimentary sequence has now revealed that two subtle paraconformities occur in this deposition sequence, one representing a significant time break of perhaps days to weeks or months, during which erosion and compaction of the lower cone occurred, the conduit cooled and solidified and a subsequent resumption of eruption took place in a new vent location. Detailed geochemical study of the juvenile clasts through this cone reveals that three separate alkali basaltic magma batches were erupted, the first and third erupted may be genetically related, with the latter showing evidence for longer periods of shallow-level fractionation. The second magma batch erupted was generated in a different mantle source area. Reconstructing the eruption sequence, the lower Ilchulbong cone was formed by eruption of magma 1. Cessation of eruption was accompanied by erosion to generate a volcano-wide unconformity, associated with reworked deposits in the lower cone flanks. The eruption resumed with magma 2 that, due to the cooled earlier conduit, was forced to erupt in a new site to the west of the initial vent. This formed the middle cone sequence over the initially formed structure. The third magma batch erupted with little or no interval after magma 2 from the same vent location, associated with cone instability and slumping, and making up the deposits of the upper cone. These results demonstrate how critical the examination for sedimentary evidence for time breaks in such eruption sequences is for detecting potential shifts in eruption chemistry and vent location. It appears that if eruption breaks are short, successive magma batches follow the same path, whereas if pauses are greater than a critical period, conduit solidification will force vent migration for subsequent magma batches. This has important implications for examining the controls of vent migration at other monogenetic volcanoes and for emergency management planning during future similar types of eruptions.

Fracture mechanics and geochemical factors influencing the emplacement mechanisms of the Stewart Lithia gem bearing granitic pegmatite, Pala District, San Diego County, California

NASA Astrophysics Data System (ADS)

Patterson, Jeffrey E.

The emplacement mechanisms and cooling characteristics of pegmatites are not well understood, yet little work has been done on this subject. Historically, it is the pegmatite mineralogy and zonation that has been the focus of attention because of fascination with giant sized crystals, diversity of mineralization, and abundance of minerals containing important strategic elements, (Li, Be, Ta, Nb, and others). In this thesis the subject of the emplacement mechanisms is a synergistic approach from geophysical and engineering viewpoints, using the principals of fracture mechanics to determine the properties related to emplacement. From this, the cooling characteristics are considered to explain the zonation of a pegmatite based upon the temperature of crystallization of each mineral. This provides a model to image the position of each mineral according to the temperature profiles over time. Finally, the mineral growth characteristics are considered in light of the boundary conditions placed upon them by the cooling period. To test these hypothetical conditions in the real world, the Stewart Lithia Pegmatite, Pala, California, has been evaluated both physically and geochemically. The structure of the pegmatite was examined along strike and along dip, as exposed in underground workings. The analyses of these data show that there are 5 discreet divisions along strike. The analyses of the geochemical data for precisely located tourmalines shows that these divisions are composed of approximately 10 discreet pulses, with the economically important "Chimney Division" containing all 10. The importance of this work is that it demonstrates the following. A complex pegmatite is more likely to consist of multiple pulses of different melt composition than a single pulse with un-explainable mineralogy and zonation; Giant crystals are more likely due to rapid polymerization of a few mineral species where the cooling rate and crystallization rate are nearly equal; The range of mineral sizes to eleven orders of magnitude is due to the minimal rate of cooling, with the smallest crystals nucleating and not growing because there is no thermal differential driving force; and gem crystals generally only occur in fluid filled miarolitic cavities.

An ion microprobe study of the intra-crystalline behavior of REE and selected trace elements in pyroxene from mare basalts with different cooling and crystallization histories

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shearer, C.K.; Papike, J.J.; Simon, S.B.

1989-05-01

To study the effects of crystallization sequence and rate on trace element zoning characteristics of pyroxenes, the authors used combined electron microprobe-ion microprobe techniques on four nearly isochemical Apollo 12 and 15 pigeonite basalts with different cooling rates and crystallization histories. Major and minor element zoning characteristics are nearly identical to those reported in the literature. All the pyroxenes have similar chondrite-normalized REE patterns: negative Eu anomalies, positive slopes as defined by Yb/Ce, and slopes of REE patterns from Ce to Sm much steeper than from Gd to Yb. These trace element zoning characteristics in pyroxene and the partitioning ofmore » trace elements between pyroxene and the melt are intimately related to the interplay among the efficiency of the crystallization process, the kinetics at the crystal-melt interface, the kinetics of plagioclase nucleation and the characteristics of the crystal chemical substitutions within both the pyroxene and the associated crystallizing phases (i.e. plagioclase).« less

Hybrid Contactless Heating and Levitation

NASA Technical Reports Server (NTRS)

Lee, M. C.

1985-01-01

Acoustic and electromagnetic fields applied. In contactless processing apparatus, acoustic and electromagnetic levitating fields employed alternately or simultaneously with amplitude of each controlled to produce various combinations of heating, cooling, and levitation. Apparatus provides rapid heating and cooling or slow heating and cooling for such processes as nucleation, crystallization, incubation, deep undercooling, and heterogeneity control.

Biological treatment of thin-film transistor liquid crystal display (TFT-LCD) wastewater using aerobic and anoxic/oxic sequencing batch reactors.

PubMed

Lei, Chin-Nan; Whang, Liang-Ming; Chen, Po-Chun

2010-09-01

The amount of pollutants produced during manufacturing processes of thin-film transistor liquid crystal display (TFT-LCD) substantially increases due to an increasing production of the opto-electronic industry in Taiwan. This study presents the treatment performance of one aerobic and one anoxic/oxic (A/O) sequencing batch reactors (SBRs) treating synthetic TFT-LCD wastewater containing dimethyl sulfoxide (DMSO), monoethanolamine (MEA), and tetra-methyl ammonium hydroxide (TMAH). The long-term monitoring results for the aerobic and A/O SBRs demonstrate that stable biodegradation of DMSO, MEA, and TMAH can be achieved without any considerably adverse impacts. The ammonium released during MEA and TMAH degradation can also be completely oxidized to nitrate through nitrification in both SBRs. Batch studies on biodegradation rates for DMSO, MEA, and TMAH under anaerobic, anoxic, and aerobic conditions indicate that effective MEA degradation can be easily achieved under all three conditions examined, while efficient DMSO and TMAH degradation can be attained only under anaerobic and aerobic conditions, respectively. The potential odor problem caused by the formation of malodorous dimethyl sulfide from DMSO degradation under anaerobic conditions, however, requires insightful consideration in treating DMSO-containing wastewater. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

Physical and Chemical Microstructural Damage in Pressed CL-20 explosives

NASA Astrophysics Data System (ADS)

Demol, Gauthier; Sandusky, Harold W.

1999-06-01

Based upon its molecular composition, its structure, and its heat of formation, it was expected that CL-20 (hexanitrohexaazaisowurtzitane) would be more energetic and more sensitive than RDX and HMX. Reports of batch-to-batch variations in the sensitivity of neat CL-20 have led to its sensitivity being ranked in the range between the sensitivity of RDX and that of PETN. The ultimate utility of CL-20 as an ingredient in explosive and propellant formulations will depend upon the ability to understand the factors that are responsible for this batch-to-batch variability, and to control the sensitivity in formulations within acceptable limits. This work is a characterization of CL-20 at various stages in its life cycle. The evolution of damage from the initial neat crystals of CL-20 to the ready-to-use pressed pellets will be described. This characterization includes physical documentation using light microscopy and Scanning Electron Microscopy. Spatially resolved chemical analysis is also performed using Fourier-Transform Infrared Spectroscopy.

Inorganic fouling mitigation by salinity cycling in batch reverse osmosis.

PubMed

Warsinger, David M; Tow, Emily W; Maswadeh, Laith A; Connors, Grace B; Swaminathan, Jaichander; Lienhard V, John H

2018-06-15

Enhanced fouling resistance has been observed in recent variants of reverse osmosis (RO) desalination which use time-varying batch or semi-batch processes, such as closed-circuit RO (CCRO) and pulse flow RO (PFRO). However, the mechanisms of batch processes' fouling resistance are not well-understood, and models have not been developed for prediction of their fouling performance. Here, a framework for predicting reverse osmosis fouling is developed by comparing the fluid residence time in batch and continuous (conventional) reverse osmosis systems to the nucleation induction times for crystallization of sparingly soluble salts. This study considers the inorganic foulants calcium sulfate (gypsum), calcium carbonate (calcite), and silica, and the work predicts maximum recovery ratios for the treatment of typical water sources using batch reverse osmosis (BRO) and continuous reverse osmosis. The prediction method is validated through comparisons to the measured time delay for CaSO 4 membrane scaling in a bench-scale, recirculating reverse osmosis unit. The maximum recovery ratio for each salt solution (CaCO 3 , CaSO 4 ) is individually predicted as a function of inlet salinity, as shown in contour plots. Next, the maximum recovery ratios of batch and conventional RO are compared across several water sources, including seawater, brackish groundwater, and RO brine. Batch RO's shorter residence times, associated with cycling from low to high salinity during each batch, enable significantly higher recovery ratios and higher salinity than in continuous RO for all cases examined. Finally, representative brackish RO brine samples were analyzed to determine the maximum possible recovery with batch RO. Overall, the induction time modeling methodology provided here can be used to allow batch RO to operate at high salinity and high recovery, while controlling scaling. The results show that, in addition to its known energy efficiency improvement, batch RO has superior inorganic fouling resistance relative to conventional RO. Copyright © 2018 Elsevier Ltd. All rights reserved.

Crystallization of lithium borate glasses

NASA Technical Reports Server (NTRS)

Goktas, A. A.; Neilson, G. F.; Weinberg, M. C.

1992-01-01

The glass-forming ability and crystallization behavior of lithium borate compositions, in the diborate-to-metaborate-range, were studied. In particular, the nature and sequence of formation of crystalline phases and the tendency toward devitrification were investigated as functions of temperature, thermal history and batch composition. It was found that the sequence of crystalline phase formation was sensitive to all of the three latter factors, and it was observed that under certain conditions metastable defect structures of the metaborate can appear.

Scanning electron microscope view of iron crystal

NASA Technical Reports Server (NTRS)

1972-01-01

A scanning electron microscope photograph of iron crystals which grow in a small vug or cavity in a recrystallized breccia (fragmented rock) from the Apollo 15 Hadley-Apennino lunar landing site. The largest crystal is three microns across. Perfectly developed crystals such as these indicate slow formation from a hot vapor as the rock was cooling. The crystals are resting on an interlocking lattice of pyroxene (calsium-magnesium-iron silicate).

Scanning electron microscope view of iron crystal

NASA Image and Video Library

1972-11-10

A scanning electron microscope photograph of iron crystals which grow in a small vug or cavity in a recrystallized breccia (fragmented rock) from the Apollo 15 Hadley-Apennino lunar landing site. The largest crystal is three microns across. Perfectly developed crystals such as these indicate slow formation from a hot vapor as the rock was cooling. The crystals are resting on an interlocking lattice of pyroxene (calsium-magnesium-iron silicate).

SBIR Grant:No-Vibration Agile Cryogenic Optical Refrigerator

DOE Office of Scientific and Technical Information (OSTI.GOV)

Epstein, Richard

2013-04-09

Optical refrigeration is currently the only all-solid-state cryocooling technology that has been demonstrated. Optical cryocoolers are devices that use laser light to cool small crystal or glass cooling elements. The cooling element absorbs the laser light and reradiates it at higher energy, an example of anti-Stokes fluorescence. The dif-ference between the energy of the outgoing and incoming light comes from the thermal energy of the cooling element, which in turn becomes colder. Entitled No-Vibration Agile Cryocoolers using Optical Refrigeration, this Phase I proposal directly addressed the continued development of the optical refrigerator components necessary to transition this scientific breakthrough intomore » National Nu-clear Security Administration (NNSA) sensor applications in line with the objectives of topic 50b. ThermoDynamic Films LLC (TDF), in collaboration with the University of New Mexico (UNM), cooled an optical-refrigerator cooling element comprised of an ytterbium-doped yttrium lithium fluoride (Yb:YLF) crystal from room tempera-ture to 123 K with about 2% efficiency. This is the world record in optical refrigera-tion and an important step toward revolutionizing cryogenic systems for sensor ap-plications. During this period, they also designed and analyzed the crucial elements of a prototype optical refrigerator including the thermal link that connects the cool-ing element with the load.« less

The effect of oxygen fugacity on the rheological evolution of crystallizing basaltic melts

NASA Astrophysics Data System (ADS)

Kolzenburg, S.; Di Genova, D.; Giordano, D.; Hess, K. U.; Dingwell, D. B.

2018-04-01

Storage and transport of silicate melts in the Earth's crust and their emplacement on the planet's surface occur almost exclusively at sub-liquidus temperatures. At these conditions, the melts undergo crystallization under a wide range of cooling-rates, deformation-rates, and oxygen fugacities (fO2). Oxygen fugacity is known to influence the thermodynamics and kinetics of crystallization in magmas and lavas. Yet, its influence on sub-liquidus rheology remains largely uncharted. We present the first rheological characterization of crystallizing lavas along natural cooling paths and deformation-rates and at varying fO2. Specifically, we report on apparent viscosity measurements for two crystallizing magmatic suspensions 1) at log ⁡ fO2 of -9.15 (quartz-fayalite-magnetite buffer, QFM, -2.1) and 2) in air. These fugacities span a range of reduced to oxidized conditions pertinent to magma migration and lava emplacement. We find that: 1) crystallization at constant cooling-rates results in a quasi-exponential increase in the apparent viscosity of the magmatic suspensions until they achieve their rheological cut off temperature (Tcutoff), where the melt effectively solidifies 2) the rheological departure and Tcutoff increase with increasing fO2 and 3) increasing fO2 results in decreased crystallization-rates. Based on the experimental results and by comparison with previous rheological isothermal studies we propose a generalisation of the effect of fO2 on the dynamic rheological evolution of natural magmatic and volcanic suspensions. We further discuss the implications for magmatic transport in plumbing and storage systems (e.g. conduits, dikes and magma chambers) and during lava flow emplacement.

Towards integrated drug substance and drug product design for an active pharmaceutical ingredient using particle engineering.

PubMed

Kougoulos, Eleftherios; Smales, Ian; Verrier, Hugh M

2011-03-01

A novel experimental approach describing the integration of drug substance and drug production design using particle engineering techniques such as sonocrystallization, high shear wet milling (HSWM) and dry impact (hammer) milling were used to manufacture samples of an active pharmaceutical ingredient (API) with diverse particle size and size distributions. The API instability was addressed using particle engineering and through judicious selection of excipients to reduce degradation reactions. API produced using a conventional batch cooling crystallization process resulted in content uniformity issues. Hammer milling increased fine particle formation resulting in reduced content uniformity and increased degradation compared to sonocrystallized and HSWM API in the formulation. To ensure at least a 2-year shelf life based on predictions using an Accelerated Stability Assessment Program, this API should have a D [v, 0.1] of 55 μm and a D [v, 0.5] of 140 μm. The particle size of the chief excipient in the drug product formulation needed to be close to that of the API to avoid content uniformity and stability issues but large enough to reduce lactam formation. The novel methodology described here has potential for application to other APIs. © 2011 American Association of Pharmaceutical Scientists

TRANSVERSE MODE ELECTRO-OPTIC MATERIALS.

DTIC Science & Technology

electro - optic modulators presently used are crystals such as KDP which exhibit a longitudinal electro - optic effect. It has been demonstrated that a more efficient modulator can be produced when a crystal having a transverse electro - optic effect is employed. Generally these crystals are produced either from the melt or from fluxes. Since melt grown crystals must be cooled through several hundred degrees and often must undergo phase transitions, these crystals are generally highly strained. Flux grown crystals are also

Comparative analysis of thermal behavior, isothermal crystallization kinetics and polymorphism of palm oil fractions.

PubMed

Zhang, Xia; Li, Lin; Xie, He; Liang, Zhili; Su, Jianyu; Liu, Guoqin; Li, Bing

2013-01-15

Thermal behavior of palm stearin (PS) and palm olein (PO) was explored by monitoring peak temperature transitions by differential scanning calorimetry (DSC). The fatty acid composition (FAC), isothermal crystallization kinetics studied by pulsed Nuclear Magnetic Resonance (pNMR) and isothermal microstructure were also compared. The results indicated that the fatty acid composition had an important influence on the crystallization process. PS and PO both exhibited more multiple endotherms than exotherms which showed irregular peak shapes. An increasing in cooling rate, generally, was associated with an increase in peak size. Application of the Avaimi equation to isothermal crystallization of PS and PO revealed different nucleation and growth mechanisms based on the Avrami exponents. PS quickly reached the end of crystallization because of more saturated triacylglycerol (TAG). The Avrami index of PS were the same as PO under the same isothermal condition at lower temperatrue, indicating that the crystallization mechanism of the two samples based on super-cooling state were the same. According to the polarized light microscope (PLM) images, crystal morphology of PS and PO was different. With the temperature increased, the structure of crystal network of both PS and PO gradually loosened.

Crystal Nucleation Using Surface-Energy-Modified Glass Substrates.

PubMed

Nordquist, Kyle A; Schaab, Kevin M; Sha, Jierui; Bond, Andrew H

2017-08-02

Systematic surface energy modifications to glass substrates can induce nucleation and improve crystallization outcomes for small molecule active pharmaceutical ingredients (APIs) and proteins. A comparatively broad probe for function is presented in which various APIs, proteins, organic solvents, aqueous media, surface energy motifs, crystallization methods, form factors, and flat and convex surface energy modifications were examined. Replicate studies ( n ≥ 6) have demonstrated an average reduction in crystallization onset times of 52(4)% (alternatively 52 ± 4%) for acetylsalicylic acid from 91% isopropyl alcohol using two very different techniques: bulk cooling to 0 °C using flat surface energy modifications or microdomain cooling to 4 °C from the interior of a glass capillary having convex surface energy modifications that were immersed in the solution. For thaumatin and bovine pancreatic trypsin, a 32(2)% reduction in crystallization onset times was demonstrated in vapor diffusion experiments ( n ≥ 15). Nucleation site arrays have been engineered onto form factors frequently used in crystallization screening, including microscope slides, vials, and 96- and 384-well high-throughput screening plates. Nucleation using surface energy modifications on the vessels that contain the solutes to be crystallized adds a layer of useful variables to crystallization studies without requiring significant changes to workflows or instrumentation.

Device for isolation of seed crystals during processing of solution

DOEpatents

Montgomery, K.E.; Zaitseva, N.P.; Deyoreo, J.J.; Vital, R.L.

1999-05-18

A device is described for isolation of seed crystals during processing of solutions. The device enables a seed crystal to be introduced into the solution without exposing the solution to contaminants or to sources of drying and cooling. The device constitutes a seed protector which allows the seed to be present in the growth solution during filtration and overheating operations while at the same time preventing the seed from being dissolved by the under saturated solution. When the solution processing has been completed and the solution cooled to near the saturation point, the seed protector is opened, exposing the seed to the solution and allowing growth to begin. 3 figs.

Relationships between molecular structure and kinetic and thermodynamic controls in lipid systems. Part III. Crystallization and phase behavior of 1-palmitoyl-2,3-stearoyl-sn-glycerol (PSS) and tristearoylglycerol (SSS) binary system.

PubMed

Bouzidi, Laziz; Narine, Suresh S

2012-01-01

The phase behavior of 1-palmitoyl-2,3-distearoyl-sn-glycerol (PSS)/tristearoylglycerol (SSS) binary system was investigated in terms of polymorphism, crystallization and melting behavior, microstructure and solid fat content (SFC) using widely different constant cooling rates. Kinetic phase diagrams were experimentally determined from the DSC heating thermograms and analyzed using a thermodynamic model to account for non-ideality of mixing. The kinetic phase diagram presented a typical eutectic behavior with a eutectic point at the 0.5(PSS) mixture with a probable precipitation line from 0.5(PSS) to 1.0(PSS), regardless of the rate at which the sample was cooled. The eutectic temperature decreased only slightly with increasing cooling rate. PSS has a strong effect on the physical properties of the PSS-SSS mixtures. In fact, the overall phase behavior of the PSS-SSS binary system was determined, for a very large part, by the asymmetrical TAG. Moreover, PSS is a key driver of the high stability observed in crystal growth, polymorphism and phase development. Levels as low as 10% PSS, when cooled slowly, and 30% when cooled rapidly, were found to be sufficient to suppress the effect of thermal processing. Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.

The Vitrification and Determination of the Crystallization Time Scales of a Zr58.5Nb2.8Cu15.6Ni12.8Al10.3 Bulk Metallic Glass Forming Liquid

NASA Technical Reports Server (NTRS)

Hays, C. C.; Schroers, J.; Johnson, W. L.; Rathz, T. J.; Hyers, R. W.; Rogers, J. R.; Robinson, M. B.; Whitaker, Ann F. (Technical Monitor)

2001-01-01

Zr58.5Nb2.8Cul5.6Nil2.8All0.3 is the first bulk glass forming liquid that does not contain beryllium to be vitrified by purely radiative cooling in the containerless electrostatic levitation process. The measured critical cooling rate is 1.75 K/s. The sluggish crystallization kinetics enable the determination of the time-temperature-transformation (TTT) diagram between the liquidus and the glass transition temperatures. At the nose of the TTT diagram, the shortest time to reach crystallization in an isothermal experiment is 32 seconds. In contrast to other bulk metallic glasses the scatter in the crystallization onset times are small at both high and low temperatures.

Experimental study of the rotational magnetocaloric effect in KTm(MoO4)2

NASA Astrophysics Data System (ADS)

Tarasenko, Róbert; Tkáč, Vladimír; Orendáčová, Alžbeta; Orendáč, Martin; Feher, Alexander

2018-06-01

An experimental study is presented of the rotational magnetocaloric effect in a KTm(MoO4)2 single crystal at temperatures above 2 K associated with the rotation of a single crystal between the magnetic easy and hard axis in constant magnetic fields up to 5 T. The magnetocaloric properties of KTm(MoO4)2 single crystals are investigated by isothermal magnetization measurements. The maximal rotational entropy change -ΔSR ≈ 9.8 J/(kgK) is achieved at 10 K in a magnetic field of 5 T. The adiabatic rotation of a single crystal in a field of 5 T at an initial temperature of 4.2 K causes cooling of the sample down to 0.5 K, which indicates an interesting possibility of using this material for cooling processes at low temperatures.

Disinfection of bacterial biofilms in pilot-scale cooling tower systems

PubMed Central

Liu, Yang; Zhang, Wei; Sileika, Tadas; Warta, Richard; Cianciotto, Nicholas P.; Packman, Aaron I.

2015-01-01

The impact of continuous chlorination and periodic glutaraldehyde treatment on planktonic and biofilm microbial communities was evaluated in pilot-scale cooling towers operated continuously for 3 months. The system was operated at a flow rate of 10,080 l day−1. Experiments were performed with a well-defined microbial consortium containing three heterotrophic bacteria: Pseudomonas aeruginosa, Klebsiella pneumoniae and Flavobacterium sp. The persistence of each species was monitored in the recirculating cooling water loop and in biofilms on steel and PVC coupons in the cooling tower basin. The observed bacterial colonization in cooling towers did not follow trends in growth rates observed under batch conditions and, instead, reflected differences in the ability of each organism to remain attached and form biofilms under the high-through flow conditions in cooling towers. Flavobacterium was the dominant organism in the community, while P. aeruginosa and K. pneumoniae did not attach well to either PVC or steel coupons in cooling towers and were not able to persist in biofilms. As a result, the much greater ability of Flavobacterium to adhere to surfaces protected it from disinfection, whereas P. aeruginosa and K. pneumoniae were subject to rapid disinfection in the planktonic state. PMID:21547755

Disinfection of bacterial biofilms in pilot-scale cooling tower systems.

PubMed

Liu, Yang; Zhang, Wei; Sileika, Tadas; Warta, Richard; Cianciotto, Nicholas P; Packman, Aaron I

2011-04-01

The impact of continuous chlorination and periodic glutaraldehyde treatment on planktonic and biofilm microbial communities was evaluated in pilot-scale cooling towers operated continuously for 3 months. The system was operated at a flow rate of 10,080 l day(-1). Experiments were performed with a well-defined microbial consortium containing three heterotrophic bacteria: Pseudomonas aeruginosa, Klebsiella pneumoniae and Flavobacterium sp. The persistence of each species was monitored in the recirculating cooling water loop and in biofilms on steel and PVC coupons in the cooling tower basin. The observed bacterial colonization in cooling towers did not follow trends in growth rates observed under batch conditions and, instead, reflected differences in the ability of each organism to remain attached and form biofilms under the high-through flow conditions in cooling towers. Flavobacterium was the dominant organism in the community, while P. aeruginosa and K. pneumoniae did not attach well to either PVC or steel coupons in cooling towers and were not able to persist in biofilms. As a result, the much greater ability of Flavobacterium to adhere to surfaces protected it from disinfection, whereas P. aeruginosa and K. pneumoniae were subject to rapid disinfection in the planktonic state.

Features of changes in electrophysical properties of silicon under the influence of thermal treatment

NASA Astrophysics Data System (ADS)

Gaidar, G. P.; Baranskii, P. I.

2018-06-01

The influence of the annealing temperatures and cooling rates of n-silicon crystals, grown by the Czochralski method and doped with phosphorus impurity, on their electric and thermoelectric properties was studied. In the region of predominantly impurity scattering a more essential dependence of the charge carrier mobility on the cooling conditions of crystals was established in comparison with the dependence on the annealing temperature. The analysis of the measurement results of tensoresistance and tenso-thermo-emf was carried out, on the basis of which the dependence of the anisotropy parameter of drag thermo-emf on the cooling rate was obtained. The feature of the anisotropy parameter of thermo-emf M in the form of its maximal deviation from the linear dependence M = M(lg(υcl)) was revealed in the region of cooling rates from 8 to 15 K/min.

White and gray pumice in pyroclastic deposits. (Invited)

NASA Astrophysics Data System (ADS)

Wright, H. M.; Cashman, K. V.

2013-12-01

Many primary pyroclastic deposits contain at least two different colors of pumice, including volumetrically dominant white and subordinate gray. White pumice is vesicular, microlite-free, and in most cases represents direct samples of the principal magma reservoir. In contrast, subordinate gray pumice with lower vesicularity and/or more abundant microlites may sample either deep recharge OR shallow vanguard magma, where both may record information on eruption triggers. Pumice may appear gray for several reasons: 1. Gray pumice has a less-evolved bulk composition than white pumice. Presence of less-evolved (generally deep-derived) magma provides information about possible recharge magma and/or pre-eruptive compositional variation in the magma storage region. A well-known example of this difference is the 1912 eruption of Novarupta [Hildreth & Fierstein, 2012], which includes white (rhyolite) and gray (andesite and dacite) pumice. 2. Gray pumice contains elevated microlite number densities and/or microlite crystallinities and is compositionally similar to white pumice. a. Gray pumice contains abundant broken crystal fragments and lithic fragments. Broken crystals and incorporated white pumice indicate passage through the primary magma reservoir. Incorporated lithic fragments indicate breakage of wall rock and creation of new transport pathways. Microlites and breadcrusted surfaces indicate slow and/or episodic ascent at shallow levels. This textural association indicates that proto-gray pumice magma played an active role in creating a conduit to the surface. In some cases, small differences in chemistry may further indicate differences in magma batches (recharge pulses). This textural variation is found in the products of high-crystallinity large-volume (Plinian or boil-over style) eruptions, as in the Cerro Galan Ignimbrite, Argentina [Wright et al., 2011]. b. Gray pumice contains abundant microlites due to differences in decompression and/or cooling history. In this case, microlites indicate shallow degassing-induced crystallization, where proto-gray pumice forms vanguard magma or a shallow conduit plug. Gray pumice originating in a shallow conduit plug is common in Vulcanian and subPlinian silicic eruptions and is seen in the 1980 Plinian and subPlinian eruptions of Mount St. Helens [Klug & Cashman, 1994; Cashman & McConnell, 2005]. c. Gray pumice may record syn-eruptive changes in the magmatic system, often manifested as crystallization caused by either decompression or cooling [cf., Gurioli et al., 2005; Andrews & Gardner, 2010]. In summary, the compositional and textural complexities of gray pumice provide detail on pre- and syn-eruptive magmatic processes that may be impossible to obtain from (dominant) white pumice alone. Subtle compositional variations may characterize melts available to recharge and destabilize the upper magma reservoir, whereas crystal textures and compositions can be compared with experimental data to infer shallow magma ascent associated with conduit formation prior to climatic activity. Thus, analysis of gray pumice in pyroclastic deposits can yield new insight into the dynamics of eruptive processes.

Semiconductor-to-metal phase change in MoTe2 layers (Conference Presentation)

NASA Astrophysics Data System (ADS)

Davydov, Albert V.; Krylyuk, Sergiy; Kalish, Irina; Meshi, Louisa; Beams, Ryan; Kalanyan, Berc; Sharma, Deepak K.; Beck, Megan; Bergeron, Hadallia; Hersam, Mark C.

2016-09-01

Molybdenum ditelluride (MoTe2), which can exist in a semiconducting prismatic hexagonal (2H) or a metallic distorted octahedral (1T') phases, is one of the very few materials that exhibit metal-semiconductor transition. Temperature-driven 2H - 1T' phase transition in bulk MoTe2 occurs at high temperatures (above 900 °C) and it is usually accompanied by Te loss. The latter can exacerbate the control over reversibility of the phase transition. Here, we study effects of high-temperature annealing on phase transition in MoTe2 single crystals. First, MoTe2 were grown in sealed evacuated quartz ampoules from polycrystalline MoTe2 powder in an iodine-assisted chemical vapor transport process at 1000 °C. The 2H and 1T' phases were stabilized by controlling the cooling rate after the growth. In particular, slow cooling at 10 °C/h rate yielded the 2H phase whereas the 1T' phase was stabilized by ice-water quenching. Next, the phase conversion was achieved by annealing MoTe2 single crystals in vacuum-sealed ampoules at 1000 °C with or without additional poly-MoTe2 powder followed by fast or slow cooling. Similarly to the CVT growth, slow cooling and quenching consistently produced 2H and 1T' phases, respectively, regardless of the initial MoTe2 crystal structure. We will discuss structural and optical properties of the as-grown and phase-converted MoTe2 single crystals using TEM, SEM/EDS, XRD, XPS and Raman. Electrical characteristics of two-terminal devices made from metallic 1T' and bottom-gated FETs made from 2H exfoliated crystals will also be presented.

Vapor Saturation as The Cause of Volcanic Eruptions at the Lassen Volcanic Center, California, as Inferred from Crystallization Pressures and Temperatures

NASA Astrophysics Data System (ADS)

De Los Reyes, A. M. A.; Putirka, K. D.; Clynne, M. A.; Scruggs, M. A.

2015-12-01

The last three silicic eruptions at the Lassen Volcanic Center occurred at Lassen Peak (27 ka and 1915-17) and Chaos Crags (1103 yrs BP). Klemetti and Clynne (2014) showed that felsic eruptions at Lassen reflect remobilization of resident rhyodacitic crystal mush by intrusion of mafic magma. To better understand the rejuvenation and eruption triggering process, we calculate crystallization temperatures and pressures from clinopyroxene-liquid equilibria on mafic enclaves that provide our closest approach to the composition of mafic magmas delivered to the shallow system. Our goal is to examine whether and to what extent cooling and crystallization occur after recharge, which bears on whether recharge, mixing, or partial crystallization (and consequent vapor saturation) provide the trigger for eruption. We use results from the cpx-liq barometer (1.7 kbar) as input to calculate T for other phases (plagioclase, olivine and amphibole) found in mafic enclave samples. Cpx crystallizes at 1100-1150 oC and olivine precipitates at similar to slightly higher temperatures. Cpx and ol are followed by plagioclase (1000-1050 oC), amphibole (875-1000 oC), and Fe-Ti oxides (1030-1050 oC). These temperatures indicate that recharge magmas are incompletely crystallized as they enter the shallow reservoir of cooler (~725-750 oC, Quinn et al., 2013) felsic crystal mush, and that significant cooling of the mafic magma occurs during mixing and prior to eruption. Such cooling intervals indicate that recharge is not the proximal cause of eruption, but rather that vapor saturation, following a period of mixing and cooling, leads to increased magma overpressure that causes eruption. Interestingly, the Lassen Peak 27 ka volcanics (at 2.09 km3), have a greater volume than either of Chaos Crags (1.2 km3) and the 1915 (0.03 km3) eruption, but our results indicate that their thermal histories are similar. This suggests that while volumes of mafic recharge may control the degree of interaction with felsic crystal mush (e.g., Clynne, 1999), and eventually the volume of erupted magma, recharge volumes do not affect eruption triggering mechanisms. Clynne MA (1999) J. Petrol, 40: 105-132.Klemetti and Clynne, 2014, PLoS One (/12:e113157. doi10.1371/journal.pone0113157)Quinn et al., 2013, AGU Fall Annual Meeting V23C-2848

Initiating Growth Of Crystals Away From Container Walls

NASA Technical Reports Server (NTRS)

Kroes, Roger L.; Reiss, Donald A.; Lehoczky, Sandor L.

1991-01-01

Nucleation controlled to obtain better crystals. In technique proposed specifically for growing large protein crystals in microgravity (where no thermal convection), small region of high supersaturation created by injection of hot concentrated solution or by use of cold probe. Crystals nucleate preferably in this small region. Also conceivable technique applied on Earth to crystallizations in melts and solutions sufficiently viscous to suppress convection to extent necessary to prevent cooling-induced nucleation in undesired sites.

INTERIOR VIEW SHOWING FURNACE KEEPER OBSERVING FURNACE THROUGH BLUE GLASS ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

INTERIOR VIEW SHOWING FURNACE KEEPER OBSERVING FURNACE THROUGH BLUE GLASS EVERY TWENTY MINUTES TO DETERMINE SIZE AND TEXTURE OF BATCH AND OTHER VARIABLES. FAN IN FRONT COOLS WORKERS AS THEY CONDUCT REPAIRS. FURNACE TEMPERATURE AT 1572 DEGREES FAHRENHEIT. - Chambers-McKee Window Glass Company, Furnace No. 2, Clay Avenue Extension, Jeannette, Westmoreland County, PA

'Nose method' of calculating critical cooling rates for glass formation

NASA Technical Reports Server (NTRS)

Weinberg, Michael C.; Uhlmann, Donald R.; Zanotto, Edgar D.

1989-01-01

The use of the so-called 'nose method' for computing critical cooling rates for glass formation is examined and compared with other methods, presenting data for the glass-forming systems SiO2, GeO2, and P2O5. It is shown that, for homogeneous crystallization, the nose-method will give an overestimate of Rc, a conclusion which was drawn after assessing the enfluence of a range of values for the parameters which control crystal growth and nucleation. The paper also proposes an alternative simple procedure (termed the 'cutoff method') for computing critical cooling rates from T-T-T diagrams, which was shown in the SiO2 and GeO2 systems to be superior to the nose method.

Controlled In Meso Phase Crystallization – A Method for the Structural Investigation of Membrane Proteins

PubMed Central

Kubicek, Jan; Schlesinger, Ramona; Baeken, Christian; Büldt, Georg; Schäfer, Frank; Labahn, Jörg

2012-01-01

We investigated in meso crystallization of membrane proteins to develop a fast screening technology which combines features of the well established classical vapor diffusion experiment with the batch meso phase crystallization, but without premixing of protein and monoolein. It inherits the advantages of both methods, namely (i) the stabilization of membrane proteins in the meso phase, (ii) the control of hydration level and additive concentration by vapor diffusion. The new technology (iii) significantly simplifies in meso crystallization experiments and allows the use of standard liquid handling robots suitable for 96 well formats. CIMP crystallization furthermore allows (iv) direct monitoring of phase transformation and crystallization events. Bacteriorhodopsin (BR) crystals of high quality and diffraction up to 1.3 Å resolution have been obtained in this approach. CIMP and the developed consumables and protocols have been successfully applied to obtain crystals of sensory rhodopsin II (SRII) from Halobacterium salinarum for the first time. PMID:22536388

The role of superheating in the formation of Glass Mountain obsidians (Long Valley, CA) inferred through crystallization of sanidine

NASA Astrophysics Data System (ADS)

Waters, Laura E.; Andrews, Benjamin J.

2016-10-01

The Glass Mountain obsidians (Long Valley, CA) are crystal poor (<8 vol%) and highly evolved (high SiO2, low Sr), and therefore, their formation required extremely efficient separation of melts from a crystal-rich source. A petrologic and experimental investigation of the mineral phases in Glass Mountain lavas identifies conditions under which phenocrysts grew and the driving mechanism for crystallization, which places constraints on the possible processes that generated the obsidians. The obsidian in this study (GM-11) is saturated in nine phases (sanidine + quartz + plagioclase + titanomagnetite + ilmenite + zircon + apatite + allanite + biotite), and results of high-resolution SEM compositional mapping and electron microprobe analysis reveal that individual sanidine crystals are normally zoned and span a range of compositions (Or40-78). Sanidines have a "granophyric" texture, characterized by intergrowths of quartz and sanidine. Mineral phases in the natural sample are compared to H2O-saturated phase equilibrium experiments conducted in cold-seal pressure vessels, over a range of conditions (700-850 °C; 75-225 MPa), and all are found to be plausible phenocrysts. Comparison of sanidine compositions from the natural sample with those grown in phase equilibrium experiments demonstrates that sanidine in the natural sample occurs in a reduced abundance. Further comparison with phase equilibrium experiments suggests that sanidine compositions track progressive loss of dissolved melt water (±cooling), suggesting that crystallization in the natural obsidian was driven predominantly by degassing resulting from decompression. It is paradoxical that an effusively (slowly) erupted lava should contain multiple phenocryst phases, including sanidine crystals that span a range of compositions with granophyric textures, and yet remain so crystal poor. To resolve this paradox, it is necessary that the solidification mechanism (degassing or cooling) that produced the sanidine crystals (and other mineral phases) must have an associated kinetic effect(s) that efficiently hinders crystal nucleation and growth. Decompression experiments conducted in this study and from the literature collectively demonstrate that the simplest way to inhibit nucleation during degassing-induced crystallization is to initiate degassing ± cooling from superliquidus conditions, and therefore, the Glass Mountain obsidians were superheated prior to crystallization.

Solid state crystal physics at very low temperatures

NASA Technical Reports Server (NTRS)

Davis, W.; Krack, K.; Richard, J. P.; Weber, J.

1980-01-01

The properties of nearly perfect crystals was studied at cryogenic temperatures. A large Helium 3 and Helium 4 dilution refrigerator has been assembled, and is described. A cryostat suitable for cooling a 35 liter volume to .020 Kelvin was designed and constructed, together with instrumentation to observe the properties of nearly perfect crystals.

Destabilization of mayonnaise induced by lipid crystallization upon freezing.

PubMed

Miyagawa, Yayoi; Ogawa, Takenobu; Nakagawa, Kyuya; Adachi, Shuji

2016-01-01

The thermal and rheological history of mayonnaise during freezing and its dispersion stability after the freeze-thaw process were investigated. Mayonnaise was cooled to freeze and stored at -20 to -40 °C while monitoring the temperature; penetration tests were conducted on the mayonnaise, which was sampled at selected times during isothermal storage at -20 °C. Significant increases in the temperature and stress values due to water-phase crystallization and subsequent oil-phase crystallization were observed. The water phase crystallized during the cooling step in all the tested mayonnaise samples. The oil phases of the prepared mayonnaise (with rapeseed oil) and commercial mayonnaise crystallized during isothermal storage after 6 and 4 h, respectively, at -20 °C. The dispersion stability was evaluated from the separation ratio, which was defined as the weight ratio of separated oil after centrifuging to the total amount of oil in the commercial mayonnaise. The separation ratio rapidly increased after 4 h of freezing. This result suggests that crystallization of the oil phase is strongly related to the dispersion stability of mayonnaise.

Laser Cooling of 2-6 Semiconductors

DTIC Science & Technology

2016-08-12

practical optical refrigeration . The challenge is the stoichiometric defect in bulk crystal which introduces mid-gap states that manifest as broad-band...cooling in semiconductor has stimulated strong interest in further scaling up towards practical optical refrigeration . The challenge is the...energy. The upconversion process is facilitated by the annihilation of phonons and leads to cooling of the matter. The concept of optical refrigeration

Rapid hydrothermal cooling above the axial melt lens at fast-spreading mid-ocean ridge

NASA Astrophysics Data System (ADS)

Zhang, Chao; Koepke, Juergen; Kirchner, Clemens; Götze, Niko; Behrens, Harald

2014-09-01

Axial melt lenses sandwiched between the lower oceanic crust and the sheeted dike sequences at fast-spreading mid-ocean ridges are assumed to be the major magma source of oceanic crust accretion. According to the widely discussed ``gabbro glacier'' model, the formation of the lower oceanic crust requires efficient cooling of the axial melt lens, leading to partial crystallization and crystal-melt mush subsiding down to lower crust. These processes are believed to be controlled by periodical magma replenishment and hydrothermal circulation above the melt lens. Here we quantify the cooling rate above melt lens using chemical zoning of plagioclase from hornfelsic recrystallized sheeted dikes drilled from the East Pacific at the Integrated Ocean Drilling Program Hole 1256D. We estimate the cooling rate using a forward modelling approach based on CaAl-NaSi interdiffusion in plagioclase. The results show that cooling from the peak thermal overprint at 1000-1050°C to 600°C are yielded within about 10-30 years as a result of hydrothermal circulation above melt lens during magma starvation. The estimated rapid hydrothermal cooling explains how the effective heat extraction from melt lens is achieved at fast-spreading mid-ocean ridges.

Liquid nitrogen dewar for protein crystal growth

NASA Technical Reports Server (NTRS)

2001-01-01

Gaseous Nitrogen Dewar apparatus developed by Dr. Alex McPherson of the University of California, Irvine for use aboard Mir and the International Space Station allows large quantities of protein samples to be crystallized in orbit. The specimens are contained either in plastic tubing (heat-sealed at each end). Biological samples are prepared with a precipitating agent in either a batch or liquid-liquid diffusion configuration. The samples are then flash-frozen in liquid nitrogen before crystallization can start. On orbit, the Dewar is placed in a quiet area of the station and the nitrogen slowly boils off (it is taken up by the environmental control system), allowing the proteins to thaw to begin crystallization. The Dewar is returned to Earth after one to four months on orbit, depending on Shuttle flight opportunities. The tubes then are analyzed for crystal presence and quality

Experimental and textural constraints on mafic enclave formation in volcanic rocks

USGS Publications Warehouse

Coombs, M.L.; Eichelberger, J.C.; Rutherford, M.J.

2002-01-01

We have used experiments and textural analysis to investigate the process of enclave formation during magma mixing at Southwest Trident volcano, Alaska. Andesite enclaves are present throughout the four dacite lava flows produced by the eruption, and resemble mafic enclaves commonly found in other volcanic rocks. Our experiments replicate the pressure-temperature-time path taken by enclave-forming andesite magma as it is engulfed in dacite during magma mixing. Pressure and temperature information for the andesite and dacite are from [Coombs et al., Contrib. Mineral. Petrol. 140 (2000) 99-118]. The andesite was annealed at 1000??C, and then cooled to 890??C at rates of 110??C h1, 10??C h1 and 2??C h1. Once cooled to 890??C, andesite was held at this lower temperature from times ranging from 1 to 40 h. The andesite that was cooled at the slower rates of 2??C h1 and 10??C h1 most resembles enclave groundmass texturally and compositionally. Based on simple thermal calculations, these rates are more consistent with cooling of the andesite groundmass below an andesite-dacite interface than with cooling of enclave-sized spheres. If enclaves do crystallize as spheres, post-crystallization disaggregation must occur. Calculations using the MELTS algorithm [Ghiorso and Sack, Contrib. Mineral. Petrol. 119 (1995) 197-212] show that for incoming andesite to become less dense than the dacite to become less dense ???34 volume % of its groundmass must crystallize to undergo~18 volume % vesiculation; these values are similar to those determined for Southwest Trident enclaves. Thus such crystallization may lead to 'flotation' of enclaves and be a viable mechanism for enclave formation and dispersal. The residual melt in the cooling experiments did not evolve to rhyolitic compositions such as seen in natural enclaves due to a lack of a decompression step in the experiments. Decompression experiments on Southwest Trident dacite suggest an average ascent rate for the eruption of ???2-3 MPa h1. An andesite experiment that was cooled and then decompressed at this rate contains melt that matches that of the natural enclaves. It is apparent that decompression (ascent)-induced crystallization occurs in enclaves, but not in the form of microlites as happens in the dacite host, due either to insufficient residence time at chamber temperatures or to the pre-existing microphenocrysts which act as sites for new growth. ?? 2002 Elsevier Science B.V. All rights reserved.

Bulk formation of a metallic glass - Pd40Ni40P20

NASA Technical Reports Server (NTRS)

Drehman, A. J.; Greer, A. L.; Turnbull, D.

