Micromechanics of Sea Urchin spines.

PubMed

Tsafnat, Naomi; Fitz Gerald, John D; Le, Hai N; Stachurski, Zbigniew H

2012-01-01

The endoskeletal structure of the Sea Urchin, Centrostephanus rodgersii, has numerous long spines whose known functions include locomotion, sensing, and protection against predators. These spines have a remarkable internal microstructure and are made of single-crystal calcite. A finite-element model of the spine's unique porous structure, based on micro-computed tomography (microCT) and incorporating anisotropic material properties, was developed to study its response to mechanical loading. Simulations show that high stress concentrations occur at certain points in the spine's architecture; brittle cracking would likely initiate in these regions. These analyses demonstrate that the organization of single-crystal calcite in the unique, intricate morphology of the sea urchin spine results in a strong, stiff and lightweight structure that enhances its strength despite the brittleness of its constituent material.

Tungsten carbide: Crystals by the ton

NASA Astrophysics Data System (ADS)

Smith, E. N.

1988-06-01

A comparison is made of the conventional process of making tungsten carbide by carburizing tungsten powder and the Macro Process wherein the tungsten carbide is formed directly from the ore concentrate by an exothermic reaction of ingredients causing a simultaneous reduction and carburization. Tons of tungsten monocarbide crystals are formed in a very rapid reaction. The process is unique in that it is self regulating and produces a tungsten carbide compound with the correct stoichiometry. The high purity with respect to oxygen and nitrogen is achieved because the reactions occur beneath the molten metal. The morphology and hardness of these crystals has been studied by various investigators and reported in the listed references.

Micromechanics of Sea Urchin Spines

PubMed Central

Tsafnat, Naomi; Fitz Gerald, John D.; Le, Hai N.; Stachurski, Zbigniew H.

2012-01-01

The endoskeletal structure of the Sea Urchin, Centrostephanus rodgersii, has numerous long spines whose known functions include locomotion, sensing, and protection against predators. These spines have a remarkable internal microstructure and are made of single-crystal calcite. A finite-element model of the spine’s unique porous structure, based on micro-computed tomography (microCT) and incorporating anisotropic material properties, was developed to study its response to mechanical loading. Simulations show that high stress concentrations occur at certain points in the spine’s architecture; brittle cracking would likely initiate in these regions. These analyses demonstrate that the organization of single-crystal calcite in the unique, intricate morphology of the sea urchin spine results in a strong, stiff and lightweight structure that enhances its strength despite the brittleness of its constituent material. PMID:22984468

Structural morphology of crystals with the barite (BaSO 4) structure: A revision and extension

NASA Astrophysics Data System (ADS)

Hartman, P.; Strom, C. S.

1989-09-01

The structural morphology of crystals with the barite (BaSO 4) structure (sulphates, chromates, perchlorates, permanganates and tetrafluoroborates) has been determined with the use of computer programs. Uniquely defined F forms are {002}, {210}, {211}, {020} and {201}. Two different F slices were found for {101} and {200}, 33 for {011}. Attachment energies and specific surface energies have been calculated for an electrostatic point charge model as a function of the charge distribution in the anion. On this basis it is concluded that {101} behaves as an F form, {200} as an S form and {011} as a K form. The theoretical growth form shows {210}, {101} and {002} as main forms. A comparison is made with habits of natural and synthetic crystals. Experiments on KCIO 4 show that {011} appears at high supersaturations (>38; ;20%). It is shown that a broken bond model provides relative attachment energies that are higher by a factor of about three.

Unique isothermal crystallization behavior of novel polyphenylene sulfide/inorganic fullerene-like WS2 nanocomposites.

PubMed

Naffakh, Mohammed; Marco, Carlos; Gómez, Marián A; Jiménez, Ignacio

2008-11-27

The isothermal crystallization of polyphenylene sulfide (PPS) nanocomposites with inorganic fullerene-like tungsten disulfide nanoparticles (IF-WS2) has been studied from a thermal and morphological point of view, using differential scanning calorimetry (DSC), scanning electron microscopy (SEM), polarized optical microscopy (POM) and time-resolved synchrotron X-ray diffraction. All the analyses revealed that the incorporation of the IF-WS2 altered significantly the crystallization behavior of PPS, in a way strongly dependent with the nanocomposite composition. The addition of IF-WS2 in 0.1 wt % proportion retarded the crystallization of PPS by increasing its fold surface free energy in a 10%. However, addition of the nanoparticles in excess of 1 wt % results in a promotion of the crystallization rate with reduction of the fold surface free energy to half the value of pure PPS.