1982-01-01

Molten spheroids of Pd40Ni40P20, of up to 0.53-cm minor diameter, were slowly cooled (1.4 K/s) on a fused silica surface under 10 to the -6 torr vacuum to a form which was entirely glassy except for some superficial crystallinity comprising less than 0.5% of the volume. The occurrence of crystallization was eliminated by subjecting the specimens to surface etching followed by a succession of heating and cooling cycles. The absence of crystallization in bulk was confirmed by X-ray diffraction, transmission electron microscopy, and calorimetry. Using the last technique, the heat of crystallization of the glass was measured to be 5.3 + or - 0.3 kJ/g atom.

On the possibility of laser cooling of Cr3+ ions doped crystals

NASA Astrophysics Data System (ADS)

Feofilov, S. P.; Kulinkin, A. B.

2018-01-01

The fluorescence of Cr3+ ions doped insulating crystals was studied under the excitation in the long-wavelength tail of the absorption spectrum ("laser cooling regime"). The 4T2 - 4A2 and 2E - 4A2 fluorescence spectra with a dominant anti-Stokes component were observed. Though no optical refrigeration was detected in the presented experiments, the spectroscopic results suggest that electron-phonon bands of Cr3+ ions are of interest for further investigations from the point of view of achieving optical refrigeration.

Compositional zoning of the bishop tuff

USGS Publications Warehouse

Hildreth, W.; Wilson, C.J.N.

2007-01-01

Compositional data for >400 pumice clasts, organized according to eruptive sequence, crystal content, and texture, provide new perspectives on eruption and pre-eruptive evolution of the >4600 km3 of zoned rhyolitic magma ejected as the BishopTuff during formation of Long Valley caldera. Proportions and compositions of different pumice types are given for each ignimbrite package and for the intercalated plinian pumice-fall layers that erupted synchronously. Although withdrawal of the zoned magma was less systematic than previously realized, the overall sequence displays trends toward greater proportions of less evolved pumice, more crystals (0-5 24 wt %), and higher FeTi-oxide temperatures (714-818??C). No significant hiatus took place during the 6 day eruption of the BishopTuff, nearly all of which issued from an integrated, zoned, unitary reservoir. Shortly before eruption, however, the zoned melt-dominant portion of the chamber was invaded by batches of disparate lower-silica rhyolite magma, poorer in crystals than most of the resident magma but slightly hotter and richer in Ba, Sr, andTi. Interaction with resident magma at the deepest levels tapped promoted growth ofTi-rich rims on quartz, Ba-rich rims on sanidine, and entrapment of near-rim melt inclusions relatively enriched in Ba and CO2.Varied amounts of mingling, even in higher parts of the chamber, led to the dark gray and swirly crystal-poor pumices sparsely present in all ashflow packages. As shown by FeTi-oxide geothermometry, the zoned rhyolitic chamber was hottest where crystal-richest, rendering any model of solidification fronts at the walls or roof unlikely.The main compositional gradient (75-195 ppm Rb; 0.8-2.2 ppm Ta; 71-154 ppm Zr; 0.40-1.73% FeO*) existed in the melt, prior to crystallization of the phenocryst suite observed, which included zircon as much as 100 kyr older than the eruption.The compositions of crystals, though themselves largely unzoned, generally reflect magma temperature and the bulk compositional gradient, implying both that few crystals settled or were transported far and that the observed crystals contributed little to establishing that gradient. Upward increases in aqueous gas and dissolved water, combined with the adiabatic gradient (for the 5 km depth range tapped) and the roofward decline in liquidus temperature of the zoned melt, prevented significant crystallization against the roof, consistent with dominance of crystal-poor magma early in the eruption and lack of any roof-rind fragments among the Bishop ejecta, before or after onset of caldera collapse. A model of secular incremental zoning is advanced wherein numerous batches of crystal-poor melt were released from a mush zone (many kilometers thick) that floored the accumulating rhyolitic melt-rich body. Each batch rose to its own appropriate level in the melt-buoyancy gradient, which was selfsustaining against wholesale convective re-homogenization, while the thick mush zone below buffered it against disruption by the deeper (non-rhyolitic) recharge that augmented the mush zone and thermally sustained the whole magma chamber. Crystal-melt fractionation was the dominant zoning process, but it took place not principally in the shallow melt-rich body but mostly in the pluton-scale mush zone before and during batchwise melt extraction. ?? Published by Oxford University Press (2007).

High performance batch production of LREBa 2Cu 3O y using novel thin film Nd-123 seed

NASA Astrophysics Data System (ADS)

Muralidhar, M.; Suzuki, K.; Fukumoto, Y.; Ishihara, A.; Tomita, M.

2011-11-01

A batch production for fabrication of LREBa2Cu3Oy (LRE: Sm, Gd, NEG) "LRE-123" pellets are developed in air and Ar-1% O2 using a novel thin film Nd-123 seeds grown on MgO crystals. The SEM and XRD results conformed that the quality and orientation of the seed crystals are excellent. On the other hand, new seeds can withstand temperatures >1100 °C, as a result, the cold seeding process was applied even to grow Sm-123 material in Air. The trapped field observed in the best 45 mm single-grain puck of Gd-123 was in the range of 1.35 T and 0.35 T at 77.3 K and 87.3 K, respectively. The average trapped field at 77.3 K in the 24 mm diameter NEG-123 samples batch lies between 0.9 and 1 T. The maximum trapped field of 1.2 T was recorded at the sample surface. Further, the maximum trapped field of 0.23 T at 77 K was recorded in a sample with 16 mm diameter of Sm-123 with 3 mol% BaO2 addition. As a result we made more then 130 single grain pucks within a couple of months. Taking advantage of the single grain batch processed material, we constructed self-made chilled levitation disk, which was used on the open day of railway technical research Institute. More then 150 children stood on the levitation disk and revel the experience of levitation. The present results prove that a high-performance good-quality class of LREBa2Cu3Oy material can be made by using a novel thin film Nd-123 seeds.

Thermo-mechanical characterization of a thermoplastic composite and prediction of the residual stresses and lamina curvature during cooling

NASA Astrophysics Data System (ADS)

Péron, Mael; Jacquemin, Frédéric; Casari, Pascal; Orange, Gilles; Bailleul, Jean-Luc; Boyard, Nicolas

2017-10-01

The prediction of process induced stresses during the cooling of thermoplastic composites still represents a challenge for the scientific community. However, a precise determination of these stresses is necessary in order to optimize the process conditions and thus lower the stresses effects on the final part health. A model is presented here, that permits the estimation of residual stresses during cooling. It relies on the nonlinear laminate theory, which has been adapted to arbitrary layup sequences. The developed model takes into account the heat transfers through the thickness of the laminate, together with the crystallization kinetics. The development of the composite mechanical properties during cooling is addressed by an incremental linear elastic constitutive law, which also considers thermal and crystallization strains. In order to feed the aforementioned model, a glass fiber and PA6.6 matrix unidirectional (UD) composite has been characterized. This work finally focuses on the identification of the material and process related parameters that lower the residual stresses level, including the ply sequence, the fiber volume fraction and the cooling rate.

Predicting the crystallization propensity of carboxylic acid buffers in frozen systems--relevance to freeze-drying.

PubMed

Sundaramurthi, Prakash; Suryanarayanan, Raj

2011-04-01

Selective crystallization of buffer components in frozen solutions is known to cause pronounced pH shifts. Our objective was to study the crystallization behavior and the consequent pH shift in frozen aqueous carboxylic acid buffers. Aqueous carboxylic acid buffers were cooled to -25°C and the pH of the solution was measured as a function of temperature. The thermal behavior of solutions during freezing and thawing was investigated by differential scanning calorimetry. The crystallized phases in frozen solution were identified by X-ray diffractometry. The malate buffer system was robust with no evidence of buffer component crystallization and hence negligible pH shift. In the citrate and tartarate systems, at initial pH

FORTRAN 77 programs for conductive cooling of dikes with temperature-dependent thermal properties and heat of crystallization

USGS Publications Warehouse

Delaney, P.T.

1988-01-01

Temperature histories obtained from transient heat-conduction theory are applicable to most dikes despite potential complicating effects related to magma flow during emplacement, groundwater circulation, and metamorphic reaction during cooling. Here. machine-independent FORTRAN 77 programs are presented to calculate temperatures in and around dikes as they cool conductively. Analytical solutions can treat thermal-property contrasts between the dike and host rocks, but cannot address the release of magmatic heat of crystallization after the early stages of cooling or the appreciable temperature dependence of thermal conductivity and diffusivity displayed by most rock types. Numerical solutions can incorporate these additional factors. The heat of crystallization can raise the initial temperature at the dike contact, ??c1, about 100??C above that which would be estimated if it were neglected, and can decrease the rate at which the front of solidified magma moves to the dike center by a factor of as much as three. Thermal conductivity and diffusivity of rocks increase with decreasing temperature and, at low temperatures, these properties increase more if the rocks are saturated with water. Models that treat these temperature dependencies yield estimates of ??c1 that are as much as 75??C beneath those which would be predicted if they were neglected. ?? 1988.

Batch and continuous (fixed-bed column) biosorption of crystal violet by Artocarpus heterophyllus (jackfruit) leaf powder.

PubMed

Saha, Papita Das; Chakraborty, Sagnik; Chowdhury, Shamik

2012-04-01

In this study, batch and fixed-bed column experiments were performed to investigate the biosorption potential of Artocarpus heterophyllus (jackfruit) leaf powder (JLP) to remove crystal violet (CV) from aqueous solutions. Batch biosorption studies were carried out as a function of solution pH, contact time, initial dye concentration and temperature. The biosorption equilibrium data showed excellent fit to the Langmuir isotherm model with maximum monolayer biosorption capacity of 43.39 mg g(-1) at pH 7.0, initial dye concentration=50 mg L(-1), temperature=293 K and contact time=120 min. According to Dubinin-Radushkevich (D-R) isotherm model, biosorption of CV by JLP was chemisorption. The biosorption kinetics followed the pseudo-second-order kinetic model. Thermodynamic analysis revealed that biosorption of CV from aqueous solution by JLP was a spontaneous and exothermic process. In order to ascertain the practical applicability of the biosorbent, fixed-bed column studies were also performed. The breakthrough time increased with increasing bed height and decreased with increasing flow rate. The Thomas model as well as the BDST model showed good agreement with the experimental results at all the process parameters studied. It can be concluded that JLP is a promising biosorbent for removal of CV from aqueous solutions. Copyright © 2011 Elsevier B.V. All rights reserved.

Nucleated Poly(L-lactic acid) with N, N‧-oxalyl bis(benzoic acid) dihydrazide

NASA Astrophysics Data System (ADS)

Tian, Liang-Liang; Cai, Yan-Hua

2018-04-01

One of the major challenges in the field of Poly(L-lactic acid) (PLLA) is the enhancement of crystallization. In the present work, the evaluation of the influence of N, N‧-oxalyl bis(benzoic acid) dihydrazide (TBOD), as a novel organic nucleating agent, on the non-isothermal crystallization, melting behavior, and thermal stability of PLLA was performed using differential scanning calorimeter and thermogravimetric analysis. Non-isothermal crystallization measurement revealed that TBOD had an excellent accelerating effect for the crystallization of PLLA in cooling, and upon the addition of 3 wt% TBOD, PLLA exhibited the highest onset crystallization temperature and the crystallization peak temperature, as well as the largest non-isothermal crystallization enthalpy. In particular, when the TBOD concentration was 1 wt% ∼ 3 wt%, the onset crystallization temperatures were higher than the theoretical ceiling temperature of crystallization, thoroughly demonstrating the powerful crystallization promoting ability of TBOD. Additionally, the non-isothermal crystallization behavior of PLLA/TBOD depended on the TBOD concentration, cooling rate as well as the final melting temperature. The melting behavior of PLLA/TBOD after non-isothermal crystallization further confirmed the effect of TBOD on the crystallization process and crystal structure of PLLA, and the appearance of the double melting peaks during melting stages was attribute to the melting-recrystallization. For melting behavior after isothermal crystallization, the crystallization temperature and crystallization time significantly affected the melting behavior of PLLA/TBOD. The addition of TBOD could not change the thermal decomposition profile of the PLLA, but the thermal stability did not regularly decrease with increasing of TBOD concentration, indicating that there might exist intermolecular interaction between PLLA and TBOD.

TURBINE COOLING FLOW AND THE RESULTING DECREASE IN TURBINE EFFICIENCY

NASA Technical Reports Server (NTRS)

Gauntner, J. W.

1994-01-01

This algorithm has been developed for calculating both the quantity of compressor bleed flow required to cool a turbine and the resulting decrease in efficiency due to cooling air injected into the gas stream. Because of the trend toward higher turbine inlet temperatures, it is important to accurately predict the required cooling flow. This program is intended for use with axial flow, air-breathing jet propulsion engines with a variety of airfoil cooling configurations. The algorithm results have compared extremely well with figures given by major engine manufacturers for given bulk metal temperatures and cooling configurations. The program calculates the required cooling flow and corresponding decrease in stage efficiency for each row of airfoils throughout the turbine. These values are combined with the thermodynamic efficiency of the uncooled turbine to predict the total bleed airflow required and the altered turbine efficiency. There are ten airfoil cooling configurations and the algorithm allows a different option for each row of cooled airfoils. Materials technology is incorporated and requires the date of the first year of service for the turbine stator vane and rotor blade. The user must specify pressure, temperatures, and gas flows into the turbine. This program is written in FORTRAN IV for batch execution and has been implemented on an IBM 3080 series computer with a central memory requirement of approximately 61K of 8 bit bytes. This program was developed in 1980.

Advanced Experimental Methods for Low-temperature Magnetotransport Measurement of Novel Materials

PubMed Central

Hagmann, Joseph A.; Le, Son T.; Richter, Curt A.; Seiler, David G.

2016-01-01

Novel electronic materials are often produced for the first time by synthesis processes that yield bulk crystals (in contrast to single crystal thin film synthesis) for the purpose of exploratory materials research. Certain materials pose a challenge wherein the traditional bulk Hall bar device fabrication method is insufficient to produce a measureable device for sample transport measurement, principally because the single crystal size is too small to attach wire leads to the sample in a Hall bar configuration. This can be, for example, because the first batch of a new material synthesized yields very small single crystals or because flakes of samples of one to very few monolayers are desired. In order to enable rapid characterization of materials that may be carried out in parallel with improvements to their growth methodology, a method of device fabrication for very small samples has been devised to permit the characterization of novel materials as soon as a preliminary batch has been produced. A slight variation of this methodology is applicable to producing devices using exfoliated samples of two-dimensional materials such as graphene, hexagonal boron nitride (hBN), and transition metal dichalcogenides (TMDs), as well as multilayer heterostructures of such materials. Here we present detailed protocols for the experimental device fabrication of fragments and flakes of novel materials with micron-sized dimensions onto substrate and subsequent measurement in a commercial superconducting magnet, dry helium close-cycle cryostat magnetotransport system at temperatures down to 0.300 K and magnetic fields up to 12 T. PMID:26863449

[Evaluation of pipetting systems. III. Micropipette precision in a routine task].

PubMed

Salas, R; Loría, A; Rocha, C

1995-01-01

To establish a norm of the precision achievable with a micropipette in an IRMA assay under routine conditions. A micropipette (Gilson) adjusted to dispense 100 microL was used by a single analyst with experience in its use. In each assay, ten aliquots of radioactive antiprolactin were pipetted in clean tubes (PRE-batch tubes), followed by pipetting of the tubes being processed in the assay, and at the end, a second pipetting of 10 aliquots in clean tubes (POST-batch tubes). The study includes the data of 15 consecutive batches during a seven month period with an overall mean of 283 tubes per batch. The PRE- and POST-tubes were read in a gamma counter (Crystal plus). The mean, SD and CV for PRE, POST and global (PRE+POST) tubes were calculated for each batch. The global CV of the 15 batches ranged from 1.6 to 6.9%, mean of 3.1%. We found no evidence of increased imprecision due to fatigue of the analyst, but surprisingly, we observed that in nine of the 15 batches there was a significant difference in the means of the PRE-tubes vs the POST-tubes (t test) without differences in precision. Thus, part of the global variability is due to what we have called pseudoimprecision (i.e. an increase in CV due to differences in means). In addition, the POST-tubes had higher values in the first 7 batches but the opposite occurred in the last 8 batches (table 2). This shift in the sign of the PRE-POST differences suggests the presence of opposite factors operating in time, i.e. one or more factors increased the volume of pipetting after using the pipette more than 150 times (batches 1-7) whereas other/others decreased it (batches 8-15). 1. Our first approximation to a norm of micropipetting precision in batches of 200-300 tubes was a CV of 3.1%. 2. This norm was influenced by a problem of pseudoimprecision detected ex-post-facto. 3. Our findings justify continuation studies to detect the pseudoimprecision and evaluate its causes prospectively.

Integrated system for temperature-controlled fast protein liquid chromatography comprising improved copolymer modified beaded agarose adsorbents and a travelling cooling zone reactor arrangement.

PubMed

Müller, Tobias K H; Cao, Ping; Ewert, Stephanie; Wohlgemuth, Jonas; Liu, Haiyang; Willett, Thomas C; Theodosiou, Eirini; Thomas, Owen R T; Franzreb, Matthias

2013-04-12

An integrated approach to temperature-controlled chromatography, involving copolymer modified agarose adsorbents and a novel travelling cooling zone reactor (TCZR) arrangement, is described. Sepharose CL6B was transformed into a thermoresponsive cation exchange adsorbent (thermoCEX) in four synthetic steps: (i) epichlorohydrin activation; (ii) amine capping; (iii) 4,4'-azobis(4-cyanovaleric acid) immobilization; and 'graft from' polymerization of poly(N-isopropylacrylamide-co-N-tert-butylacrylamide-co-acrylic acid-co-N,N'-methylenebisacrylamide). FT-IR, (1)H NMR, gravimetry and chemical assays allowed precise determination of the adsorbent's copolymer composition and loading, and identified the initial epoxy activation step as a critical determinant of 'on-support' copolymer loading, and in turn, protein binding performance. In batch binding studies with lactoferrin, thermoCEX's binding affinity and maximum adsorption capacity rose smoothly with temperature increase from 20 to 50 °C. In temperature shifting chromatography experiments employing thermoCEX in thermally jacketed columns, 44-51% of the lactoferrin adsorbed at 42 °C could be desorbed under binding conditions by cooling the column to 22 °C, but the elution peaks exhibited strong tailing. To more fully exploit the potential of thermoresponsive chromatography adsorbents, a new column arrangement, the TCZR, was developed. In TCZR chromatography, a narrow discrete cooling zone (special assembly of copper blocks and Peltier elements) is moved along a bespoke fixed-bed separation columnfilled with stationary phase. In tests with thermoCEX, it was possible to recover 65% of the lactoferrin bound at 35 °C using 8 successive movements of the cooling zone at a velocity of 0.1mm/s; over half of the recovered protein was eluted in the first peak in more concentrated form than in the feed. Intra-particle diffusion of desorbed protein out of the support pores, and the ratio between the velocities of the cooling zone and mobile phase were identified as the main parameters affecting TCZR performance. In contrast to conventional systems, which rely on cooling the whole column to effect elution and permit only batch-wise operation, TCZR chromatography generates sharp concentrated elution peaks without tailing effects and appears ideally suited for continuous operation. Copyright © 2013 Elsevier B.V. All rights reserved.

Measuring and modelling the structure of chocolate

NASA Astrophysics Data System (ADS)

Le Révérend, Benjamin J. D.; Fryer, Peter J.; Smart, Ian; Bakalis, Serafim

2015-01-01

The cocoa butter present in chocolate exists as six different polymorphs. To achieve the desired crystal form (βV), traditional chocolate manufacturers use relatively slow cooling (<2°C/min). A newer generation of rapid cooling systems has been suggested requiring further understanding of fat crystallisation. To allow better control and understanding of these processes and newer rapid cooling processes, it is necessary to understand both heat transfer and crystallization kinetics. The proposed model aims to predict the temperature in the chocolate products during processing as well as the crystal structure of cocoa butter throughout the process. A set of ordinary differential equations describes the kinetics of fat crystallisation. The parameters were obtained by fitting the model to a set of DSC curves. The heat transfer equations were coupled to the kinetic model and solved using commercially available CFD software. A method using single crystal XRD was developed using a novel subtraction method to quantify the cocoa butter structure in chocolate directly and results were compared to the ones predicted from the model. The model was proven to predict phase change temperature during processing accurately (±1°C). Furthermore, it was possible to correctly predict phase changes and polymorphous transitions. The good agreement between the model and experimental data on the model geometry allows a better design and control of industrial processes.

Crystallization and Cooling of a Deep Silicate Magma Ocean

NASA Astrophysics Data System (ADS)

Wolf, A. S.; Bower, D. J.

2015-12-01

Impact and accretion simulations of terrestrial planet formation suggest that giant impacts are both common and expected to produce extensive melting. The moon-forming impact, for example, likely melted the majority of Earth's mantle to produce a global magma ocean that subsequently cooled and crystallized (e.g. Nakajima and Stevenson, 2015). Understanding the cooling process is critical to determining magma ocean lifetimes and recognizing possible remnant signatures of the magma ocean in present-day mantle heterogeneities (i.e. Labrosse et al., 2007). Modeling this evolution is challenging, however, due to the vastly different timescales and lengthscales associated with turbulent convection (magma ocean) and viscous creep (present-day mantle), in addition to uncertainties in material properties and chemical partitioning. We consider a simplified spherically-symmetric (1-D) magma ocean to investigate both its evolving structure and cooling timescale. Extending the work of Abe (1993), mixing-length theory is employed to determine convective heat transport, producing a high resolution model that captures the ultra-thin boundary layer (few cms) at the surface of the magma ocean. The thermodynamics of mantle melting are represented using a pseudo-one-component model, which retains the simplicity of a standard one-component model while introducing a finite temperature interval for melting (important for multi-component systems). We derive a new high P-T equation of state (EOS) formulation designed to capture the energetics and physical properties of the partially molten system using parameters that are readily interpreted in the context of magma ocean crystallization. This model is used to determine the cooling timescale for a variety of plausible thermodynamic models, with special emphasis on comparing the center-outwards vs bottom-up cooling scenarios that arise from the assumed EOS (e.g., Mosenfelder et al., 2009; Stixrude et al., 2009).

Enhanced cooling of Yb:YLF using astigmatic Herriott cell (Conference Presentation)

NASA Astrophysics Data System (ADS)

Gragossian, Aram; Meng, Junwei; Ghasemkhani, Mohammadreza; Albrecht, Alexander R.; Tonelli, Mauro; Sheik-Bahae, Mansoor

2017-02-01

Optical refrigeration of solids requires crystals with exceptional qualities. Crystals with external quantum efficiencies (EQE) larger than 99% and background absorptions of 4×10-4cm-1 have been cooled to cryogenic temperatures using non resonant cavities. Estimating the cooling efficiency requires accurate measurements of the above mentioned quantities. Here we discuss measurements of EQE and background absorption for two high quality Yb:YLF samples. For any given sample, to reach minimum achievable temperatures heat generated by fluorescence must be removed from the surrounding clamshell and more importantly, absorption of the laser light must be maximized. Since the absorption coefficient drops at lower temperatures the only option is to confine laser light in a cavity until almost 100% of the light is absorbed. This can be achieved by placing the crystal between a cylindrical and spherical mirror to form an astigmatic Herriott cell. In this geometry light enters through a hole in the middle of the spherical mirror and if the entrance angle is correct, it can make as many round trips as required to absorb all the light. At 120 K 60 passes and 150 passes at 100K ensures more than 95% absorption of the laser light. 5 and 10% Yb:YLF crystals placed in such a cell cool to sub 90K temperatures. Non-contact temperature measurements are more challenging for such a geometry. Reabsorption of fluorescence for each pass must be taken into account for accurate temperature measurements by differential luminescence thermometry (DLT). Alternatively, we used part of the spectrum that is not affected by reabsorption.

Efficient calcium lactate production by fermentation coupled with crystallization-based in situ product removal.

PubMed

Xu, Ke; Xu, Ping

2014-07-01

Lactic acid is a platform chemical with various industrial applications, and its derivative, calcium lactate, is an important food additive. Fermentation coupled with in situ product removal (ISPR) can provide more outputs with high productivity. The method used in this study was based on calcium lactate crystallization. Three cycles of crystallization were performed during the fermentation course using a Bacillus coagulans strain H-1. As compared to fed-batch fermentation, this method showed 1.7 times higher average productivity considering seed culture, with 74.4% more L-lactic acid produced in the fermentation with ISPR. Thus, fermentation coupled with crystallization-based ISPR may be a biotechnological alternative that provides an efficient system for production of calcium lactate or lactic acid. Copyright © 2014 Elsevier Ltd. All rights reserved.

Effects of high pressure on microstructure evolution and crystallization mechanisms during solidification of nickel

NASA Astrophysics Data System (ADS)

Zhang, Hai-Tao; Mo, Yun-Fei; Liu, Rang-Su; Tian, Ze-An; Liu, Hai-Rong; Hou, Zhao-Yang; Zhou, Li-Li; Liang, Yong-Chao; Peng, Ping

2018-03-01

To deeply understand the effects of high pressure on microstructural evolutions and crystallization mechanisms of liquid metal Ni during solidification process, MD simulation studies have been performed under 7 pressures of 0 ˜ 30 GPa, at cooling rate of 1.0 × 1011 K s-1. Adopting several microstructural analyzing methods, especially the cluster-type index method (CTIM-2) to analyze the local microstructures in the system. It is found that the pressure has important influence on the formation and evolution of microstructures, especially of the main basic clusters in the system. All the simulation systems are directly solidified into crystal structures, and the 1421, 1422, 1441 and 1661 bond-types, as well the FCC (12 0 0 0 12 0), HCP (12 0 0 0 6 6) and BCC (14 6 0 8 0 0) clusters play a key role in the microstructure transitions from liquid to crystal structures. The crystallization temperature T c is enhanced almost linearly with the increase of pressure. Highly interesting, it is found for the first time that there is an important phase transformation point from FCC to BCC structures between 20 ˜ 22.5 GPa during the solidification processes from the same initial liquid system at the same cooling rate. And the effect of increasing pressure is similar to that of decreasing cooling rate for the phase transformation of microstructures during solidification process of liquid metal Ni system, though they have different concrete effecting mechanisms.

Ultrasound assisted crystallization of mefenamic acid: Effect of operating parameters and comparison with conventional approach.

PubMed

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.

Differentiation and magma mixing on Kilauea's east rift zone: A further look at the eruptions of 1955 and 1960. Part II. The 1960 lavas

USGS Publications Warehouse

Wright, T.L.; Helz, R.T.

1996-01-01

New and detailed petrographic observations, mineral compositional data, and whole-rock vs glass compositional trends document magma mixing in lavas erupted from Kilauea's lower east rift zone in 1960. Evidence includes the occurrence of heterogeneous phenocryst assemblages, including resorbed and reversely zoned minerals in the lavas inferred to be hybrids. Calculations suggest that this mixing, which is shown to have taken place within magma reservoirs recharged at the end of the 1955 eruption, involved introduction of four different magmas. These magmas originated beneath Kilauea's summit and moved into the rift reservoirs beginning 10 days after the eruption began. We used microprobe analyses of glass to calculate temperatures of liquids erupted in 1955 and 1960. We then used the calculated proportions of stored and recharge components to estimate the temperature of the recharge components, and found those temperatures to be consistent with the temperature of the same magmas as they appeared at Kilauea's summit. Our studies reinforce conclusions reached in previous studies of Kilauea's magmatic plumbing. We infer that magma enters shallow storage beneath Kilauea's summit and also moves laterally into the fluid core of the East rift zone. During this process, if magmas of distinctive chemistry are present, they retain their chemical identity and the amount of cooling is comparable for magma transported either upward or laterally to eruption sites. Intrusions within a few kilometers of the surface cool and crystallize to produce fractionated magma. Magma mixing occurs both within bodies of previously fractionated magma and when new magma intersects a preexisting reservoir. Magma is otherwise prevented from mixing, either by wall-rock septa or by differing thermal and density characteristics of the successive magma batches.

Effect of cooling rate on magnetic domain structure and magnetic properties of Tb0.27Dy0.73Fe1.95 alloys solidified in high magnetic field

NASA Astrophysics Data System (ADS)

Liu, Tie; Dong, Meng; Gao, Pengfei; Xiao, Yubao; Yuan, Yi; Wang, Qiang

2018-05-01

In this work, Tb0.27Dy0.73Fe1.95 alloys were solidified in a high magnetic field of 4.4 T at various cooling rates. Changes in the magnetostriction, crystal orientation, magnetization, and magnetic domain of the solidified alloys were investigated. The application of the magnetic field can induce <111> orientation of (Tb, Dy)Fe2 phase. However, the effect of the magnetic field is strongly dependent on the cooling rate. The alloy solidified at 5 °C/min shows the highest magnetostriction, strongest <111> orientation, best contrast of light and dark in the domain image, and fastest magnetization, and followed in descending order by the alloys solidified at 1.5 °C/min and 60 °C/min. The change in the magnetostriction of the alloys can be attributed to the changes in crystal orientation and magnetic domain structure caused by both the magnetic field and cooling rate.

Hindered settling and the formation of layered intrusions

NASA Astrophysics Data System (ADS)

Bons, Paul D.; Baur, Albrecht; Elburg, Marlina A.; Lindhuber, Matthias J.; Marks, Michael A. W.; Soesoo, Alvar; van Milligen, Boudewijn P.; Walte, Nicolas P.

2015-04-01

Layered intrusions are characterized by (often repetitive) layering on a range of scales. Many explanations for the formation of such layering have been proposed over the past decades. We investigated the formation of "mats" by hindered crystal settling, a model that was first suggested by Lauder (1964). The interaction of sinking and rising crystals leads to the amplification of perturbations in crystal density within a magma chamber, a process similar to the formation of traffic jams in dense traffic (Bons et al., 2015). Once these "crystal traffic jams" form they constitute a barrier for further settling of crystals. Between these barriers, the magma evolves in a semi-closed system in which stratification may develop by gravitational sorting. Barriers, and therefore layers, form sequentially during inward cooling of the magma chamber. Barring later equilibration, mineralogical and geochemical trends within the layers are repetitive, but with variations due to the random process of initial perturbation formation. Layers can form in the transition between two end-member regimes: (1) in a fast cooling and/or viscous magma crystals cannot sink or float a significant distance and minerals are distributed homogeneously throughout the chamber; (2) in a slow cooling and/or low-viscosity magma crystals can quickly settle at the top and bottom of the chamber and crystals concentrations are never high enough to form "traffic jams". As a result, heavy and light minerals get fully separated in the chamber. Between these two end members, crystals can sink and float a significant distance, but not the whole height of the magma chamber before entrapment in "traffic jams". We illustrate the development of layers with numerical models and compare the results with the layered nepheline syenites (kakortokites) of the Ilímaussaq intrusion in SW Greenland. References: Bons, P.D., Baur, A., Elburg, M.A., Lindhuber, M.J., Marks, M.A.W., Soesoo, A., van Milligen, B.P., Walte, N.P. 2015. Layered intrusions and traffic jams. Geology 43, 71-74 Lauder, W. 1964. Mat formation and crystal settling in magma. Nature 202, 1100-1101.

LSSA large area silicon sheet task continuous Czochralski process development

NASA Technical Reports Server (NTRS)

Rea, S. N.

1978-01-01

A Czochralski crystal growing furnace was converted to a continuous growth facility by installation of a premelter to provide molten silicon flow into the primary crucible. The basic furnace is operational and several trial crystals were grown in the batch mode. Numerous premelter configurations were tested both in laboratory-scale equipment as well as in the actual furnace. The best arrangement tested to date is a vertical, cylindrical graphite heater containing small fused silicon test tube liner in which the incoming silicon is melted and flows into the primary crucible. Economic modeling of the continuous Czochralski process indicates that for 10 cm diameter crystal, 100 kg furnace runs of four or five crystals each are near-optimal. Costs tend to asymptote at the 100 kg level so little additional cost improvement occurs at larger runs. For these conditions, crystal cost in equivalent wafer area of around $20/sq m exclusive of polysilicon and slicing was obtained.

Effect of solvent on crystallization behavior of xylitol

NASA Astrophysics Data System (ADS)

Hao, Hongxun; Hou, Baohong; Wang, Jing-Kang; Lin, Guangyu

2006-04-01

Effect of organic solvents content on crystallization behavior of xylitol was studied. Solubility and crystallization kinetics of xylitol in methanol-water system were experimentally determined. It was found that the solubility of xylitol at various methanol content all increases with increase of temperature. But it decreases when increasing methanol content at constant temperature. Based on the theory of population balance, the nucleation and growth rates of xylitol in methanol-water mixed solvents were calculated by moments method. From a series of experimental population density data of xylitol gotten from a batch-operated crystallizer, parameters of crystal nucleation and growth rate equations at different methanol content were got by the method of nonlinear least-squares. By analyzing, it was found that the content of methanol had an apparent effect on nucleation and growth rate of xylitol. At constant temperature, the nucleation and growth rate of xylitol all decrease with increase of methanol content.

Adaptation of in-situ microscopy for crystallization processes

NASA Astrophysics Data System (ADS)

Bluma, A.; Höpfner, T.; Rudolph, G.; Lindner, P.; Beutel, S.; Hitzmann, B.; Scheper, T.

2009-08-01

In biotechnological and pharmaceutical engineering, the study of crystallization processes gains importance. An efficient analytical inline sensor could help to improve the knowledge about these processes in order to increase efficiency and yields. The in-situ microscope (ISM) is an optical sensor developed for the monitoring of bioprocesses. A new application for this sensor is the monitoring in downstream processes, e.g. the crystallization of proteins and other organic compounds. This contribution shows new aspects of using in-situ microscopy to monitor crystallization processes. Crystals of different chemical compounds were precipitated from supersaturated solutions and the crystal growth was monitored. Exemplified morphological properties and different forms of crystals could be distinguished on the basis of offline experiments. For inline monitoring of crystallization processes, a special 0.5 L stirred tank reactor was developed and equipped with the in-situ microscope. This reactor was utilized to carry out batch experiments for crystallizations of O-acetylsalicyclic acid (ASS) and hen egg white lysozyme (HEWL). During the whole crystallization process, the in-situ microscope system acquired images directly from the crystallization broth. For the data evaluation, an image analysis algorithm was developed and implemented in the microscope analysis software.

Pd-Ag chronometry of IVA iron meteorites and the crystallization and cooling of a protoplanetary core

DOE PAGES

Matthes, M.; Fischer-Godde, M.; Kruijer, T. S.; ...

2017-09-07

To constrain the timescales and processes involved in the crystallization and cooling of protoplanetary cores, we examined the Pd-Ag isotope systematics of the IVA iron meteorites Muonionalusta and Gibeon. A Pd-Ag isochron for Muonionalusta provides an initial 107Pd/ 108Pd = (2.57 ± 0.07) × 10 -5. The three metal samples analyzed from Gibeon plot below the Muonionalusta isochron, but these samples also show significant effects of cosmic ray-induced neutron capture reactions, as is evident from 196Pt excesses in the Gibeon samples. After correction for neutron capture effects on Ag isotopes, the Gibeon samples plot on the Muonionalusta isochron, indicating thatmore » these two IVA irons have indistinguishable initial 107Pd/ 108Pd. Collectively, the Pd-Ag data indicate cooling of the IVA core below Pd-Ag closure between 2.9 ± 0.4 Ma and 8.9 ± 0.6 Ma after CAI formation, where this age range reflects uncertainties in the initial 107Pd/ 108Pd ratios of the solar system, which in turn result from uncertainties in the Pb-Pb age of Muonionalusta. The Ag isotopic data indicate that the IVA core initially evolved with a modestly elevated Pd/Ag, but the low Ag concentrations measured for some metal samples indicate derivation from a source with much lower Ag contents and, hence, higher Pd/Ag. These contrasting observations can be reconciled if the IVA irons crystallized from an initially more Ag-rich core, followed by extraction of Fe-S melts during compaction of the nearly solidified core. Owing to its strong tendency to partition into Fe-S melts, Ag was removed from the IVA core during compaction, leading to the very low Ag concentration observed in metal samples of IVA irons. Alternatively, Ag was lost by evaporation from a still molten metallic body just prior to the onset of crystallization. The Pd-Ag isotopic data indicate that Muonionalusta cooled at >500 K/Ma through the Pd-Ag closure temperature of ~900 K, consistent with the rapid cooling inferred from metallographic cooling rates for IVA irons. Finally, combined, these observations are consistent with cooling of IVA irons in a metallic body with little or no silicate mantle.« less

Pd-Ag chronometry of IVA iron meteorites and the crystallization and cooling of a protoplanetary core

NASA Astrophysics Data System (ADS)

Matthes, M.; Fischer-Gödde, M.; Kruijer, T. S.; Kleine, T.

2018-01-01

To constrain the timescales and processes involved in the crystallization and cooling of protoplanetary cores, we examined the Pd-Ag isotope systematics of the IVA iron meteorites Muonionalusta and Gibeon. A Pd-Ag isochron for Muonionalusta provides an initial 107Pd/108Pd = (2.57 ± 0.07) × 10-5. The three metal samples analyzed from Gibeon plot below the Muonionalusta isochron, but these samples also show significant effects of cosmic ray-induced neutron capture reactions, as is evident from 196Pt excesses in the Gibeon samples. After correction for neutron capture effects on Ag isotopes, the Gibeon samples plot on the Muonionalusta isochron, indicating that these two IVA irons have indistinguishable initial 107Pd/108Pd. Collectively, the Pd-Ag data indicate cooling of the IVA core below Pd-Ag closure between 2.9 ± 0.4 Ma and 8.9 ± 0.6 Ma after CAI formation, where this age range reflects uncertainties in the initial 107Pd/108Pd ratios of the solar system, which in turn result from uncertainties in the Pb-Pb age of Muonionalusta. The Ag isotopic data indicate that the IVA core initially evolved with a modestly elevated Pd/Ag, but the low Ag concentrations measured for some metal samples indicate derivation from a source with much lower Ag contents and, hence, higher Pd/Ag. These contrasting observations can be reconciled if the IVA irons crystallized from an initially more Ag-rich core, followed by extraction of Fe-S melts during compaction of the nearly solidified core. Owing to its strong tendency to partition into Fe-S melts, Ag was removed from the IVA core during compaction, leading to the very low Ag concentration observed in metal samples of IVA irons. Alternatively, Ag was lost by evaporation from a still molten metallic body just prior to the onset of crystallization. The Pd-Ag isotopic data indicate that Muonionalusta cooled at >500 K/Ma through the Pd-Ag closure temperature of ∼900 K, consistent with the rapid cooling inferred from metallographic cooling rates for IVA irons. Combined, these observations are consistent with cooling of IVA irons in a metallic body with little or no silicate mantle.

Pd-Ag chronometry of IVA iron meteorites and the crystallization and cooling of a protoplanetary core

DOE Office of Scientific and Technical Information (OSTI.GOV)

Matthes, M.; Fischer-Godde, M.; Kruijer, T. S.

To constrain the timescales and processes involved in the crystallization and cooling of protoplanetary cores, we examined the Pd-Ag isotope systematics of the IVA iron meteorites Muonionalusta and Gibeon. A Pd-Ag isochron for Muonionalusta provides an initial 107Pd/ 108Pd = (2.57 ± 0.07) × 10 -5. The three metal samples analyzed from Gibeon plot below the Muonionalusta isochron, but these samples also show significant effects of cosmic ray-induced neutron capture reactions, as is evident from 196Pt excesses in the Gibeon samples. After correction for neutron capture effects on Ag isotopes, the Gibeon samples plot on the Muonionalusta isochron, indicating thatmore » these two IVA irons have indistinguishable initial 107Pd/ 108Pd. Collectively, the Pd-Ag data indicate cooling of the IVA core below Pd-Ag closure between 2.9 ± 0.4 Ma and 8.9 ± 0.6 Ma after CAI formation, where this age range reflects uncertainties in the initial 107Pd/ 108Pd ratios of the solar system, which in turn result from uncertainties in the Pb-Pb age of Muonionalusta. The Ag isotopic data indicate that the IVA core initially evolved with a modestly elevated Pd/Ag, but the low Ag concentrations measured for some metal samples indicate derivation from a source with much lower Ag contents and, hence, higher Pd/Ag. These contrasting observations can be reconciled if the IVA irons crystallized from an initially more Ag-rich core, followed by extraction of Fe-S melts during compaction of the nearly solidified core. Owing to its strong tendency to partition into Fe-S melts, Ag was removed from the IVA core during compaction, leading to the very low Ag concentration observed in metal samples of IVA irons. Alternatively, Ag was lost by evaporation from a still molten metallic body just prior to the onset of crystallization. The Pd-Ag isotopic data indicate that Muonionalusta cooled at >500 K/Ma through the Pd-Ag closure temperature of ~900 K, consistent with the rapid cooling inferred from metallographic cooling rates for IVA irons. Finally, combined, these observations are consistent with cooling of IVA irons in a metallic body with little or no silicate mantle.« less

Effect of Fe2O3 on the crystallization behavior of glass-ceramics produced from naturally cooled yellow phosphorus furnace slag

NASA Astrophysics Data System (ADS)

Liu, Hong-pan; Huang, Xiao-feng; Ma, Li-ping; Chen, Dan-li; Shang, Zhi-biao; Jiang, Ming

2017-03-01

CaO-Al2O3-SiO2 (CAS) glass-ceramics were prepared via a melting method using naturally cooled yellow phosphorus furnace slag as the main raw material. The effects of the addition of Fe2O3 on the crystallization behavior and properties of the prepared glass-ceramics were studied by differential thermal analysis, X-ray diffraction, and scanning electron microscopy. The crystallization activation energy was calculated using the modified Johnson-Mehl-Avrami equation. The results show that the intrinsic nucleating agent in the yellow phosphorus furnace slag could effectively promote the crystallization of CAS. The crystallization activation energy first increased and then decreased with increasing amount of added Fe2O3. At 4wt% of added Fe2O3, the crystallization activation energy reached a maximum of 676.374 kJ·mol-1. The type of the main crystalline phase did not change with the amount of added Fe2O3. The primary and secondary crystalline phases were identified as wollastonite (CaSiO3) and hedenbergite (CaFe(Si2O6)), respectively.

Improvement in Stability of SPring-8 Standard X-Ray Monochromators with Water-Cooled Crystals

NASA Astrophysics Data System (ADS)

Yamazaki, Hiroshi; Shimizu, Yasuhiro; Miura, Takanori; Tanaka, Masayuki; Kishimoto, Hikaru; Matsuzaki, Yasuhisa; Shimizu, Nobtaka; Kawano, Yoshiaki; Kumasaka, Takashi; Yamamoto, Masaki; Koganezawa, Tomoyuki; Sato, Masugu; Hirosawa, Ichiro; Senba, Yasunori; Ohashi, Haruhiko; Goto, Shunji; Ishikawa, Tetsuya

2010-06-01

SPring-8 standard double-crystal monochromators containing water-cooled crystals were stabilized to a sufficient level to function as a part of optics components to supply stable microfocused x-ray beams, by determining causes of the instability and then removing them. The instability was caused by two factors—thermal deformation of fine stepper stages in the monochromator, which resulted in reduction in beam intensity with time, and vibrations of coolant supply units and vacuum pumps, which resulted in fluctuation in beam intensity. We remodeled the crystal holders to maintain the stage temperatures constant with water, attached x-ray and electron shields to the stages in order to prevent their warming up, introduced accumulators in the water circuits to absorb pressure pulsation, used polyurethane tubes to stabilize water flow, and placed rubber cushions un der scroll vacuum pumps. As a result, the intensity reduction rate of the beam decreased from 26% to 1% per hour and the intensity fluctuation from 13% to 1%. The monochromators were also modified to prevent radiation damage to the crystals, materials used as a water seal, and motor cables.

Growth, structural, thermal, dielectric and optical studies on HBST crystal: A potential THz emitter

NASA Astrophysics Data System (ADS)

Ma, Yuzhe; Teng, Bing; Cao, Lifeng; Zhong, Degao; Ji, Shaohua; Teng, Fei; Liu, Jiaojiao; Yao, Yuan; Tang, Jie; Tong, Jiaming

2018-02-01

The efficient organic nonlinear optical material 4-hydroxy benzaldehyde-N-methyl 4-stilbazolium tosylate (HBST) was grown from methanol by slope nucleation method combined with slow cooling (SNM-SC) for the first time. The optimum growth conditions based on the cooling rate was further investigated. The single crystal X-ray diffraction (XRD) revealed that the chromophores of HBST crystal make an angle of about 33° with respect to the a-axis, which is close to the optimum of Terahertz (THz)-wave generation and electro-optics applications. NMR and FT-IR spectral studies have been performed to ascertain various functional groups present in the sample. Futhermore, the thermal stability and decomposition stages were analyzed through TG-DTA and DSC techniques. The dielectric constant and dielectric loss of HBST crystal have been studied. Critical optical properties like the absorption coefficient, refractive index, cut-off wavelength and band gap energy were calculated. Photoluminescence (PL) exication studies indicated green emission occured at 507 nm. All the results of HBST crystal make it a promising candidate in the fields of optoelectronic and the generation of THz.

Vitrification and devitrification of micro-droplets

NASA Astrophysics Data System (ADS)

Ryoun Youn, Jae; Song, Young Seok

2012-11-01

Vitrification can be achieved by flash freezing and thawing (i.e. quenching) when ice crystal formation is inhibited in a cryogenic environment. Such ultra-rapid cooling and rewarming occurs due to the large temperature difference between the liquid and its surrounding medium. Here, we analyze the crystallization behavior of a droplet (i.e. vitrification and devitrification) by using a numerical model. The numerical results were found to explain the experimental observations successfully. The findings showed that for successful cryopreservation not only sufficiently fast cooling, but also rewarming processes should be designed and controlled to avoid devitrification of a droplet.

Manufacturing unique glasses in space

NASA Technical Reports Server (NTRS)

Happe, R. P.

1976-01-01

An air suspension melting technique is described for making glasses from substances which to date have been observed only in the crystalline condition. A laminar flow vertical wind tunnel was constructed for suspending oxide melts that were melted using the energy from a carbon dioxide laser beam. By this method it is possible to melt many high-melting-point materials without interaction between the melt and crucible material. In addition, space melting permits cooling to suppress crystal growth. If a sufficient amount of under cooling is accompanied by a sufficient increase in viscosity, crystallization will be avoided entirely and glass will result.

Atomistic insights into the nanosecond long amorphization and crystallization cycle of nanoscale G e2S b2T e5 : An ab initio molecular dynamics study

NASA Astrophysics Data System (ADS)

Branicio, Paulo S.; Bai, Kewu; Ramanarayan, H.; Wu, David T.; Sullivan, Michael B.; Srolovitz, David J.

2018-04-01

The complete process of amorphization and crystallization of the phase-change material G e2S b2T e5 is investigated using nanosecond ab initio molecular dynamics simulations. Varying the quench rate during the amorphization phase of the cycle results in the generation of a variety of structures from entirely crystallized (-0.45 K/ps) to entirely amorphized (-16 K/ps). The 1.5-ns annealing simulations indicate that the crystallization process depends strongly on both the annealing temperature and the initial amorphous structure. The presence of crystal precursors (square rings) in the amorphous matrix enhances nucleation/crystallization kinetics. The simulation data are used to construct a combined continuous-cooling-transformation (CCT) and temperature-time-transformation (TTT) diagram. The nose of the CCT-TTT diagram corresponds to the minimum time for the onset of homogenous crystallization and is located at 600 K and 70 ps. That corresponds to a critical cooling rate for amorphization of -4.5 K/ps. The results, in excellent agreement with experimental observations, suggest that a strategy that utilizes multiple quench rates and annealing temperatures may be used to effectively optimize the reversible switching speed and enable fast and energy-efficient phase-change memories.

Sterilization by Cooling in Isochoric Conditions: The Case of Escherichia coli

PubMed Central

Salinas-Almaguer, Samuel; Angulo-Sherman, Abril; Sierra-Valdez, Francisco Javier; Mercado-Uribe, Hilda

2015-01-01

High hydrostatic pressure (HHP) affects the structure, metabolism and survival of micro-organisms including bacteria. For this reason HHP is a promising treatment in the food industry. The aim of this work is to evaluate the effect of high pressure, under isochoric cooling conditions, on Escherichia coli, where such high pressure develops due to the fact water cannot expand. We combine survival curves obtained by spectrophotometry and images of atomic force microscopy in this study. Our results show that cooling at -20 and -30°C leads to a partial destruction of a Escherichia coli population. However, cooling at -15°C causes a total extermination of bacteria. This intriguing result is explained by the phase diagram of water. In the first case, the simultaneous formation of ice III and ice Ih crystals provides a safe environment for bacteria. In the second case (-15°C) Escherichia coli remains in a metastable and amorphous free-of-crystals liquid subjected to high pressure. Our work is the first experimental study carried out to inactivate Escherichia coli under isochoric cooling conditions. Unlike HHP, which is based on the application of an external load to augment the pressure, this technique only requires cooling. The method could be used for annihilation of other Escherichia coli strains and perhaps other micro-organisms. PMID:26480032

Nucleation control and separation of paracetamol polymorphs through swift cooling crystallization process

NASA Astrophysics Data System (ADS)

Sudha, C.; Srinivasan, K.

2014-09-01

Polymorphic nucleation behavior of pharmaceutical solid paracetamol has been investigated by performing swift cooling crystallization process. Saturated aqueous solution prepared at 318 K was swiftly cooled to 274 K in steps of every 1 K in the temperature range from 274 K to 313 K with uniform stirring of 100 rpm. The resultant supersaturation generated in the mother solution favours the nucleation of three different polymorphs of paracetamol. Lower supersaturation region σ=0.10-0.83 favours stable mono form I; the intermediate supersaturation region σ=0.92-1.28 favours metastable ortho form II and the higher supersaturation region σ=1.33-1.58 favours unstable form III polymorphic nucleation. Depending upon the level of supersaturation generated during swift cooling process and the corresponding solubility limit and metastable zone width (MSZW) of each polymorph, the nucleation of a particular polymorph occurs in the system. The type of polymorphs was identified by in-situ optical microscopy and the internal structure was confirmed by Powder X-ray diffraction (PXRD) study. By this novel approach, the preferred nucleation regions of all the three polymorphs of paracetamol are optimized in terms of different cooling ranges employed during the swift cooling process. Also solution mediated polymorphic transformations from unstable to mono and ortho to mono polymorphs have been studied by in-situ.

Recent volcanic history of Irazu volcano, Costa Rica: alternation and mixing of two magma batches, and pervasive mixing

USGS Publications Warehouse

Alvarado, Guillermo E.; Carr, Michael J.; Turrin, Brent D.; Swisher, Carl C.; Schmincke, Hans-Ulrich; Hudnut, Kenneth W.

2006-01-01

40Ar/39Ar dates, field observations, and geochemical data are reported for Irazú volcano, Costa Rica. Volcanism dates back to at least 854 ka, but has been episodic with lava shield construction peaks at ca. 570 ka and 136–0 ka. The recent volcanic record on Irazú volcano comprises lava flows and a variety of Strombolian and phreatomagmatic deposits, with a long-term trend toward more hydrovolcanic deposits. Banded scorias and hybridized rocks reflect ubiquitous magma mixing and commingling. Two distinct magma batches have been identified. One magma type or batch, Haya, includes basalt with higher high field strength (HFS) and rare-earth element contents, suggesting a lower degree melt of a subduction modified mantle source. The second batch, Sapper, has greater enrichment of large ion lithophile elements (LILE) relative to HFS elements and rare-earth elements, suggesting a higher subduction signature. The recent volcanic history at Irazú records two and one half sequences of the following pattern: eruptions of the Haya batch; eruptions of the Sapper batch; and finally, an unusually clear unconformity, indicating a pause in eruptions. In the last two sequences, strongly hybridized magma erupted after the eruption of the Haya batch. The continuing presence of two distinct magma batches requires two active magma chambers. The common occurrence of hybrids is evidence for a small, nearer to the surface chamber for mixing the two batches. Estimated pre-eruptive temperatures based on two-pyroxene geothermometry range from ∼1000–1176 °C in basalts to 922 °C in hornblende andesites. Crystallization occurred mainly between 4.6 and 3 kb as measured by different geobarometers. Hybridized rocks show intermediate pressures and temperatures. High silica magma occurs in very small volumes as banded scorias but not as lava flows. Although eruptions at Irazú are not often very explosive, the pervasiveness of magma mixing presents the danger of larger, more explosive hybrid eruptions.

Fast Cooling and Vitrification of Aqueous Solutions for Cryopreservation

NASA Astrophysics Data System (ADS)

Warkentin, Matt; Husseini, Naji; Berejnov, Viatcheslav; Thorne, Robert

2006-03-01

In many applications, a small volume of aqueous solution must be cooled at a rate sufficient to produce amorphous solid water. Two prominent examples include flash-freezing of protein crystals for X-ray data collection and freezing of cells (i.e. spermatozoa) for cryopreservation. The cooling rate required to vitrify pure water (˜10^6 K/s) is unattainable for volumes that might contain cells or protein crystals, but the required rate can be reduced by adding cryoprotectants. We report the first measurements of the critical concentration required to produce a vitrified sample as a function of the sample's volume, the cryogen into which the sample is plunged, and the temperature of the cryogen, for a wide range of cryoprotectants. These experiments have broad practical consequences for cryopreservation, and provide insight into the physics of glass formation in aqueous systems.

The Effect of Solution Thermal History on Chicken Egg White Lysozyme Nucleation

NASA Technical Reports Server (NTRS)

Burke, Michael W.; Judge, Russell A.; Pusey, Marc L.

2001-01-01

Proteins are highly flexible molecules and often exhibit defined conformational changes in response to changes in the ambient temperature. Chicken egg white lysozyme has been previously shown to undergo an apparent structural change when warmed above the tetragonal/orthorhombic phase transition temperature. This is reflected by a change in the habit of the tetragonal and orthorhombic crystals so formed. In this study, we show that possible conformational changes induced by heating are stable and apparently non-reversible by simple cooling. Exposure of protein solutions to temperatures above the phase change transition temperature, before combining with precipitant solution to begin crystallization, reduces final crystal numbers. Protein that is briefly warmed to 37 C, then cooled shows no sign of reversal to the unheated nucleation behavior even after storage for four weeks at 4 C. The change in nucleation behavior of tetragonal lysozyme crystals, attributed to a structural shift, occurs faster the greater the exposure to temperature above the equi-solubility point for the two phases. Heating for 2 hours at 48 C reduces crystal numbers by 20 fold in comparison to the same solution heated for the same time at 30 C. Thermal treatment of solutions is therefore a possible tool to reduce crystal numbers and increase crystal size. The effects of a protein's previous thermal history are now shown to be a potentially critical factor in subsequent macromolecule crystal nucleation and growth studies.

The Effect of Solution Thermal History on Chicken Egg White Lysozyme Nucleation

NASA Technical Reports Server (NTRS)

Burke, Michael W.; Judge, Russell A.; Pusey, Marc L.; Rose, M. Franklin (Technical Monitor)

2000-01-01

Proteins are highly flexible molecules and often exhibit defined conformational changes in response to changes in the ambient temperature. Chicken egg white lysozyme has been previously shown to undergo an apparent structural change when warmed above the tetragonal/orthorhombic phase transition temperature. This is reflected by a change in the habit of the tetragonal and orthorhombic crystals so formed. In this study we show that possible conformational changes induced by heating are stable and apparently non- reversible by simple cooling. Exposure of protein solutions to temperatures above the phase change transition temperature, before combining with precipitant solution to begin crystallization, reduces final crystal numbers. Protein that is briefly warmed to 37 C, then cooled shows no sign of reversal to the unheated nucleation behavior even after storage for 4 weeks at 4 C. The change in nucleation behavior of tetragonal lysozyme crystals, attributed to a structural shift, occurs faster the greater the exposure to temperature above the equi-solubility point for the two phases. Heating for 2 h at 48 C reduces crystal numbers by 20 fold in comparison to the same solution heated for the same time at 30 C. Thermal treatment of solutions is therefore a possible tool to reduce crystal numbers and increase crystal size. The effects of a protein's previous thermal history are now shown to be a potentially critical factor in subsequent macromolecule crystal nucleation and growth studies.

-Based Slag System

NASA Astrophysics Data System (ADS)

Jiang, Binbin; Wang, Wanlin; Sohn, Il; Wei, Juan; Zhou, Lejun; Lu, Boxun

2014-06-01

The crystallization behavior of a CaO-Al2O3-based slag system with various ZrO2 content (from 1 to 5 wt pct) and CaO/Al2O3 (C/A) ratio (from 0.8 to 1.2) has been studied by using single hot thermocouple technology (SHTT) in this article. The continuous-cooling-transformation (CCT) diagrams and time-temperature-transformation (TTT) diagrams of the above slag system were constructed for the analysis of the varying crystallization behaviors. The results suggested that Al2O3 tended to enhance the slag samples crystallization when the C/A ratio ranged from 0.8 to 1.2, and the critical cooling rate and crystallization temperature increased with the decrease of C/A ratio; meanwhile, the incubation time was also getting shorter with the reduction of C/A ratio. The addition of ZrO2 would enhance the crystallization of slag samples because of the induced heterogeneous nucleation of molten slag. However, the general crystallization was determined by the balance between molten slag viscosity and heterogeneous nucleation, such that Sample 3 (C/A = 1.0, ZrO2 = 3 pct, B2O3 = 10 pct, Li2O = 3 pct [in wt pct]) would demonstrate the strongest crystallization kinetics in a high-temperature zone. The different crystals formed during the tests were also analyzed by scanning electron microscopy (SEM) and X-ray diffraction (XRD).

Vitrification of copper flotation waste.

PubMed

Karamanov, Alexander; Aloisi, Mirko; Pelino, Mario

2007-02-09

The vitrification of an hazardous iron-rich waste (W), arising from slag flotation of copper production, was studied. Two glasses, containing 30wt% W were melted for 30min at 1400 degrees C. The first batch, labeled WSZ, was obtained by mixing W, blast furnace slag (S) and zeolite tuff (Z), whereas the second, labeled WG, was prepared by mixing W, glass cullet (G), sand and limestone. The glass frits showed high chemical durability, measured by the TCLP test. The crystallization of the glasses was evaluated by DTA. The crystal phases formed were identified by XRD resulting to be pyroxene and wollastonite solid solutions, magnetite and hematite. The morphology of the glass-ceramics was observed by optical and scanning electron microscopy. WSZ composition showed a high rate of bulk crystallization and resulted to be suitable for producing glass-ceramics by a short crystallization heat-treatment. WG composition showed a low crystallization rate and good sinterability; glass-ceramics were obtained by sinter-crystallization of the glass frit.

Lab-on-a-Chip Based Protein Crystallization

NASA Technical Reports Server (NTRS)

vanderWoerd, Mark J.; Brasseur, Michael M.; Spearing, Scott F.; Whitaker, Ann F. (Technical Monitor)

2001-01-01

We are developing a novel technique with which we will grow protein crystals in very small volumes, utilizing chip-based, microfluidic ("LabChip") technology. This development, which is a collaborative effort between NASA's Marshall Space Flight Center and Caliper Technologies Corporation, promises a breakthrough in the field of protein crystal growth. Our initial results obtained from two model proteins, Lysozyme and Thaumatin, show that it is feasible to dispense and adequately mix protein and precipitant solutions on a nano-liter scale. The mixtures have shown crystal growth in volumes in the range of 10 nanoliters to 5 microliters. In addition, large diffraction quality crystals were obtained by this method. X-ray data from these crystals were shown to be of excellent quality. Our future efforts will include the further development of protein crystal growth with LabChip(trademark) technology for more complex systems. We will initially address the batch growth method, followed by the vapor diffusion method and the liquid-liquid diffusion method. The culmination of these chip developments is to lead to an on orbit protein crystallization facility on the International Space Station. Structural biologists will be invited to utilize the on orbit Iterative Biological Crystallization facility to grow high quality macromolecular crystals in microgravity.

Non-isothermal crystallization of poly(etheretherketone) aromatic polymer composite

NASA Technical Reports Server (NTRS)

Cebe, Peggy

1988-01-01

The nonisothermal crystallization kinetics of PEEK APC-2 and of 450G neat resin PEEK material were compared using a differential scanning calorimeter to monitor heat flow during crystallization; the effects of cooling rate on the crystallization temperature, the degree of crystallinity, and the conversion rate were investigated. A modified Avrami (1940) analysis was used to describe nonisothermal crystallization kinetics. It was found that, compared with the 450G neat resin PEEK, the nonisothermal crystallization of the PEEK APC-2 composite is characterized by higher initiation temperature, higher heat flow maximum temperature, and greater relative conversion by primary processes.

The initial cooling of pahoehoe flow lobes

USGS Publications Warehouse

Keszthelyi, L.; Denlinger, R.

1996-01-01

In this paper we describe a new thermal model for the initial cooling of pahoehoe lava flows. The accurate modeling of this initial cooling is important for understanding the formation of the distinctive surface textures on pahoehoe lava flows as well as being the first step in modeling such key pahoehoe emplacement processes as lava flow inflation and lava tube formation. This model is constructed from the physical phenomena observed to control the initial cooling of pahoehoe flows and is not an empirical fit to field data. We find that the only significant processes are (a) heat loss by thermal radiation, (b) heat loss by atmospheric convection, (c) heat transport within the flow by conduction with temperature and porosity-dependent thermal properties, and (d) the release of latent heat during crystallization. The numerical model is better able to reproduce field measurements made in Hawai'i between 1989 and 1993 than other published thermal models. By adjusting one parameter at a time, the effect of each of the input parameters on the cooling rate was determined. We show that: (a) the surfaces of porous flows cool more quickly than the surfaces of dense flows, (b) the surface cooling is very sensitive to the efficiency of atmospheric convective cooling, and (c) changes in the glass forming tendency of the lava may have observable petrographic and thermal signatures. These model results provide a quantitative explanation for the recently observed relationship between the surface cooling rate of pahoehoe lobes and the porosity of those lobes (Jones 1992, 1993). The predicted sensitivity of cooling to atmospheric convection suggests a simple field experiment for verification, and the model provides a tool to begin studies of the dynamic crystallization of real lavas. Future versions of the model can also be made applicable to extraterrestrial, submarine, silicic, and pyroclastic flows.

Investigations into the low temperature behavior of jet fuels: Visualization, modeling, and viscosity studies

NASA Astrophysics Data System (ADS)

Atkins, Daniel L.

Aircraft operation in arctic regions or at high altitudes exposes jet fuel to temperatures below freeze point temperature specifications. Fuel constituents may solidify and remain within tanks or block fuel system components. Military and scientific requirements have been met with costly, low freeze point specialty jet fuels. Commercial airline interest in polar routes and the use of high altitude unmanned aerial vehicles (UAVs) has spurred interest in the effects of low temperatures and low-temperature additives on jet fuel. The solidification of jet fuel due to freezing is not well understood and limited visualization of fuel freezing existed prior to the research presented in this dissertation. Consequently, computational fluid dynamics (CFD) modeling that simulates jet fuel freezing and model validation were incomplete prior to the present work. The ability to simulate jet fuel freezing is a necessary tool for fuel system designers. An additional impediment to the understanding and simulation of jet fuel freezing has been the absence of published low-temperature thermo-physical properties, including viscosity, which the present work addresses. The dissertation is subdivided into three major segments covering visualization, modeling and validation, and viscosity studies. In the first segment samples of jet fuel, JPTS, kerosene, Jet A and Jet A containing additives, were cooled below their freeze point temperatures in a rectangular, optical cell. Images and temperature data recorded during the solidification process provided information on crystal habit, crystallization behavior, and the influence of the buoyancy-driven flow on freezing. N-alkane composition of the samples was determined. The Jet A sample contained the least n-alkane mass. The cooling of JPTS resulted in the least wax formation while the cooling of kerosene yielded the greatest wax formation. The JPTS and kerosene samples exhibited similar crystallization behavior and crystal habits during cooling. Low-temperature additives modified the crystal habit of the Jet A fuel. Crystal shapes and sizes were recorded for use in future computational modeling. In the second segment, a computational fluid dynamics model was developed that simulates the solidification of jet fuel due to freezing in a buoyancy-driven flow. Flow resistance caused by porous crystal structures that exist in liquid-solid regions is simulated through the use of a momentum resistance source term. (Abstract shortened by UMI.)

Vacuum electrolysis of quartz

DOEpatents

King, James Claude

1976-01-13

The disclosure is directed to a method for processing quartz used in fabricating crystal resonators such that transient frequency change of resonators exposed to pulse irradiation is virtually eliminated. The method involves heating the crystal quartz in a hydrogen-free atmosphere while simultaneously applying an electric field in the Z-axis direction of the crystal. The electric field is maintained during the cool-down phase of the process.

A General Strategy for Nanohybrids Synthesis via Coupled Competitive Reactions Controlled in a Hybrid Process

PubMed Central

Wang, Rongming; Yang, Wantai; Song, Yuanjun; Shen, Xiaomiao; Wang, Junmei; Zhong, Xiaodi; Li, Shuai; Song, Yujun

2015-01-01

A new methodology based on core alloying and shell gradient-doping are developed for the synthesis of nanohybrids, realized by coupled competitive reactions, or sequenced reducing-nucleation and co-precipitation reaction of mixed metal salts in a microfluidic and batch-cooling process. The latent time of nucleation and the growth of nanohybrids can be well controlled due to the formation of controllable intermediates in the coupled competitive reactions. Thus, spatiotemporal-resolved synthesis can be realized by the hybrid process, which enables us to investigate nanohybrid formation at each stage through their solution color changes and TEM images. By adjusting the bi-channel solvents and kinetic parameters of each stage, the primary components of alloyed cores and the second components of transition metal doping ZnO or Al2O3 as surface coatings can be successively formed. The core alloying and shell gradient-doping strategy can efficiently eliminate the crystal lattice mismatch in different components. Consequently, varieties of gradient core-shell nanohybrids can be synthesized using CoM, FeM, AuM, AgM (M = Zn or Al) alloys as cores and transition metal gradient-doping ZnO or Al2O3 as shells, endowing these nanohybrids with unique magnetic and optical properties (e.g., high temperature ferromagnetic property and enhanced blue emission). PMID:25818342

Assessment of the Dehydration-Greenhouse Feedback Over the Arctic During Winter

NASA Astrophysics Data System (ADS)

Girard, E.; Stefanof, A.; Peltier-Champigny, M.; Munoz-Alpizar, R.; Dueymes, G.; Jean-Pierre, B.

2007-12-01

The effect of pollution-derived sulphuric acid aerosols on the aerosol-cloud-radiation interactions is investigated over the Arctic for February 1990. Observations suggest that acidic aerosols can decrease the heterogeneous nucleation rate of ice crystals and lower the homogeneous freezing temperature of haze droplets. Based on these observations, we hypothesize that the cloud thermodynamic phase is modified in polluted air mass (Arctic haze). Cloud ice number concentration is reduced, thus promoting further ice crystal growth by the Bergeron-Findeisen process. Hence, ice crystals reach larger sizes and low-level ice crystal precipitation from mixed-phase clouds increases. Enhanced dehydration of the lower troposphere contributes to decrease the water vapour greenhouse effect and cool the surface. A positive feedback is created between surface cooling and air dehydration, accelerating the cold air production. This process is referred to as the dehydration-greenhouse feedback (DGF). Simulations performed using an arctic regional climate model for February 1990, February and March 1985 and 1995 are used to assess the potential effect of the DGF on the Arctic climate. Results show that the DGF has an important effect over the Central and Eurasian Arctic, which is the coldest part of the Arctic with a surface cooling ranging between 0 and -3K. Moreover, the lower tropospheric cooling over the Eurasian and Central Arctic strengthens the atmospheric circulation at upper level, thus increasing the aerosol transport from the mid-latitudes and enhancing the DGF. Over warmer areas, the increased aerosol concentration (caused by the DGF) leads to longer cloud lifetime, which contributes to warm these areas. It is also shown that the maximum ice nuclei reduction must be of the order of 100 to get a significant effect.

Intracellular ice and cell survival in cryo-exposed embryonic axes of recalcitrant seeds of Acer saccharinum: an ultrastructural study of factors affecting cell and ice structures

PubMed Central

Wesley-Smith, James; Berjak, Patricia; Pammenter, N. W.; Walters, Christina

2014-01-01

Background and Aims Cryopreservation is the only long-term conservation strategy available for germplasm of recalcitrant-seeded species. Efforts to cryopreserve this form of germplasm are hampered by potentially lethal intracellular freezing events; thus, it is important to understand the relationships among cryo-exposure techniques, water content, structure and survival. Methods Undried embryonic axes of Acer saccharinum and those rapidly dried to two different water contents were cooled at three rates and re-warmed at two rates. Ultrastructural observations were carried out on radicle and shoot tips prepared by freeze-fracture and freeze-substitution to assess immediate (i.e. pre-thaw) responses to cooling treatments. Survival of axes was assessed in vitro. Key Results Intracellular ice formation was not necessarily lethal. Embryo cells survived when crystal diameter was between 0·2 and 0·4 µm and fewer than 20 crystals were distributed per μm2 in the cytoplasm. Ice was not uniformly distributed within the cells. In fully hydrated axes cooled at an intermediate rate, the interiors of many organelles were apparently ice-free; this may have prevented the disruption of vital intracellular machinery. Intracytoplasmic ice formation did not apparently impact the integrity of the plasmalemma. The maximum number of ice crystals was far greater in shoot apices, which were more sensitive than radicles to cryo-exposure. Conclusions The findings challenge the accepted paradigm that intracellular ice formation is always lethal, as the results show that cells can survive intracellular ice if crystals are small and localized in the cytoplasm. Further understanding of the interactions among water content, cooling rate, cell structure and ice structure is required to optimize cryopreservation treatments without undue reliance on empirical approaches. PMID:24368198

Intracellular ice and cell survival in cryo-exposed embryonic axes of recalcitrant seeds of Acer saccharinum: an ultrastructural study of factors affecting cell and ice structures.

PubMed

Wesley-Smith, James; Berjak, Patricia; Pammenter, N W; Walters, Christina

2014-03-01

Cryopreservation is the only long-term conservation strategy available for germplasm of recalcitrant-seeded species. Efforts to cryopreserve this form of germplasm are hampered by potentially lethal intracellular freezing events; thus, it is important to understand the relationships among cryo-exposure techniques, water content, structure and survival. Undried embryonic axes of Acer saccharinum and those rapidly dried to two different water contents were cooled at three rates and re-warmed at two rates. Ultrastructural observations were carried out on radicle and shoot tips prepared by freeze-fracture and freeze-substitution to assess immediate (i.e. pre-thaw) responses to cooling treatments. Survival of axes was assessed in vitro. Intracellular ice formation was not necessarily lethal. Embryo cells survived when crystal diameter was between 0·2 and 0·4 µm and fewer than 20 crystals were distributed per μm(2) in the cytoplasm. Ice was not uniformly distributed within the cells. In fully hydrated axes cooled at an intermediate rate, the interiors of many organelles were apparently ice-free; this may have prevented the disruption of vital intracellular machinery. Intracytoplasmic ice formation did not apparently impact the integrity of the plasmalemma. The maximum number of ice crystals was far greater in shoot apices, which were more sensitive than radicles to cryo-exposure. The findings challenge the accepted paradigm that intracellular ice formation is always lethal, as the results show that cells can survive intracellular ice if crystals are small and localized in the cytoplasm. Further understanding of the interactions among water content, cooling rate, cell structure and ice structure is required to optimize cryopreservation treatments without undue reliance on empirical approaches.

A new petrological and geophysical investigation of the present-day plumbing system of Mount Vesuvius

NASA Astrophysics Data System (ADS)

Pommier, A.; Tarits, P.; Hautot, S.; Pichavant, M.; Scaillet, B.; Gaillard, F.

2010-07-01

A model of the electrical resistivity of Mt. Vesuvius has been elaborated to investigate the present structure of the volcanic edifice. The model is based on electrical conductivity measurements in the laboratory, on geophysical information, in particular, magnetotelluric (MT) data, and on petrological and geochemical constraints. Both 1-D and 3-D simulations explored the effect of depth, volume and resistivity of either one or two reservoirs in the structure. For each configuration tested, modeled MT transfer functions were compared to field transfer functions from field magnetotelluric studies. The field electrical data are reproduced with a shallow and very conductive layer (˜0.5 km depth, 1.2 km thick, 5 ohm.m resistive) that most likely corresponds to a saline brine present beneath the volcano. Our results are also compatible with the presence of cooling magma batches at shallow depths (<3-4 km depth). The presence of a deeper body at ˜8 km depth, as suggested by seismic studies, is consistent with the observed field transfer functions if such a body has an electrical resistivity > ˜100 ohm.m. According to a petro-physical conductivity model, such a resistivity value is in agreement either with a low-temperature, crystal-rich magma chamber or with a small quantity of hotter magma interconnected in the resistive surrounding carbonates. However, the low quality of MT field data at long periods prevent from placing strong constraints on a potential deep magma reservoir. A comparison with seismic velocity values tends to support the second hypothesis. Our findings would be consistent with a deep structure (8-10 km depth) made of a tephriphonolitic magma at 1000°C, containing 3.5 wt%H2O, 30 vol.% crystals, and interconnected in carbonates in proportions ˜45% melt -55% carbonates.

Microgravity

NASA Image and Video Library

2001-01-24

Gaseous Nitrogen Dewar apparatus developed by Dr. Alex McPherson of the University of California, Irvine for use aboard Mir and the International Space Station allows large quantities of protein samples to be crystallized in orbit. The specimens are contained either in plastic tubing (heat-sealed at each end). Biological samples are prepared with a precipitating agent in either a batch or liquid-liquid diffusion configuration. The samples are then flash-frozen in liquid nitrogen before crystallization can start. On orbit, the Dewar is placed in a quiet area of the station and the nitrogen slowly boils off (it is taken up by the environmental control system), allowing the proteins to thaw to begin crystallization. The Dewar is returned to Earth after one to four months on orbit, depending on Shuttle flight opportunities. The tubes then are analyzed for crystal presence and quality

Facile control of silica nanoparticles using a novel solvent varying method for the fabrication of artificial opal photonic crystals

NASA Astrophysics Data System (ADS)

Gao, Weihong; Rigout, Muriel; Owens, Huw

2016-12-01

In this work, the Stöber process was applied to produce uniform silica nanoparticles (SNPs) in the meso-scale size range. The novel aspect of this work was to control the produced silica particle size by only varying the volume of the solvent ethanol used, whilst fixing the other reaction conditions. Using this one-step Stöber-based solvent varying (SV) method, seven batches of SNPs with target diameters ranging from 70 to 400 nm were repeatedly reproduced, and the size distribution in terms of the polydispersity index (PDI) was well maintained (within 0.1). An exponential equation was used to fit the relationship between the particle diameter and ethanol volume. This equation allows the prediction of the amount of ethanol required in order to produce particles of any target diameter within this size range. In addition, it was found that the reaction was completed in approximately 2 h for all batches regardless of the volume of ethanol. Structurally coloured artificial opal photonic crystals (PCs) were fabricated from the prepared SNPs by self-assembly under gravity sedimentation.

A study on cooling characteristics of clathrate compound as low temperature latent heat storage material

NASA Astrophysics Data System (ADS)

Kim, Chang Oh; Kim, Jin Heung; Chung, Nak Kyu

2007-07-01

Materials that can store low temperature latent heat are organic/inorganic chemicals, eutectic salt system and clathrate compound. Clathrate compound is the material that host compound in hydrogen bond forms cage and guest compound is included into it and combined. Crystallization of hydrate is generated at higher temperature than that of ice from pure water. And physical properties according to temperature are stable and congruent melting phenomenon is occurred without phase separation and it has relatively high latent heat. But clathrate compound still has supercooling problem occurred in the course of phase change and supercooling should be minimized because it affects efficiency of equipment very much. Therefore, various studies on additives to restrain this or heat storage methods are needed. Supercooling is the phenomenon that low temperature thermal storage material is not crystallized and existed as liquid for some time under phase change temperature. Because phase change into solid is delayed and it is existed as liquid due to this, heat transfer from low temperature thermal storage material is lowered. Therefore it is not crystallized at original phase change temperature and crystallized after cooled as much as supercooling degree and operation time of refrigerator is increased. In this study was investigated the cooling characteristics of the clathrate compound as a low temperature latent heat storage material. And additive was added to clathrate compound and its supercooling restrain effect was studied experimentally.

Silicon crystals: Process for manufacturing wafer-like silicon crystals with a columnar structure

NASA Technical Reports Server (NTRS)

Authier, B.

1978-01-01

Wafer-like crystals suitable for making solar cells are formed by pouring molten Si containing suitable dopants into a mold of the desired shape and allowing it to solidify in a temperature gradient, whereby the large surface of the melt in contact with the mold is kept at less than 200 D and the free surface is kept at a temperature of 200-1000 D higher, but below the melting point of Si. The mold can also be made in the form of a slit, whereby the 2 sides of the mold are kept at different temperatures. A mold was milled in the surface of a cylindrical graphite block 200 mm in diameter. The granite block was induction heated and the bottom of the mold was cooled by means of a water-cooled Cu plate, so that the surface of the mold in contact with one of the largest surfaces of the melt was held at approximately 800 D. The free surface of the melt was subjected to thermal radiation from a graphite plate located 2 mm from the surface and heated to 1500 D. The Si crystal formed after slow cooling to room temperature had a columnar structure and was cut with a diamond saw into wafers approximately 500 mm thick. Solar cells prepared from these wafers had efficiencies of 10 to 11%.

Batch manufacturing: Six strategic needs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ash, R.H.; Chappell, D.A.

1995-08-01

Since the advent of industrial digital control systems in the mid-1970s, industry has had the promise of integrated, configurable digital batch control systems to replace the morass of electromechanical devices like relays and stepping switches, recorders, and indicators which comprised the components of previous generations of batch control systems - the {open_quotes}monolithic monsters{close_quotes} of the 1960s and earlier. To help fulfill that promise, there have been many wide-ranging proprietary automation solutions for batch control since 1975, many of them technically excellent. However, even the best examples suffered from the lack of a common language and unifying concept permitting separate systemsmore » to be interconnected and work together. Today, some 20 years after the digital revolution began, industry has microprocessors, memory chips, data highways, and other marvelous technology to help automate the control of discontinuous processes. They also are on the way to having an accepted standard for batch automation, ISA S88. Batching systems are at once conceptually simple but executionally complex. The notion of adding ingredients one at a time to a vat, mixing, and then processing into final form is as old as the stone age. Every homemaker on earth, male or female, is familiar with how to follow a recipe to create some sumptuous item of culinary delight. Food recipes, so familiar and ubiquitous, are really just microcosms of the S88 recipe standard. They contain the same components: (1) Header (name and description of item being prepared, sometimes serving size); (2) Formula (list and amount of ingredients); (3) Equipment requirements (pans, mixing and cooking equipment); (4) Procedure (description of order of ingredient addition, mixing and other processing steps, baking/cooling time, and other processing steps); and (5) Other information (safety, cautions, and other miscellaneous instructions).« less

Vitrification of incinerated tannery sludge in silicate matrices for chromium stabilization.

PubMed

Varitis, S; Kavouras, P; Pavlidou, E; Pantazopoulou, E; Vourlias, G; Chrissafis, K; Zouboulis, A I; Karakostas, Th; Komninou, Ph

2017-01-01

The vitrification process was applied for the stabilization and solidification of a rich in chromium ash that was the by-product of incineration of tannery sludge. Six different batch compositions were produced, based on silica as the glass former and sodium and calcium oxides as flux agents. As-vitrified products (monoliths) were either composed of silicate matrices with separated from the melt Eskolaite (Cr 2 O 3 ) crystallites or were homogeneous glasses (in one case). All as-vitrified products were thermally treated in order to transform them to partially crystallized, i.e. devitrified products. Devitrification is an important part of the work since studying the transformation of the initial as-vitrified products into glass-ceramics with better properties could result to stabilized products with potential added value. The devitrified products were diversified by the effective crystallization mode and separated crystal phase composition. These variations originated from differences in: (a) batch composition of the initial as-vitrified products and (b) thermal treatment conditions. In devitrified products crystallization led to the separation of Devitrite (Na 2 Ca 3 Si 6 O 16 ), Combeite (Na 4 Ca 4 Si 6 O 18 ) and Wollastonite (CaSiO 3 ) crystalline phases, while Eskolaite crystallites were not affected by thermal treatment. Leaching test results revealed that chromium was successfully stabilized inside the as-vitrified monoliths. Devitrification impairs chromium stabilization, only in the case where the initial as-vitrified product was a homogeneous glass. In all other cases, devitrification did not affect successful chromium stabilization. Copyright © 2016 Elsevier Ltd. All rights reserved.

Programming scale-free optics in disordered ferroelectrics.

PubMed

Parravicini, Jacopo; Conti, Claudio; Agranat, Aharon J; DelRe, Eugenio

2012-06-15

Using the history dependence of a dipolar glass hosted in a compositionally disordered lithium-enriched potassium tantalate niobate (KTN:Li) crystal, we demonstrate scale-free optical propagation at tunable temperatures. The operating equilibration temperature is determined by previous crystal spiralling in the temperature/cooling-rate phase space.

Concomitant Ordering and Symmetry Lowering

ERIC Educational Resources Information Center

Boo, William O. J.; Mattern, Daniell L.

2008-01-01

Examples of concomitant ordering include magnetic ordering, Jahn-Teller cooperative ordering, electronic ordering, ionic ordering, and ordering of partially-filled sites. Concomitant ordering sets in when a crystal is cooled and always lowers the degree of symmetry of the crystal. Concomitant ordering concepts can also be productively applied to…

Calcium phosphates recovery from digester supernatant by fast precipitation and recrystallization

NASA Astrophysics Data System (ADS)

Vasenko, Liubov; Qu, Haiyan

2018-01-01

Conditional solubility of dicalcium phosphate dihydrate (DCPD) and hydroxyapatite (HAp) in digester supernatant was determined as a function of pH and was compared to its conditional solubility in distilled water. Conditional solubility of both substances in digester supernatant at pH >5-6 was higher than their conditional solubility in pure water due to the presence of impurities, and this influence is more significant for HAp. Amorphous CaP was precipitated through a fast precipitation process from digester supernatant with initial total phosphate concentration 0.008 mol/L and 0.015 mol/L and Ca/P ratios 2 and 5. The amorphous CaP can be subsequently recrystallized into crystalline CaP. Obtained amorphous products have Ca/P ratio > 1, which allow performing the recrystallization process without further Ca dosing into the system. Batch recrystallization of the amorphous products resulted in crystallization of HAp, DCPD or their mixture depending on the conditions of the process. Maximum achieved P-recovery was 69.5%. The increase of phosphate concentration and the addition of seeding decreased the yield of the process but promoted crystallization of DCPD. The increase of Ca/P ratio had a positive effect on the total P-recovery. Compared with the direct batch crystallization of CaP from digester supernatant, the two-step process with fast precipitation and recrystallization significantly improved the color of the obtained products.

Petrogenesis of Mount Rainier andesite: magma flux and geologic controls on the contrasting differentiation styles at stratovolcanoes of the southern Washington Cascades

USGS Publications Warehouse

Sisson, Thomas W.; Salters, V.J.M.; Larson, P.B.

2013-01-01

The dominant cause of magmatic evolution at Mount Rainier, however, is inferred to be a version of in situ crystallization-differentiation and mixing (Langmuir, 1989) wherein small magma batches stall as crustal intrusions and solidify extensively, yielding silicic residual liquids with trace element concentrations influenced by accessory mineral saturation. Subsequent magmas ascending through the intrusive plexus entrain and mix with the residual liquids and low-degree re-melts of those antecedent intrusions, producing hybrid andesites and dacites. Mount St. Helens volcanic rocks have geochemical similarities to those at Mount Rainier, and may also result from in situ differentiation and mixing due to low and intermittent long-term magma supply, accompanied by modest crustal assimilation. Andesites and dacites of Mount Adams isotopically overlap the least contaminated Mount Rainier magmas and derive from similar parental magma types, but have trace element variations more consistent with progressive crystallization-differentiation, probably due to higher magma fluxes leading to slower crystallization of large magma batches, allowing time for progressive separation of minerals from melt. Mount Adams also sits atop the southern projection of a regional anticlinorium, so Eocene sediments are absent, or are at shallow crustal levels, and so are cold and difficult to assimilate. Differences between southwest Washington stratovolcanoes highlight some ways that crustal geology and magma flux are primary factors in andesite generation.

Investigation of the solid state properties of amoxicillin trihydrate and the effect of powder pH.

PubMed

Ghassempour, Alireza; Rafati, Hasan; Adlnasab, Laleh; Bashour, Yosef; Ebrahimzadeh, Homeira; Erfan, Mohammad

2007-11-09

The purpose of this research was to investigate some physicochemical and solid-state properties of amoxicillin trihydrate (AMT) with different powder pH within the pharmacopoeia-specified range. AMT batches prepared using Dane salt method with the pH values from 4.39 to 4.97 were subjected to further characterization studies. Optical and scanning electron microscopy showed that different batches of AMT powders were similar in crystal habit, but the length of the crystals increased as the pH increased. Further solid-state investigations using powder x-ray diffraction (PXRD) demonstrated the same PXRD pattern, but the intensity of the peaks raised by the powder pH, indicated increased crystallinity. Differential scanning calorimetry (DSC) studies further confirmed that as the powder pH increased, the crystallinity and, hence, thermal stability of AMT powders increased. Searching for the possible cause of the variations in the solid state properties, HPLC analysis showed that despite possessing the requirements of the United States Pharmacopoeia (USP) for purity/impurity profile, there was a direct relationship between the increase of the powder pH and the purity of AMT, and also decrease in the impurity I (alpha-Hydroxyphenylglycine) concentration in AMT powder. Recrystallization studies confirmed that the powder pH could be controlled by adjusting the pH of the crystallization.

Crystallization and preliminary X-ray characterization of the eukaryotic replication terminator Reb1-Ter DNA complex.

PubMed

Jaiswal, Rahul; Singh, Samarendra K; Bastia, Deepak; Escalante, Carlos R

2015-04-01

The Reb1 protein from Schizosaccharomyces pombe is a member of a family of proteins that control programmed replication termination and/or transcription termination in eukaryotic cells. These events occur at naturally occurring replication fork barriers (RFBs), where Reb1 binds to termination (Ter) DNA sites and coordinates the polar arrest of replication forks and transcription approaching in opposite directions. The Reb1 DNA-binding and replication-termination domain was expressed in Escherichia coli, purified and crystallized in complex with a 26-mer DNA Ter site. Batch crystallization under oil was required to produce crystals of good quality for data collection. Crystals grew in space group P2₁, with unit-cell parameters a = 68.9, b = 162.9, c = 71.1 Å, β = 94.7°. The crystals diffracted to a resolution of 3.0 Å. The crystals were mosaic and required two or three cycles of annealing. This study is the first to yield structural information about this important family of proteins and will provide insights into the mechanism of replication and transcription termination.

Crystallization, flow and thermal histories of lunar and terrestrial compositions

NASA Technical Reports Server (NTRS)

Uhlmann, D. R.

1979-01-01

Contents: a kinetic treatment of glass formation; effects of nucleating heterogeneities on glass formation; glass formation under continuous cooling conditions; crystallization statistics; kinetics of crystal nucleation; diffusion controlled crystal growth; crystallization of lunar compositions; crystallization between solidus and liquidus; crystallization on reheating a glass; temperature distributions during crystallization; crystallization of anorthite and anorthite-albite compositions; effect of oxidation state on viscosity; diffusive creep and viscous flow; high temperature flow behavior of glass-forming liquids, a free volume interpretation; viscous flow behavior of lunar compositions; thermal history of orange soil material; breccias formation by viscous sintering; viscous sintering; thermal histories of breccias; solute partitioning and thermal history of lunar rocks; heat flow in impact melts; and thermal histories of olivines.

In situ visualization of domain structure evolution during field cooling in 0.67PMN-0.33PT single crystal

NASA Astrophysics Data System (ADS)

Ushakov, A. D.; Esin, A. A.; Chezganov, D. S.; Turygin, A. P.; Akhmatkhanov, A. R.; Hu, Q.; Sun, L.; Wei, X.; Shur, V. Ya

2017-10-01

The evolution of the domain structure during in-field cooling was in situ studied in [001]-cut single crystals of relaxor ferroelectric (1-x)Pb(Mg1/3Nb2/3)O3-xPbTiO3 (PMN-PT) with x = 0.33 with maximum of dielectric permittivity at 150°C. The main stages of domain evolution have been separated. The visualization of the static as-grown and polarized domain structures with high spatial resolution by piezoresponse force microscopy and scanning electron microscopy allowed measuring the characteristic features of maze and needle-like domain structures.

On the behaviour and origin of the major deep level (EL2) in GaAs

NASA Technical Reports Server (NTRS)

Lagowski, J.; Parsey, J. M.; Kaminska, M.; Wada, K.; Gatos, H. C.

1982-01-01

In an extensive crystal growth and characterization study of Bridgman-grown GaAs it was established that the following factors affect the concentration of the EL2 level: (1) the As pressure during growth; (2) the partial pressure of Ga2O; (3) the concentration of shallow donors and acceptors; and (4) the post-growth cooling cycle. The role of these factors is qualitatively and quantitatively explained by attributing the 0.82 eV donor state to the antisite defect As-sub-Ga formed as a result of Ga-vacancy migration during the post-growth cooling of the crystals.

Crystallization and transformation of polymorphic forms of trioleoyl glycerol and 1,2-dioleoyl-3-rac-linoleoyl glycerol.

PubMed

Bayés-García, Laura; Calvet, Teresa; Cuevas-Diarte, Miquel Àngel; Ueno, Satoru; Sato, Kiyotaka

2013-08-08

This study examined the influence of different thermal treatments on the crystallization and transformation of trioleoyl glycerol (OOO) and 1,2-dioleoyl-3-rac-linoleoyl glycerol (OOL). Two triacylglycerol (TAG) samples were cooled at 0.5-15 °C·min(-1) and heated at 2 and 15 °C·min(-1). The polymorphic characteristics of the two TAGs were analyzed in situ using differential scanning calorimetry, Raman spectroscopy, and synchrotron radiation X-ray diffraction. Multiple polymorphic forms were identified in OOO (α, β'2, β'1, β2, and β1) and OOL (α, β'2, and β'1). Larger quantities of more stable forms (e.g., β2 and β1 of OOO and β'1 of OOL) were obtained when the samples were slowly cooled and heated. In contrast, less stable polymorphs were obtained with increased cooling and heating rates. Polymorphic transformations occurred in either solid-state or melt-mediation and were influenced by heating rates. The results were analyzed by considering the activation energies for crystallization and transformation of stable and less stable polymorphic forms in comparison with previous studies on 1,3-dipalmitoyl-2-oleoyl-glycerol and 1, 3-dioleoyl-2-palmitoyl-glycerol.

Evaluating the mush extraction + multiple magma batch model for the Lake City magmatic system (Colorado, USA) using zircon U/Pb TIMS-TEA

NASA Astrophysics Data System (ADS)

Pamukcu, A. S.; Schoene, B.; Deering, C. D.

2016-12-01

Volcanic eruptions that involve a wide range of magma types highlight questions on genetic and geometric relationships between magmas in the crust prior to eruption. The Lake City magmatic system (Colorado, USA) is one such example: exposed in the caldera are ignimbrites from the 23 Ma Sunshine Peak Tuff, which range in composition and crystallinity with time (crystal-poor rhyolite to crystal-rich trachyte), and resurgent intrusions of porphyritic syenite, monzonite, and dacite (Hon 1987). Field relations and bulk rock geochemistry suggest the Lake City magmatic system was complex, with magmas of these various types existing concurrently as multiple magma batches, though not necessarily always in contact (Kennedy et al. 2015). Geochemical modeling further suggests that the crystal-poor rhyolites were liquids extracted from a syenitic mush and that the crystal-rich trachytes are remobilized portions of this cumulate. To address the genetic and geometric links between these magmas in more detail, we utilize TIMS-TEA to assess U/Pb zircon geochronology and trace element geochemistry in concert. For each eruptive unit/magma type, zircons were roughly separated into size groupings (small, medium, large), imaged by cathodoluminescence (CL), and analyzed individually by CA-ID-TIMS. Preliminary results indicate that zircons crystallized over a period of 177±31 ky, which is within the range suggested by Ar/Ar geochronology (80-300 ky, Bove et al. 2001). Consistent with the current model for the Lake City system, zircons from the rhyolites and trachytes overlap in age, while those of the dacites are younger. There is no clear relationship between age and CL zoning pattern or crystal size (e.g., small crystals are not always the youngest). We can further address relationships between the rhyolite, trachyte, and syenite using TEA to assess trace elements of the dated zircons. Rhyolite-MELTS models suggest that zircons crystallized in a rhyolitic melt derived from the trachyte/syenite will have similar LREEs and MREEs but higher HREEs than those that crystallized in the mush. In addition, if the trachytes are remobilized cumulates that are represented by the post-caldera syenites, we expect that trace element contents of zircon from these units will be largely similar.

Crystal growth of intermetallic clathrates: Floating zone process and ultra rapid crystallization

NASA Astrophysics Data System (ADS)

Prokofiev, A.; Yan, X.; Ikeda, M.; Löffler, S.; Paschen, S.

2014-09-01

We studied the crystal growth process of type-I transition metal clathrates in two different regimes: a regime of moderate cooling rate, realized with the floating zone technique, and a regime of ultra rapid cooling, realized by the melt spinning technique. In the former regime, bulk Ba8AuxSi46-x and Ba8Cu4.8GaxGe41.2-x single crystals were grown. We investigated segregation effects of the constituting elements by measurements of the composition profiles along the growth direction. The compositional non-uniformity results in a spatial variation of the electrical resistivity which is discussed as well. Structural features of clathrates and their extremely low thermal conductivities imply specifics in growth behavior which manifest themselves most pronouncedly in a rapid crystallization process. Our melt spinning experiments on Ba8Au5Si41 and Ba8Ni3.5Si42.5 (and earlier on some other clathrates) have revealed surprisingly large grains of at least 1 μm. Because of the anomalously high growth rate of the clathrate phase the formation of impurity phases is considerably kinetically suppressed. We present our scanning and transmission electron microscopy investigations of melt spun samples and discuss structural, thermodynamic and kinetic aspects of the unusual clathrate nucleation and crystallization.

Operation condition for continuous anti-solvent crystallization of CBZ-SAC cocrystal considering deposition risk of undesired crystals

NASA Astrophysics Data System (ADS)

Nishimaru, Momoko; Nakasa, Miku; Kudo, Shoji; Takiyama, Hiroshi

2017-07-01

Crystallization operation of cocrystal production has deposition risk of undesired crystals. Simultaneously, continuous manufacturing processes are focused on. In this study, conditions for continuous cocrystallization considering risk reduction of undesired crystals deposition were investigated on the view point of thermodynamics and kinetics. The anti-solvent cocrystallization was carried out in four-component system of carbamazepine, saccharin, methanol and water. From the preliminary batch experiment, the relationships among undesired crystal deposition, solution composition decided by mixing ratio of solutions, and residence time for the crystals were considered, and then the conditions of continuous experiment were decided. Under these conditions, the continuous experiment was carried out. The XRD patterns of obtained crystals in the continuous experiment showed that desired cocrystals were obtained without undesired crystals. This experimental result was evaluated by using multi-component phase diagrams from the view point of the operation point's movement. From the evaluation, it was found that there is a certain operation condition which the operation point is fixed with time in the specific domain without the deposition risk of undesired single component crystals. It means the possibility of continuous production of cocrystals without deposition risk of undesired crystals was confirmed by using multi-component phase diagrams.

Rheological Characterization of Molten Polymer-Drug Dispersions as a Predictive Tool for Pharmaceutical Hot-Melt Extrusion Processability.

PubMed

Van Renterghem, Jeroen; Vervaet, Chris; De Beer, Thomas

2017-11-01

The aim of this study was to investigate (i) the influence of drug solid-state (crystalline or dissolved in the polymer matrix) on the melt viscosity and (ii) the influence of the drug concentration, temperature and shear rate on polymer crystallization using rheological tests. Poly (ethylene oxide) (PEO) (100.000 g/mol) and physical mixtures (PM) containing 10-20-30-40% (w/w) ketoprofen or 10% (w/w) theophylline in PEO were rheologically characterized. Rheological tests were performed (frequency and temperature sweeps in oscillatory shear as well as shear-induced crystallization experiments) to obtain a thorough understanding of the flow behaviour and crystallization of PEO-drug dispersions. Theophylline did not dissolve in PEO as the complex viscosity (η*) of the drug-polymer mixture increased as compared to that of neat PEO. In contrast, ketoprofen dissolved in PEO and acted as a plasticizer, decreasing η*. Acting as a nucleating agent, theophylline induced the crystallization of PEO upon cooling from the melt. On the other hand, ketoprofen inhibited crystallization upon cooling. Moreover, higher concentrations of ketoprofen in the drug-polymer mixture increasingly inhibited polymer crystallization. However, shear-induced crystallization was observed for all tested mixtures containing ketoprofen. The obtained rheological results are relevant for understanding and predicting HME processability (e.g., barrel temperature selection) and downstream processing such as injection moulding (e.g., mold temperature selection).

Phase transformations, anisotropic pyroelectric energy harvesting and electrocaloric properties of (Pb,La)(Zr,Sn,Ti)O3 single crystals.

PubMed

Zhuo, Fangping; Li, Qiang; Gao, Jinghan; Yan, Qingfeng; Zhang, Yiling; Xi, Xiaoqing; Chu, Xiangcheng

2017-05-31

(Pb,La)(Zr,Sn,Ti)O 3 (PLZST) single crystals with their chemical composition located at the tetragonal antiferroelectric region are grown via the flux method in a PbO-PbF 2 -B 2 O 3 mixture. Segregation of the Ti 4+ component in the as-grown crystals is observed due to the strong affinity between the oxygen anion and Ti 4+ ions. The critical electric field of the antiferroelectric to ferroelectric phase transition is determined to be about 0.5 kV mm -1 . The electric field induced ferroelectric phase transforms back into the antiferroelectric phase at a depolarization temperature of 125 °C. Anisotropy of the harvested energy density and electrocaloric behaviors are achieved for the [100], [110] and [111]-oriented PLZST crystals. Based on the thermodynamic theory approach, all the abovementioned behaviors originate from the anisotropic total entropy change. Enhanced electrocaloric strength (0.3 K mm kV -1 ) and the harvested energy density of 0.62 J cm -3 are obtained in the [111]-oriented PLZST crystals. Our results demonstrate the competence of PLZST single crystals for cooling devices and pyroelectric energy harvesting and provide new opportunities to improve energy harvesting density and electrocaloric properties via the anisotropic structural layout, which make the PLZST crystals attractive for solid state cooling devices and energy conversion technologies.

The effects of crystallization and residual glass on the chemical durability of iron phosphate waste forms containing 40 wt% of a high MoO3 Collins-CLT waste

NASA Astrophysics Data System (ADS)

Hsu, Jen-Hsien; Bai, Jincheng; Kim, Cheol-Woon; Brow, Richard K.; Szabo, Joe; Zervos, Adam

2018-03-01

The effects of cooling rate on the chemical durability of iron phosphate waste forms containing up to 40 wt% of a high MoO3 Collins-CLT waste simulant were determined at 90 °C using the product consistency test (PCT). The waste form, designated 40wt%-5, meets appropriate Department of Energy (DOE) standards when rapidly quenched from the melt (as-cast) and after slow cooling following the CCC (canister centerline cooling)-protocol, although the quenched glass is more durable. The analysis of samples from the vapor hydration test (VHT) and the aqueous corrosion test (differential recession test) reveals that rare earth orthophosphate (monazite) and Zr-pyrophosphate crystals that form on cooling are more durable than the residual glass in the 40wt%-5 waste form. The residual glass in the CCC-treated samples has a greater average phosphate chain length and a lower Fe/P ratio, and those contribute to its faster corrosion kinetics.

Geochemistry, thermometry and isotope ratios on the same zircon crystals: the tandem use of quadrupole LA-ICPMS and CA-TIMS

NASA Astrophysics Data System (ADS)

Olin, P. H.; Schmitz, M. D.; Crowley, J. L.

2011-12-01

Current trends in igneous petrology include the extraction of diverse geochemical information from smaller sample targets by ever more efficient and cost effective means. Igneous zircons are repositories of several types of petrogenetic information, such as magmatic crystallization ages obtained using U-Pb geochronology, magmatic temperatures using Ti-in-zircon geothermometry, and magmatic differentiation and/or mixing trends using trace element contents. Here we demonstrate a tandem quadrupole LA-ICPMS and CA-TIMS approach on single zircon crystals and within domains in single crystals, which extracts all of these data from a single laser spot analysis and then guides the acquisition of CA-TIMS ages at precisions relevant to magmatic histories. We present data from zircon-bearing intrusive and extrusive rocks spanning the compositional spectrum, and highlight results from silicic volcanic rocks with different affinities. The utility of our approach is illustrated in zircons from the Temora diorite, a commonly used standard material which we analysed using 25-μm ablation spots placed on dozens of grains which had been previously annealed and chemically abraded prior to mounting in epoxy. Our LA-ICPMS results illustrate a 3- to 5-fold variation in trace element concentrations and trace element ratios over >150 degrees of cooling as estimated from Ti-in-zircon thermometry. Some geochemical parameters (e.g., Nb/Ta variations and Eu anomalies) are consistent with crystal fractionation during progressive crystallization, while others are bimodal (e.g., Hf and U contents), suggesting the mixing of crystal/magma batches prior to final solidification. LA-ICPMS U-Pb spot ages reproduce the accepted CA-TIMS age within 2% precision and accuracy, while our CA-TIMS results on the same grains constrain the development of the observed geochemical variability to within 100 ka. Other zircon standard materials to be presented include Plesovich syenite, FC1 gabbro, and R33 diorite. Analyses of zircons from selected western Snake River Plain silicic volcanic units further demonstrate the capability of our approach. These units are targeted with the overarching goal of better understanding magmatism in the region and to identify geochemical fingerprints to better distinguish among and to correlate between units. Several rhyolites distributed along the northern margin of the plain have LA-ICPMS ages of ca. 11 Ma, within error of each other and their CA-TIMS ages, and reveal differences in temperatures of crystallization and trace element contents and ratios. Individual units have crystallization temperatures that span 100 degrees or more, and show correlations with whole-rock major and trace element contents and ratios. In many cases, zircon geochemical parameters such as REE and Y contents, and Nb/Ta and Th/U ratios allow units proximal to each other to be distinguished from one another while also providing fingerprints to correlate to distal units on the south side of the plain or elsewhere in the province.

Unsteady High Turbulence Effects on Turbine Blade Film Cooling Heat Transfer Performance Using a Transient Liquid Crystal Technique

NASA Technical Reports Server (NTRS)

Han, J. C.; Ekkad, S. V.; Du, H.; Teng, S.

2000-01-01

Unsteady wake effect, with and without trailing edge ejection, on detailed heat transfer coefficient and film cooling effectiveness distributions is presented for a downstream film-cooled gas turbine blade. Tests were performed on a five-blade linear cascade at an exit Reynolds number of 5.3 x 10(exp 5). Upstream unsteady wakes were simulated using a spoke-wheel type wake generator. Coolant blowing ratio was varied from 0.4 to 1.2; air and CO2 were used as coolants to simulate different density ratios. Surface heat transfer and film effectiveness distributions were obtained using a transient liquid crystal technique; coolant temperature profiles were determined with a cold wire technique. Results show that Nusselt numbers for a film cooled blade are much higher compared to a blade without film injection. Unsteady wake slightly enhances Nusselt numbers but significantly reduces film effectiveness versus no wake cases. Nusselt numbers increase only slic,htly but film cooling, effectiveness increases significantly with increasing, blowing ratio. Higher density coolant (CO2) provides higher effectiveness at higher blowing ratios (M = 1.2) whereas lower density coolant (Air) provides higher 0 effectiveness at lower blowing ratios (M = 0.8). Trailing edge ejection generally has more effect on film effectiveness than on the heat transfer, typically reducing film effectiveness and enhancing heat transfer. Similar data is also presented for a film cooled cylindrical leading edge model.

Survival of plant tissue at super-low temperatures v. An electron microscope study of ice in cortical cells cooled rapidly.

PubMed

Sakai, A; Otsuka, K

1967-12-01

Experiments were carried out with cortical cells in twig bark of mulberry trees in winter in order to clarify the mechanism of survival at super-low temperatures with rapid cooling and rewarming. Attention was given to the relation between the existence of intracellular ice crystals and survival.Cortical cells were cooled rapidly by direct immersion into liquid nitrogen or isopentane cooled at various temperatures. After immersion, they were freeze-substituted with absolute ethanol at -78 degrees . They were then embedded, sectioned and examined under the electron microscope for the presence and distribution of cavities left after ice removal.Cells were found to remain alive and contain no ice cavities when immersed rapidly into isopentane baths kept below -60 degrees . Those cells at intermediate temperatures from -20 degrees to -45 degrees , were almost all destroyed. It was also observed that many ice cavities were contained in the cells immersed rapidly into isopentane baths at -30 degrees . The data seem to indicate that no ice crystals were formed when cooled rapidly by direct immersion into isopentane baths below -60 degrees or into liquid nitrogen.The tissue sections immersed in liquid nitrogen were rapidly transferred to isopentane baths at temperatures ranging from -70 degrees to -10 degrees before rapid rewarming. There was little damage when samples were held at temperatures below -50 degrees for 10 minutes or below -60 degrees for 16 hours. No cavities were found in these cells. Above -45 degrees , and especially at -30 degrees , however, all cells were completely destroyed even when exposed only for 1 minute. Many ice cavities were observed throughout these cells. The results obtained may be explained in terms of the growth rate of intracellular ice crystals.

Fragile morphotropic phase boundary and phase stability in the near-surface region of the relaxor ferroelectric (1 -x ) Pb (Z n1 /3N b2 /3) O3-x PbTi O3 : [001] field-cooled phase diagrams

NASA Astrophysics Data System (ADS)

Wang, Yaojin; Wang, Ding; Yuan, Guoliang; Ma, He; Xu, Feng; Li, Jiefang; Viehland, D.; Gehring, Peter M.

2016-11-01

We have examined the effects of field cooling on the phase diagram of the relaxor system (1 -x ) Pb (Z n1 /3N b2 /3) O3-x PbTi O3 (PZN-x PT ) for compositions near the morphotropic phase boundary (MPB). High-resolution diffraction measurements using Cu Kα x rays, which probe ≈3 μ m below the crystal surface, were made on field-cooled (FC) single-crystal specimens of PZN-4.5 %PT and PZN-6.5 %PT under electric fields of 1 and 2 kV/cm applied along [001] and combined with previous neutron diffraction data, which probe the entire crystal volume, for FC PZN-8 %PT [Ohwada et al., Phys. Rev. B 67, 094111 (2003), 10.1103/PhysRevB.67.094111]. A comparison to the zero-field-cooled (ZFC) PZN-x PT phase diagram reveals several interesting features: (1) The short-range monoclinic phase observed in the ZFC state on the low-PT side of the MPB is replaced by a monoclinic MA phase; (2) field cooling extends the tetragonal phase to higher temperatures and lower-PT concentrations; (3) the orthorhombic phase near the MPB is replaced by a monoclinic MC phase; (4) the vertical MPB in the ZFC phase diagram bends significantly towards the low-PT side in the FC state. These results demonstrate that both the phase stability and the nature of the MPB in PZN-PT within the near-surface regions are fragile in the presence of electric fields.

Comprehensive Evaluation of Biological Growth Control by Chlorine-Based Biocides in Power Plant Cooling Systems Using Tertiary Effluent

PubMed Central

Chien, Shih-Hsiang; Dzombak, David A.; Vidic, Radisav D.

2013-01-01

Abstract Recent studies have shown that treated municipal wastewater can be a reliable cooling water alternative to fresh water. However, elevated nutrient concentration and microbial population in wastewater lead to aggressive biological proliferation in the cooling system. Three chlorine-based biocides were evaluated for the control of biological growth in cooling systems using tertiary treated wastewater as makeup, based on their biocidal efficiency and cost-effectiveness. Optimal chemical regimens for achieving successful biological growth control were elucidated based on batch-, bench-, and pilot-scale experiments. Biocide usage and biological activity in planktonic and sessile phases were carefully monitored to understand biological growth potential and biocidal efficiency of the three disinfectants in this particular environment. Water parameters, such as temperature, cycles of concentration, and ammonia concentration in recirculating water, critically affected the biocide performance in recirculating cooling systems. Bench-scale recirculating tests were shown to adequately predict the biocide residual required for a pilot-scale cooling system. Optimal residuals needed for proper biological growth control were 1, 2–3, and 0.5–1 mg/L as Cl2 for NaOCl, preformed NH2Cl, and ClO2, respectively. Pilot-scale tests also revealed that Legionella pneumophila was absent from these cooling systems when using the disinfectants evaluated in this study. Cost analysis showed that NaOCl is the most cost-effective for controlling biological growth in power plant recirculating cooling systems using tertiary-treated wastewater as makeup. PMID:23781129

Comprehensive Evaluation of Biological Growth Control by Chlorine-Based Biocides in Power Plant Cooling Systems Using Tertiary Effluent.

PubMed

Chien, Shih-Hsiang; Dzombak, David A; Vidic, Radisav D

2013-06-01

Recent studies have shown that treated municipal wastewater can be a reliable cooling water alternative to fresh water. However, elevated nutrient concentration and microbial population in wastewater lead to aggressive biological proliferation in the cooling system. Three chlorine-based biocides were evaluated for the control of biological growth in cooling systems using tertiary treated wastewater as makeup, based on their biocidal efficiency and cost-effectiveness. Optimal chemical regimens for achieving successful biological growth control were elucidated based on batch-, bench-, and pilot-scale experiments. Biocide usage and biological activity in planktonic and sessile phases were carefully monitored to understand biological growth potential and biocidal efficiency of the three disinfectants in this particular environment. Water parameters, such as temperature, cycles of concentration, and ammonia concentration in recirculating water, critically affected the biocide performance in recirculating cooling systems. Bench-scale recirculating tests were shown to adequately predict the biocide residual required for a pilot-scale cooling system. Optimal residuals needed for proper biological growth control were 1, 2-3, and 0.5-1 mg/L as Cl 2 for NaOCl, preformed NH 2 Cl, and ClO 2 , respectively. Pilot-scale tests also revealed that Legionella pneumophila was absent from these cooling systems when using the disinfectants evaluated in this study. Cost analysis showed that NaOCl is the most cost-effective for controlling biological growth in power plant recirculating cooling systems using tertiary-treated wastewater as makeup.

Improvement in Stability of SPring-8 Standard X-Ray Monochromators with Water-Cooled Crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yamazaki, Hiroshi; Shimizu, Nobtaka; Kumasaka, Takashi

2010-06-23

SPring-8 standard double-crystal monochromators containing water-cooled crystals were stabilized to a sufficient level to function as a part of optics components to supply stable microfocused x-ray beams, by determining causes of the instability and then removing them. The instability was caused by two factors--thermal deformation of fine stepper stages in the monochromator, which resulted in reduction in beam intensity with time, and vibrations of coolant supply units and vacuum pumps, which resulted in fluctuation in beam intensity. We remodeled the crystal holders to maintain the stage temperatures constant with water, attached x-ray and electron shields to the stages in ordermore » to prevent their warming up, introduced accumulators in the water circuits to absorb pressure pulsation, used polyurethane tubes to stabilize water flow, and placed rubber cushions under scroll vacuum pumps. As a result, the intensity reduction rate of the beam decreased from 26% to 1% per hour and the intensity fluctuation from 13% to 1%. The monochromators were also modified to prevent radiation damage to the crystals, materials used as a water seal, and motor cables.« less

Growth, structural, thermal, dielectric and optical studies on HBST crystal: A potential THz emitter.

PubMed

Ma, Yuzhe; Teng, Bing; Cao, Lifeng; Zhong, Degao; Ji, Shaohua; Teng, Fei; Liu, Jiaojiao; Yao, Yuan; Tang, Jie; Tong, Jiaming

2018-02-05

The efficient organic nonlinear optical material 4-hydroxy benzaldehyde-N-methyl 4-stilbazolium tosylate (HBST) was grown from methanol by slope nucleation method combined with slow cooling (SNM-SC) for the first time. The optimum growth conditions based on the cooling rate was further investigated. The single crystal X-ray diffraction (XRD) revealed that the chromophores of HBST crystal make an angle of about 33° with respect to the a-axis, which is close to the optimum of Terahertz (THz)-wave generation and electro-optics applications. NMR and FT-IR spectral studies have been performed to ascertain various functional groups present in the sample. Futhermore, the thermal stability and decomposition stages were analyzed through TG-DTA and DSC techniques. The dielectric constant and dielectric loss of HBST crystal have been studied. Critical optical properties like the absorption coefficient, refractive index, cut-off wavelength and band gap energy were calculated. Photoluminescence (PL) exication studies indicated green emission occured at 507nm. All the results of HBST crystal make it a promising candidate in the fields of optoelectronic and the generation of THz. Copyright © 2017 Elsevier B.V. All rights reserved.

The effect of growth temperature on the irreversibility line of MPMG YBCO bulk with Y2O3 layer

NASA Astrophysics Data System (ADS)

Kurnaz, Sedat; Çakır, Bakiye; Aydıner, Alev

2017-07-01

In this study, three kinds of YBCO samples which are named Y1040, Y1050 and Y1060 were fabricated by Melt-Powder-Melt-Growth (MPMG) method without a seed crystal. Samples seem to be single crystal. The compacted powders were located on a crucible with a buffer layer of Y2O3 to avoid liquid to spread on the furnace plate and also to support crystal growth. YBCO samples were investigated by magnetoresistivity (ρ-T) and magnetization (M-T) measurements in dc magnetic fields (parallel to c-axis) up to 5 T. Irreversibility fields (Hirr) and upper critical fields (Hc2) were obtained using 10% and 90% criteria of the normal state resistivity value from ρ-T curves. M-T measurements were carried out using the zero field cooling (ZFC) and field cooling (FC) processes to get irreversible temperature (Tirr). Fitting of the irreversibility line results to giant flux creep and vortex glass models were discussed. The results were found to be consistent with the results of the samples fabricated using a seed crystal. At the fabrication of MPMG YBCO, optimized temperature for crystal growth was determined to be around 1050-1060 °C.

Samples for estimating primary volatiles in Martian magmas and ancient atmospheric pressures on Mars

NASA Technical Reports Server (NTRS)

Anderson, A. T., Jr.

1988-01-01

Inclusions of glass are likely to be present in phenocrysts in volcanic rocks from Mars, because these occur in volcanic rocks from both Earth and Moon. The usefulness of the inclusions depends upon their size and composition. The compositions of tiny inclusions may be modified by diffusion during growth of the enclosing crystal, the modifications increasing with melt viscosity (silica). Slow cooling results in crystallization and possible redistribution of volatiles, the effects increasing with decreasing silica. Primary volatile concentrations are best sought in inclusions larger than about 50 micrometer diameter in olivine or chromite crystals from quickly cooled basaltic scoria. Such crystals may be present in sands, but it would be preferable to extract them from individual rocks which could be dated and compositionally characterized. This would allow eventual understanding of the role of time and place in outgassing and volcanism on Mars. Analyses of volatiles in inclusions of more siliceous glass in non-basaltic rocks will reveal whether deep outgassing occurs and whether surface volatiles are recycled. Most volcanic crystals contain inclusions, but large inclusions can be uncommon. In the case of terrestrial basalts sample masses of several hundred grams are generally sufficient.

Photonic crystal wave guide for non-cryogenic cooled carbon nanotube based middle wave infrared sensors

NASA Astrophysics Data System (ADS)

Fung, Carmen Kar Man; Xi, Ning; Lou, Jianyong; Lai, King Wai Chiu; Chen, Hongzhi

2010-10-01

We report high sensitivity carbon nanotube (CNT) based middle wave infrared (MWIR) sensors with a two-dimensional photonic crystal waveguide. MWIR sensors are of great importance in a variety of current military applications including ballistic missile defense, surveillance and target detection. Unlike other existing MWIR sensing materials, CNTs exhibit low noise level and can be used as new nano sensing materials for MWIR detection where cryogenic cooling is not required. However, the quantum efficiency of the CNT based infrared sensor is still limited by the small sensing area and low incoming electric field. Here, a photonic nanostructure is used as a resonant cavity for boosting the electric field intensity at the position of the CNT sensing element. A two-dimensional photonic crystal with periodic holes in a polymer thin film is fabricated and a resonant cavity is formed by removing holes from the array of the photonic crystal. Based on the design of the photonic crystal topologies, we theoretically study the electric field distribution to predict the resonant behavior of the structure. Numerical simulations reveal the field is enhanced and almost fully confined to the defect region of the photonic crystal. To verify the electric field enhancement effect, experiments are also performed to measure the photocurrent response of the sensor with and without the photonic crystal resonant cavity. Experimental results show that the photocurrent increases ~3 times after adding the photonic crystal resonant cavity.

Solid-state characterization of mefenamic acid.

PubMed

Panchagnula, Ramesh; Sundaramurthy, Prakash; Pillai, Omathanu; Agrawal, Shrutidevi; Raj, Yasvanth Ashok

2004-04-01

The purpose of this study was to characterize mefenamic acid (MA) from commercial samples and samples crystallized from different solvents. Various techniques used for characterization included microscopy (hot stage microscopy, scanning electron microscopy), intrinsic dissolution rate, differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy and powder X-ray diffractometry (pXRD). The commercial samples varied in their crystal habit, thermal behavior, and intrinsic dissolution rate. It was found that the commercial samples were polymorphic Form I, which converted to Form II on heating in a DSC pan. Similarly, compression in an intrinsic dissolution rate (IDR) press resulted in the conversion of Form I to Form II. On the other hand, the samples recrystallized from different solvents under varying conditions yielded different crystal habits. Stirring and degree of supersaturation significantly influenced the crystal habit in all the solvents used in the study. Samples crystallized from ethanol and tetrahydrofuran yielded Form I, which behaved similarly to the commercial samples (M1 and M3). Recrystallization from ethyl acetate at a fast cooling rate yielded Form I, which on melting crystallized to Form II. The form I crystallized from ethyl acetate by fast cooling converted partially to form II on storing at ambient conditions. Forms I and II of MA were enantiotropically related. The results demonstrate the variable material characteristics of the commercial samples of MA and the influence of the crystallizing conditions on the formation of the polymorphs. Copyright 2004 Wiley-Liss, Inc. and the American Pharmacists Association.

Growth, structural, optical, thermal and mechanical properties of ammonium pentaborate single crystal.

PubMed

Balakrishnan, T; Bhagavannarayana, G; Ramamurthi, K

2008-11-15

Nonlinear optical single crystals of ammonium pentaborate (APB) were grown by the slow cooling method from aqueous solution. Grown crystal was characterized by powder X-ray diffraction (PXRD) and FT-IR spectral analysis. Perfection of the grown crystal was evaluated by high-resolution X-ray diffractometry (HRXRD). The effect of nylon threading on the perfection of the grown bigger crystal was also studied by HRXRD. The range and percentage of optical transmission was ascertained by recording UV-vis-NIR spectrum. Thermal properties were investigated by TG-DTA and DSC analyses. Its mechanical hardness was estimated by Vickers microhardness tester.

Phononic crystal devices

DOEpatents

El-Kady, Ihab F [Albuquerque, NM; Olsson, Roy H [Albuquerque, NM

2012-01-10

Phononic crystals that have the ability to modify and control the thermal black body phonon distribution and the phonon component of heat transport in a solid. In particular, the thermal conductivity and heat capacity can be modified by altering the phonon density of states in a phononic crystal. The present invention is directed to phononic crystal devices and materials such as radio frequency (RF) tags powered from ambient heat, dielectrics with extremely low thermal conductivity, thermoelectric materials with a higher ratio of electrical-to-thermal conductivity, materials with phononically engineered heat capacity, phononic crystal waveguides that enable accelerated cooling, and a variety of low temperature application devices.

Survival of mouse oocytes after being cooled in a vitrification solution to −196°C at 95° to 70,000°C/min and warmed at 610° to 118,000°C/min: A new paradigm for cryopreservation by vitrification☆

PubMed Central

Mazur, Peter; Seki, Shinsuke

2011-01-01

There is great interest in achieving reproducibly high survivals of mammalian oocytes (especially human) after cryopreservation, but the results to date have not matched the interest. A prime cause of cell death is the formation of more than trace amounts of intracellular ice, and one strategy to avoid it is vitrification. In vitrification procedures, cells are loaded with high concentrations of glass-inducing solutes and cooled to −196°C at rates high enough to presumably induce the glassy state. In the last decade, several devices have been developed to achieve very high cooling rates. Nearly all in the field have assumed that the cooling rate is the critical factor. The purpose of our study was to test that assumption by examining the consequences of cooling mouse oocytes in a vitrification solution at four rates ranging from 95°C/min to 69,250°C/min to −196°C and for each cooling rate, subjecting them to five warming rates back above 0°C at rates ranging from 610°C/min to 118,000°C/min. In samples warmed at the highest rate (118,000°C/min), survivals were 70 to 85% regardless of the prior cooling rate. In samples warmed at the lowest rate (610°C/min), survivals were low regardless of the prior cooling rate, but decreased from 25% to 0% as the cooling rate was increased from 95°C/min to 69,000°C/min. Intermediate cooling and warming rates gave intermediate survivals. The especially high sensitivity of survival to warming rate suggests that either the crystallization of intracellular glass during warming or the growth by recrystallization of small intracellular ice crystals formed during cooling are responsible for the lethality of slow warming. PMID:21055397

Survival of mouse oocytes after being cooled in a vitrification solution to -196°C at 95° to 70,000°C/min and warmed at 610° to 118,000°C/min: A new paradigm for cryopreservation by vitrification.

PubMed

Mazur, Peter; Seki, Shinsuke

2011-02-01

There is great interest in achieving reproducibly high survivals of mammalian oocytes (especially human) after cryopreservation, but the results to date have not matched the interest. A prime cause of cell death is the formation of more than trace amounts of intracellular ice, and one strategy to avoid it is vitrification. In vitrification procedures, cells are loaded with high concentrations of glass-inducing solutes and cooled to -196°C at rates high enough to presumably induce the glassy state. In the last decade, several devices have been developed to achieve very high cooling rates. Nearly all in the field have assumed that the cooling rate is the critical factor. The purpose of our study was to test that assumption by examining the consequences of cooling mouse oocytes in a vitrification solution at four rates ranging from 95 to 69,250°C/min to -196°C and for each cooling rate, subjecting them to five warming rates back above 0°C at rates ranging from 610 to 118,000°C/min. In samples warmed at the highest rate (118,000°C/min), survivals were 70% to 85% regardless of the prior cooling rate. In samples warmed at the lowest rate (610°C/min), survivals were low regardless of the prior cooling rate, but decreased from 25% to 0% as the cooling rate was increased from 95 to 69,000°C/min. Intermediate cooling and warming rates gave intermediate survivals. The especially high sensitivity of survival to warming rate suggests that either the crystallization of intracellular glass during warming or the growth by recrystallization of small intracellular ice crystals formed during cooling are responsible for the lethality of slow warming. Copyright © 2010 Elsevier Inc. All rights reserved.

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.

Northwest Africa 5790: Revisiting nakhlite petrogenesis

NASA Astrophysics Data System (ADS)

Jambon, A.; Sautter, V.; Barrat, J.-A.; Gattacceca, J.; Rochette, P.; Boudouma, O.; Badia, D.; Devouard, B.

2016-10-01

Northwest Africa 5790, the latest nakhlite find, is composed of 58 vol.% augite, 6% olivine and 36% vitrophyric intercumulus material. Its petrology is comparable to previously discovered nakhlites but with key differences: (1) Augite cores display an unusual zoning between Mg# 54 and 60; (2) Olivine macrocrysts have a primary Fe-rich core composition (Mg# = 35); (3) The modal proportion of mesostasis is the highest ever described in a nakhlite; (4) It is the most magnetite-rich nakhlite, together with MIL 03346, and exhibits the least anisotropic fabric. Complex primary zoning in cumulus augite indicates resorption due to complex processes such as remobilization of former cumulates in a new magma batch. Textural relationships indicate unambiguously that olivine was growing around resorbed augite, and that olivine growth was continuous while pyroxene growth resumed at a final stage. Olivine core compositions (Mg# = 35) are out of equilibrium with the augite core compositions (Mg# 60-63) and with the previously inferred nakhlite parental magma (Mg# = 29). The presence of oscillatory zoning in olivine and augite precludes subsolidus diffusion that could have modified olivine compositions. NWA 5790 evidences at least two magma batches before eruption, with the implication that melt in equilibrium with augite cores was never in contact with olivine. Iddingsite is absent. Accordingly, the previous scenarios for nakhlite petrogenesis must be revised. The first primary parent magmas of nakhlites generated varied augite cumulates at depth (Mg# 66-60) as they differentiated to different extents. A subsequent more evolved magma batch entrained accumulated augite crystals to the surface where they were partly resorbed while olivine crystallized. Trace element variations indicate unambiguously that they represent consanguineous but different magma batches. The compositional differences among the various nakhlites suggest a number of successive lava flows. To account for all observations we propose a petrogenetic model for nakhlites based on several (at least three) thick flows. Although NWA 5790 belongs to the very top of one flow, it should come from the lowest flow sampled, based on the lack of iddingsite.

Study of recrystallization and devitrification of lunar glass

NASA Technical Reports Server (NTRS)

Ulrich, D. R.

1974-01-01

The technique of differential thermal analysis (DTA) was applied to the study of the Apollo 17 orange soil (74220,63) and the Apollo 16 glass coated anorthite (64455,21). These glasses show accentuated exotherms of strain relief in the annealing range which is indicative of rapid cooling. These are amenable to interpretation by comparison to the known history of synthetic glasses. Synthetic glasses were prepared whose similarity in behavior between the lunar glasses and their synthetic analogs is striking. Approximate rates of cooling of the lunar glasses were determined from comparative DTA of lunar and synthetic glasses and from the determination of the relation of strain relief in the annealing range to quench rate. At higher temperatures the glasses show exotherms of crystallization. The crystallization products associated with the exothermic reactions have been identified by X-ray diffraction and the surface morphologies developed by strain relief and crystallization have been characterized with scanning electron microscopy.

Rapid cooling and cold storage in a silicic magma reservoir recorded in individual crystals.

PubMed

Rubin, Allison E; Cooper, Kari M; Till, Christy B; Kent, Adam J R; Costa, Fidel; Bose, Maitrayee; Gravley, Darren; Deering, Chad; Cole, Jim

2017-06-16

Silicic volcanic eruptions pose considerable hazards, yet the processes leading to these eruptions remain poorly known. A missing link is knowledge of the thermal history of magma feeding such eruptions, which largely controls crystallinity and therefore eruptability. We have determined the thermal history of individual zircon crystals from an eruption of the Taupo Volcanic Zone, New Zealand. Results show that although zircons resided in the magmatic system for 10 3 to 10 5 years, they experienced temperatures >650° to 750°C for only years to centuries. This implies near-solidus long-term crystal storage, punctuated by rapid heating and cooling. Reconciling these data with existing models of magma storage requires considering multiple small intrusions and multiple spatial scales, and our approach can help to quantify heat input to and output from magma reservoirs. Copyright © 2017, American Association for the Advancement of Science.

Influence of additive L-phenylalanine on stabilization of metastable α-form of L-glutamic acid in cooling crystallization

NASA Astrophysics Data System (ADS)

Quang, Khuu Chau; Nhan, Le Thi Hong; Huyen, Trinh Thi Thanh; Tuan, Nguyen Anh

2017-09-01

The influence of additive amino acid L-phenylalanine on stabilization of metastable α-form of L-glutamic acid was investigated in cooling crystallization. The present study found that the additive L-phenylalanine could be used to stabilize the pure metastable α-form in L-glutamic acid crystallization, where the additive concentration of 0.05-0.1 (g/L) was sufficient to stabilize the 100% wt metastable α-form in solid product at L-glutamic acid concentration of 30-45 (g/L). Additionally, the present results indicated that the adsorption of additive L-phenylalanine on the (001) surface of α-form was more favorable than that of the β-form molecular, so the nucleation sites of stable β-form was occupied by additive molecular, which resulted in inhibition of nucleation and growth of β-form, allowing stabilization of metastable α-form.

Direct Measurement of Water States in Cryopreserved Cells Reveals Tolerance toward Ice Crystallization

PubMed Central

Huebinger, Jan; Han, Hong-Mei; Hofnagel, Oliver; Vetter, Ingrid R.; Bastiaens, Philippe I.H.; Grabenbauer, Markus

2016-01-01

Complex living systems such as mammalian cells can be arrested in a solid phase by ultrarapid cooling. This allows for precise observation of cellular structures as well as cryopreservation of cells. The state of water, the main constituent of biological samples, is crucial for the success of cryogenic applications. Water exhibits many different solid states. If it is cooled extremely rapidly, liquid water turns into amorphous ice, also called vitreous water, a glassy and amorphous solid. For cryo-preservation, the vitrification of cells is believed to be mandatory for cell survival after freezing. Intracellular ice crystallization is assumed to be lethal, but experimental data on the state of water during cryopreservation are lacking. To better understand the water conditions in cells subjected to freezing protocols, we chose to directly analyze their subcellular water states by cryo-electron microscopy and tomography, cryoelectron diffraction, and x-ray diffraction both in the cryofixed state and after warming to different temperatures. By correlating the survival rates of cells with their respective water states during cryopreservation, we found that survival is less dependent on ice-crystal formation than expected. Using high-resolution cryo-imaging, we were able to directly show that cells tolerate crystallization of extra- and intracellular water. However, if warming is too slow, many small ice crystals will recrystallize into fewer but bigger crystals, which is lethal. The applied cryoprotective agents determine which crystal size is tolerable. This suggests that cryoprotectants can act by inhibiting crystallization or recrystallization, but they also increase the tolerance toward ice-crystal growth. PMID:26541066

Crystallization of the collagen-like polypeptide (PPG)10 aboard the International Space Station. 1. Video observation.

PubMed

Vergara, Alessandro; Corvino, Ermanno; Sorrentino, Giosué; Piccolo, Chiara; Tortora, Alessandra; Carotenuto, Luigi; Mazzarella, Lelio; Zagari, Adriana

2002-10-01

Single chains of the collagen model polypeptide with sequence (Pro-Pro-Gly)(10), hereafter referred to as (PPG)(10), aggregate to form rod-shaped triple helices. Crystals of (PPG)(10) were grown in the Advanced Protein Crystallization Facility (APCF) both onboard the International Space Station (ISS) and on Earth. The experiments allow the direct comparison of four different crystallization environments for the first time: solution in microgravity ((g), agarose gel in (g, solution on earth, and gel on earth. Both on board and on ground, the crystal growth was monitored by a CCD video camera. The image analysis provided information on the spatial distribution of the crystals, their movement and their growth rate. The analysis of the distribution of crystals reveals that the crystallization process occurs as it does in batch conditions. Slow motions have been observed onboard the ISS. Different to Space-Shuttle experiment, the crystals onboard the ISS moved coherently and followed parallel trajectories. Growth rate and induction time are very similar both in gel and in solution, suggesting that the crystal growth rate is controlled by the kinetics at the interface under the used experimental conditions. These results provide the first data in the crystallogenesis of (PPG)(10), which is a representative member of non-globular, rod-like proteins.

Uranyl nitrate hexahydrate solubility in nitric acid and its crystallization selectivity in the presence of nitrate salts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Burns, Jonathan D.; Moyer, Bruce A.

The solubility of uranyl nitrate hexahydrate was determined as a function of nitric acid concentration and temperature, and the crystallization yield was calculated. Results showed an increase in crystal formation at lower initial nitric acid concentrations upon cooling a saturated solution of U(VI) from 50 °C to 2 °C, with over 70% recovery of U(VI) mass at all nitric acid concentrations and nearly quantitative recovery starting at 4 M HNO 3. A direct correlation between the change in mother liquor volume percent and U mass removal percent was observed. By reducing the cooling rate from roughly 4.0 °C/min to 0.22more » °C/min, the separation factor was increased from 3.88 to 15.7 to greater than 81 for the separation of U(VI) from Sr, Cs, and Nd. At the slower cooling rate, the separation factors were measured as a function of acidity for 2.0–4.3 M HNO 3, showing a decrease in selectivity with a decrease in the acidity. There was also no indication that tetravalent metal double-salt precipitation occurred with either Zr 4+ or Ce 4+. Here, these results indicate that a high-yield, high purity hexavalent actinide crystallization scheme may offer attractive benefits for nuclear-fuel recycle in that only a single very simple and well-understood technology is employed, and the use of organic compounds and solvents is avoided.« less

Raman scattering evidence of hydrohalite formation on frozen yeast cells.

PubMed

Okotrub, K A; Surovtsev, N V

2013-02-01

We studied yeast cells in physiological solution during freezing by Raman microspectroscopy technique. The purpose was to find out the origin of a sharp peak near ∼3430cm(-1) in Raman spectrum of frozen mammalian cells, observed earlier (J. Dong et al., Biophys. J. 99 (2010) 2453), which presumably could be used as an indicator of intracellar ice appearance. We have shown that this line (actually doublet of 3408 and 3425cm(-1)) corresponds to Raman spectrum of hydrohalite (NaCl⋅2H(2)O), which is formed as the result of the eutectic crystallization of the liquid solution around the cells. We also show that the spatial distribution of hydrohalite in the sample significantly depends on the cooling rate. At lower cooling rate (1°C/min), products of eutectic crystallization form layer on the cell surface which thickness varies for different cells and can reach ∼1μm in thickness. At higher cooling rate (20°C/min), the hydrohalite distribution appears more homogeneous, in the sample, and the eutectic crystallization layer around the cells was estimated to be less than ∼20nm. These experimental results are consistent with scenarios predicted by the two-factor hypothesis for freezing induced cell injury. This work demonstrates a potential of Raman microspectroscopy to study peculiarities of the eutectic crystallization around single cells in vivo with the high spatial resolution. Copyright © 2012 Elsevier Inc. All rights reserved.

Uranyl nitrate hexahydrate solubility in nitric acid and its crystallization selectivity in the presence of nitrate salts

DOE PAGES

Burns, Jonathan D.; Moyer, Bruce A.

2017-10-23

The solubility of uranyl nitrate hexahydrate was determined as a function of nitric acid concentration and temperature, and the crystallization yield was calculated. Results showed an increase in crystal formation at lower initial nitric acid concentrations upon cooling a saturated solution of U(VI) from 50 °C to 2 °C, with over 70% recovery of U(VI) mass at all nitric acid concentrations and nearly quantitative recovery starting at 4 M HNO 3. A direct correlation between the change in mother liquor volume percent and U mass removal percent was observed. By reducing the cooling rate from roughly 4.0 °C/min to 0.22more » °C/min, the separation factor was increased from 3.88 to 15.7 to greater than 81 for the separation of U(VI) from Sr, Cs, and Nd. At the slower cooling rate, the separation factors were measured as a function of acidity for 2.0–4.3 M HNO 3, showing a decrease in selectivity with a decrease in the acidity. There was also no indication that tetravalent metal double-salt precipitation occurred with either Zr 4+ or Ce 4+. Here, these results indicate that a high-yield, high purity hexavalent actinide crystallization scheme may offer attractive benefits for nuclear-fuel recycle in that only a single very simple and well-understood technology is employed, and the use of organic compounds and solvents is avoided.« less

Origin of ultramafic xenoliths containing exsolved pyroxenes from Hualalai Volcano, Hawaii

USGS Publications Warehouse

Bohrson, W.A.; Clague, D.A.

1988-01-01

Hualalai Volcano, Hawaii, is best known for the abundant and varied xenoliths included in the historic 1800 Kaupulehu alkalic basalt flow. Xenoliths, which range in composition from dunite to anorthosite, are concentrated at 915-m elevation in the flow. Rare cumulate ultramafic xenoliths, which include websterite, olivine websterite, wehrlite, and clinopyroxenite, display complex pyroxene exsolution textures that indicate slow cooling. Websterite, olivine websterite, and one wehrlite are spinel-bearing orthopyroxene +olivine cumulates with intercumulus clinopyroxene +plagioclase. Two wehrlite samples and clinopyroxenite are spinel-bearing olivine cumulates with intercumulus clinopyroxene+orthopyroxene + plagioclase. Two-pyroxene geothermometry calculations, based on reconstructed pyroxene compositions, indicate that crystallization temperatures range from 1225?? to 1350?? C. Migration or unmixing of clinopyroxene and orthopyroxene stopped between 1045?? and 1090?? C. Comparisons of the abundance of K2O in plagioclase and the abundances of TiO2 and Fe2O3in spinel of xenoliths and mid-ocean ridge basalt, and a single 87Sr/ 86Sr determination, indicate that these Hualalai xenoliths are unrelated to mid-ocean ridge basalt. Similarity between the crystallization sequence of these xenoliths and the experimental crystallization sequence of a Hawaiian olivine tholeiite suggest that the parental magma of the xenoliths is Hualalai tholeiitic basalt. Xenoliths probably crystallized between about 4.5 and 9 kb. The 155??-230?? C of cooling which took place over about 120 ka - the age of the youngest Hualalai tholeiitic basalt - yield maximum cooling rates of 1.3??10-3-1.91??10-3 ??C/yr. Hualalai ultramafic xenoliths with exsolved pyroxenes crystallized from Hualalai tholeiitic basalt and accumulated in a magma reservoir located between 13 and 28 km below sealevel. We suspect that this reservoir occurs just below the base of the oceanic crust at about 19 km below sealevel. ?? 1988 Springer-Verlag.

Thermal History and Crystallinity of Sheet Intrusions

NASA Astrophysics Data System (ADS)

Whittington, A. G.; Nabelek, P. I.; Hofmeister, A.

2011-12-01

Magma emplaced in a sheet intrusion has two potential fates: to crystallize, or quench to glass. Rapidly chilled sheet margins are typically glassy or microcrystalline, while interiors are coarser-grained. The actual textures result from a combination of thermal history and crystallization kinetics, which are related by various feedback mechanisms. The thermal history of cooling sheet intrusions is often approximated using the analytical solution for a semi-infinite half-space, which uses constant thermal properties such as heat capacity (CP), thermal diffusivity (D) and thermal conductivity (k = DρCP), where ρ is density. In reality, both CP and D are strongly T-dependent for glasses and crystals, and melts have higher CP and lower D than crystals or glasses. Another first-order feature ignored in the analytical solution is latent heat of crystallization (ΔHxt), which can be implemented numerically as extra heat capacity over the crystallization interval. For rhyolite melts, D is ~0.5 mm2s-1 and k is ~1.5 Wm-1K-1, which are similar to those of major crustal rock types and granitic protoliths at magmatic temperatures, suggesting that changes in thermal properties accompanying partial melting of the crust should be relatively minor. Numerical models of hot (~920°C liquidus for 0.5 wt.% H2O) shallow rhyolite intrusions indicate that the key difference in thermal history between bodies that quench to obsidian, and those that crystallize, results from the release of latent heat of crystallization, which enables bodies that crystallize to remain at high temperatures for much longer times. The time to solidification is similar in both cases, however, because solidification requires cooling through the glass transition (Tg ~620°C) in the first case, and cooling only to the solidus (~770°C) in the second. For basaltic melts, D is ~0.3 mm2s-1 and k is ~1.0 Wm-1K-1, compared to ~0.6 mm2s-1 and 2.5 Wm-1K-1 for crystalline basalt or peridotite at magmatic temperatures, suggesting that changes in thermal properties accompanying partial melting of the mantle or crystallization of basalt may be important. Numerical models of basaltic sheet intrusions indicate that they will almost always crystallize, even at sheet margins, because their emplacement temperature (~1220°C) is sufficiently high that the country rock adjacent to the sheet will be raised above the Tg of the melt (~650°C). The long period of time spent above Tg, combined with the rapid crystallization kinetics of basaltic melts, ensures that crystallization is near-complete, even if the crystal size is small, except where unusually rapid chilling occurs due to efficient convective or radiative losses (for example subaerial, subaqeous or subglacial lava flows).

Method for single crystal growth of photovoltaic perovskite material and devices

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Jinsong; Dong, Qingfeng

Systems and methods for perovskite single crystal growth include using a low temperature solution process that employs a temperature gradient in a perovskite solution in a container, also including at least one small perovskite single crystal, and a substrate in the solution upon which substrate a perovskite crystal nucleates and grows, in part due to the temperature gradient in the solution and in part due to a temperature gradient in the substrate. For example, a top portion of the substrate external to the solution may be cooled.

Numerical simulation of flow and melting characteristics of seawater-ice crystals two-phase flow in inlet straight pipe of shell and tube heat exchanger of polar ship

NASA Astrophysics Data System (ADS)

Xu, Li; Huang, Chang-Xu; Huang, Zhen-Fei; Sun, Qiang; Li, Jie

2018-05-01

The ice crystal particles are easy to enter into the seawater cooling system of polar ship together with seawater when it sails in the Arctic. They are easy to accumulate in the pipeline, causing serious blockage of the cooling pipe. In this study, the flow and melting characteristics of ice particles-seawater two-phase flow in inlet straight pipe of shell-and-tube heat exchanger were numerically simulated by using Eulerian-Eulerian two-fluid model coupled with the interphase heat and mass transfer model. The influences of inlet ice packing factor, ice crystal particle diameter, and inlet velocity on the distribution and melting characteristics of ice crystals were investigated. The degree of asymmetry of the distribution of ice crystals in the cross section decreases gradually when the IPF changes from 5 to 15%. The volume fractions of ice crystals near the top of the outlet cross section are 19.59, 19.51, and 22.24% respectively for ice packing factor of 5, 10 and 15%. When the particle diameter is 0.5 mm, the ice crystals are gradually stratified during the flow process. With particle diameters of 1.0 and 2.0 mm, the region with the highest volume fraction of ice crystals is a small circle and the contours in the cloud map are compact. The greater the inlet flow velocity, the less stratified the ice crystals and the more obvious the turbulence on the outlet cross section. The average volume fraction of ice crystals along the flow direction is firstly rapidly reduced and then stabilized after 300 mm.

NE-CAT Upgrade of the Bending Magnet Beamline 8BM at the ALS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang Jun; Ogata, Craig; Yang Xiaochun

2007-01-19

NE-CAT, North East Collaborative Access Team, bending magnet beamline (8BM) is a beamline for protein crystallography. Recently, the beamline has undergone upgrades of its x-ray optics, control system, and the addition of a robot automounter. The first crystal of the double crystal monochromator was replaced by a new design offered by Oxford Danfysik with a micro-finned, direct water-cooled crystal assembly that would provide better cooling and reduced thermal distortion, pressure induced bulge, and residual strain. Gear reduced motors were added to enhance the torque of the bender and obtain better control. For measuring displacement of the bender directly, two linearmore » variable differential transformers (LVDT) were installed to the second crystal assembly. Early optics characterization and analysis has been carried out. Besides the upgrade of the optical components, the Blu-Ice control system originally developed at SSRL has been implemented. The installation of an automated robotic sample mounting system, from the ALS, was carried out in collaboration with the engineering group at LBNL. Preliminary results are presented.« less

Protein Crystallization.

PubMed

McPherson, Alexander

2017-01-01

Protein crystallization was discovered by chance nearly 200 years ago and was developed in the late nineteenth century as a powerful purification tool, and a demonstration of chemical purity. The crystallization of proteins, nucleic acids, and large biological complexes, such as viruses, depends on the creation of a solution that is supersaturated in the macromolecule, but exhibits conditions that do not significantly perturb its natural state. Supersaturation is produced through the addition of mild precipitating agents such as neutral salts or polymers, and by manipulation of various parameters that include temperature, ionic strength, and pH. Also important in the crystallization process are factors that can affect the structural state of the macromolecule, such as metal ions, inhibitors, cofactors, or other conventional small molecules. A variety of approaches have been developed that combine the spectrum of factors that effect and promote crystallization, and among the most widely used are vapor diffusion, dialysis, batch, and liquid-liquid diffusion. Successes in macromolecular crystallization have multiplied rapidly in recent years due to the advent of practical, easy-to-use screening kits, and the application of laboratory robotics.

Zaoyang chondrite cooling history from pyroxene Fe(2+)-Mg intracrystalline ordering and exolutions

NASA Technical Reports Server (NTRS)

Molin, G. M.; Tribaudino, M.; Brizi, E.

1993-01-01

The Zaoyang ordinary chondrite fell as a single 14.15-kg mass in Hubey province (China) in October 1984 and was classified as a non-brecciated H5 chondrite, shock facies b. Cooling rate in pyroxenes can be calculated down to about 1000 C by using fine textures and at still lower temperatures (700 to 200 C) by intracrystalline ordering processes. The crystal chemistry of clinopyroxene and orthopyroxene from the matrix of the H5 Zaoyang chondrite has been investigated by X-ray structure refinement and detailed microprobe analysis. By comparison with terrestrial pyroxenes cell and polyhedral volumes in clino- and orthopyroxenes show a low crystallization pressure. Fe(2+) and Mg are rather disordered in M1 and M2 sites of clino- and orthopyroxenes; the closure temperatures of the exchange reaction are 600 and 512 C respectively, which is consistent with a quite fast cooling rate, estimated of the order of one degree per day. The closure temperature for the intercrystalline Ca-Mg exchange reaction for clino- and orthopyroxene showing clinopyroxene lamellae about 10 microns thick. Kinetic evaluations based on the thickness of exolved lamellae give a cooling rate of not more than a few degrees per 10(exp 4) years. The different cooling rates obtained from Fe(2+)-Mg intracrystalline partitioning and exolution lamellae suggest an initial episode of slow cooling at 900 C, followed by faster cooling at temperatures of 600-500 C at low pressure conditions. The most probable scenario of the meteorite history seems that the exolved orthopyroxene entered the parental chondrite body after exolution had taken place at high temperature. Subsequent fast cooling occurred at low temperature after the formation of the body.

Access to small size distributions of nanoparticles by microwave-assisted synthesis. Formation of Ag nanoparticles in aqueous carboxymethylcellulose solutions in batch and continuous-flow reactors

NASA Astrophysics Data System (ADS)

Horikoshi, Satoshi; Abe, Hideki; Torigoe, Kanjiro; Abe, Masahiko; Serpone, Nick

2010-08-01

This article examines the effect(s) of the 2.45-GHz microwave (MW) radiation in the synthesis of silver nanoparticles in aqueous media by reduction of the diaminesilver(i) complex, [Ag(NH3)2]+, with carboxymethylcellulose (CMC) in both batch-type and continuous-flow reactor systems with a particular emphasis on the characteristics of the microwaves in this process and the size distributions. This microwave thermally-assisted synthesis is compared to a conventional heating (CH) method, both requiring a reaction temperature of 100 °C to produce the nanoparticles, in both cases leading to the formation of silver colloids with different size distributions. Reduction of the diaminesilver(i) precursor complex, [Ag(NH3)2]+, by CMC depended on the solution temperature. Cooling the reactor during the heating process driven with 390-Watt microwaves (MW-390W/Cool protocol) yielded silver nanoparticles with sizes spanning the range 1-2 nm. By contrast, the size distribution of Ag nanoparticles with 170-Watt microwaves (no cooling; MW-170W protocol) was in the range 1.4-3.6 nm (average size ~3 nm). The overall results suggest the potential for a scale-up process in the microwave-assisted synthesis of nanoparticles. Based on the present data, a flow-through microwave reactor system is herein proposed for the continuous production of silver nanoparticles. The novel flow reactor system (flow rate, 600 mL min-1) coupled to 1200-Watt microwave radiation generated silver nanoparticles with a size distribution 0.7-2.8 nm (average size ca. 1.5 nm).

Evaluation of a method for heat transfer measurements and thermal visualization using a composite of a heater element and liquid crystals. [thermal performance of turbine blade cooling configurations

NASA Technical Reports Server (NTRS)

Hippensteele, S. A.; Russell, L. M.; Stepka, F. S.

1981-01-01

Commercially available elements of a composite consisting of a plastic sheet coated with liquid crystal, another sheet with a thin layer of a conducting material (gold or carbon), and copper bus bar strips were evaluated and found to provide a simple, convenient, accurate, and low-cost measuring device for use in heat transfer research. The particular feature of the composite is its ability to obtain local heat transfer coefficients and isotherm patterns that provide visual evaluation of the thermal performances of turbine blade cooling configurations. Examples of the use of the composite are presented.

Engineering evaluation of magma cooling-tower demonstration at Nevada Power Company's Sunrise Station

NASA Astrophysics Data System (ADS)

1980-11-01

The Magma Cooling Tower (MCT) process utilizes a falling film heat exchanger integrated into an induced draft cooling tower to evaporate waste water. A hot water source such as return cooling water provides the energy for evaporation. Water quality control is maintained by removing potential scaling constituents to make concentrations of the waste water possible without scaling heat transfer surfaces. A pilot-scale demonstration test of the MCT process was performed from March 1979 through June 1979 at Nevada Power Company's Sunrise Station in Las Vegas, Nevada. The pilot unit extracted heat from the powerplant cooling system to evaporate cooling tower blowdown. Two water quality control methods were employed: makeup/sidestream softening and fluidized bed crystallization. The 11 week softening mode test was successful.

Multicomponent Diffusion in Experimentally Cooled Melt Inclusions

NASA Astrophysics Data System (ADS)

Saper, L.; Stolper, E.

2017-12-01

Glassy olivine-hosted melt inclusions are compositionally zoned, characterized by a boundary layer depleted in olivine-compatible components that extends into the melt inclusion from its wall. The boundary layer forms in response to crystallization of olivine and relaxes with time due to diffusive exchange with the interior of the inclusion. At magmatic temperatures, the time scale for homogenization of inclusions is minutes to hours. Preservation of compositional gradients in natural inclusions results from rapid cooling upon eruption. A model of MgO concentration profiles that couples crystal growth and diffusive relaxation of a boundary layer can be used to solve for eruptive cooling rates [1]. Controlled cooling-rate experiments were conducted to test the accuracy of the model. Mauna Loa olivine containing >80 µm melt inclusions were equilibrated at 1225°C in a 1-atm furnace for 24 hours, followed by linear cooling at rates of 102 - 105 °C/hr. High-resolution concentration profiles of 40 inclusions were obtained using an electron microprobe. The model of [1] fits the experimental data with low residuals and the best-fit cooling rates are within 30% of experimental values. The initial temperature of 1225 °C is underestimated by 65°C. The model was modified using (i) MELTS to calculate the interface melt composition as a function of temperature, and (ii) a concentration-dependent MgO diffusion coefficient using the functional form of [2]. With this calibration the best-fit starting temperatures are within 5°C of the experimental values and the best-fit cooling rates are within 20% of experimental rates. The evolution of the CaO profile during cooling is evidence for strong diffusive coupling between melt components. Because CaO is incompatible in olivine, CaO concentrations are expected to be elevated in the boundary layer adjacent to the growing olivine. Although this is observed at short time scales, as the profile evolves the CaO concentration near the crystal interface becomes increasingly depleted. The drawdown in CaO can be explained by non-ideal mixing that leads to increases in the CaO activity coefficient in the melt. A regular solution model [3] can be used to describe the evolution of the CaO profiles. [1]Newcombe et al (2014) CMP 168 [2] Zhang (2010) RevMineralGeochem 72 [3] Ghiorso & Sack (1995) CMP 119

A step towards long-wavelength protein crystallography: subjecting protein crystals to a vacuum

PubMed Central

Panjikar, Santosh; Thomsen, Lars; O’Donnell, Kane Michael; Riboldi-Tunnicliffe, Alan

2015-01-01

Using the UHV experimental endstation on the soft X-ray beamline at the Australian Synchrotron, lysozyme and proteinase K crystals have been exposed to a vacuum of 10−5 mbar, prior to flash-cooling in a bath of liquid nitrogen. Subsequent data collection on the MX2 beamline at the Australian Synchrotron demonstrated that, for lysozyme and proteinase K, it is possible to subject these mounted crystals to a vacuum pressure of 10−5 mbar without destroying the crystal lattice. Despite the lower data quality of the vacuum-pumped crystals compared with control crystals, it is demonstrated that the protein crystals can survive in a vacuum under suitable conditions. PMID:26089765

Cupric oxide inclusions in cuprous oxide crystals grown by the floating zone method

NASA Astrophysics Data System (ADS)

Frazer, Laszlo; Chang, Kelvin B.; Poeppelmeier, Kenneth R.; Ketterson, John B.

2015-06-01

Phase-pure cuprous oxide (Cu2O) crystals are difficult to grow since cupric oxide can form within the crystal as the crystal is cooled to ambient conditions. Vacancies are the solute which causes precipitation of macroscopic defects. Therefore, even when a mostly phase-pure single crystal is used as a feed rod, cupric oxide inclusions persist in the recrystallized solid. Control of the thermal profile during crystal growth, however, can improve phase-purity; a slow counter-rotation rate of the feed and seed rods results in fewer inclusions. Cupric oxide can be removed by annealing, which produces a factor of 540 ± 70 increase in phase-purity.

Cupric oxide inclusions in cuprous oxide crystals grown by the floating zone method

PubMed Central

Frazer, Laszlo; Chang, Kelvin B; Poeppelmeier, Kenneth R; Ketterson, John B

2015-01-01

Phase-pure cuprous oxide (Cu2O) crystals are difficult to grow since cupric oxide can form within the crystal as the crystal is cooled to ambient conditions. Vacancies are the solute which causes precipitation of macroscopic defects. Therefore, even when a mostly phase-pure single crystal is used as a feed rod, cupric oxide inclusions persist in the recrystallized solid. Control of the thermal profile during crystal growth, however, can improve phase-purity; a slow counter-rotation rate of the feed and seed rods results in fewer inclusions. Cupric oxide can be removed by annealing, which produces a factor of 540 ± 70 increase in phase-purity. PMID:27877798

Crystal nucleation in metallic alloys using x-ray radiography and machine learning

PubMed Central

Arteta, Carlos; Lempitsky, Victor

2018-01-01

The crystallization of solidifying Al-Cu alloys over a wide range of conditions was studied in situ by synchrotron x-ray radiography, and the data were analyzed using a computer vision algorithm trained using machine learning. The effect of cooling rate and solute concentration on nucleation undercooling, crystal formation rate, and crystal growth rate was measured automatically for thousands of separate crystals, which was impossible to achieve manually. Nucleation undercooling distributions confirmed the efficiency of extrinsic grain refiners and gave support to the widely assumed free growth model of heterogeneous nucleation. We show that crystallization occurred in temporal and spatial bursts associated with a solute-suppressed nucleation zone. PMID:29662954

Study of the growth and pyroelectric properties of TGS crystals doped with aniline-family dipolar molecules

NASA Astrophysics Data System (ADS)

Zhang, Kecong; Song, Jiancheng; Wang, Min; Fang, Changshui; Lu, Mengkai

1987-04-01

TGS crystals doped with aniline-family dipolar molecules (aniline, 2-aminobenzoic acid, 3-aminobenzoic acid, 3-aminobenzene-sulphonic acid, 4-aminobenzenesulphonic acid and 4-nitroraniline) have been grown by the slow-cooling solution method. The influence of these dopants on the growth habits, crystal morphology pyroelectric properties, and structure parameters of TGS crystals has been systematically investigated. The effects of the domain structure of the seed crystal on the pyroelectric properties of the doped crystals have been studied. It is found that the spontaneous polarization (P), pyroelectric coefficient (lambda), and internal bias field of the doped crystals are slightly higher than those of the pure TGS, and the larger the dipole moment of the dopant molecule, the higher the P and lambda of the doped TGS crystal.

Morphological diversity of nitroguanidine crystals with enhanced mechanical performance and thermodynamic stability

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.

Thermal properties of poly(3-hydroxybutyrate)/vegetable fiber composites

NASA Astrophysics Data System (ADS)

Vitorino, Maria B. C.; Reul, Lízzia T. A.; Carvalho, Laura H.; Canedo, Eduardo L.

2015-05-01

The present work studies the thermal properties of composites of poly(3-hydroxybutyrate) (PHB) - a fully biodegradable semi-crystalline thermo-plastic obtained from renewable resources through low-impact biotechno-logical process, biocompatible and non-toxic - and vegetable fiber from the fruit (coconut) of babassu palm tree. PHB is a highly crystalline resin and this characteristic leads to suboptimal properties in some cases. Consequently, thermal properties, in particular those associated with the crystallization of the matrix, are important to judge the suitability of the compounds for specific applications. PHB/babassu composites with 0-50% load were prepared in an internal mixer. Two different types of babassu fibers with two different particle size ranges were compounded with PHB and test specimens molded by compression. Melting and crystallization behavior were studied by differential scanning calorimetry (DSC) at heating/cooling rates between 2 and 30°C/min. Several parameters, including melting point, crystallization temperature, crystallinity, and rate of crystallization, were estimated as functions of load and heating/cooling rates. Results indicate that fibers do not affect the melting process, but facilitate crystallization from the melt. Crystallization temperatures are 30 to 40°C higher for the compounds compared with the neat resin. However, the amount of fiber added has little effect on crystallinity and the degree of crystallinity is hardly affected by the load. Fiber type and initial particle size do not have a significant effect on thermal properties.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sundaramurthi, Prakash; Suryanarayanan, Raj

To effectively inhibit succinate buffer crystallization and the consequent pH changes in frozen solutions. Using differential scanning calorimetry (DSC) and X-ray diffractometry (XRD), the crystallization behavior of succinate buffer in the presence of either (i) a crystallizing (glycine, mannitol, trehalose) or (ii) a non-crystallizing cosolute (sucrose) was evaluated. Aqueous succinate buffer solutions, 50 or 200 mM, at pH values 4.0 or 6.0 were cooled from room temperature to -25 C at 0.5 C/min. The pH of the solution was measured as a function of temperature using a probe designed to function at low temperatures. The final lyophiles prepared from thesemore » solutions were characterized using synchrotron radiation. When the succinic acid solution buffered to pH 4.0, in the absence of a cosolute, was cooled, there was a pronounced shift in the freeze-concentrate pH. Glycine and mannitol, which have a tendency to crystallize in frozen solutions, remained amorphous when the initial pH was 6.0. Under this condition, they also inhibited buffer crystallization and prevented pH change. At pH 4.0 (50 mM initial concentration), glycine and mannitol crystallized and did not prevent pH change in frozen solutions. While sucrose, a non-crystallizing cosolute, did not completely prevent buffer crystallization, the extent of crystallization was reduced. Sucrose decomposition, based on XRD peaks attributable to {beta}-D-glucose, was observed in frozen buffer solutions with an initial pH of 4.0. Trehalose completely inhibited crystallization of the buffer components when the initial pH was 6.0 but not at pH 4.0. At the lower pH, the crystallization of both trehalose dihydrate and buffer components was evident. When retained amorphous, sucrose and trehalose effectively inhibited succinate buffer component crystallization and the consequent pH shift. However, when trehalose crystallized or sucrose degraded to yield a crystalline decomposition product, crystallization of buffer was observed. Similarly, glycine and mannitol, two widely used bulking agents, inhibited buffer component crystallization only when retained amorphous. In addition to stabilizing the active pharmaceutical ingredient, lyoprotectants may prevent solution pH shift by inhibiting buffer crystallization.« less

Mechanical and Thermal Properties of Polypropylene Composites Reinforced with Lignocellulose Nanofibers Dried in Melted Ethylene-Butene Copolymer

PubMed Central

Iwamoto, Shinichiro; Yamamoto, Shigehiro; Lee, Seung-Hwan; Ito, Hirokazu; Endo, Takashi

2014-01-01

Lignocellulose nanofibers were prepared by the wet disk milling of wood flour. First, an ethylene-butene copolymer was pre-compounded with wood flour or lignocellulose nanofibers to prepare master batches. This process involved evaporating the water of the lignocellulose nanofiber suspension during compounding with ethylene-butene copolymer by heating at 105 °C. These master batches were compounded again with polypropylene to obtain the final composites. Since ethylene-butene copolymer is an elastomer, its addition increased the impact strength of polypropylene but decreased the stiffness. In contrast, the wood flour- and lignocellulose nanofiber-reinforced composites showed significantly higher flexural moduli and slightly higher flexural yield stresses than did the ethylene-butene/polypropylene blends. Further, the wood flour composites exhibited brittle fractures during tensile tests and had lower impact strengths than those of the ethylene-butene/polypropylene blends. On the other hand, the addition of the lignocellulose nanofibers did not decrease the impact strength of the ethylene-butene/polypropylene blends. Finally, the addition of wood flour and the lignocellulose nanofibers increased the crystallization temperature and crystallization rate of polypropylene. The increases were more remarkable in the case of the lignocellulose nanofibers than for wood flour. PMID:28788222

Formation of co-crystals: Kinetic and thermodynamic aspects

NASA Astrophysics Data System (ADS)

Gagnière, E.; Mangin, D.; Puel, F.; Rivoire, A.; Monnier, O.; Garcia, E.; Klein, J. P.

2009-04-01

Co-crystallisation is a recent method of great interest for the pharmaceutical industry, since pharmaceutical co-crystals represent useful materials for drug products. In this study, an active pharmaceutical ingredient (carbamazepine (CBZ)) co-crystallized with a vitamin (nicotinamide (NCT)) was chosen as a model substance. This work was focused on the construction of a phase diagram for the system CBZ/NCT, split in six domains for kinetic reasons (the different solid phases which might appear during the crystallisation) and in four domains according to thermodynamic aspects (the stable final phase obtained). Although co-crystals are not ionic compounds, the supersaturation of co-crystals can be evaluated by considering the solubility product. Batch crystallisation operations were carried out in a stirred vessel equipped with an in situ video probe. This latter device was a powerful analysis tool to monitor the CBZ/NCT co-crystals and single CBZ crystals since these two crystalline phases grown in ethanol exhibited needle and platelet habits. As concerns kinetics, the different solid phases which might appear during the experiments were observed and competed against each others. In accordance with thermodynamics, the stable solid form was obtained at the end of the operation. Finally some preliminary results indicate that the nucleation of co-crystals may be favoured by the presence of CBZ crystals. Epitaxial relationships between CBZ/NCT co-crystals and CBZ crystals were suspected.

About Small Streams and Shiny Rocks: Macromolecular Crystal Growth in Microfluidics

NASA Technical Reports Server (NTRS)

vanderWoerd, Mark; Ferree, Darren; Spearing, Scott; Monaco, Lisa; Molho, Josh; Spaid, Michael; Brasseur, Mike; Curreri, Peter A. (Technical Monitor)

2002-01-01

We are developing a novel technique with which we have grown diffraction quality protein crystals in very small volumes, utilizing chip-based, microfluidic ("LabChip") technology. With this technology volumes smaller than achievable with any laboratory pipette can be dispensed with high accuracy. We have performed a feasibility study in which we crystallized several proteins with the aid of a LabChip device. The protein crystals are of excellent quality as shown by X-ray diffraction. The advantages of this new technology include improved accuracy of dispensing for small volumes, complete mixing of solution constituents without bubble formation, highly repeatable recipe and growth condition replication, and easy automation of the method. We have designed a first LabChip device specifically for protein crystallization in batch mode and can reliably dispense and mix from a range of solution constituents. We are currently testing this design. Upon completion additional crystallization techniques, such as vapor diffusion and liquid-liquid diffusion will be accommodated. Macromolecular crystallization using microfluidic technology is envisioned as a fully automated system, which will use the 'tele-science' concept of remote operation and will be developed into a research facility aboard the International Space Station.

Patterning two-dimensional chalcogenide crystals of Bi2Se3 and In2Se3 and efficient photodetectors

PubMed Central

Zheng, Wenshan; Xie, Tian; Zhou, Yu; Chen, Y.L.; Jiang, Wei; Zhao, Shuli; Wu, Jinxiong; Jing, Yumei; Wu, Yue; Chen, Guanchu; Guo, Yunfan; Yin, Jianbo; Huang, Shaoyun; Xu, H.Q.; Liu, Zhongfan; Peng, Hailin

2015-01-01

Patterning of high-quality two-dimensional chalcogenide crystals with unique planar structures and various fascinating electronic properties offers great potential for batch fabrication and integration of electronic and optoelectronic devices. However, it remains a challenge that requires accurate control of the crystallization, thickness, position, orientation and layout. Here we develop a method that combines microintaglio printing with van der Waals epitaxy to efficiently pattern various single-crystal two-dimensional chalcogenides onto transparent insulating mica substrates. Using this approach, we have patterned large-area arrays of two-dimensional single-crystal Bi2Se3 topological insulator with a record high Hall mobility of ∼1,750 cm2 V−1 s−1 at room temperature. Furthermore, our patterned two-dimensional In2Se3 crystal arrays have been integrated and packaged to flexible photodetectors, yielding an ultrahigh external photoresponsivity of ∼1,650 A W−1 at 633 nm. The facile patterning, integration and packaging of high-quality two-dimensional chalcogenide crystals hold promise for innovations of next-generation photodetector arrays, wearable electronics and integrated optoelectronic circuits. PMID:25898022

High sensitivity spectroscopic and thermal characterization of cooling efficiency for optical refrigeration materials

NASA Astrophysics Data System (ADS)

Melgaard, Seth D.; Seletskiy, Denis V.; Di Lieto, Alberto; Tonelli, Mauro; Sheik-Bahae, Mansoor

2012-03-01

Since recent demonstration of cryogenic optical refrigeration, a need for reliable characterization tools of cooling performance of different materials is in high demand. We present our experimental apparatus that allows for temperature and wavelength dependent characterization of the materials' cooling efficiency and is based on highly sensitive spectral differencing technique or two-band differential spectral metrology (2B-DSM). First characterization of a 5% w.t. ytterbium-doped YLF crystal showed quantitative agreement with the current laser cooling model, as well as measured a minimum achievable temperature (MAT) at 110 K. Other materials and ion concentrations are also investigated and reported here.

Dependence of the residual surface resistance of superconducting radio frequency cavities on the cooling dynamics around T{sub c}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Romanenko, A., E-mail: aroman@fnal.gov; Grassellino, A., E-mail: annag@fnal.gov; Melnychuk, O.

We report a strong effect of the cooling dynamics through T{sub c} on the amount of trapped external magnetic flux in superconducting niobium cavities. The effect is similar for fine grain and single crystal niobium and all surface treatments including electropolishing with and without 120 °C baking and nitrogen doping. Direct magnetic field measurements on the cavity walls show that the effect stems from changes in the flux trapping efficiency: slow cooling leads to almost complete flux trapping and higher residual resistance, while fast cooling leads to the much more efficient flux expulsion and lower residual resistance.

The influence of cooling parameters on the speed of continuous steel casting

NASA Astrophysics Data System (ADS)

Tirian, G. O.; Gheorghiu, C. A.; Hepuţ, T.; Chioncel, C. P.

2018-01-01

This paper analyzes the cooling parameters of the continuous casting speed. In the researches carried out we aimed to establish some correlation equations between the parameters characterizing the continuous casting process, the temperature of the steel at the entrance to the crystallizer, the superheating of the steel and the flow of the cooling water in the crystallizer and different zones of the secondary cooling. Parallel to these parameters were also the values for the casting speed. The research was made for the casting of round ϕ270mm semi-finished steel products. The steel was developed in an electric EBT furnace with a capacity of 100t, treated in L.F. (Ladle - Furnace) and VD (Vacuum-Degassing) and poured in a 5-wire continuous casting plant. The obtained data was processed in MATLAB using three types of correlation equations. The obtained results are presented both in the analytical and graphical form, each correlation being analyzed from the technological point of view, indicating the optimal values for the independent parameters monitored. In the analysis we present a comparison between the results obtained after the three types of equations for each correlation.

Recalescence during crystallization of stardust: Resolution of the amorphous interstellar medium paradox

NASA Astrophysics Data System (ADS)

Whittington, A. G.; Sehlke, A.; Speck, A. K.

2017-12-01

Dust that coalesces to form planetary systems originates around dying stars, before passing into the interstellar medium (ISM). Historically, observations of broad smooth features in the 10-µm region suggested that dust in circumstellar regions, and in the ISM, was mostly amorphous rather than crystalline. With improved space telescope capabilities, crystalline silicates were discovered in the circumstellar regions around both young and old stars, although they remain undetected in the ISM. Despite intensive study the precise conditions that lead to the formation of crystalline silicates are still unknown, and their absence in the ISM remains problematic. Here we show that recalescence (spontaneous reheating) of rapidly crystallizing dust can explain the formation and apparent disappearance of crystalline silicates in space. We have documented recalescence in rapidly crystallizing Mg-rich silicate melts, with local heating at the crystallization front exceeding 160˚C in some cases. In circumstellar dust shells, amorphous grains with similar compositions condense at temperatures near their glass transition, and if they crystallize, they will recalesce. The higher temperature (T) of newly crystallized dust allows crystalline spectral features to be seen, because flux emitted depends on T4. After cooling to ambient temperature, crystalline spectral features in the ISM are concealed by volumetrically dominant amorphous dust. Our results explain the existence of crystalline silicate pre-solar grains, which are older than the solar system, and have implications for radiative transfer modeling and hydrodynamics of dusty environments, which are sensitive to small variations in optical properties. Our observations of mm-scale temperature differences up to 100˚C in cooling lava suggest that thermal imaging of basaltic lava flows needs to be conducted with mm-scale spatial resolution (see figure; crucible is 5mm diameter). Temperatures recorded with low spatial resolution, which average cooler melt and hotter crystals in a single pixel, will systematically overestimate the temperature of the liquid phase. Only the surface of a lava flow is likely to cool quickly enough for recalescence to occur, but this is precisely the part of the lava that is monitored by thermal imaging.

Laboratory studies of crystal growth in magma

NASA Astrophysics Data System (ADS)

Hammer, J. E.; Welsch, B. T.; First, E.; Shea, T.

2012-12-01

The proportions, compositions, and interrelationships among crystalline phases and glasses in volcanic rocks cryptically record pre-eruptive intensive conditions, the timing of changes in crystallization environment, and the devolatilization history of eruptive ascent. These parameters are recognized as important monitoring tools at active volcanoes and interpreting geologic events at prehistoric and remote eruptions, thus motivating our attempts to understand the information preserved in crystals through an experimental appoach. We are performing laboratory experiments in mafic, felsic, and intermediate composition magmas to study the mechanisms of crystal growth in thermochemical environments relevant to volcanic environments. We target features common to natural crystals in igneous rocks for our experimental studies of rapid crystal growth phenomena: (1) Surface curvature. Do curved interfaces and spongy cores represent evidence of dissolution (i.e., are they corrosion features), or do they record the transition from dendritic to polyhedral morphology? (2) Trapped melt inclusions. Do trapped liquids represent bulk (i.e., far-field) liquids, boundary layer liquids, or something intermediate, depending on individual species diffusivity? What sequence of crystal growth rates leads to preservation of sealed melt inclusions? (3) Subgrain boundaries. Natural phenocrysts commonly exhibit tabular subgrain regions distinguished by small angle lattice misorientations or "dislocation lamellae" and undulatory extinction. Might these crystal defects be produced as dendrites undergo ripening? (4) Clusters. Contacting clusters of polymineralic crystals are the building blocks of cumulates, and are ubiquitous features of mafic volcanic rocks. Are plagioclase and clinopyroxene aligned crystallographically, suggesting an epitaxial (surface energy) relationship? (5) Log-normal size distribution. What synthetic cooling histories produce "natural" distributions of crystal sizes, and are phenocrystic textures uniquely attributed to staged cooling? In addition, we seek to explore the limitations of the experimental approach. Which aspects of natural crystallization sequences are adequately reproduced in experimental charges, and which are compromised by the obligatory reduced temporal and spatial scales of crystal growth experiments? What are the implications of synthetic starting materials and thermal pre-treatments for nucleation, growth, heterophase equilibria, and textural maturation?

Preparation of cerium halide solvate complexes

DOEpatents

Vasudevan, Kalyan V; Smith, Nickolaus A; Gordon, John C; McKigney, Edward A; Muenchaussen, Ross E

2013-08-06

Crystals of a solvated cerium(III) halide solvate complex resulted from a process of forming a paste of a cerium(III) halide in an ionic liquid, adding a solvent to the paste, removing any undissolved solid, and then cooling the liquid phase. Diffusing a solvent vapor into the liquid phase also resulted in crystals of a solvated cerium(III) halide complex.

Nucleation kinetics of urea succinic acid –ferroelectric single crystal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dhivya, R.; Voohrees College, Vellore-632014, Tamilnadu; Vizhi, R. Ezhil, E-mail: rezhilvizhi@vit.ac.in, E-mail: revizhi@gmail.com

2015-06-24

Single crystals of Urea Succinic Acid (USA) were grown by slow cooling technique. The crystalline system was confirmed by powder X-ray diffraction. The metastable zonewidth were carried out for various temperatures i.e., 35°, 40°, 45° and 50°C. The induction period is experimentally determined and various nucleation parameters have been estimated.

Development of Casting Process for Pressings of Pistons of Car Augmented Engines

NASA Astrophysics Data System (ADS)

Korostelev, V. F.; Denisov, M. S.

2017-01-01

Results of a study aimed at formation of a single-phase fine-grained structure in pistons during their production process involving isostatic pressing of liquid metal prior to the start of crystallization, pressing of the crystallizing metal, and holding under pressure in the process of cooling to the shop temperature are presented.

Thermo-elastic behaviour of liquid crystal elastomer

NASA Astrophysics Data System (ADS)

J, Jessy P.; Mani, Santosh A.; Amare, Jyoti R.; Gharde, Rita A.

2015-06-01

The effect of temperature on Liquid Crystal Elastomer was studied to understand thermo-elastic behaviour of these fantastic soft materials. The investigations were performed using Polarizing Microscopy Studies (PMS) and Differential Thermal Analysis (DTA). The relative length shows hysteresis as function of temperature. As temperature increases, the length shrinks, while it returns to original shape on cooling.

Thermo-Physical Properties of B2O3-Containing Mold Flux for High Carbon Steels in Thin Slab Continuous Casters: Structure, Viscosity, Crystallization, and Wettability

NASA Astrophysics Data System (ADS)

Park, Jun-Yong; Kim, Gi Hyun; Kim, Jong Bae; Park, Sewoong; Sohn, Il

2016-08-01

The effect of B2O3 on the thermo-physical properties of commercial mold fluxes, including the viscosity, crystallization behavior, and wettability, was investigated. Viscosity was measured using the rotating spindle method, and CCT (continuous cooling transformation) diagrams were obtained to investigate the crystallization behavior at various cooling rates using CLSM (confocal laser scanning microscope). The wettability of the fluxes was determined by measuring the contact angles at 1573 K (1300 °C) using the digital images generated by the sessile drop method and were used to calculate the surface tension, interfacial tension, and work of adhesion for Flux A (existing flux) and B (modified flux). These thermo-physical properties were correlated with the structural analysis obtained using FT-IR (Fourier transform-infrared), Raman and MAS-NMR (magic angle spin-nuclear magnetic resonance) spectroscopy. In addition, DTA (differential thermal analysis) was performed on the samples to measure the liquidus temperatures. Higher B2O3 concentrations resulted in lower liquidus temperatures, consequently decreasing the viscosity, the break temperature, and the crystallization temperature. However, B2O3 addition accelerated crystal growth owing to the higher diffusion kinetics of the cations, which also reduced the size of the liquid/solid co-existing region.

Fabrication and characterization of poly(L-lactic acid) gels induced by fibrous complex crystallization with solvents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Matsuda, Yasuhiro; Fukatsu, Akinobu; Wang, Yangyang

2014-01-01

Complex crystal induced gelation of poly(L-lactic acid) (PLLA) solutions was studied for a series of solvents, including N,N-dimethylformamide (DMF). By cooling the solutions prepared at elevated temperatures, PLLA gels were produced in solvents that induced complex crystals ( -crystals) with PLLA. Fibrous structure of PLLA in the gel with DMF was observed by polarizing optical microscopy, field emission electron microscopy, and atomic force microscopy. Upon heating, the crystal form of PLLA in the DMF gel changed from -crystal to a-crystal, the major crystal form in common untreated PLLA films, but the morphology and high elastic modulus of the gel remainedmore » until the a-crystal dissolved at higher temperature. In addition, a solvent exchanging method was developed, which allowed PLLA gels to be prepared in other useful solvents that do not induce -crystals without losing the morphology and mechanical properties.« less

Crystallization techniques in wastewater treatment: An overview of applications.

PubMed

Lu, Haijiao; Wang, Jingkang; Wang, Ting; Wang, Na; Bao, Ying; Hao, Hongxun

2017-04-01

As a by-product of industrial or domestic activities, wastewater of different compositions has caused serious environmental problems all over the world. Facing the challenge of wastewater treatment, researchers have begun to make use of crystallization techniques in wastewater treatment. Crystallization techniques have many advantages, such as high efficiency, energy saving, low costs, less space occupation and so on. In recent decades, crystallization is considered as one of promising techniques for wastewater treatment, especially for desalination, water and salt recovery. It has been widely used in engineering applications all over the world. In this paper, various crystallization techniques in wastewater treatment are summarized, mainly including evaporation crystallization, cooling crystallization, reaction crystallization, drowning-out crystallization and membrane distillation crystallization. Overall, they are mainly used for desalination, water and salt recovery. Their applications, advantages and disadvantages were compared and discussed in detail. Copyright © 2017 Elsevier Ltd. All rights reserved.

Fractionation of lithium isotopes in magmatic systems as a natural consequence of cooling

NASA Astrophysics Data System (ADS)

Gallagher, Kerry; Elliott, Tim

2009-02-01

High-temperature, diffusive fractionation has been invoked to account for striking Li isotopic variability recently observed within individual phenocrysts and xenolith minerals. It has been argued that chemical potential gradients required to drive such diffusion arise from changes in Li partitioning between coexisting phases during cooling. If so, Li isotopic zoning should be a common occurrence but the role of temperature-dependent partition coefficients in generating Li isotopic variability remains to be tested in a quantitative manner. Here we consider a basic scenario of a phenocryst in a cooling lava, using simple parameterisations of the temperature dependence of Li partitioning and diffusivity in clinopyroxene. Our model initially produces an asymmetric isotope profile across the crystal with a δ7Li minimum that remains close to the edge of a crystal. Such a distinctive shape mimics Li isotopic profiles documented in some olivine and clinopyroxene phenocrysts, which have isotopically normal cores but anomalously light rims. The temperature dependence of both the diffusivity and the partition coefficient of Li are key factors in generating this form of diffusion profile. Continued diffusion leads to an inversion in the sense of isotopic change between core and rim and results in the whole phenocryst attaining markedly light isotopic values. Our calculations show that significant Li isotopic zoning can occur as a natural consequence of cooling magmatic systems. Crystals that have experienced more complex thermal histories (e.g. re-entrained cumulates versus true phenocrysts) will therefore exhibit contrasting isotopic profiles and, as such, these data may be useful for tracing sub-volcanic processes.

Example of a Fluid-Phase Change Examined with MD Simulation: Evaporative Cooling of a Nanoscale Droplet.

PubMed

Ao, Takashi; Matsumoto, Mitsuhiro

2017-10-24

We carried out a series of molecular dynamics simulations in order to examine the evaporative cooling of a nanoscale droplet of a Lennard-Jones liquid. After thermally equilibrating a droplet at a temperature T ini /T t ≃ 1.2 (T t is the triple-point temperature), we started the evaporation into vacuum by removing vaporized particles and monitoring the change in droplet size and the temperature inside. As free evaporation proceeds, the droplet reaches a deep supercooled liquid state of T/T t ≃ 0.7. The temperature was found to be uniform in spite of the fast evaporative cooling on the surface. The time evolution of the evaporating droplet properties was satisfactorily explained with a simple one-dimensional phase-change model. After a sufficiently long run, the supercooled droplet was crystallized into a polycrystalline fcc structure. The crystallization is a stochastic nucleation process. The time and the temperature of inception were evaluated over 42 samples, which indicate the existence of a stability limit.

Temperature nonuniformity occurring during the cooling process of a KDP crystal and its effects on second-harmonic generation.

PubMed

Liang, Yingchun; Su, Ruifeng; Lu, Lihua; Liu, Haitao

2014-08-10

The temperature nonuniformity occurring during the cooling process of a KDP crystal is studied, along with its effects on the second-harmonic generation (SHG) of a high-average-power laser. A comprehensive model is proposed incorporating principles of thermodynamics, mechanics, and optics, and it is applied to investigate the temperature nonuniformity and its effects. The temperature rise caused by linear absorption is calculated, while the temperature nonuniformity occurring during the cooling process is analyzed using the finite-element method (FEM). The stress induced by the nonuniformity is then studied using the FEM, and the trend of its change is determined. Moreover, the changes in refractive index caused by the stress are calculated, the results of which are used to determine the variations in the induced phase mismatch. The SHG efficiency considering the phase mismatch is eventually obtained by solving the coupling wave equations. The results demonstrate that the temperature nonuniformity has negative effects on the SHG efficiency.

Radiative cooling of solar absorbers using a visibly transparent photonic crystal thermal blackbody.

PubMed

Zhu, Linxiao; Raman, Aaswath P; Fan, Shanhui

2015-10-06

A solar absorber, under the sun, is heated up by sunlight. In many applications, including solar cells and outdoor structures, the absorption of sunlight is intrinsic for either operational or aesthetic considerations, but the resulting heating is undesirable. Because a solar absorber by necessity faces the sky, it also naturally has radiative access to the coldness of the universe. Therefore, in these applications it would be very attractive to directly use the sky as a heat sink while preserving solar absorption properties. Here we experimentally demonstrate a visibly transparent thermal blackbody, based on a silica photonic crystal. When placed on a silicon absorber under sunlight, such a blackbody preserves or even slightly enhances sunlight absorption, but reduces the temperature of the underlying silicon absorber by as much as 13 °C due to radiative cooling. Our work shows that the concept of radiative cooling can be used in combination with the utilization of sunlight, enabling new technological capabilities.

Radiative cooling of solar absorbers using a visibly transparent photonic crystal thermal blackbody

PubMed Central

Zhu, Linxiao; Raman, Aaswath P.; Fan, Shanhui

2015-01-01

A solar absorber, under the sun, is heated up by sunlight. In many applications, including solar cells and outdoor structures, the absorption of sunlight is intrinsic for either operational or aesthetic considerations, but the resulting heating is undesirable. Because a solar absorber by necessity faces the sky, it also naturally has radiative access to the coldness of the universe. Therefore, in these applications it would be very attractive to directly use the sky as a heat sink while preserving solar absorption properties. Here we experimentally demonstrate a visibly transparent thermal blackbody, based on a silica photonic crystal. When placed on a silicon absorber under sunlight, such a blackbody preserves or even slightly enhances sunlight absorption, but reduces the temperature of the underlying silicon absorber by as much as 13 °C due to radiative cooling. Our work shows that the concept of radiative cooling can be used in combination with the utilization of sunlight, enabling new technological capabilities. PMID:26392542

Radiative cooling of solar absorbers using a visibly transparent photonic crystal thermal blackbody

DOE PAGES

Zhu, Linxiao; Raman, Aaswath P.; Fan, Shanhui

2015-09-21

A solar absorber, under the sun, is heated up by sunlight. In many applications, including solar cells and outdoor structures, the absorption of sunlight is intrinsic for either operational or aesthetic considerations, but the resulting heating is undesirable. Because a solar absorber by necessity faces the sky, it also naturally has radiative access to the coldness of the universe. Therefore, in these applications it would be very attractive to directly use the sky as a heat sink while preserving solar absorption properties. In this paper, we experimentally demonstrate a visibly transparent thermal blackbody, based on a silica photonic crystal. Whenmore » placed on a silicon absorber under sunlight, such a blackbody preserves or even slightly enhances sunlight absorption, but reduces the temperature of the underlying silicon absorber by as much as 13 °C due to radiative cooling. Lastly, our work shows that the concept of radiative cooling can be used in combination with the utilization of sunlight, enabling new technological capabilities.« less

Thermochemical Properties of the 1-Ethyl-3-Methylimidazolium Bis(trifluoromethylsulfonyl)imide Ionic Liquid under Conditions of Equilibrium with Atmospheric Moisture

NASA Astrophysics Data System (ADS)

Ramenskaya, L. M.; Grishina, E. P.; Kudryakova, N. O.

2018-01-01

Thermochemical properties of the 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide ionic liquid [EMim]NTf2 containing moisture absorbed from the atmosphere (0.242 wt %) are investigated. The phase behavior and thermal stability relative to salt dried in vacuum are studied by means of thermogravimetry and differential scanning calorimetry at different heating and cooling rates. The glass transition, crystallization, and melting temperatures, the enthalpies of phase transitions, and the changes in heat capacity during the formation of glass are determined. It is established that the absorbed water crystallizes at a temperature of around -40.6°C and has virtually no effect on the thermal stability and phase behavior of the salt. Rapid cooling results in the ionic liquid transitioning into the glass state at -91.7 °C and the formation of three mesophases with different melting temperatures; one crystalline modification that melts at a temperature of -19.3°C forms upon slow cooling.

A High Power Frequency Doubled Fiber Laser

NASA Technical Reports Server (NTRS)

Thompson, Robert J.; Tu, Meirong; Aveline, Dave; Lundblad, Nathan; Maleki, Lute

2003-01-01

This viewgraph presentation reports on the development of a high power 780 nm laser suitable for space applications of laser cooling. A possible solution is to use frequency doubling of high power 1560 nm telecom lasers. The presentation shows a diagram of the frequency conversion, and a graph of the second harmonic generation in one crystal, and the use of the cascading crystals. Graphs show the second harmonic power as a function of distance between crystals, second harmonic power vs. pump power, tunability of laser systems.

Habit modification of potassium acid phthalate (KAP) single crystals by impurities

NASA Astrophysics Data System (ADS)

Murugakoothan, P.; Mohan Kumar, R.; Ushasree, P. M.; Jayavel, R.; Dhanasekaran, R.; Ramasamy, P.

1999-12-01

Nonlinear optical materials potassium dihydrogen phosphate (KDP), urea and L-arginine phosphate (LAP)-doped KAP crystals were grown by the slow cooling method. The LAP-doped crystals show pronounced habit modification compared to KDP and urea doping. The effect of these impurities on growth kinetics, surface morphology, habit modification, structure, optical and mechanical properties have been studied. Among the three impurities, urea doping yields high mechanical stability and optical transmission and for KDP and LAP doping there is a decrease in optical transmission.

Seeded Physical Vapor Transport of Cadmium-Zinc Telluride Crystals: Growth and Characterization

NASA Technical Reports Server (NTRS)

Palosz, W.; George, M. A.; Collins, E. E.; Chen, K.-T.; Zhang, Y.; Burger, A.

1997-01-01

Crystals of Cd(1-x)Zn(x)Te with x = 0.2 and 40 g in weight were grown on monocrystalline cadmium-zinc telluride seeds by closed-ampoule physical vapor transport with or without excess (Cd + Zn) in the vapor phase. Two post-growth cool-down rates were used. The crystals were characterized using low temperature photoluminescence, atomic force microscopy, chemical etching, X-ray diffraction and electrical measurements. No formation of a second, ZnTe-rich phase was observed.

Vibrational, calorimetric and nonlinear optical studies of melaminium-bis(trichloroacetate) monohydrate molecular ionic crystal

NASA Astrophysics Data System (ADS)

Debrus, S.; Marchewka, M. K.; Drozd, M.; Ratajczak, H.

2007-04-01

The efficiency of second harmonic generation for melaminium bis(trichloroacetate) was estimated relatively to KDP: deff = 3.09 deff (KDP). Room temperature FT IR and FT Raman spectra were recorded. Some spectral features of this new crystal are referred to corresponding one for melamine crystal as well as for other trichloroacetates. Differential scanning calorimetric measurements performed on powder sample indicate the phase transition point at approximately 276 and 239 K for heating and cooling, respectively.

Laser cooling and imaging of individual radioactive +90Sr ions

NASA Astrophysics Data System (ADS)

Jung, Kyunghun; Iwata, Yoshihiro; Miyabe, Masabumi; Yamamoto, Kazuhiro; Yonezu, Tomohisa; Wakaida, Ikuo; Hasegawa, Shuichi

2017-10-01

We have developed an apparatus integrating resonance-ionization, ion-trap, and laser-cooling techniques for an ultratrace radioactive isotope 90Sr analysis. Trapped +90Sr isotope ions were laser cooled, and their 4 d 3/2 2D →5 p 1/2 2P transition isotope shift was experimentally measured to be -281 (17 ) MHz by comparing individual spectra of +88Sr and +90Sr ions. Crystallization of +90Sr was carried out using the resonance frequency value confirmed in our experiment, and then +90Sr individual ions were successfully observed.

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.

Design study of a laser-cooled infrared sensor

DOE PAGES

Hehlen, Markus Peter; Boncher, William Lawrence; Love, Steven Paul

2015-03-10

The performance of a solid-state optical refrigerator is the result of a complex interplay of numerous optical and thermal parameters. We present a first preliminary study of an optical cryocooler using ray-tracing techniques. A numerical optimization identified a non-resonant cavity with astigmatism. This geometry offered more efficient pump absorption by the YLF:10%Yb laser-cooling crystal compared to non-resonant cavities without astigmatism that have been pursued experimentally so far. Ray tracing simulations indicate that ~80% of the incident pump light can absorbed for temperatures down to ~100 K. Calculations of heat loads, cooling power, and net payload heat lift are presented. Theymore » show that it is possible to cool a payload to a range of 90–100 K while producing a net payload heat lift of 80 mW and 300 mW when pumping a YLF:10%Yb crystal with 20 W and 50 W at 1020 nm, respectively. This performance is suited to cool HgCdTe infrared detectors that are used for sensing in the 8–12 μm atmospheric window. While the detector noise would be ~6× greater at 100 K than at 77 K, the laser refrigerator would introduce no vibrations and thus eliminate sources of microphonic noise that are limiting the performance of current systems.« less

History Dependence of the Microstructure on Time-Dependent Deformation During In-Situ Cooling of a Nickel-Based Single-Crystal Superalloy

NASA Astrophysics Data System (ADS)

Panwisawas, Chinnapat; D'Souza, Neil; Collins, David M.; Bhowmik, Ayan; Roebuck, Bryan

2018-05-01

Time-dependent plastic deformation through stress relaxation and creep deformation during in-situ cooling of the as-cast single-crystal superalloy CMSX-4® has been studied via neutron diffraction, transmission electron microscopy, electro-thermal miniature testing, and analytical modeling across two temperature regimes. Between 1000 °C and 900 °C, stress relaxation prevails and gives rise to softening as evidenced by a decreased dislocation density and the presence of long segment stacking faults in γ phase. Lattice strains decrease in both the γ matrix and γ' precipitate phases. A constitutive viscoplastic law derived from in-situ isothermal relaxation test under-estimates the equivalent plastic strain in the prediction of the stress and strain evolution during cooling in this case. It is thereby shown that the history dependence of the microstructure needs to be taken into account while deriving a constitutive law and which becomes even more relevant at high temperatures approaching the solvus. Higher temperature cooling experiments have also been carried out between 1300 °C and 1150 °C to measure the evolution of stress and plastic strain close to the γ' solvus temperature. In-situ cooling of samples using ETMT shows that creep dominates during high-temperature deformation between 1300 °C and 1220 °C, but below a threshold temperature, typically 1220 °C work hardening begins to prevail from increasing γ' fraction and resulting in a rapid increase in stress. The history dependence of prior accumulated deformation is also confirmed in the flow stress measurements using a single sample while cooling. The saturation stresses in the flow stress experiments show very good agreement with the stresses measured in the cooling experiments when viscoplastic deformation is dominant. This study demonstrates that experimentation during high-temperature deformation as well as the history dependence of the microstructure during cooling plays a key role in deriving an accurate viscoplastic constitutive law for the thermo-mechanical process during cooling from solidification.

Hot Stuff? Thermal Imaging Applied to Cryocrystallography

NASA Technical Reports Server (NTRS)

Snell, E. H.

2004-01-01

In the past we have used thermal imaging techniques to visualize the cryocooling processes of macromolecular crystals. From these images it was clear that a cold wave progresses through a crystal starting at the face closest to the origin of the cold stream and ending at the point furthest away. During these studies we used large volume crystals, which were clearly distinguished fiom the loop holding them. These large crystals, originally grown for neutron diffiaction studies, were chosen deliberately to enhance the imaging. As an extension to this work, we present used thermal imaging to study small crystals, held in a cryo-loop, in the presence of vitrified mother liquor. The different d a r e d transmission and reflectance properties of the crystal in comparison to the mother liquor surrounding it are thought to be the parameter that produces the contrast that makes the crystal visible. An application of this technology may be the determination of the exact location of small crystals in a cryo-loop. Data fkom initial tests in support of application development was recorded for lysozyme crystals and for bFGF/dna complex crystals, which were cryocooled and imaged in large loops, both with visible light mad with h i k e d rdi&tion. The crystals were clearly distinguished from the vitrified solution in the infiared spectrum, while in the case of the bFGF/dna complex the illumination had to be carefully manipulated to make the crystal visible in the visible spectrum. These results suggest that the thermal imaging may be more sensitive than visual imaging for automated location of small crystals. However, further work on small crystals robotically mounted at SSRL did not clearly visualize those crystals. The depth of field of the camera proved to be limiting and a different cooling geometry was used, compared to the previous, successful experiments. Analysis to exploit multiple images to improve depth of field and experimental work to understand cooling geometry effects is ongoing. These results will be presented along with advantages and disadvantages of the technique and a discussion of how it might be applied.

Growth of silicon carbide crystals on a seed while pulling silicon crystals from a melt

NASA Technical Reports Server (NTRS)

Ciszek, T. F.; Schwuttke, G. H. (Inventor)

1979-01-01

A saturated solution of silicon and an element such as carbon having a segregation coefficient less than unity is formed by placing a solid piece of carbon in a body of molten silicon having a temperature differential decreasing toward the surface. A silicon carbide seed crystal is disposed on a holder beneath the surface of the molten silicon. As a rod or ribbon of silicon is slowly pulled from the melt, a supersaturated solution of carbon in silicon is formed in the vicinity of the seed crystal. Excess carbon is emitted from the solution in the form of silicon carbide which crystallizes on the seed crystal held in the cool region of the melt.

Crystallization of baria-titania-silica glasses

NASA Technical Reports Server (NTRS)

Ray, Chandra S.; Day, Delbert E.

1986-01-01

The critical cooling rate for glass formation, Rc, and the crystallization kinetics of the compositions (1/2)(100-x)BaO-(1/2)(100-x)TiO2-(x)SiO2 with x = 20, 25, 30, 33.3, and 40 mol pct were studied using a thermal image furnace. Crystallization was studied under nonisothermal conditions, and the data were analyzed using the Johnson-Mehl-Avrami equation. The Rc and activation energy for crystallization both decrease with increasing silica content. Fresnoite, Ba2TiSi2O8, crystallized from all of the glasses when they were reheated. The infrared absorption spectra of the glasses and crystals show that they both contain (Si2O7) and square pyramidal (TiO5) groups.

Evidence of monotropic hexatic tilted smectic phase in the phase sequence of ferroelectric liquid crystal

NASA Astrophysics Data System (ADS)

Różycka, Anna; Deptuch, Aleksandra; Jaworska-Gołąb, Teresa; Węgłowska, Dorota; Marzec, Monika

2018-02-01

Physical properties of a new ferroelectric liquid crystal have been studied by complementary methods: differential scanning calorimetry, polarizing optical microscopy, dielectric and X-ray diffraction. It was found that next to enantiotropic ferroelectric smectic C* phase, the monotropic smectic phase appears at cooling. X-ray diffraction measurements allowed to identify this phase as hexatic tilted smectic. Temperature dependence of spontaneous polarization, tilt angle of molecules and switching time were found in both liquid crystalline phases at cooling. Based on the dielectric results, the dielectric processes were identified as Goldstone mode in the smectic C* phase, whereas as the bond-orientation-like phason and the bulk domain mode in the monotropic hexatic tilted smectic phase.

Dynamic crystallization of silicate melts

NASA Technical Reports Server (NTRS)

Russell, W. J.

1984-01-01

Two types of furnaces with differing temperature range capabilities were used to provide variations in melt temperatures and cooling rates in a study of the effects of heterogeneous nucleation on crystallization. Materials of chondrule composition were used to further understanding of how the disequilibrium features displayed by minerals in rocks are formed. Results show that the textures of natural chondrules were duplicated. It is concluded that the melt history is dominant over cooling rate and composition in controlling texture. The importance of nuclei, which are most readily derived from preexisting crystalline material, support an origin for natural chondrules based on remelting of crystalline material. This would be compatible with a simple, uniform chondrule forming process having only slight variations in thermal histories resulting in the wide range of textures.

Cryogenics for the MuCool Test Area (MTA)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Darve, Christine; Norris, Barry; Pei, Liu-Jin

2005-09-01

MuCool Test Area (MTA) is a complex of buildings at Fermi National Accelerator Laboratory, which are dedicated to operate components of a cooling cell to be used for Muon Collider and Neutrino Factory R&D. The long-term goal of this facility is to test ionization cooling principles by operating a 25-liter liquid hydrogen (LH{sub 2}) absorber embedded in a 5 Tesla superconducting solenoid magnet. The MTA solenoid magnet will be used with RF cavities exposed to a high intensity beam. Cryogens used at the MTA include LHe, LN{sub 2} and LH{sub 2}. The latter dictates stringent system design for hazardous locations.more » The cryogenic plant is a modified Tevatron refrigerator based on the Claude cycle. The implementation of an in-house refrigerator system and two 300 kilowatt screw compressors is under development. The helium refrigeration capacity is 500 W at 14 K. In addition the MTA solenoid magnet will be batch-filled with LHe every 2 days using the same cryo-plant. This paper reviews cryogenic systems used to support the Muon Collider and Neutrino Factory R&D programs and emphasizes the feasibility of handling cryogenic equipment at MTA in a safe manner.« less

Cryogenics for the MuCool Test Area (MTA)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Darve, Christine; Norris, Barry; Pei, Liujin

2006-03-20

MuCool Test Area (MTA) is a complex of buildings at Fermi National Accelerator Laboratory, which are dedicated to operate components of a cooling cell to be used for Muon Collider and Neutrino Factory R and D. The long-term goal of this facility is to test ionization cooling principles by operating a 25-liter liquid hydrogen (LH2) absorber embedded in a 5 Tesla superconducting solenoid magnet. The MTA solenoid magnet will be used with RF cavities exposed to a high intensity beam. Cryogens used at the MTA include LHe, LN2 and LH2. The latter dictates stringent system design for hazardous locations. Themore » cryogenic plant is a modified Tevatron refrigerator based on the Claude cycle. The implementation of an in-house refrigerator system and two 300 kilowatt screw compressors is under development. The helium refrigeration capacity is 500 W at 14 K. In addition the MTA solenoid magnet will be batch-filled with LHe every 2 days using the same cryo-plant. This paper reviews cryogenic systems used to support the Muon Collider and Neutrino Factory R and D programs and emphasizes the feasibility of handling cryogenic equipment at MTA in a safe manner.« less

Stamp forming optimization for formability and crystallinity

NASA Astrophysics Data System (ADS)

Donderwinkel, T. G.; Rietman, B.; Haanappel, S. P.; Akkerman, R.

2016-10-01

The stamp forming process is well suited for high volume production of thermoplastic composite parts. The process can be characterized as highly non-isothermal as it involves local quench-cooling of a molten thermoplastic composite blank where it makes contact with colder tooling. The formability of the thermoplastic composite depends on the viscoelastic material behavior of the matrix material, which is sensitive to temperature and degree of crystallinity. An experimental study was performed to determine the effect of temperature and crystallinity on the storage modulus during cooling for a woven glass fiber polyamide-6 composite material. An increase of two decades in modulus was observed during crystallization. As this will significantly impede the blank formability, the onset of crystallization effectively governs the time available for forming. Besides the experimental work, a numerical model is developed to study the temperature and crystallinity throughout the stamp forming process. A process window can be determined by feeding the model with the experimentally obtained data on crystallization.

Structure, phonon properties, and order-disorder transition in the metal formate framework of [NH4][Mg(HCOO)3].

PubMed

Mączka, Mirosław; Pietraszko, Adam; Macalik, Bogusław; Hermanowicz, Krzysztof

2014-01-21

We report the synthesis, crystal structure, thermal, dielectric, IR, and Raman studies of [NH4][Mg(HCOO)3] formate. Single-crystal X-ray diffraction shows that it crystallizes in the hexagonal space group P6322, with orientationally disordered NH4(+) ions located in the cages of the network. Upon cooling, [NH4][Mg(HCOO)3] undergoes a phase transition at around 255 K to the ferroelectric P63 structure. Raman and IR spectra show a strong increase in intensity of the N-H stretching bands as well as narrowing of the bands related to the NH4(+) ions upon cooling. These changes indicate that the phase transition is due to orientational ordering of the NH4(+) ions. Analysis of the Raman data show, however, that the rotational and translational motions of NH4(+) do not freeze completely at the phase transition but exhibit further slowing down below 255 K, and the motional freezing becomes nearly complete below 140 K.

Selective synthesis of human milk fat-style structured triglycerides from microalgal oil in a microfluidic reactor packed with immobilized lipase

DOE PAGES

Wang, Jun; Liu, Xi; Wang, Xu -Dong; ...

2016-08-18

Human milk fat-style structured triacylglycerols were produced from microalgal oil in a continuous microfluidic reactor packed with immobilized lipase for the first time. A remarkably high conversion efficiency was demonstrated in the microreactor with reaction time being reduced by 8 times, Michaelis constant decreased 10 times, the lipase reuse times increased 2.25-fold compared to those in a batch reactor. In addition, the content of palmitic acid at sn-2 position (89.0%) and polyunsaturated fatty acids at sn-1, 3 positions (81.3%) are slightly improved compared to the product in a batch reactor. The increase of melting points (1.7 °C) and decrease ofmore » crystallizing point (3 °C) implied higher quality product was produced using the microfluidic technology. The main cost can be reduced from 212.3 to 14.6 per batch with the microreactor. Altogether, the microfluidic bioconversion technology is promising for modified functional lipids production allowing for cost-effective approach to produce high-value microalgal coproducts.« less

Selective synthesis of human milk fat-style structured triglycerides from microalgal oil in a microfluidic reactor packed with immobilized lipase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Jun; Liu, Xi; Wang, Xu -Dong

Human milk fat-style structured triacylglycerols were produced from microalgal oil in a continuous microfluidic reactor packed with immobilized lipase for the first time. A remarkably high conversion efficiency was demonstrated in the microreactor with reaction time being reduced by 8 times, Michaelis constant decreased 10 times, the lipase reuse times increased 2.25-fold compared to those in a batch reactor. In addition, the content of palmitic acid at sn-2 position (89.0%) and polyunsaturated fatty acids at sn-1, 3 positions (81.3%) are slightly improved compared to the product in a batch reactor. The increase of melting points (1.7 °C) and decrease ofmore » crystallizing point (3 °C) implied higher quality product was produced using the microfluidic technology. The main cost can be reduced from 212.3 to 14.6 per batch with the microreactor. Altogether, the microfluidic bioconversion technology is promising for modified functional lipids production allowing for cost-effective approach to produce high-value microalgal coproducts.« less

Selective synthesis of human milk fat-style structured triglycerides from microalgal oil in a microfluidic reactor packed with immobilized lipase.

PubMed

Wang, Jun; Liu, Xi; Wang, Xu-Dong; Dong, Tao; Zhao, Xing-Yu; Zhu, Dan; Mei, Yi-Yuan; Wu, Guo-Hua

2016-11-01

Human milk fat-style structured triacylglycerols were produced from microalgal oil in a continuous microfluidic reactor packed with immobilized lipase for the first time. A remarkably high conversion efficiency was demonstrated in the microreactor with reaction time being reduced by 8 times, Michaelis constant decreased 10 times, the lipase reuse times increased 2.25-fold compared to those in a batch reactor. In addition, the content of palmitic acid at sn-2 position (89.0%) and polyunsaturated fatty acids at sn-1, 3 positions (81.3%) are slightly improved compared to the product in a batch reactor. The increase of melting points (1.7°C) and decrease of crystallizing point (3°C) implied higher quality product was produced using the microfluidic technology. The main cost can be reduced from $212.3 to $14.6 per batch with the microreactor. Overall, the microfluidic bioconversion technology is promising for modified functional lipids production allowing for cost-effective approach to produce high-value microalgal coproducts. Copyright © 2016 Elsevier Ltd. All rights reserved.

Cultivation characteristics of immobilized Aspergillus oryzae for kojic acid production.

PubMed

Kwak, M Y; Rhee, J S

1992-04-15

Aspergillus oryzae in situ grown from spores entrapped in calcium alginate gel beads was used for the production of kojic acid. The immobilized cells in flask cultures produced kojic acid in a linear proportion while maintaining the stable metabolic activity for a prolonged production period. Kojic acid was accumulated up to a high concentration of 83 g/L, at which the kojic acid began to crystallize, and, thus, the culture had to be replaced with fresh media for the next batch culture. The overall productivities of two consecutive cultivations were higher than that of free mycelial fermentation. However, the production rate of kojic acid by the immobilized cells was suddenly decreased with the appearance of central cavernae inside the immobilized gel beads after 12 days of the third batch cultivation.

Microgravity

NASA Image and Video Library

2004-04-15

Comparison of Germanium Telluride (GeTe) Crystals grown on Earth (left) and in space (right) during the Skylab SL-3 mission. These crystals were grown using a vapor transport crystal growth method in the Multipurpose Electric Furnace System (MEFS). Crystals grown on earth are needles and platelettes with distorted surfaces and hollow growth habits. The length of the ground-based needle is approximately 2 mm and the average lenth of the platelets is 1 mm. The dull appearance of the Skylab crystals resulted from condensation of the transport agent during the long cooling period dictated by the Skylab furnace. In a dedicated process, this would be prevented by removing the ampoule from the furnace and quenching the vapor source.

Optical parameters and dispersion behavior of potassium magnesium chloride sulfate single crystals doped with Co+2 ions

NASA Astrophysics Data System (ADS)

Abu El-Fadl, A.; Abd-Elsalam, A. M.

2018-05-01

Single crystals of potassium magnesium chloride sulfate (KMCS) doped with cobalt ions were grown by slow cooling method. Powder XRD study confirmed the monoclinic structure of the grown crystals. The functional group vibrations were checked through FTIR spectroscopy measurements. In optical studies, the absorbance behavior of the crystals and their optical energy gap were established by Tauc plot. The refractive index, the extinction coefficient and other optical constants were calculated for the grown crystals. The normal dispersion of the refractive index was analyzed according to single oscillator Sellmeier's model. The Urbach's rule was applied to analyze the localized states density in the forbidden gap.

Habit modification of epsomite in the presence of urea

NASA Astrophysics Data System (ADS)

Ramalingom, S.; Podder, J.; Narayana Kalkura, S.; Bocelli, G.

2003-01-01

The pure and urea doped epsomite (MgSO 4·7H 2O) crystals were grown at low temperature by the slow cooling technique. The effect of pH on the growth rate of pure MgSO 4·7H 2O was studied. It was found that the higher pH values increased the growth rate and the size of the crystals. The quantity of urea present in the doped magnesium sulphate crystals was estimated. The incorporation of urea into the mother solution was found to promote the growth rate. The habit of the crystals changed from orthorhombic to tetragonal. Further, there was an increase of microhardness of the crystals on doping of urea.

Nepheline structural and chemical dependence on melt composition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marcial, José; Crum, Jarrod; Neill, Owen

Nepheline crystallizes upon slow-cooling in some melts concentrated in Na2O and Al2O3, which can result in a residual glass phase of low chemical durability. Nepheline can incorporate many components often found in high-level waste radioactive borosilicate glass, including glass network ions (e.g., Si, Al, Fe), alkali metals (e.g., Cs, K, Na, and possibly Li), alkaline-earth metals (e.g., Ba, Sr, Ca, Mg), and transition metals (e.g., Mn, and possibly Cr, Zn, Ni). When crystallized from melts of different compositions, nepheline chemistry varies as a function of starting glass composition. Five simulated high level nuclear waste borosilicate glasses shown to crystallize largemore » fractions of nepheline on slow cooling, were selected for study. These melts constituted a range of Al2O3, B2O3, CaO, Na2O, K2O, Fe2O3, and SiO2 compositions. Compositional analyses of nepheline crystals in glass by electron probe micro-analysis (EPMA) indicate that boron is unlikely to be present in any significant concentration, if at all, in nepheline. Also, several models are presented for calculating the fraction of vacancies in the nepheline structure.« less

Low-Ca pyroxenes from LL group chondritic meteorites: Crystal structural studies and implications for their thermal histories

NASA Astrophysics Data System (ADS)

Artioli, G.; Davoli, G.

1994-12-01

Crystal structural refinements of one orthorhombic (Pbca) and two monoclinic (P21/c) single crystals, from chondrules of low-Ca pyroxenes from unequilibrated chondritic meteorites of the LL group, were carried out. The intracrystalline Fe-Mg distribution between the M1 and M2 crystallographic sites of the Parnallee (LL-3) orthoenstatite is suggestive of very rapid cooling, whereas both the structural state and intracrystalline Fe-Mg distribution in the Soko Banja (LL-4) and Jolomba (LL-6) clinoenstaties indicate rapid cooling from the high temperature polymorphs, with no significant re-equilibration at lower temperatures. These results imply that thermal metamorphism in the parent body, if present, was insufficient to allow re-equilibration of the pyroxene minerals to low temperature, ordered crystal structures. The data also indicate that, assuming low or mild pressure and shock effects, there is no well defined correlation between equilibrium temperature of the mineral phases and the alleged petrologic type of the meteorites. This evidence is consistent with a rubble pile model for the parent body accretional history, or with an onion shell model with very low thermal peak metamorphism, as is assumed for a very small object.

A New Freezing Method Using Pre-Dehydration by Microwave-Vacuum Drying

NASA Astrophysics Data System (ADS)

Tsuruta, Takaharu; Hamidi, Nurkholis

Partial dehydration by microwave-vacuum drying has been applied to tuna and strawberry in order to reduce cell-damages caused by the formation of large ice-crystals during freezing. The samples were subjected to microwave vacuum drying at pressure of 5 kPa and temperature less than 27°C to remove small amount of water prior to freezing. The tuna were cooled by using the freezing chamber at temperature -50°C or -150°C, while the strawberries were frozen at temperature -30°C or -80°C, respectively. The temperature transients in tuna showed that removing some water before freezing made the freezing time shorter. The observations of ice crystal clearly indicated that rapid cooling and pre-dehydration prior to freezing were effective in minimizing the size of ice crystal. It is also understood that the formation of large ice crystals has a close relation to the cell damages. After thawing, the observation of microstructure was done on the tuna and strawberry halves. The pre-dehydrated samples showed a better structure than the un-dehydrated one. It is concluded that the pre-dehydration by microwave-vacuum drying is one promising method for the cryo-preservation of foods.

Single-crystal diamond nanomechanical resonators with quality factors exceeding one million

NASA Astrophysics Data System (ADS)

Tao, Y.; Boss, J. M.; Moores, B. A.; Degen, C. L.

2014-04-01

Diamond has gained a reputation as a uniquely versatile material, yet one that is intricate to grow and process. Resonating nanostructures made of single-crystal diamond are expected to possess excellent mechanical properties, including high-quality factors and low dissipation. Here we demonstrate batch fabrication and mechanical measurements of single-crystal diamond cantilevers with thickness down to 85 nm, thickness uniformity better than 20 nm and lateral dimensions up to 240 μm. Quality factors exceeding one million are found at room temperature, surpassing those of state-of-the-art single-crystal silicon cantilevers of similar dimensions by roughly an order of magnitude. The corresponding thermal force noise for the best cantilevers is ~5·10-19 N Hz-1/2 at millikelvin temperatures. Single-crystal diamond could thus directly improve existing force and mass sensors by a simple substitution of resonator material. Presented methods are easily adapted for fabrication of nanoelectromechanical systems, optomechanical resonators or nanophotonic devices that may lead to new applications in classical and quantum science.

Hot Views on Cold Crystals: The Application of Thermal Imaging in Cryocrystallography

NASA Technical Reports Server (NTRS)

Snell, Eddie

2003-01-01

We have used thermal imaging techniques to visualize the cryocooling processes of macromolecular crystals. Cryocooling is a common technique used for structural data collection to reduce radiation damage in intense X-ray beams and decrease the thermal motion of the atoms. From the thermal images it was clear that during cryocooling a cold wave progresses through a crystal starting at the face closest to the origin of the cold stream and ending at the point furthest away. As an extension to this work, we used thermal imaging to study small crystals, held in a cryo-loop, in the presence of vitrified mother liquor. The different infrared transmission and reflectance properties of the crystal in comparison to the mother liquor surrounding it are thought to be the parameter that produces the contrast that makes the crystal visible. An application of this technology may be the determination of the exact location of small crystals in a cryo-loop for automated structural genomics studies. Data from initial tests in support of application development was recorded for lysozyme crystals and for bFGF/dna complex crystals, which were cryocooled and imaged in large loops, both with visible light and with infrared radiation. The crystals were clearly distinguished from the vitrified solution in the infrared spectrum, while in the case of the bFGF/dna complex the illumination had to be carefully manipulated to make the crystal visible in the visible spectrum. These results suggest that the thermal imaging may be more sensitive than visual imaging for automated location of small crystals. However, further work on small crystals robotically mounted at SSRL did not clearly visualize those crystals. The depth of field of the camera proved to be limiting and a different cooling geometry was used, compared to the previous, successful experiments. Analysis to exploit multiple images to improve depth of field and experimental work to understand cooling geometry effects is ongoing. These results will be presented along with advantages and disadvantages of the technique and a discussion of how it might be applied.

The Effects of Thermal History on Nucleation of Tetragonal Lysozyme Crystals, or Hot Protein and Cold Nucleation

NASA Technical Reports Server (NTRS)

Burke, Michael; Judge, Russell; Pusey, Marc

2000-01-01

Chicken egg white lysozyme has a well characterized thermally driven phase transition. Between pH 4.2 and 5.2, the transition temperature, as defined by the point where the tetragonal and orthorhombic solubilities are equal, is a function of the pH, salt (precipitant) type and concentration, and most likely of the buffer concentration as well. This phase transition can be carried out with protein solution alone, prior to addition of precipitant solution. Warming a lysozyme solution above the phase transition point, then cooling it back below this point, has been shown to affect the subsequent nucleation rate, as determined by the numbers and size of crystals formed, but not the growth rate for the tetragonal crystal form . We have now measured the kinetics of this process and investigated its reversibility. The transition effects are progressive with temperature, having a half time of about 1 hour at 37C at pH 4.8. After holding a lysozyme solution at 37C (prior to addition of precipitant) for 16 hours, then cooling it back to 4C no return to the pre-warmed nucleation kinetics are observed after at least 4 weeks. Orthorhombic lysozyme crystals apparently do not undergo the flow-induced growth cessation of tetragonal lysozyme crystals. Putting the protein in the orthorhombic form does not affect the averaged face growth kinetics, only nucleation, for tetragonal crystals. This differential behaviour may be exploited to elucidate how and where flow affects the lysozyme crystal growth process. The presentation will focus on the results of these and ongoing studies in this area.

Beating Homogeneous Nucleation and Tuning Atomic Ordering in Glass-Forming Metals by Nanocalorimetry.

PubMed

Zhao, Bingge; Yang, Bin; Abyzov, Alexander S; Schmelzer, Jürn W P; Rodríguez-Viejo, Javier; Zhai, Qijie; Schick, Christoph; Gao, Yulai

2017-12-13

In this paper, the amorphous Ce 68 Al 10 Cu 20 Co 2 (atom %) alloy was in situ prepared by nanocalorimetry. The high cooling and heating rates accessible with this technique facilitate the suppression of crystallization on cooling and the identification of homogeneous nucleation. Different from the generally accepted notion that metallic glasses form just by avoiding crystallization, the role of nucleation and growth in the crystallization behavior of amorphous alloys is specified, allowing an access to the ideal metallic glass free of nuclei. Local atomic configurations are fundamentally significant to unravel the glass forming ability (GFA) and phase transitions in metallic glasses. For this reason, isothermal annealing near T g from 0.001 s to 25,000 s following quenching becomes the strategy to tune local atomic configurations and facilitate an amorphous alloy, a mixed glassy-nanocrystalline state, and a crystalline sample successively. On the basis of the evolution of crystallization enthalpy and overall latent heat on reheating, we quantify the underlying mechanism for the isothermal nucleation and crystallization of amorphous alloys. With Johnson-Mehl-Avrami method, it is demonstrated that the coexistence of homogeneous and heterogeneous nucleation contributes to the isothermal crystallization of glass. Heterogeneous rather than homogeneous nucleation dominates the isothermal crystallization of the undercooled liquid. For the mixed glassy-nanocrystalline structure, an extraordinary kinetic stability of the residual glass is validated, which is ascribed to the denser packed interface between amorphous phase and ordered nanocrystals. Tailoring the amorphous structure by nanocalorimetry permits new insights into unraveling GFA and the mechanism that correlates local atomic configurations and phase transitions in metallic glasses.

The role of diffusion-controlled oscillatory nucleation in the formation of line rock in pegmatite-aplite dikes

USGS Publications Warehouse

Webber, K.L.; Falster, A.U.; Simmons, W.B.; Foord, E.E.

1997-01-01

The George Ashley Block (GAB), located in the Pala Pegmatite District, San Diego County, California, is a composite pegmatite-aplite dike of 8 m thickness displaying striking mineralogical layering in the aphte portion of the dike, referred to as line rock. Rhythmic layering is characterized by garnet-rich bands alternating with albite-quartz-muscovite-rich bands. Cumulus textures are notably absent from the layered portion of the dike. Elongated quartz, megacrysts are oriented perpendicular to the garnet-rich layers and poikilitically include garnet, albite, and muscovite. Calculated crystal-free magma viscosity with 3% H2O is 106.2 Pa s and the calculated settling velocity for garnet is 0??51 cm/year. Conductive cooling calculations based on emplacement of a 650??C dike into 150?? C fractured gabbroic country rock at 1??5 kbar, and accounting for latent heat of crystallization, demonstrate that the line rock portion of the dike cools to 550?? C in about 1 year. Crystal size distribution studies also suggest very rapid nucleation and crystallization. Diffusion-controlled gel crystallization experiments yield textures virtually identical to those observed in the layered aplite, including rhythmic banding, colloform layering, and band discontinuities. Thus, observed textures and calculated magmatic parameters suggest that mineralogical layering in the GAB results from an in situ diffusion-controlled process of oscillatory nucleation and crystallization. We propose that any event that promotes strong undercooling has the potential to initiate rapid heterogeneous nucleation and oscillatory crystal growth, leading to the development of a layer of excluded components in front of the crystallization front, and the formation of line rock.

Kinetics of Fe2+-Mg order-disorder in orthopyroxene: experimental studies and applications to cooling rates of rocks

NASA Astrophysics Data System (ADS)

Stimpfl, M.; Ganguly, J.; Molin, G.

2005-10-01

We determined the forward rate constant (K+) for the Fe2+-Mg order-disorder between the M2 and M1 sites of orthopyroxene (OPx), which is described by the homogeneous reaction Fe2+ (M2) + Mg(M1) ↔ Mg(M2) + Fe2+ (M1), by both ordering and disordering experiments at isothermal condition and also by continuous cooling experiments. The rate constant was determined as a function of temperature in the range of 550-750°C, oxygen fugacity between quartz-fayalite-iron and Ni-NiO buffers, and at compositions of 16 and 50 mol% ferrosilite component. The K+ value derived from disordering experiment was found to be larger than that derived from ordering experiment at 550°C, while at T>580°C, these two values are essentially the same. The fO2 dependence of the rate constant can be described by the relation K+ α (fO2) n with n=5.5-6.5, which is compatible with the theoretically expected relation. The Arrhenius relation at the WI buffer condition is given by ln (C_{text{o}} {text{K}}^+) = - {41511 - 12600{text{X}}_{{text{Fe}}} }/{{T({text{K}})}} + 28.26 + 5.27{text{X}}_{{text{Fe}}}, min^{-1} where C o represents the total number of M2 + M1 sites occupied by Fe2+ and Mg per unit volume of the crystal. The above relation can be used to calculate the cooling rates of natural OPx crystals around the closure temperature ( T c) of Fe-Mg ordering, which are usually below 300°C for slowly cooled rocks. We determined the Fe-Mg ordering states of several OPx crystals (˜ Fs50) from the Central Gneissic Complex (Khtada Lake), British Columbia, which yields T c ˜290°C. Numerical simulation of the change of Fe2+-Mg ordering in OPx as a function of temperature using the above expression of rate constant and a non-linear cooling model yields quenched values of ordering states that are in agreement with the observed values for cooling rates of 11-17°C/Myr below 300°C. The inferred cooling rate is in agreement with the available geochronological constraints.

Dependence of the residual surface resistance of superconducting radio frequency cavities on the cooling dynamics around T c

DOE Office of Scientific and Technical Information (OSTI.GOV)

Romanenko, A.; Grassellino, A.; Melnychuk, O.

We report a strong effect of the cooling dynamics throughmore » $$T_\\mathrm{c}$$ on the amount of trapped external magnetic flux in superconducting niobium cavities. The effect is similar for fine grain and single crystal niobium and all surface treatments including electropolishing with and without 120$$^\\circ$$C baking and nitrogen doping. Direct magnetic field measurements on the cavity walls show that the effect stems from changes in the flux trapping efficiency: slow cooling leads to almost complete flux trapping and higher residual resistance while fast cooling leads to the much more efficient flux expulsion and lower residual resistance.« less

Preparation of Desirable Porous Cell Structure Polylactide/Wood Flour Composite Foams Assisted by Chain Extender

PubMed Central

Wang, Youyong; Song, Yongming; Du, Jun; Xi, Zhenhao; Wang, Qingwen

2017-01-01

Polylactide (PLA)/wood flour composite foam were prepared through a batch foaming process. The effect of the chain extender on the crystallization behavior and dynamic rheological properties of the PLA/wood flour composites were investigated as well as the crystal structure and cell morphology of the composite foams. The incorporation of the chain extender enhanced the complex viscosity and storage modulus of PLA/wood flour composites, indicating the improved melt elasticity. The chain extender also led to a decreased crystallization rate and final crystallinity of PLA/wood flour composites. With an increasing chain extender content, a finer and more uniform cell structure was formed, and the expansion ratio of PLA/wood flour composite foams was much higher than without the chain extender. Compared to the unfoamed composites, the crystallinity of the foamed PLA/wood flour composites was improved and the crystal was loosely packed. However, the new crystalline form was not evident. PMID:28846604

Rapid cooling rates at an active mid-ocean ridge from zircon thermochronology

USGS Publications Warehouse

Schmitt, Axel K.; Perfit, Michael R.; Rubin, Kenneth H.; Stockli, Daniel F.; Smith, Matthew C.; Cotsonika, Laurie A.; Zellmer, Georg F.; Ridley, W. Ian

2011-01-01

Oceanic spreading ridges are Earth's most productive crust generating environment, but mechanisms and rates of crustal accretion and heat loss are debated. Existing observations on cooling rates are ambiguous regarding the prevalence of conductive vs. convective cooling of lower oceanic crust. Here, we report the discovery and dating of zircon in mid-ocean ridge dacite lavas that constrain magmatic differentiation and cooling rates at an active spreading center. Dacitic lavas erupted on the southern Cleft segment of the Juan de Fuca ridge, an intermediate-rate spreading center, near the intersection with the Blanco transform fault. Their U–Th zircon crystallization ages (29.3-4.6+4.8 ka; 1δ standard error s.e.) overlap with the (U–Th)/He zircon eruption age (32.7 ± 1.6 ka) within uncertainty. Based on similar 238U-230Th disequilibria between southern Cleft dacite glass separates and young mid-ocean ridge basalt (MORB) erupted nearby, differentiation must have occurred rapidly, within ~ 10–20 ka at most. Ti-in-zircon thermometry indicates crystallization at 850–900 °C and pressures > 70–150 MPa are calculated from H2O solubility models. These time-temperature constraints translate into a magma cooling rate of ~ 2 × 10-2 °C/a. This rate is at least one order-of-magnitude faster than those calculated for zircon-bearing plutonic rocks from slow spreading ridges. Such short intervals for differentiation and cooling can only be resolved through uranium-series (238U–230Th) decay in young lavas, and are best explained by dissipating heat convectively at high crustal permeability.

The magma plumbing system in the Mariana Trough back-arc basin at 18° N

NASA Astrophysics Data System (ADS)

Lai, Zhiqing; Zhao, Guangtao; Han, Zongzhu; Huang, Bo; Li, Min; Tian, Liyan; Liu, Bo; Bu, Xuejiao

2018-04-01

Mafic magmas are common in back-arc basin, once stalled in the crust, these magmas may undergo different evolution. In this paper, compositional and textural variations of plagioclase as well as mineral-melt geothermobarometry are presented for basalts erupted from the central Mariana Trough (CMT). These data reveal crystallization conditions and we attempt a reconstruction of the magma plumbing system of the CMT. Plagioclase megacrysts, phenocrysts, microphenocrysts, microlites, olivine, spinel, and clinopyroxene have been recognized in basalt samples, using BSE images and compositional features. The last three minerals are homogeneous as microphenocrysts. Mineral-melt barometry indicates that plagioclase crystals crystallized and eventually grew into phenocrysts and megacrysts in mush zone with depth of 5-9 km, in which the normal zoning plagioclases crystallized in the interval of various batches of basic magma recharging. Plagioclase megacrysts and phenocrysts were dissolved and/or resorbed, when new basic magmas injected into the mush zone near Moho depth. It is inferred that magma extracted from the mush zone, and adiabatically ascended via different pathways. Some basaltic magmas underwent plagioclase and clinopyroxene microphenocrysts crystallization in low-pressure before eruption. Plagioclase microlites and outermost rims probably crystallized after eruption.

Introduction to protein crystallization

PubMed Central

McPherson, Alexander; Gavira, Jose A.

2014-01-01

Protein crystallization was discovered by chance about 150 years ago and was developed in the late 19th century as a powerful purification tool and as a demonstration of chemical purity. The crystallization of proteins, nucleic acids and large biological complexes, such as viruses, depends on the creation of a solution that is supersaturated in the macromolecule but exhibits conditions that do not significantly perturb its natural state. Supersaturation is produced through the addition of mild precipitating agents such as neutral salts or polymers, and by the manipulation of various parameters that include temperature, ionic strength and pH. Also important in the crystallization process are factors that can affect the structural state of the macromolecule, such as metal ions, inhibitors, cofactors or other conventional small molecules. A variety of approaches have been developed that combine the spectrum of factors that effect and promote crystallization, and among the most widely used are vapor diffusion, dialysis, batch and liquid–liquid diffusion. Successes in macromolecular crystallization have multiplied rapidly in recent years owing to the advent of practical, easy-to-use screening kits and the application of laboratory robotics. A brief review will be given here of the most popular methods, some guiding principles and an overview of current technologies. PMID:24419610

Introduction to protein crystallization.

PubMed

McPherson, Alexander; Gavira, Jose A

2014-01-01

Protein crystallization was discovered by chance about 150 years ago and was developed in the late 19th century as a powerful purification tool and as a demonstration of chemical purity. The crystallization of proteins, nucleic acids and large biological complexes, such as viruses, depends on the creation of a solution that is supersaturated in the macromolecule but exhibits conditions that do not significantly perturb its natural state. Supersaturation is produced through the addition of mild precipitating agents such as neutral salts or polymers, and by the manipulation of various parameters that include temperature, ionic strength and pH. Also important in the crystallization process are factors that can affect the structural state of the macromolecule, such as metal ions, inhibitors, cofactors or other conventional small molecules. A variety of approaches have been developed that combine the spectrum of factors that effect and promote crystallization, and among the most widely used are vapor diffusion, dialysis, batch and liquid-liquid diffusion. Successes in macromolecular crystallization have multiplied rapidly in recent years owing to the advent of practical, easy-to-use screening kits and the application of laboratory robotics. A brief review will be given here of the most popular methods, some guiding principles and an overview of current technologies.

Chromite in komatiites: 3D morphologies with implications for crystallization mechanisms

NASA Astrophysics Data System (ADS)

Godel, Bélinda; Barnes, Stephen J.; Gürer, Derya; Austin, Peter; Fiorentini, Marco L.

2013-01-01

High-resolution X-ray computed tomography has been carried out on a suite of komatiite samples representing a range of volcanic facies, chromite contents and degrees of alteration and metamorphism, to reveal the wide range of sizes, shapes and degrees of clustering that chromite grains display as a function of cooling history. Dendrites are spectacularly skeletal chromite grains formed during very rapid crystallization of supercooled melt in spinifex zones close to flow tops. At slower cooling rates in the interiors of thick flows, chromite forms predominantly euhedral grains. Large clusters (up to a dozen of grains) are characteristic of liquidus chromite, whereas fine dustings of mostly individual ~20-μm grains form by in situ crystallization from trapped intercumulus liquid. Chromite in coarse-grained olivine cumulates from komatiitic dunite bodies occurs in two forms: as clusters or chains of euhedral crystals, developing into "chicken-wire" texture where chromite is present in supra-cotectic proportions; and as strongly dendritic, semi-poikilitic grains. These dendritic grains are likely to have formed by rapid crescumulate growth from magma that was close to its liquidus temperature but supersaturated with chromite. In some cases, this process seems to have been favoured by nucleation of chromite on the margins of sulphide liquid blebs. This texture is a good evidence for the predominantly cumulus origin of oikocrysts and in situ origin of heteradcumulate textures. Our 3D textural analysis confirms that the morphology of chromite crystals is a distinctive indicator of crystallization environment even in highly altered rocks.

Structural evolution in the crystallization of rapid cooling silver melt

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tian, Z.A., E-mail: ze.tian@gmail.com; Laboratory for Simulation and Modelling of Particulate Systems School of Materials Science and Engineering, University of New South Wales, Sydney, NSW 2052; Dong, K.J.

2015-03-15

The structural evolution in a rapid cooling process of silver melt has been investigated at different scales by adopting several analysis methods. The results testify Ostwald’s rule of stages and Frank conjecture upon icosahedron with many specific details. In particular, the cluster-scale analysis by a recent developed method called LSCA (the Largest Standard Cluster Analysis) clarified the complex structural evolution occurred in crystallization: different kinds of local clusters (such as ico-like (ico is the abbreviation of icosahedron), ico-bcc like (bcc, body-centred cubic), bcc, bcc-like structures) in turn have their maximal numbers as temperature decreases. And in a rather wide temperaturemore » range the icosahedral short-range order (ISRO) demonstrates a saturated stage (where the amount of ico-like structures keeps stable) that breeds metastable bcc clusters. As the precursor of crystallization, after reaching the maximal number bcc clusters finally decrease, resulting in the final solid being a mixture mainly composed of fcc/hcp (face-centred cubic and hexagonal-closed packed) clusters and to a less degree, bcc clusters. This detailed geometric picture for crystallization of liquid metal is believed to be useful to improve the fundamental understanding of liquid–solid phase transition. - Highlights: • A comprehensive structural analysis is conducted focusing on crystallization. • The involved atoms in our analysis are more than 90% for all samples concerned. • A series of distinct intermediate states are found in crystallization of silver melt. • A novelty icosahedron-saturated state breeds the metastable bcc state.« less

Laser refrigeration, alignment and rotation of levitated Yb3+:YLF nanocrystals

NASA Astrophysics Data System (ADS)

Rahman, A. T. M. Anishur; Barker, P. F.

2017-10-01

The ability to cool and manipulate levitated nanoparticles in vacuum is a promising tool for exploring macroscopic quantum mechanics1,2, precision measurements of forces3 and non-equilibrium thermodynamics4,5. The extreme isolation afforded by optical levitation offers a low-noise, undamped environment that has been used to measure zeptonewton forces3 and radiation pressure shot noise6, and to demonstrate centre-of-mass motion cooling7,8. Ground-state cooling and the creation of macroscopic quantum superpositions are now within reach, but control of both the centre of mass and internal temperature is required. While cooling the centre-of-mass motion to micro-kelvin temperatures has now been achieved, the internal temperature has remained at or above room temperature. Here, we realize a nanocryostat by refrigerating levitated Yb3+:YLF nanocrystals to 130 K using anti-Stokes fluorescence cooling, while simultaneously using the optical trapping field to align the crystal to maximize cooling.

Green-diode-pumped femtosecond Ti:Sapphire laser with up to 450 mW average power.

PubMed

Gürel, K; Wittwer, V J; Hoffmann, M; Saraceno, C J; Hakobyan, S; Resan, B; Rohrbacher, A; Weingarten, K; Schilt, S; Südmeyer, T

2015-11-16

We investigate power-scaling of green-diode-pumped Ti:Sapphire lasers in continuous-wave (CW) and mode-locked operation. In a first configuration with a total pump power of up to 2 W incident onto the crystal, we achieved a CW power of up to 440 mW and self-starting mode-locking with up to 200 mW average power in 68-fs pulses using semiconductor saturable absorber mirror (SESAM) as saturable absorber. In a second configuration with up to 3 W of pump power incident onto the crystal, we achieved up to 650 mW in CW operation and up to 450 mW in 58-fs pulses using Kerr-lens mode-locking (KLM). The shortest pulse duration was 39 fs, which was achieved at 350 mW average power using KLM. The mode-locked laser generates a pulse train at repetition rates around 400 MHz. No complex cooling system is required: neither the SESAM nor the Ti:Sapphire crystal is actively cooled, only air cooling is applied to the pump diodes using a small fan. Because of mass production for laser displays, we expect that prices for green laser diodes will become very favorable in the near future, opening the door for low-cost Ti:Sapphire lasers. This will be highly attractive for potential mass applications such as biomedical imaging and sensing.

Erythritol: crystal growth from the melt.

PubMed

Lopes Jesus, A J; Nunes, Sandra C C; Ramos Silva, M; Matos Beja, A; Redinha, J S

2010-03-30

The structural changes occurring on erythritol as it is cooled from the melt to low temperature, and then heated up to the melting point have been investigated by differential scanning calorimetry (DSC), polarized light thermal microscopy (PLTM), X-ray powder diffraction (PXRD) and Fourier transform infrared spectroscopy (FTIR). By DSC, it was possible to set up the conditions to obtain an amorphous solid, a crystalline solid, or a mixture of both materials in different proportions. Two crystalline forms have been identified: a stable and a metastable one with melting points of 117 and 104 degrees C, respectively. The fusion curve decomposition of the stable form revealed the existence of three conformational structures. The main paths of the crystallization from the melt were followed by PLTM. The texture and colour changes allowed the characterization of the different phases and transitions in which they are involved on cooling as well as on heating processes. The type of crystallization front and its velocity were also followed by microscopic observation. These observations, together with the data provided by PXRD, allowed elucidating the transition of the metastable form into the stable one. The structural changes occurring upon the cooling and subsequent heating processes, namely those arising from intermolecular hydrogen bonds, were also accompanied by infrared spectroscopy. Particular attention was given to the spectral changes occurring in the OH stretching region. Copyright (c) 2009 Elsevier B.V. All rights reserved.

In situ crystallization and transformation kinetics of polymorphic forms of saturated-unsaturated-unsaturated triacylglycerols: 1-palmitoyl-2,3-dioleoyl glycerol, 1-stearoyl-2,3-dioleoyl glycerol, and 1-palmitoyl-2-oleoyl-3-linoleoyl glycerol.

PubMed

Bayés-García, L; Calvet, T; Cuevas-Diarte, M A; Ueno, S

2016-07-01

We examined the influence of dynamic thermal treatment (variation of cooling/heating rates) on the polymorphic crystallization and transformation pathways of 1-palmitoyl-2,3-dioleoyl glycerol (POO), 1-stearoyl-2,3-dioleoyl glycerol (SOO), and 1-palmitoyl-2-oleoyl-3-linoleoyl glycerol (POL), which are major saturated-unsaturated-unsaturated (SUU) triacylglycerols (TAGs) of vegetable oils and animal fats (e.g., palm oil, olive oil, and Iberian ham fat). Using mainly a combination of differential scanning calorimetry (DSC) and synchrotron radiation X-ray diffraction (SR-XRD), we analyzed the polymorphic behavior of TAGs when high (15°Cmin -1 ), intermediate (2°Cmin -1 ), and low (0.5°Cmin -1 ) cooling and heating rates were applied. Multiple polymorphic forms were detected in POO, SOO, and POL (sub-α, α, β' 2 , and β' 1 ). Transient disordered phases, defined as kinetic liquid crystal (KLC) phases, were determined in POO and SOO for the first time. The results demonstrated that more stable forms were directly obtained from the melt by decreasing the cooling rates, whereas less stable forms predominated at high cooling rates, as confirmed in our previous work. Regarding heating rate variation, we confirmed that the nature of the polymorphic transformations observed (solid-state, transformation through KLC phase, or melt-mediation) depended largely on the heating rate. These results were discussed considering the activation energies involved in each process and compared with previous studies on TAGs with different saturated-unsaturated structures (1,3-dioleoyl-2-palmitoylglycerol, 1,3-dipalmitoyl-2-oleoyl-glycerol, trioleoyl glycerol, and 1,2-dioleoyl-3-linoleoyl glycerol). Copyright © 2016 Elsevier Ltd. All rights reserved.

Microstructural Indicators Of Convection In Sills And Dykes

NASA Astrophysics Data System (ADS)

Holness, M. B.; Neufeld, J. A.; Gilbert, A. J.; Macdonald, R.

2016-12-01

The question of whether or not convection occurs in crustal magma chambers is a vexed one, with some advocating vigorous convection while others argue that convection is weak and short-lived. We argue that microstructural analysis is key to determining whether crystallization took place in solidification fronts or whether crystals grew suspended in a convecting magma before settling. The 168m, composite, Shiant Isles Main Sill is dominated by a 140m unit, of which the lower 45m contains olivine phenocrysts. The phenocrysts first fine upwards, then coarsen upwards. The coarsening-upwards sequence contains clustered olivines. Both the extent of sintering and average cluster size increase upwards. The coarsening-upwards sequence is mirrored at the roof. The fining-upwards sequence formed by rapid settling of incoming cargo crystals, while the coarsening-upwards sequence represents post-emplacement growth and clustering of grains suspended in a convecting magma. Convection is also recorded by plagioclase grain shape. Well-facetted and compact plagioclase grains are platy in rapidly-cooled rocks and blocky in slowly-cooled rocks. Plagioclase grain shape varies smoothly across mafic sills, consistent with growth in solidification fronts. In contrast, grain shape is invariant across mafic dykes, consistent with growth as individual grains and clusters suspended in a convecting magma. Convection in sills occurs when the critical Rayleigh number is exceeded, but cooling at vertical walls always results in convective instabilities. That the Shiant Isles Main Sill records prolonged and vigorous convection, while other sills of comparable thickness record grain growth predominantly in solidification fronts, is most likely due to the composite nature of the Shiant. The 140m unit is underlain by 23m of picrite which intruded shortly before - the strongly asymmetric cooling and absence of a cold, stagnant basal thermal boundary layer make convection throughout the sill more likely.

The formation of supercooled brines, viscous liquids, and low-temperature perchlorate glasses in aqueous solutions relevant to Mars

NASA Astrophysics Data System (ADS)

Toner, J. D.; Catling, D. C.; Light, B.

2014-05-01

Salt solutions on Mars can stabilize liquid water at low temperatures by lowering the freezing point of water. The maximum equilibrium freezing-point depression possible, known as the eutectic temperature, suggests a lower temperature limit for liquid water on Mars; however, salt solutions can supercool below their eutectic before crystallization occurs. To investigate the magnitude of supercooling and its variation with salt composition and concentration, we performed slow cooling and warming experiments on pure salt solutions and saturated soil-solutions of MgSO4, MgCl2, NaCl, NaClO4, Mg(ClO4)2, and Ca(ClO4)2. By monitoring solution temperatures, we identified exothermic crystallization events and determined the composition of precipitated phases from the eutectic melting temperature. Our results indicate that supercooling is pervasive. In general, supercooling is greater in more concentrated solutions and with salts of Ca and Mg. Slowly cooled MgSO4, MgCl2, NaCl, and NaClO4 solutions investigated in this study typically supercool 5-15 °C below their eutectic temperature before crystallizing. The addition of soil to these salt solutions has a variable effect on supercooling. Relative to the pure salt solutions, supercooling decreases in MgSO4 soil-solutions, increases in MgCl2 soil-solutions, and is similar in NaCl and NaClO4 soil-solutions. Supercooling in MgSO4, MgCl2, NaCl, and NaClO4 solutions could marginally extend the duration of liquid water during relatively warm daytime temperatures in the martian summer. In contrast, we find that Mg(ClO4)2 and Ca(ClO4)2 solutions do not crystallize during slow cooling, but remain in a supercooled, liquid state until forming an amorphous glass near -120 °C. Even if soil is added to the solutions, a glass still forms during cooling. The large supercooling effect in Mg(ClO4)2 and Ca(ClO4)2 solutions has the potential to prevent water from freezing over diurnal and possibly annual cycles on Mars. Glasses are also potentially important for astrobiology because of their ability to preserve pristine cellular structures intact compared to solutions that crystallize.

Continuous-Flow In-Line Solvent-Swap Crystallization of Vitamin D3

PubMed Central

2017-01-01

A continuous tandem in-line evaporation–crystallization is presented. The process includes an in-line solvent-swap step, suitable to be coupled to a capillary based cooler. As a proof of concept, this setup is tested in a direct in-line acetonitrile mediated crystallization of Vitamin D3. This configuration is suitable to be coupled to a new end-to-end continuous microflow synthesis of Vitamin D3. By this procedure, vitamin particles can be crystallized in continuous flow and isolated using an in-line continuous filtration step. In one run in just 1 min of cooling time, ∼50% (w/w) crystals of Vitamin D3 are directly obtained. Furthermore, the polymorphic form as well as crystals shape and size properties are described in this paper.

Genetic significance of the 867 cm- 1 out-of-plane Raman mode in graphite associated with V-bearing green grossular

NASA Astrophysics Data System (ADS)

Thomas, Rainer; Rericha, Adolf; Pohl, Walter L.; Davidson, Paul

2018-03-01

SE Kenya is the world's largest producer of green vanadium grossular gemstones (tsavorite). Samples from one of the mines near Mwatate, and of occurrences in Tanzania yielded remarkable new insights into the genesis of tsavorite. Graphite is intimately associated with V-grossular and is one of the keys to understanding its origin. In the course of this study we found five different types of graphite. Surprisingly, in one graphite type the "Raman-forbidden" and IR-active 867 cm- 1 band was observed. In this communication, we attempt to find an explanation for this unusual phenomenon. Additionally, our observations also address some of the issues pertaining to the origin of the green grossular-dominated rocks (grossularites), as well as the gem quality tsavorite crystals, since we propose that the anomalous spectroscopic behavior of the graphite is related to the unusual conditions during crystallization of both the grossular and graphite from a near-supercritical volatile- and sulfur-rich silicate melt. The massive green vanadium grossular contains abundant unequivocal crystallized melt inclusions, while the transparent gem quality grossular (tsavorite) displays only fluid inclusions. On the basis of inclusion studies we suggest that anatectic melts originated in the peculiar evaporitic host lithology of the tsavorite deposits. Near peak metamorphic temperatures ( 700 °C) these liquids occurred as a supercritical volatile-rich "fluid/melt phase" characterized by complete miscibility between H2O and silicate liquid. Relatively dry liquid batches precipitated non-transparent green grossular, whereas wet batches segregated fluids that formed transparent tsavorite.

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

Optical properties of bulk gallium nitride single crystals grown by chloride-hydride vapor-phase epitaxy

NASA Astrophysics Data System (ADS)

Agyekyan, V. F.; Borisov, E. V.; Serov, A. Yu.; Filosofov, N. G.

2017-12-01

A gallium nitride crystal 5 mm in thickness was grown by chloride-hydride vapor-phase epitaxy on a sapphire substrate, from which the crystal separated during cooling. At an early stage, a three-dimensional growth mode was implemented, followed by a switch to a two-dimensional mode. Spectra of exciton reflection, exciton luminescence, and Raman scattering are studied in several regions characteristic of the sample. Analysis of these spectra and comparison with previously obtained data for thin epitaxial GaN layers with a wide range of silicon doping enabled conclusions about the quality of the crystal lattice in these characteristic regions.

Imaging and engineering the nanoscale-domain structure of a Sr0.61Ba0.39Nb2O6 crystal using a scanning force microscope

NASA Astrophysics Data System (ADS)

Terabe, K.; Takekawa, S.; Nakamura, M.; Kitamura, K.; Higuchi, S.; Gotoh, Y.; Gruverman, A.

2002-09-01

We have investigated the ferroelectric domain structure formed in a Sr0.61Ba0.39Nb2O6 single crystal by cooling the crystal through the Curie point. Imaging the etched surface structure using a scanning force microscope (SFM) in both the topographic mode and the piezoresponse mode revealed that a multidomain structure of nanoscale islandlike domains was formed. The islandlike domains could be inverted by applying an appropriate voltage using a conductive SFM tip. Furthermore, a nanoscale periodically inverted-domain structure was artificially fabricated using the crystal which underwent poling treatment.

Iron single crystal growth from a lithium-rich melt

NASA Astrophysics Data System (ADS)

Fix, M.; Schumann, H.; Jantz, S. G.; Breitner, F. A.; Leineweber, A.; Jesche, A.

2018-03-01

α -Fe single crystals of rhombic dodecahedral habit were grown from a Li84N12Fe∼3 melt. Crystals of several millimeter along a side form at temperatures around T ≈ 800 ° C. Upon further cooling the growth competes with the formation of Fe-doped Li3N. The b.c.c. structure and good sample quality of α -Fe single crystals were confirmed by X-ray and electron diffraction as well as magnetization measurements and chemical analysis. A nitrogen concentration of 90 ppm was detected by means of carrier gas hot extraction. Scanning electron microscopy did not reveal any sign of iron nitride precipitates.

Three-dimensional analysis of dislocation multiplication during thermal process of grown silicon with different orientations

NASA Astrophysics Data System (ADS)

Gao, B.; Nakano, S.; Harada, H.; Miyamura, Y.; Kakimoto, K.

2017-09-01

We used an advanced 3D model to study the effect of crystal orientation on the dislocation multiplication in single-crystal silicon under accurate control of the cooling history of temperature. The incorporation of the anisotropy effect of the crystal lattice into the model has been explained in detail, and an algorithm for accurate control of the temperature in the furnace has also been presented. This solver can dynamically track the history of dislocation generation for different orientations during thermal processing of single-crystal silicon. Four orientations, [001], [110], [111], and [112], have been examined, and the comparison of dislocation distributions has been provided.

Origin of ultramafic xenoliths containing exsolved pyroxenes from Hualalai Volcano, Hawaii

NASA Astrophysics Data System (ADS)

Bohrson, Wendy A.; Clague, David A.

1988-10-01

Hualalai Volcano, Hawaii, is best known for the abundant and varied xenoliths included in the historic 1800 Kaupulehu alkalic basalt flow. Xenoliths, which range in composition from dunite to anorthosite, are concentrated at 915-m elevation in the flow. Rare cumulate ultramafic xenoliths, which include websterite, olivine websterite, wehrlite, and clinopyroxenite, display complex pyroxene exsolution textures that indicate slow cooling. Websterite, olivine websterite, and one wehrlite are spinel-bearing orthopyroxene +olivine cumulates with intercumulus clinopyroxene +plagioclase. Two wehrlite samples and clinopyroxenite are spinel-bearing olivine cumulates with intercumulus clinopyroxene+orthopyroxene + plagioclase. Two-pyroxene geothermometry calculations, based on reconstructed pyroxene compositions, indicate that crystallization temperatures range from 1225° to 1350° C. Migration or unmixing of clinopyroxene and orthopyroxene stopped between 1045° and 1090° C. Comparisons of the abundance of K2O in plagioclase and the abundances of TiO2 and Fe2O3in spinel of xenoliths and mid-ocean ridge basalt, and a single 87Sr/ 86Sr determination, indicate that these Hualalai xenoliths are unrelated to mid-ocean ridge basalt. Similarity between the crystallization sequence of these xenoliths and the experimental crystallization sequence of a Hawaiian olivine tholeiite suggest that the parental magma of the xenoliths is Hualalai tholeiitic basalt. Xenoliths probably crystallized between about 4.5 and 9 kb. The 155° 230° C of cooling which took place over about 120 ka — the age of the youngest Hualalai tholeiitic basalt — yield maximum cooling rates of 1.3×10-3 1.91×10-3 °C/yr. Hualalai ultramafic xenoliths with exsolved pyroxenes crystallized from Hualalai tholeiitic basalt and accumulated in a magma reservoir located between 13 and 28 km below sealevel. We suspect that this reservoir occurs just below the base of the oceanic crust at about 19 km below sealevel.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hehlen, Markus Peter; Boncher, William Lawrence; Love, Steven Paul

The performance of a solid-state optical refrigerator is the result of a complex interplay of numerous optical and thermal parameters. We present a first preliminary study of an optical cryocooler using ray-tracing techniques. A numerical optimization identified a non-resonant cavity with astigmatism. This geometry offered more efficient pump absorption by the YLF:10%Yb laser-cooling crystal compared to non-resonant cavities without astigmatism that have been pursued experimentally so far. Ray tracing simulations indicate that ~80% of the incident pump light can absorbed for temperatures down to ~100 K. Calculations of heat loads, cooling power, and net payload heat lift are presented. Theymore » show that it is possible to cool a payload to a range of 90–100 K while producing a net payload heat lift of 80 mW and 300 mW when pumping a YLF:10%Yb crystal with 20 W and 50 W at 1020 nm, respectively. This performance is suited to cool HgCdTe infrared detectors that are used for sensing in the 8–12 μm atmospheric window. While the detector noise would be ~6× greater at 100 K than at 77 K, the laser refrigerator would introduce no vibrations and thus eliminate sources of microphonic noise that are limiting the performance of current systems.« less

Ultrafast Electric Field Pulse Control of Giant Temperature Change in Ferroelectrics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qi, Y.; Liu, S.; Lindenberg, A. M.

There is a surge of interest in developing environmentally friendly solid-state-based cooling technology. Here, we point out that a fast cooling rate (≈ 10 11 K/s) can be achieved by driving solid crystals to a high-temperature phase with a properly designed electric field pulse. Specifically, we predict that an ultrafast electric field pulse can cause a giant temperature decrease up to 32 K in PbTiO 3 occurring on few picosecond time scales. Here, we explain the underlying physics of this giant electric field pulse-induced temperature change with the concept of internal energy redistribution: the electric field does work on amore » ferroelectric crystal and redistributes its internal energy, and the way the kinetic energy is redistributed determines the temperature change and strongly depends on the electric field temporal profile. This concept is supported by our all-atom molecular dynamics simulations of PbTiO 3 and BaTiO 3. Moreover, this internal energy redistribution concept can also be applied to understand electrocaloric effect. We further propose new strategies for inducing giant cooling effect with ultrafast electric field pulse. This Letter offers a general framework to understand electric-field-induced temperature change and highlights the opportunities of electric field engineering for controlled design of fast and efficient cooling technology.« less

Ultrafast Electric Field Pulse Control of Giant Temperature Change in Ferroelectrics

DOE PAGES

Qi, Y.; Liu, S.; Lindenberg, A. M.; ...

2018-01-30

There is a surge of interest in developing environmentally friendly solid-state-based cooling technology. Here, we point out that a fast cooling rate (≈ 10 11 K/s) can be achieved by driving solid crystals to a high-temperature phase with a properly designed electric field pulse. Specifically, we predict that an ultrafast electric field pulse can cause a giant temperature decrease up to 32 K in PbTiO 3 occurring on few picosecond time scales. Here, we explain the underlying physics of this giant electric field pulse-induced temperature change with the concept of internal energy redistribution: the electric field does work on amore » ferroelectric crystal and redistributes its internal energy, and the way the kinetic energy is redistributed determines the temperature change and strongly depends on the electric field temporal profile. This concept is supported by our all-atom molecular dynamics simulations of PbTiO 3 and BaTiO 3. Moreover, this internal energy redistribution concept can also be applied to understand electrocaloric effect. We further propose new strategies for inducing giant cooling effect with ultrafast electric field pulse. This Letter offers a general framework to understand electric-field-induced temperature change and highlights the opportunities of electric field engineering for controlled design of fast and efficient cooling technology.« less

Ultrafast Electric Field Pulse Control of Giant Temperature Change in Ferroelectrics

NASA Astrophysics Data System (ADS)

Qi, Y.; Liu, S.; Lindenberg, A. M.; Rappe, A. M.

2018-01-01

There is a surge of interest in developing environmentally friendly solid-state-based cooling technology. Here, we point out that a fast cooling rate (≈1011 K /s ) can be achieved by driving solid crystals to a high-temperature phase with a properly designed electric field pulse. Specifically, we predict that an ultrafast electric field pulse can cause a giant temperature decrease up to 32 K in PbTiO3 occurring on few picosecond time scales. We explain the underlying physics of this giant electric field pulse-induced temperature change with the concept of internal energy redistribution: the electric field does work on a ferroelectric crystal and redistributes its internal energy, and the way the kinetic energy is redistributed determines the temperature change and strongly depends on the electric field temporal profile. This concept is supported by our all-atom molecular dynamics simulations of PbTiO3 and BaTiO3 . Moreover, this internal energy redistribution concept can also be applied to understand electrocaloric effect. We further propose new strategies for inducing giant cooling effect with ultrafast electric field pulse. This Letter offers a general framework to understand electric-field-induced temperature change and highlights the opportunities of electric field engineering for controlled design of fast and efficient cooling technology.

Enhanced magnetocaloric properties and critical behavior of (Fe0.72Cr0.28)3Al alloys for near room temperature cooling

NASA Astrophysics Data System (ADS)

Sharma, V.; Maheshwar Repaka, D. V.; Chaudhary, V.; Ramanujan, R. V.

2017-04-01

Magnetic cooling is an environmentally friendly, energy efficient, thermal management technology relying on high performance magnetocaloric materials (MCM). Current research has focused on low cost, corrosion resistant, rare earth (RE) free MCMs. We report the structural and magnetocaloric properties of novel, low cost, RE free, iron based (Fe0.72Cr0.28)3Al alloys. The arc melted buttons and melt spun ribbons possessed the L21 crystal structure and B2 crystal structure, respectively. A notable enhancement of 33% in isothermal entropy change (-ΔS m) and 25% increase in relative cooling power (RCP) for the ribbons compared to the buttons can be attributed to higher structural disorder in the Fe-Cr and Fe-Al sub-lattices of the B2 structure. The critical behavior was investigated using modified Arrott plots, the Kouvel-Fisher plot and the critical isotherm technique; the critical exponents were found to correspond to the short-range order 3D Heisenberg model. The field and temperature dependent magnetization curves of (Fe0.72Cr0.28)3Al alloys revealed their soft magnetic nature with negligible hysteresis. Thus, these alloys possess promising performance attributes for near room temperature magnetic cooling applications.

Naturally occurring reverse tilt domains in a high-pretilt alignment nematic liquid crystal

NASA Astrophysics Data System (ADS)

Wang, Ruiting; Atherton, Timothy J.; Zhu, Minhua; Petschek, Rolfe G.; Rosenblatt, Charles

2007-08-01

A cell whose substrates were coated with the polyamic acid SE1211 (Nissan Chemical Industries) and baked at high temperatures was filled with a nematic liquid crystal in the isotropic phase. On cooling into the nematic phase, naturally occurring and temporally and thermally robust reverse tilt domains separated by thin filamentlike walls were observed. The properties of these structures are reported.

Crystallization of probucol from solution and the glassy state.

PubMed

Kawakami, Kohsaku; Ohba, Chie

2017-01-30

Crystallization of probucol (PBL) from both solution and glassy solid state was investigated. In the crystallization study from solution, six solvents and three methods, i.e., evaporation, addition of a poor solvent, and cooling on ice, were used to obtain various crystal forms. In addition to common two crystal forms (forms I and II), two further forms (forms III and cyclohexane-solvate) were found in this study, and their thermodynamic relationships were determined. Forms I and II are likely to be enantiotropically related with thermodynamic transition temperature below 5°C. Isothermal crystallization studies revealed that PBL glass initially crystallized into form III between 25 and 50°C, and then transformed to form I. The isothermal crystallization appears to be a powerful option to find uncommon crystal forms. The crystallization of PBL was identified to be pressure controlled, thus the physical stability of PBL glass is higher than that of typical compounds. Copyright © 2016 Elsevier B.V. All rights reserved.

TEM study on a new Zr-(Fe, Cu) phase in furnace-cooled Zr-1.0Sn-0.3Nb-0.3Fe-0.1Cu alloy

NASA Astrophysics Data System (ADS)

Liu, Yushun; Qiu, Risheng; Luan, Baifeng; Hao, Longlong; Tan, Xinu; Tao, Boran; Zhao, Yifan; Li, Feitao; Liu, Qing

2018-06-01

A new Zr-(Fe, Cu) phase was found in furnace-cooled Zr-1.0Sn-0.3Nb-0.3Fe- 0.1Cu alloy and alloys aged at 580 °C for 10min, 2 h and 10 h. Electron diffraction experiment shows the crystal structure of this phase to be body-centered tetragonal with unit cell dimensions determined to be a = b = 6.49 Å, c = 5.37 Å. Its possible space groups have been discussed and the reason accounting for its formation is believed to be the addition of Cu according to the atom-level images. In addition, no crystal structural or chemical composition changes were observed throughout the aging process.

Magnetic order of Nd 5 Pb 3 single crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yan, Jiaqiang; Ochi, Masayuki; Cao, Huibo B.

We report millimeter-sized Nd 5Pb 3 single crystals grown out of a Nd–Co flux. We experimentally study the magnetic order of Nd 5Pb 3 single crystals by measuring the anisotropic magnetic properties, electrical resistivity under high pressure up to 8 GPa, specific heat, and neutron single crystal diffraction. Two successive magnetic orders are observed at T N1 = 44 K and T N2 = 8 K. The magnetic cells can be described with a propagation vector $k=(0.5, 0, 0)$ . Cooling below T N1, Nd1 and Nd3 order forming ferromagnetic stripes along the b-axis, and the ferromagnetic stripes are coupledmore » antiferromagnetically along the a-axis for the $k=(0.5, 0, 0)$ magnetic domain. Cooling below T N2, Nd2 orders antiferromagnetically to nearby Nd3 ions. All ordered moments align along the crystallographic c-axis. The magnetic order at T N1 is accompanied by a quick drop of electrical resistivity upon cooling and a lambda-type anomaly in the temperature dependence of specific heat. At T N2, no anomaly was observed in electrical resistivity but there is a weak feature in specific heat. The resistivity measurements under hydrostatic pressures up to 8 GPa suggest a possible phase transition around 6 GPa. Our first-principles band structure calculations show that Nd 5Pb 3 has the same electronic structure as does Y 5Si 3 which has been reported to be a one-dimensional electride with anionic electrons that do not belong to any atom. Our study suggests that R 5Pb 3 (R = rare earth) can be a materials playground for the study of magnetic electrides. To conclude, this deserves further study after experimental confirmation of the presence of anionic electrons.« less

Magnetic order of Nd 5 Pb 3 single crystals

DOE PAGES

Yan, Jiaqiang; Ochi, Masayuki; Cao, Huibo B.; ...

2018-03-02

We report millimeter-sized Nd 5Pb 3 single crystals grown out of a Nd–Co flux. We experimentally study the magnetic order of Nd 5Pb 3 single crystals by measuring the anisotropic magnetic properties, electrical resistivity under high pressure up to 8 GPa, specific heat, and neutron single crystal diffraction. Two successive magnetic orders are observed at T N1 = 44 K and T N2 = 8 K. The magnetic cells can be described with a propagation vector $k=(0.5, 0, 0)$ . Cooling below T N1, Nd1 and Nd3 order forming ferromagnetic stripes along the b-axis, and the ferromagnetic stripes are coupledmore » antiferromagnetically along the a-axis for the $k=(0.5, 0, 0)$ magnetic domain. Cooling below T N2, Nd2 orders antiferromagnetically to nearby Nd3 ions. All ordered moments align along the crystallographic c-axis. The magnetic order at T N1 is accompanied by a quick drop of electrical resistivity upon cooling and a lambda-type anomaly in the temperature dependence of specific heat. At T N2, no anomaly was observed in electrical resistivity but there is a weak feature in specific heat. The resistivity measurements under hydrostatic pressures up to 8 GPa suggest a possible phase transition around 6 GPa. Our first-principles band structure calculations show that Nd 5Pb 3 has the same electronic structure as does Y 5Si 3 which has been reported to be a one-dimensional electride with anionic electrons that do not belong to any atom. Our study suggests that R 5Pb 3 (R = rare earth) can be a materials playground for the study of magnetic electrides. To conclude, this deserves further study after experimental confirmation of the presence of anionic electrons.« less

Sludge granulation and performance of a low superficial gas velocity sequencing batch reactor (SBR) in the treatment of prepared sanitary wastewater.

PubMed

Ji, Guodong; Zhai, Fengmin; Wang, Rongjing; Ni, Jinren

2010-12-01

A sequencing batch reactor (SBR) employing a low superficial gas velocity was used to produce aerobic granular sludge for wastewater treatment. At a gas velocity of 0.0056 m s(-1) sludge containing a mixture of light yellow and black granules with similar functional groups was quickly formed. The black granules contained crystals of CaCO(3), FeS, and Fe(2)O(3) as well as filamentous bacteria that strengthened the particles and reduced the mass transfer resistance. No inorganic crystals were detected in the yellow sludge granules, and their structure was maintained through cohesion mediated by extracellular polymeric substances (EPS). The light yellow granules were denser and offered better settling performance than the black granules, enhancing the settling properties of the mixed sludge. During a 12-h cycle, the maximum reductions in chemical oxygen demand (COD), NH(3)-N, and total nitrogen (TN) occurred at 240, 480, and 360 min with removal efficiencies of 90%, 90%, and 54%. When the cycle time was limited to 480 min, self-dissolution of the granules was avoided while sill maintaining removal efficiencies for COD, NH(3)-N, and TN of 88%, 90%, and 53%. 2010 Elsevier Ltd. All rights reserved.

Current trends in protein crystallization.

PubMed

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.

Self-powdering and nonlinear optical domain structures in ferroelastic β‧-Gd2(MoO4)3 crystals formed in glass

NASA Astrophysics Data System (ADS)

Tsukada, Y.; Honma, T.; Komatsu, T.

2009-08-01

Ferroelastic β'-Gd 2(MoO 4) 3, (GMO), crystals are formed through the crystallization of 21.25Gd 2O 3-63.75MoO 3-15B 2O 3 glass (mol%), and two scientific curious phenomena are observed. (1) GMO crystals formed in the crystallization break into small pieces with a triangular prism or pyramid shape having a length of 50-500 μm spontaneously during the crystallizations in the inside of an electric furnace, not during the cooling in air after the crystallization. This phenomenon is called "self-powdering phenomenon during crystallization" in this paper. (2) Each self-powdered GMO crystal grain shows a periodic domain structure with different refractive indices, and a spatially periodic second harmonic generation (SHG) depending on the domain structure is observed. It is proposed from polarized micro-Raman scattering spectra and the azimuthal dependence of second harmonic intensities that GMO crystals are oriented in each crystal grain and the orientation of (MoO 4) 2- tetrahedra in GMO crystals changes periodically due to spontaneous strains in ferroelastic GMO crystals.

The Feasibility of Bulk Crystallization as an Industrial Purification and Production Technique for Proteins

NASA Technical Reports Server (NTRS)

Judge, Russell A.; Forsythe, Elizabeth L.; Johns, Michael R.; Pusey, Marc L.; White, Edward T.

1998-01-01

Bulk crystallization in stirred vessels is used industrially for the recovery and purification of many inorganic and organic materials. Although much has been written on the crystallization of proteins for X-ray diffraction analysis, very little has been reported on the application of bulk crystallization in stirred vessels. In this study, a 1-liter, seeded, stirred, batch crystallizer was used with ovalbumin as a model protein to test the feasibility of this crystallization method as a recovery and purification process for proteins. Results were obtained for ovalbumin solubility, nucleation thresholds, crystal breakage and crystal growth kinetics in bulk solution under a range of operating conditions of pH and ammonium sulphate concentration (Judge et al., 1996). Experiments were also performed to determine the degree of purification that can be achieved by the crystallization of ovalbumin from a mixture of proteins. The effect of the presence of these proteins upon the ovalbumin crystal growth kinetics was also investigated (Judge et al., 1995). All of these aspects are essential for the design of bulk crystallization processes which have not previously been reported for proteins. Results from a second study that investigated the effect of structurally different proteins on the solubility, crystal growth rates and crystal purity of chicken egg white lysozyme are also presented (Judge et al., 1997). In this case face growth rates were measured using lysozyme purified by liquid chromatography and the effect of the addition of specific protein impurities were observed on the (110) and (101) crystal faces. In these two studies the results are presented to show the feasibility and purifying ability of crystallization as a production process for proteins.

Realization of an all-solid-state cryocooler using optical refrigeration

NASA Astrophysics Data System (ADS)

Meng, Junwei; Albrecht, Alexander R.; Gragossian, Aram; Lee, Eric; Volpi, Azzurra; Ghasemkhani, Mohammadreza; Hehlen, Markus P.; Epstein, Richard I.; Sheik-Bahae, Mansoor

2018-05-01

Optical refrigeration of rare-earth-doped solids has reached the boiling point of argon, 87 K, and is expected to cool to that of nitrogen, 77 K, in the near future. This technology is poised to pave the way to compact, reliable, and vibrationfree all-solid-state optical cryocoolers. By attaching the Yb:YLF cooling crystal to a cold finger via a double 90° kink thermal link, we have cooled a silicon temperature sensor to below 151 K. An advanced design of the thermal link and the clamshell surrounding the cooled assembly successfully controlled the flow of heat and radiation to allow cooling of a payload to cryogenic temperatures. Key elements of the design were a low-absorption thermal link material, an optimized thermal link geometry, and a spectrally-selective coating of the clamshell.

Macromolecular Crystal Growth by Means of Microfluidics

NASA Technical Reports Server (NTRS)

vanderWoerd, Mark; Ferree, Darren; Spearing, Scott; Monaco, Lisa; Molho, Josh; Spaid, Michael; Brasseur, Mike; Curreri, Peter A. (Technical Monitor)

2002-01-01

We have performed a feasibility study in which we show that chip-based, microfluidic (LabChip(TM)) technology is suitable for protein crystal growth. This technology allows for accurate and reliable dispensing and mixing of very small volumes while minimizing bubble formation in the crystallization mixture. The amount of (protein) solution remaining after completion of an experiment is minimal, which makes this technique efficient and attractive for use with proteins, which are difficult or expensive to obtain. The nature of LabChip(TM) technology renders it highly amenable to automation. Protein crystals obtained in our initial feasibility studies were of excellent quality as determined by X-ray diffraction. Subsequent to the feasibility study, we designed and produced the first LabChip(TM) device specifically for protein crystallization in batch mode. It can reliably dispense and mix from a range of solution constituents into two independent growth wells. We are currently testing this design to prove its efficacy for protein crystallization optimization experiments. In the near future we will expand our design to incorporate up to 10 growth wells per LabChip(TM) device. Upon completion, additional crystallization techniques such as vapor diffusion and liquid-liquid diffusion will be accommodated. Macromolecular crystallization using microfluidic technology is envisioned as a fully automated system, which will use the 'tele-science' concept of remote operation and will be developed into a research facility for the International Space Station as well as on the ground.

Low field magnetocaloric effect in bulk and ribbon alloy La(Fe0.88Si0.12)13

NASA Astrophysics Data System (ADS)

Vuong, Van-Hiep; Do-Thi, Kim-Anh; Nguyen, Duy-Thien; Nguyen, Quang-Hoa; Hoang, Nam-Nhat

2018-03-01

Low-field magnetocaloric effect occurred in itinerant metamagnetic materials is at core for magnetic cooling application. This works reports the magnetocaloric responses obtained at 1.35 T for the silicon-doped iron-based binary alloy La(Fe0.88Si0.12)13 in the bulk and ribbon form. Both samples possess a same symmetry but with different crystallite sizes and lattice parameters. The ribbon sample shows a larger maximum entropy change (nearly 8.5 times larger) and a higher Curie temperature (5 K higher) in comparison with that of the bulk sample. The obtained relative cooling power for the ribbon is also larger and very promising for application (RCP = 153 J/kg versus 25.2 J/kg for the bulk). The origin of the effect observed is assigned to the occurrence of negative magnetovolume effect in the ribbon structure with limit crystallization, caused by rapid cooling process at the preparation, which induced smaller crystallite size and large lattice constant at the overall weaker local crystal field.

Crystallization Behavior of Perovskite in the Synthesized High-Titanium-Bearing Blast Furnace Slag Using Confocal Scanning Laser Microscope

NASA Astrophysics Data System (ADS)

Hu, Meilong; Liu, Lu; Lv, Xuewei; Bai, Chenguang; Zhang, Shengfu

2014-01-01

The isothermal phase composition of high-titanium-bearing slag (23 mass pct TiO2) under an argon atmosphere during cooling process from 1723 K (1450 °C) was calculated by FactSage.6.3 (CRCT-ThermFact Inc., Montréal, Canada). Three main phases, which were perovskite, titania spinel, and clinopyroxene, could form during the cooling process and they precipitated at 1713 K, 1603 K, and 1498 K (1440 °C, 1330 °C, and 1225 °C), respectively. The nonisothermal crystallization process of perovskite in synthesized high-titanium-bearing slag was studied in situ by a confocal scanning laser microscope (CSLM) with cooling rate of 30 K/min. The results showed that the primary phase was perovskite that precipitated at 1703 K (1430 °C). The whole precipitation and growth process of perovskite was obtained, whereas other phases formed as glass under the current experimental conditions. Perovskite grew along a specific growth track and finally appeared with snowflake morphology. The growing kinetics of perovskite formation from molten slag were also mentioned.

Heat transfer and performance characteristics of axial cooling fans with downstream guide vanes

NASA Astrophysics Data System (ADS)

Terzis, Alexandros; Stylianou, Ioannis; Kalfas, Anestis I.; Ott, Peter

2012-04-01

This study examines experimentally the effect of stators on the performance and heat transfer characteristics of small axial cooling fans. A single fan impeller, followed by nine stator blades in the case of a complete stage, was used for all the experimental configurations. Performance measurements were carried out in a constant speed stage performance test rig while the transient liquid crystal technique was used for the heat transfer measurements. Full surface heat transfer coefficient distributions were obtained by recording the temperature history of liquid crystals on a target plate. The experimental data indicated that the results are highly affected by the flow conditions at the fan outlet. Stators can be beneficial in terms of pressure drop and efficiency, and thus more economical operation, as well as, in the local heat transfer distribution at the wake of the stator blades if the fan is installed very close to the cooling object. However, as the separation distance increases, enhanced heat transfer rate in the order of 25% is observed in the case of the fan impeller.

Crystallization Temperatures of Lower Crustal Gabbros from the Oman Ophiolite and the Persistence of the 'Mush Zone' at Intermediate/Fast Spreading Ridges

NASA Astrophysics Data System (ADS)

VanTongeren, J. A.

2017-12-01

Oceanic crust is formed when mantle-derived magmas are emplaced at the ridge axis, a zone of intense rifting and extension. Magmas begin to cool and crystallize on-axis, forming what is termed the "Mush Zone", a region of partially molten rocks. Several attempts have been made to understand the nature of the Mush Zone at fast spreading mid-ocean ridges, specifically how much partial melt exists and how far off-axis the Mush Zone extends. Geophysical estimates of P-wave velocity perturbations at the East Pacific Rise show a region of low velocity approximately 1.5-2.5 km off-axis, which can be interpreted to be the result of higher temperature [e.g. Dunn et al., 2000, JGR] or the existence of partial melt. New petrological and geochemical data and methods allow for the calculation of the lateral extent of the Mush Zone in the lower oceanic crust on exposed sections collected from the Oman ophiolite, a paleo-fast/intermediate spreading center. I will present new data quantifying the crystallization temperatures of gabbros from the Wadi Khafifah section of lower oceanic gabbros from the Oman ophiolite. Crystallization temperatures are calculated with the newly developed plagioclase-pyroxene REE thermometer of Sun and Liang [2017, Contrib. Min. Pet.]. There does not appear to be any systematic change in the crystallization temperature of lower crustal gabbros with depth in the crust. In order to quantify the duration of crystallization and the lateral extent of the Mush Zone of the lower crust, crystallization temperatures are paired with estimates of the solidus temperature and cooling rate determined from the same sample, previously constrained by the Ca diffusion in olivine geothermometer/ geospeedometer [e.g. VanTongeren et al., 2008 EPSL]. There is no systematic variation in the closure temperature of Ca in olivine, or the cooling rate to the 800°C isotherm. These results show that gabbros throughout the lower crust of the Oman ophiolite remain in a partially molten state for an average of 10,000 years. Assuming a paleo-spreading rate similar to that of the East Pacific Rise, this translates to a "Mush Zone" of partially molten rock up to 1 km off-axis, slightly less than the low velocity zone observed geophysically on the East Pacific Rise.

Morphology and antimony segregation of spangles on batch hot-dip galvanized coatings

NASA Astrophysics Data System (ADS)

Peng, Shu; Lu, Jintang; Che, Chunshan; Kong, Gang; Xu, Qiaoyu

2010-06-01

Spangles produced by batch hot-dip galvanizing process have a rougher surface and a greater surface segregation of alloying element compared with those in continuous hot-dip galvanizing line (CGL), owing to the cooling rate of the former is much smaller than that of the later. Therefore, typical spangles on a batch hot-dipped Zn-0.05Al-0.2Sb alloy coating were investigated. The chemical, morphological characterization and identification of the phases on the spangles were examined by scanning electron microscopy (SEM), backscattered electron imaging (BSE), atomic force microscopy (AFM), energy dispersive spectroscopy (EDS) and X-ray diffraction analysis (XRD). The results showed that the coating surface usually exhibited three kinds of spangles: shiny, feathery and dull spangle, of which extensively antimony surface segregation was detected. The nature of precipitate on the coating surface was identified as β-Sb 3Zn 4, The precipitated β-Sb 3Zn 4 particles distributed randomly on the shiny spangle surface, both β-Sb 3Zn 4 particles and dentritic segregation of antimony dispersed in the dendritic secondary arm spacings of the feathery spangle and on the whole dull spangle surface. The dentritic segregation of antimony and precipitation of Sb 3Zn 4 compound are discussed by a proposed model.

Thermophysical properties of carboxylic and amino acid buffers at subzero temperatures: relevance to frozen state stabilization.

PubMed

Sundaramurthi, Prakash; Suryanarayanan, Raj

2011-06-02

Macromolecules and other thermolabile biologicals are often buffered and stored in frozen or dried (freeze-dried) state. Crystallization of buffer components in frozen aqueous solutions and the consequent pH shifts were studied in carboxylic (succinic, malic, citric, tartaric acid) and amino acid (glycine, histidine) buffers. Aqueous buffer solutions were cooled from room temperature (RT) to -25 °C and the pH of the solution was measured as a function of temperature. The thermal behavior of frozen solutions was investigated by differential scanning calorimetry (DSC), and the crystallized phases were identified by X-ray diffractometry (XRD). Based on the solubility of the neutral species of each buffer system over a range of temperatures, it was possible to estimate its degree of supersaturation at the subambient temperature of interest. This enabled us to predict its crystallization propensity in frozen systems. The experimental and the predicted rank orderings were in excellent agreement. The malate buffer system was robust with no evidence of buffer component crystallization and hence negligible pH shift. In the citrate and tartrate systems, at initial pH < pK(a)(2), only the most acidic buffer component (neutral form) crystallized on cooling, causing an increase in the freeze-concentrate pH. In glycine buffer solutions, when the initial pH was ∼3 units < isoelectric pH (pI = 5.9), β-glycine crystallization caused a small decrease in pH, while a similar effect but in the opposite direction was observed when the initial pH was ∼3 units > pI. In the histidine buffer system, depending on the initial pH, either histidine or histidine HCl crystallized.

Mouse Embryo Cryopreservation by Rapid Cooling.

PubMed

Shaw, Jillian

2018-05-01

Embryo cryopreservation has been used to archive mouse strains. Protocols have evolved over this time and now vary considerably in terms of cryoprotectant solution, cooling and warming rates, methods to add and remove cryoprotectant, container or carrier type, volume of cryoprotectant, the stage of preimplantation development, and the use of additional treatments such as blastocyst puncture and microinjection. The rapid cooling methods use concentrated solutions of cryoprotectants to reduce the water content of the cell before cooling commences, thus preventing the formation of ice crystals. Embryos are equilibrated with the cryoprotectants, loaded into a carrier, and then rapidly cooled (e.g., by being plunged directly into LN 2 or onto a surface cooled in LN 2 ). The rapid cooling methods eliminate the need for controlled-rate freezers and seeding procedures. However, they are much more sensitive to minor variations when performing the steps. The rapid-cooling protocol described here is suitable for use with plastic insemination straws. Because it uses relatively large volumes, it is less technically demanding than some other methods that use minivolume devices. © 2018 Cold Spring Harbor Laboratory Press.

On the longevity of silicic magma based on multi-isotope investigation of zircons and modeling their survivals destinies

NASA Astrophysics Data System (ADS)

Bindeman, I. N.; Wotzlaw, J. F.; Melnik, O. E.

2015-12-01

Large volumes of crystal poor, near-liquidus rhyolites are erupted worldwide as tuffs and lavas in rift and hot spots more common previously on early earth, creating temporally very high magma production rates. In this contribution we combine results of IDTIMS dating of zircons with numerical modeling of zircon crystallization. New investigation of zircons in major Yellowstone tuffs: Huckleberry Ridge (Members A,B,C), Mesa Falls, and Lava Creek (A,B) tuffs was done by a combination of in situ measurements of oxygen isotopes followed by ID-TIMS U-Pb dating, Hf isotopes and trace elemental investigation of single crystals. We discover that nearly all zircons are of eruption age, but display significant isotope (O,Hf) diversity and often show decoupled O and Hf isotope systematics. This record rapid (~103yrs) double or triple remelting and sequestration from diverse Archean crust and hydrothermally altered shallow-crustal rocks from previous eruptive cycles, followed by effective mixing of co-existing magma reservoirs with diverse zircons prior to eruptions. Similar results characterize other studied Snake River Plain rhyolites in pre-Yellowstone Heise complex. These results collectively suggest that zircons crystallize after reheating above saturation rejuvenation in isotopically-diverse areas of the crust in the magma plumbing system. Modeling of zircon and quartz dissolution and crystallization trajectories outline conditions of survival (inheritance) vs complete dissolution on conductive timescales, and when combined with a phase diagram, magma T-t paths can be computed. Zircon rejuvenation requires hot, >770-800°C peak temperatures lasting 10-102yrs. We speculate that near liquidus hot and dry Yellowstone rhyolites are kept alive in a multi-batch state by a series of interconnected pods and sills that can rapidly get thermomechanically assembled into large, shallow and eruptable supervolcanoic magma bodies. We suggest that overpressure and roof dynamics and rheology plays a more important role than magma buyoncy. The runaway batch assembly process creates temporally very high magma production rates, orders of magnitude higher than for arc volcanoes. Such views have implication for the state of the magma chamber under Yellowstone and similar supervolcanoes elsewhere.

Removal of Dissolved Silica using Calcinated Hydrotalcite in Real-life Applications.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sasan, Koroush; Brady, Patrick Vane.; Krumhansl, James L.

Water shortages are a growing global problem. Reclamation of industrial and municipal wastewater will be necessary in order to mitigate water scarcity. However, many operational challenges, such as silica scaling, prevent large scale water reuse. Previously, our team at Sandia has demonstrated the use of selective ion exchange materials, such as calcinated hydrotalcite (HTC, (Mg 6 Al 2 (OH) 16 (CO 3 )*4H 2 O)), for the low cost removal of silica from synthetic cooling tower water. However, it is not currently know if calcinated HTC has similar capabilities in realistic applications. The purpose of this study was to investigatemore » the ability of calcinated HTC to remove silica from real cooling tower water. This was investigated under both batch and continuous conditions, and in the presence of competing ions. It was determined that calcinated HTC behaved similarly in real and synthetic cooling tower water; the HTC is highly selective for the silica even in the presence of competing cations. Therefore, the data concludes that calcinated HTC is a viable anti-scaling pretreatment for the reuse of industrial wastewaters.« less

Barium iodide and strontium iodide crystals andd scintillators implementing the same

DOEpatents

Payne, Stephen A; Cherepy, Nerine J; Hull, Giulia E; Drobshoff, Alexander D; Burger, Arnold

2013-11-12

In one embodiment, a material comprises a crystal comprising strontium iodide providing at least 50,000 photons per MeV. A scintillator radiation detector according to another embodiment includes a scintillator optic comprising europium-doped strontium iodide providing at least 50,000 photons per MeV. A scintillator radiation detector in yet another embodiment includes a scintillator optic comprising SrI.sub.2 and BaI.sub.2, wherein a ratio of SrI.sub.2 to BaI.sub.2 is in a range of between 0:1 A method for manufacturing a crystal suitable for use in a scintillator includes mixing strontium iodide-containing crystals with a source of Eu.sup.2+, heating the mixture above a melting point of the strontium iodide-containing crystals, and cooling the heated mixture near the seed crystal for growing a crystal. Additional materials, systems, and methods are presented.

Control of the orientation and photoinduced phase transitions of macrocyclic azobenzene.

PubMed

Uchida, Emi; Sakaki, Kouji; Nakamura, Yumiko; Azumi, Reiko; Hirai, Yuki; Akiyama, Haruhisa; Yoshida, Masaru; Norikane, Yasuo

2013-12-16

Photoinduced phase transitions caused by photochromic reactions bring about a change in the state of matter at constant temperature. Herein, we report the photoinduced phase transitions of crystals of a photoresponsive macrocyclic compound bearing two azobenzene groups (1) at room temperature on irradiation with UV (365 nm) and visible (436 nm) light. The trans/trans isomer undergoes photoinduced phase transitions (crystal-isotropic phase-crystal) on UV light irradiation. The photochemically generated crystal exhibited reversible phase transitions between the crystal and the mesophase on UV and visible light irradiation. The molecular order of the randomly oriented crystals could be increased by irradiating with linearly polarized visible light, and the value of the order parameter was determined to be -0.84. Heating enhances the thermal cis-to-trans isomerization and subsequent cooling returned crystals of the trans/trans isomer. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The performance studies of DKDP crystals grown by a rapid horizontal growth method

NASA Astrophysics Data System (ADS)

Xie, Xiaoyi; Qi, Hongji; Wang, Bin; Wang, Hu; Chen, Duanyang; Shao, Jianda

2018-04-01

A deuterated potassium dihydrogen phosphate (DKDP) crystal with about 70% deuterium level was grown by a rapid horizontal growth method with independent design equipment, which includes a continuous filtration system. The cooling program during crystal growth was designed according to a self-developed software to catch the size of growing crystal in real time. The crystal structure, optical performance and laser induced damage threshold (LIDT) of this DKDP crystal were investigated in this paper. The deuterium concentration of the crystal was confirmed by the neutron diffraction technique, which was effective and available in determining a complete range of deuteration level. The dielectric property was measured to evaluate the perfection of the lattice. The transmittance and LIDT were carried out further to evaluate the optical and functional properties of this DKDP crystal grown in the rapid horizontal growth technique. All of the detailed characterization for DKDP figured out that the 70% deuterated KDP crystal grown in this way had relatively good qualities.

Mold Flux Crystallization and Mold Thermal Behavior

NASA Astrophysics Data System (ADS)

Peterson, Elizabeth Irene

Mold flux plays a small but critical role in the continuous casting of steel. The carbon-coated powder is added at the top of the water-cooled copper mold, over time it melts and infiltrates the gap between the copper mold and the solidifying steel strand. Mold powders serve five primary functions: (1) chemical insulation, (2) thermal insulation, (3) lubrication between the steel strand and mold, (4) absorption of inclusions, and (5) promotion of even heat flux. All five functions are critical to slab casting, but surface defect prevention is primarily controlled through even heat flux. Glassy fluxes have high heat transfer and result in a thicker steel shell. Steels with large volumetric shrinkage on cooling must have a crystalline flux to reduce the radiative heat transfer and avoid the formation of cracks in the shell. Crystallinity plays a critical role in steel shell formation, therefore it is important to study the thermal conditions that promote each phase and its morphology. Laboratory tests were performed to generate continuous cooling transformation (CCT) and time-temperature-transformation (TTT) diagrams. Continuous cooling transformation tests were performed in an instrumented eight cell step chill mold. Results showed that cuspidine was the only phase formed in conventional fluxes and all observed structures were dendritic. An isothermal tin bath quench method was also developed to isothermally age glassy samples. Isothermal tests yielded different microstructures and different phases than those observed by continuous cooling. Comparison of aged tests with industrial flux films indicates similar faceted structures along the mold wall, suggesting that mold flux first solidifies as a glass along the mold wall, but the elevated temperature devitrifies the glassy structure forming crystals that cannot form by continuous cooling.

Temperature dependence of Ti:Sapphire fluorescence spectra for the design of cryogenic cooled Ti:Sapphire CPA laser.

PubMed

Burton, Harry; Debardelaben, Christopher; Amir, Wafa; Planchon, Thomas A

2017-03-20

The fluorescence spectra of titanium doped sapphire (Ti:Sapphire) crystals were measured for temperature ranging from 300K to 77K. The resulting gain cross-section line shapes were calculated and used in a three-dimensional amplification model to illustrate the importance of the precise knowledge of these fluorescence spectra for the design of cryogenic cooled Ti:Sapphire based chirped-pulse laser amplifiers.

Solid-State Laser Cooling of Ytterbium-Doped Tungstate Crystals

DTIC Science & Technology

2001-01-01

namely the heavy metal fluoride glass ZBLAN and yttrium aluminum garnet . Favorable properties of the ytterbium-tungstates include exceptionally high...Optical refrigeration in Nd-doped yttrium aluminum garnet ,” Phys. Rev. Lett. 21, 1172 (1968). 2M.S. Chang, S.S. Elliott, T.K. Gustafson, C. Hu, and...idea gained experimental feasibility. Even with this tool, early failures to optically cool condensed media such as Nd3+ doped in yttrium aluminum

The effect of ultrasonic intensity on the crystal structure of palm oil.

PubMed

Patrick, Maria; Blindt, Renoo; Janssen, Jo

2004-05-01

It has been known for a long time that both the crystal structure and kinetics of crystallisation can be affected by ultrasound. In the past systems used have relied on high power ultrasonic probes to produce crystals. The majority of these probes produce cavitation in the system and it has been difficult to differentiate between effects caused by the ultrasound alone or by the cavitation produced by ultrasound on the crystal structure. Some materials, such as fats, are very susceptible to the production of free radicals that lead to "off-flavours" being obtained. These "off-flavours" are easily produced when the standard high power probes are used. This has meant that, although the crystal structure of the final product might be improved, the presence of 'off' flavours has prevented ultrasound being considered as a commercial technique for the crystallisation of edible fats. At Unilever R&D a system has been developed which can investigate the effect of ultrasound on the crystallisation of fats under controlled conditions covering a range of intensities and cooling rates. The intensity levels used were both below and above the cavitational threshold. By keeping the cooling regime constant it has been possible to show that the structure of the final product can vary from a material looking similar to cottage cheese through to a fine cream simply by varying the ultrasonic intensity. This paper describes the effect of ultrasound on both the crystal structure and kinetics of palm oil crystallisation at intensities below and above the cavitational threshold.

Improved growth method of (SN) x single crystals

NASA Astrophysics Data System (ADS)

Nakada, Ichiroh

1981-12-01

The crystal growth of pure and sizable single crystals of polysulfur nitride (SN) x was improved by adopting a monitor system with a quadrapole mass spectrometer and a Pirani gauge. The mass spectrometer helped to find a temperature appropriate for trapping (SN) 2 selectively on a cold finger and removing other unnecessary or harmful materials produced by the thermal decomposition of (SN) 4 as well as out-gassing water vapour from the glass wall. Leakage of gasses in the vessel was monitored with the Pirani gauge. With a heat pipe the crystal tube is cooled locally so that only a small number of nuclei start to grow. (SN) x single crystals with dimensions of 1 to 6 mm in edge size have been obtained. The relation between the crystal habit and the crystallographic axes has also been determined.

Thermal evolution of old white dwarfs

NASA Astrophysics Data System (ADS)

Kozhberov, Andrew

2017-11-01

This work is devoted to a description of thermodynamic properties of Coulomb crystals which are expected to form in white dwarf interiors. Effects of magnetic field, isotopic impurities, polarization of the electron background and crystal lattice type on the thermal evolution of white dwarfs are discussed. It is shown that the electron polarization could play a noticeable role in the cooling process. While other parameters in concern do not make a significant impact.

Crystallization of Ca-Al-Rich Inclusions: Experimental Studies on the Effects of Repeated Heating Events

NASA Technical Reports Server (NTRS)

Paque, Julie M.; Lofgren, Gary E.; Le, Loan

2000-01-01

The observed textures and chemistry of Ca-Al-rich inclusions (CAIs) are presumed to be the culmination of a series of repeated heating and cooling events in the early history of the solar nebula. We have examined the effects of these heating/cooling cycles experimentally on a bulk composition representing an average Type B Ca-Al-rich inclusion composition. We have tested the effect of the nature of the starting material. Although the most recent and/or highest temperature event prior to incorporation into the parent body dominates the texture and chemistry of the CAI, prior events also affect the phase compositions and textures. We have determined that heating precursor grains to about 1275 C prior to the final melting event increases the likelihood of anorthite crystallization in subsequent higher temperature events and a prior high temperature even that produced dendritic melilite results in melilite that shows evidence of rapid crystallization in subsequent lower temperature events. Prior low temperature pre-crystallization events produce final ran products with pyroxene compositions similar to Type B Ca-Al-rich inclusions, and the glass (residual liquid) composition is more anorthitic than any other experiments to date. The addition of Pt powder to the starting material appears to enhance the ability of anorthite to nucleate from this composition.

Crystallization control for remediation of an FetO-rich CaO-SiO2-Al2O3-MgO EAF waste slag.

PubMed

Jung, Sung Suk; Sohn, Il

2014-01-01

In this work, the crystallization behavior of synthesized FetO-rich electric arc furnace (EAF) waste slags with a basicity range of 0.7 to 1.08 was investigated. Crystal growth in the melts was observed in situ using a confocal laser scanning microscope, and a delayed crystallization for higher-basicity samples was observed in the continuous cooling transformation and time temperature transformation diagrams. This result is likely due to the polymerization of the melt structure as a result of the increased number of network-forming FeO4 and AlO4 units, as suggested by Raman analysis. The complex incorporation of Al and Fe ions in the form of AlO4 and FeO4 tetrahedral units dominant in the melt structure at a higher basicity constrained the precipitation of a magnetic, nonstoichiometric, and Fe-rich MgAlFeO4 primary phase. The growth of this spinel phase caused a clear compositional separation from amorphous phase during isothermal cooling at 1473 K leading to a clear separation between the primary and amorphous phases, allowing an efficient magnetic separation of Fe compounds from the slag for effective remediation and recycling of synthesized EAF waste slags for use in higher value-added ordinary Portland cement.

Crystal growth and analysis of ohmic contact and magneto-optical isolator properties of cadmium manganese telluride

NASA Astrophysics Data System (ADS)

Prakasam, Mythili; Viraphong, Oudomsack; Teulé-Gay, Lionel; Decourt, Rodolphe; Veber, Philippe; Víllora, Encarnación G.; Shimamura, Kiyoshi

2011-03-01

Cd1-xMnxTe (x=0.1, 0.3, 0.5, 0.7 and 0.9) (CMT) single crystals were grown by the vertical Bridgman method. The optical studies reveal that with the increase in Mn concentration, the band gap values increase, which is attributed to s, p-d exchange interaction between the band carriers and Mn ions. Faraday rotation angle of the grown CMT (x=0.5) crystals were measured at the following wavelengths: 825, 1060 and 1575 nm. It was inferred that CMT exhibit larger Faraday effect (3-6 times larger than terbium-gallium garnet (TGG) currently used for optical isolators) making it as an efficient material for optical isolator at longer wavelengths. Field-cooled and zero field-cooled magnetizations of CMT were measured as a function of temperature and magnetic field. The spin-glass like behavior of CMT and their tendency to decrease in magnitude with increasing Mn concentration have been analyzed. The metal contacts on the Cd1-xMnxTe (x=0.1, 0.5, 0.7 and 0.9) crystals have been made with various metals and metal alloys to establish the ohmic contact. The detector characteristics of CMT have been tested using γ-rays with 511 keV (22 Na) and 59.5 keV (241 Am).

Accessing protein conformational ensembles using room-temperature X-ray crystallography

PubMed Central

Fraser, James S.; van den Bedem, Henry; Samelson, Avi J.; Lang, P. Therese; Holton, James M.; Echols, Nathaniel; Alber, Tom

2011-01-01

Modern protein crystal structures are based nearly exclusively on X-ray data collected at cryogenic temperatures (generally 100 K). The cooling process is thought to introduce little bias in the functional interpretation of structural results, because cryogenic temperatures minimally perturb the overall protein backbone fold. In contrast, here we show that flash cooling biases previously hidden structural ensembles in protein crystals. By analyzing available data for 30 different proteins using new computational tools for electron-density sampling, model refinement, and molecular packing analysis, we found that crystal cryocooling remodels the conformational distributions of more than 35% of side chains and eliminates packing defects necessary for functional motions. In the signaling switch protein, H-Ras, an allosteric network consistent with fluctuations detected in solution by NMR was uncovered in the room-temperature, but not the cryogenic, electron-density maps. These results expose a bias in structural databases toward smaller, overpacked, and unrealistically unique models. Monitoring room-temperature conformational ensembles by X-ray crystallography can reveal motions crucial for catalysis, ligand binding, and allosteric regulation. PMID:21918110

Theoretical modeling on the laser-induced phase deformation of liquid crystal optical phased shifter

NASA Astrophysics Data System (ADS)

Zhou, Zhuangqi; Wang, Xiangru; Zhuo, Rusheng; He, Xiaoxian; Wu, Liang; Wang, Xiaolin; Tan, Qinggui; Qiu, Qi

2018-03-01

To improve the working condition of liquid crystal phase shifter on incident laser power, a theoretical model on laser induced phase distortion is built on the physics of heat deposition and heat transfer. Four typical factors (absorption, heat sink structure, cooling fluid rate, and substrate) are analyzed to evaluate the influence of phase distortion when a relative high-power laser is pumped into the liquid crystal phase shifter. Flow rate of cooling fluid and heat sink structure are the most important two factors on improving the limit of incident laser power. Meanwhile, silicon wafer is suggested to replace the back glass contacting the heat sink, because of its higher heat transfer coefficient. If the device is fabricated on the conditions that: the total absorption is 5% and it has a strong heat sink structure with a flow rate of 0.01 m/s, when the incident laser power is 110W, the laser-induced phase deformation on the center is diminished to be less than 0.06, and the maximum temperature increase on the center is less than 1K degree.

Use of spray-cooling technology for development of microencapsulated capsicum oleoresin for the growing pig as an alternative to in-feed antibiotics: a study of release using in vitro models.

PubMed

Meunier, J-P; Cardot, J-M; Manzanilla, E G; Wysshaar, M; Alric, M

2007-10-01

The aim of this study was to develop sustained release microspheres of capsicum oleoresin as an alternative to in-feed additives. Two spray-cooling technologies, a fluidized air bed using a spray nozzle system and a vibrating nozzle system placed on top of a cooling tower, were used to microencapsulate 20% of capsicum oleoresin in a hydrogenated, rapeseed oil matrix. Microencapsulation was intended to reduce the irritating effect of capsicum oleoresin and to control its release kinetics during consumption by the animal. Particles produced by the fluidized air bed process (batch F1) ranged from 180 to 1,000 microm in size. The impact of particle size on release of capsaicin, the main active compound of capsicum oleoresin, was studied after sieving batch F1 to obtain 4 formulations: F1a (180 to 250 microm), F1b (250 to 500 microm), F1c (500 to 710 microm), and F1d (710 to 1,000 microm). The vibrating nozzle system can produce a monodispersive particle size distribution. In this study, particles of 500 to 710 microm were made (batch F2). The release kinetics of the formulations was estimated in a flow-through cell dissolution apparatus (CFC). The time to achieve a 90% dissolution value (T90%) of capsaicin for subbatches of F1 increased with the increase in particle size (P < 0.05), with the greatest value of 165.5 +/- 13.2 min for F1d. The kinetics of dissolution of F2 was slower than all F1 subbatches, with a T90% of 422.7 +/- 30.0 min. Nevertheless, because CFC systems are ill suited for experiments with solid feed and thus limit their predictive values, follow-up studies were performed on F1c and F2 using an in vitro dynamic model that simulated more closely the digestive environment. For both formulations a lower quantity of capsaicin dialyzed was recorded under fed condition vs. fasting condition with 46.9% +/- 1.0 vs. 74.7% +/- 2.7 for F1c and 32.4% +/- 1.4 vs. 44.2% +/- 2.6 for F2, respectively. This suggests a possible interaction between capsaicin and the feed matrix. Moreover, 40.4 +/- 3.9% of the total capsaicin intake in F2 form was dialyzed after 8 h of digestion when feed had been granulated vs. 32.4 +/- 1.4% when feed had not been granulated, which suggests that the feed granulation process could lead to a partial degradation of the microspheres and to a limitation of the sustained release effect. This study demonstrates the potential and the limitations of spray-cooling technology to encapsulate feed additives.

Finding the Cold Needle in a Warm Haystack: Infrared Imaging Applied to Locating Cryo-cooled Crystals in Loops

NASA Technical Reports Server (NTRS)

Snell, Edward; vanderWoerd, Mark

2003-01-01

Thermally imaging the cryocooling processes of crystals has been demonstrated showing the progression of a cold wave through a crystal from the face closest to the origin of the coldstream ending at the point furthest away. During these studies large volume crystals were clearly distinguished from the loop holding them. Large volume crystals, used for neutron studies, were chosen deliberately to enhance the imaging. The different infrared transmission and reflectance properties of the crystal in comparison to the cryo-protectant are thought to be the parameter that produces the contrast making the crystal visible. As an application of the technology to locating crystals, more small crystals of lysozyme and a bFGF/dna complex were cryo-protected and imaged in large loops. The crystals were clearly distinguished from the vitrified solution. In the case of the bFGF/dna complex the illumination had to be carefully manipulated to enable the crystal to be seen in the visible spectrum. These preliminary results will be presented along with advantages and disadvantages of the technique and a discussion of how it might be applied.

Update on the NASA Glenn Propulsion Systems Lab Ice Crystal Cloud Characterization (2015, 2016)

NASA Technical Reports Server (NTRS)

Van Zante, Judith; Bencic, Timothy; Ratvasky, Thomas

2016-01-01

NASA Glenn's Propulsion Systems Lab, an altitude engine test facility, was outfitted with a spray system to generate ice crystals in 2011. Turbine engines and driven rigs can experience ice crystal icing at flight altitudes, temperatures and Mach numbers. To support these tests, four ice crystal characterizations have been conducted in two different facility configurations. In addition, super-cooled liquid and mixed phase clouds have also been generated. This paper represents a work in progress. It will describe some of the 11-parameter calibration space, and how those parameters interact with each other, the instrumentation used to characterize the cloud and present a sample of the cloud characterization results.

Strong Coupling of Microwave Photons to Antiferromagnetic Fluctuations in an Organic Magnet.

PubMed

Mergenthaler, Matthias; Liu, Junjie; Le Roy, Jennifer J; Ares, Natalia; Thompson, Amber L; Bogani, Lapo; Luis, Fernando; Blundell, Stephen J; Lancaster, Tom; Ardavan, Arzhang; Briggs, G Andrew D; Leek, Peter J; Laird, Edward A

2017-10-06

Coupling between a crystal of di(phenyl)-(2,4,6-trinitrophenyl)iminoazanium radicals and a superconducting microwave resonator is investigated in a circuit quantum electrodynamics (circuit QED) architecture. The crystal exhibits paramagnetic behavior above 4 K, with antiferromagnetic correlations appearing below this temperature, and we demonstrate strong coupling at base temperature. The magnetic resonance acquires a field angle dependence as the crystal is cooled down, indicating anisotropy of the exchange interactions. These results show that multispin modes in organic crystals are suitable for circuit QED, offering a platform for their coherent manipulation. They also utilize the circuit QED architecture as a way to probe spin correlations at low temperature.

Strong Coupling of Microwave Photons to Antiferromagnetic Fluctuations in an Organic Magnet

NASA Astrophysics Data System (ADS)

Mergenthaler, Matthias; Liu, Junjie; Le Roy, Jennifer J.; Ares, Natalia; Thompson, Amber L.; Bogani, Lapo; Luis, Fernando; Blundell, Stephen J.; Lancaster, Tom; Ardavan, Arzhang; Briggs, G. Andrew D.; Leek, Peter J.; Laird, Edward A.

2017-10-01

Coupling between a crystal of di(phenyl)-(2,4,6-trinitrophenyl)iminoazanium radicals and a superconducting microwave resonator is investigated in a circuit quantum electrodynamics (circuit QED) architecture. The crystal exhibits paramagnetic behavior above 4 K, with antiferromagnetic correlations appearing below this temperature, and we demonstrate strong coupling at base temperature. The magnetic resonance acquires a field angle dependence as the crystal is cooled down, indicating anisotropy of the exchange interactions. These results show that multispin modes in organic crystals are suitable for circuit QED, offering a platform for their coherent manipulation. They also utilize the circuit QED architecture as a way to probe spin correlations at low temperature.

Fast and scalable purification of a therapeutic full-length antibody based on process crystallization.

PubMed

Smejkal, Benjamin; Agrawal, Neeraj J; Helk, Bernhard; Schulz, Henk; Giffard, Marion; Mechelke, Matthias; Ortner, Franziska; Heckmeier, Philipp; Trout, Bernhardt L; Hekmat, Dariusch

2013-09-01

The potential of process crystallization for purification of a therapeutic monoclonal IgG1 antibody was studied. The purified antibody was crystallized in non-agitated micro-batch experiments for the first time. A direct crystallization from clarified CHO cell culture harvest was inhibited by high salt concentrations. The salt concentration of the harvest was reduced by a simple pretreatment step. The crystallization process from pretreated harvest was successfully transferred to stirred tanks and scaled-up from the mL-scale to the 1 L-scale for the first time. The crystallization yield after 24 h was 88-90%. A high purity of 98.5% was reached after a single recrystallization step. A 17-fold host cell protein reduction was achieved and DNA content was reduced below the detection limit. High biological activity of the therapeutic antibody was maintained during the crystallization, dissolving, and recrystallization steps. Crystallization was also performed with impure solutions from intermediate steps of a standard monoclonal antibody purification process. It was shown that process crystallization has a strong potential to replace Protein A chromatography. Fast dissolution of the crystals was possible. Furthermore, it was shown that crystallization can be used as a concentrating step and can replace several ultra-/diafiltration steps. Molecular modeling suggested that a negative electrostatic region with interspersed exposed hydrophobic residues on the Fv domain of this antibody is responsible for the high crystallization propensity. As a result, process crystallization, following the identification of highly crystallizable antibodies using molecular modeling tools, can be recognized as an efficient, scalable, fast, and inexpensive alternative to key steps of a standard purification process for therapeutic antibodies. Copyright © 2013 Wiley Periodicals, Inc.

The role of mass transport in protein crystallization.

PubMed

García-Ruiz, Juan Manuel; Otálora, Fermín; García-Caballero, Alfonso

2016-02-01

Mass transport takes place within the mesoscopic to macroscopic scale range and plays a key role in crystal growth that may affect the result of the crystallization experiment. The influence of mass transport is different depending on the crystallization technique employed, essentially because each technique reaches supersaturation in its own unique way. In the case of batch experiments, there are some complex phenomena that take place at the interface between solutions upon mixing. These transport instabilities may drastically affect the reproducibility of crystallization experiments, and different outcomes may be obtained depending on whether or not the drop is homogenized. In diffusion experiments with aqueous solutions, evaporation leads to fascinating transport phenomena. When a drop starts to evaporate, there is an increase in concentration near the interface between the drop and the air until a nucleation event eventually takes place. Upon growth, the weight of the floating crystal overcomes the surface tension and the crystal falls to the bottom of the drop. The very growth of the crystal then triggers convective flow and inhomogeneities in supersaturation values in the drop owing to buoyancy of the lighter concentration-depleted solution surrounding the crystal. Finally, the counter-diffusion technique works if, and only if, diffusive mass transport is assured. The technique relies on the propagation of a supersaturation wave that moves across the elongated protein chamber and is the result of the coupling of reaction (crystallization) and diffusion. The goal of this review is to convince protein crystal growers that in spite of the small volume of the typical protein crystallization setup, transport plays a key role in the crystal quality, size and phase in both screening and optimization experiments.

Formation of anorthosite-Gabbro rhythmic phase layering: an example at North Arm Mountain, Bay of Isands ophiolite

USGS Publications Warehouse

Komor, S.C.; Elthon, D.

1990-01-01

Rhythmically layered anorthosite and gabbro are exposed in a 4-10-m thick interval at the base of the layered gabbro unit on North Arm Mountain, one of four massifs that compose the Bay of Islands ophiolite, Newfoundland. The rhythmically layered interval is sandwiched between thick layers of adcumulate to orthocumulate uniform gabbro. Calculated fractional crystallization paths and correlated cryptic variation patterns suggest that uniform and rhythmically layered gabbros represent 20-30% in situ crystallization of two distinct magma batches, one more evolved and the other more primitive. When the more primitive magma entered the crystallization site of the NA300-301 gabbros, it is estimated to have been ~40??C hotter than the resident evolved magma, and may have been chilled by contact with a magma chamber margin composed of uniform gabbro. In this model, chilling caused the liquid to become supercooled with respect to plagioclase nucleation temperatures, resulting in crystallization of gabbro deficient in plagioclase relative to equilibrium cotectic proportions. Subtraction of a plagioclase-poor melagabbro enriched the liquid in normative plagioclase, which in turn led to crystallization of an anorthosite layer. -from Authors

Highly Adsorptive, MOF-Functionalized Nonwoven Fiber Mats for Hazardous Gas Capture Enabled by Atomic Layer Deposition

DTIC Science & Technology

2014-03-20

ligands, [ 3 ] exhibit high surface area, good thermal stability, and have signifi cant synthetic versatility, ena- bling structures with tunable pore...sizes and adjustable internal functionality. [ 4 ] MOF synthesis usually follows wet solvo- thermal batch methods, producing pow- ders that require...surface areas—limiting applicability. For example, Kuesgens et al. grew HKUST-1 crystals on pulp fibers using direct solvo- thermal synthesis and found

Synthesis of renewable diesel through hydrodeoxygenation reaction from nyamplung oil (Calophyllum Inophyllum oil) using NiMo/Z and NiMo/C catalysts with rapid heating and cooling method

NASA Astrophysics Data System (ADS)

Susanto, B. H.; Prakasa, M. B.; Shahab, M. H.

2016-11-01

The synthesis of metal nanocrystal was conducted by modification preparation from simple heating method which heating and cooling process run rapidly. The result of NiMo/Z 575 °C characterizations are 33.73 m2/gram surface area and 31.80 nm crystal size. By used NiMo/C 700 °C catalyst for 30 minutes which had surface area of 263.21 m2/gram, had 31.77 nm crystal size, and good morphology, obtained catalyst with high activity, selectivity, and stability. After catalyst activated, synthesis of renewable diesel performed in hydrogenation reactor at 375 °C, 12 bar, and 800 rpm. The result of conversion was 81.99%, yield was 68.08%, and selectivity was 84.54%.

Development of a Single-Pass Amplifier for an Optical Stochastic Cooling Proof-of-Principle Experiment at Fermilab's IOTA Facility

DOE Office of Scientific and Technical Information (OSTI.GOV)

Andorf, M. B.; Lebedev, V. A.; Piot, P.

2015-06-01

Optical stochastic cooling (OSC) is a method of beam cooling which is expected to provide cooling rates orders of magnitude larger than ordinary stochastic cooling. Light from an undulator (the pickup) is amplified and fed back onto the particle beam via another undulator (the kicker). Fermilab is currently exploring a possible proof-of-principle experiment of the OSC at the integrable-optics test accelerator (IOTA) ring. To implement effective OSC a good correction of phase distortions in the entire band of the optical amplifier is required. In this contribution we present progress in experimental characterization of phase distortions associated to a Titanium Sapphiremore » crystal laser-gain medium (a possible candidate gain medium for the OSC experiment to be performed at IOTA). We also discuss a possible option for a mid-IR amplifier« less

An investigation of the effect of processing conditions on the lamellar and spherulitic morphology of polyhydroxyalkanoates

NASA Astrophysics Data System (ADS)

Xie, Yuping; Akpalu, Yvonne A.

2007-03-01

Polyhydroxyalkanoates (PHAs) have recently attracted much interest because of their biodegradability and biocompatibility. Since the ultimate properties of polymers can be controlled by processing conditions, particularly cooling rates, the systematic and thorough understanding of the effects of cooling rates on the final morphology and the resulting mechanical properties of PHAs is necessary and important. In this presentation, the lamellar (tens of nanometers), fibrillar (several hundred nanometers) and spherulitic (˜μm) morphologies of poly (3-hydroxybutyric acid) (PHB) and the copolymer poly (3-hydroxybutyric acid-co-3-hydroxyvaleric acid) (PHBV) crystallized under different cooling rates were studied using small angle X-ray scattering, ultra small angle X-ray scattering, and polarized optical microscopy, respectively. The morphology was observed to depend strongly on cooling rate. The influence of cooling rate on the morphology and mechanical properties such as toughness, tensile strength and overall stress-strain behavior will be discussed.

Crystal growth in a microgravity environment

NASA Technical Reports Server (NTRS)

Kroes, Roger L. (Inventor); Reiss, Donald A. (Inventor); Lehoczky, Sandor L. (Inventor)

1992-01-01

Gravitational phenomena, including convection, sedimentation, and interactions of materials with their containers all affect the crystal growth process. If they are not taken into consideration they can have adverse effects on the quantity and quality of crystals produced. As a practical matter, convection, and sedimentation can be completely eliminated only under conditions of low gravity attained during orbital flight. There is, then, an advantage to effecting crystallization in space. In the absence of convection in a microgravity environment cooling proceeds by thermal diffusion from the walls to the center of the solution chamber. This renders control of nucleation difficult. Accordingly, there is a need for a new improved nucleation process in space. Crystals are nucleated by creating a small localized region of high relative supersaturation in a host solution at a lower degree of supersaturation.

Lead halide perovskites: Crystal-liquid duality, phonon glass electron crystals, and large polaron formation

PubMed Central

Miyata, Kiyoshi; Atallah, Timothy L.; Zhu, X.-Y.

2017-01-01

Lead halide perovskites have been demonstrated as high performance materials in solar cells and light-emitting devices. These materials are characterized by coherent band transport expected from crystalline semiconductors, but dielectric responses and phonon dynamics typical of liquids. This “crystal-liquid” duality implies that lead halide perovskites belong to phonon glass electron crystals, a class of materials believed to make the most efficient thermoelectrics. We show that the crystal-liquid duality and the resulting dielectric response are responsible for large polaron formation and screening of charge carriers, leading to defect tolerance, moderate charge carrier mobility, and radiative recombination properties. Large polaron formation, along with the phonon glass character, may also explain the marked reduction in hot carrier cooling rates in these materials. PMID:29043296

Update on the NASA Glenn Propulsion Systems Lab Ice Crystal Cloud Characterization (2015)

NASA Technical Reports Server (NTRS)

Van Zante, Judith F.; Bencic, Timothy J.; Ratvasky, Thomas P.

2016-01-01

NASA Glenn's Propulsion Systems Lab (PSL), an altitude engine test facility, was outfitted with a spray system to generate ice crystals. The first ice crystal characterization test occurred in 2012. At PSL, turbine engines and driven rigs can experience ice crystal icing at flight altitudes, temperatures and Mach numbers. To support these tests, four ice crystal characterizations have been conducted in two different facility configurations. In addition, super-cooled liquid and mixed phase clouds have also been generated. This paper will discuss the recent learning from the previous two calibrations. It will describe some of the 12-parameter calibration space, and how those parameters interact with each other, the instrumentation used to characterize the cloud and present a sample of the cloud characterization results.