Hexagonal platelet-like magnetite as a biosignature of thermophilic iron-reducing bacteria and its applications to the exploration of the modern deep, hot biosphere and the emergence of iron-reducing bacteria in early precambrian oceans.

PubMed

Li, Yi-Liang

2012-12-01

Dissimilatory iron-reducing bacteria are able to enzymatically reduce ferric iron and couple to the oxidation of organic carbon. This mechanism induces the mineralization of fine magnetite crystals characterized by a wide distribution in size and irregular morphologies that are indistinguishable from authigenic magnetite. Thermoanaerobacter are thermophilic iron-reducing bacteria that predominantly inhabit terrestrial hot springs or deep crusts and have the capacity to transform amorphous ferric iron into magnetite with a size up to 120 nm. In this study, I first characterize the formation of hexagonal platelet-like magnetite of a few hundred nanometers in cultures of Thermoanaerobacter spp. strain TOR39. Biogenic magnetite with such large crystal sizes and unique morphology has never been observed in abiotic or biotic processes and thus can be considered as a potential biosignature for thermophilic iron-reducing bacteria. The unique crystallographic features and strong ferrimagnetic properties of these crystals allow easy and rapid screening for the previous presence of iron-reducing bacteria in deep terrestrial crustal samples that are unsuitable for biological detection methods and, also, the search for biogenic magnetite in banded iron formations that deposited only in the first 2 billion years of Earth with evidence of life.

Effects of inorganic ions on morphology of octacalcium phosphate grown on cation selective membrane at physiological temperature and pH in relation to enamel formation

NASA Astrophysics Data System (ADS)

Iijima, Mayumi; Moriwaki, Yutaka

1989-05-01

The crystal growth of octacalcium phosphate (OCP) is of particular interest, since there is a possibility that OCP is formed in the early stage of tooth enamel formation. In this study, the effects of CO2-3, Mg2+ and F-ions on the morphology of OCP were investigated in a membrane system, where a cation selective membrane was used to simulate amelogenesis. Reactions were carried out at pH 6.3, 6.5 and 6.8 for 3 days at 37°C. In most cases, these ions suppressed the crystal growth in the c-axis direction of OCP, particularly when they coexisted. The morphology of OCP crystal changed from ribbon-like to flake-like, depending on the inhibitory activity. The inhibitory activity, particularly that of F - ion, was suppressed at pH lower than pH 6.8. Antagonistic effect of Mg2+ and F-ion was observed at pH 6.5. In the case of F - ion, OCP crystals showed a unique pattern, which suggests hydrolysis of OCP and subsequent growth of apatite. These findings indicate that inorganic ions, particularly F - ion, influence the growth of OCP. Although CO2-3, Mg2+andF-ions coexisted, extended growth in the c-axis direction of OCP took place at pH 6.0.

Characteristics of zircons from volcanic ash-derived tonsteins in Late Permian coal fields of eastern Yunnan, China

USGS Publications Warehouse

Zhou, Y.; Ren, Y.; Tang, D.; Bohor, B.

1994-01-01

Kaolinitic tonsteins of altered synsedimentary volcanic ash-fall origin are well developed in the Late Permian coal-bearing formations of eastern Yunnan Province. Because of their unique origin, wide lateral extent, relatively constant thickness and sharp contacts with enclosing strata, great importance has been attached to these isochronous petrographic markers. In order to compare tonsteins with co-existing, non-cineritic claystones and characterize the individuality of tonsteins from different horizons for coal bed correlation, a semi-quantitative method was developed that is based on statistical analyses of the concentration and morphology of zircons and their spatial distribution patterns. This zircon-based analytical method also serves as a means for reconstructing volcanic ash-fall dispersal patterns. The results demonstrate that zircons from claystones of two different origins (i.e., tonstein and non-cineritic claystone) differ greatly in their relative abundances, crystal morphologies and spatial distribution patterns. Tonsteins from the same area but from different horizons are characterized by their own unique statistical patterns in terms of zircon concentration values and morphologic parameters (crystal length, width and the ratio of these values), thus facilitating stratigraphic correlation. Zircons from the same tonstein horizon also show continuous variation in these statistical patterns as a function of areal distribution, making it possible to identify the main path and direction in which the volcanic source materials were transported by prevailing winds. ?? 1994.

Strain-relief by single dislocation loops in calcite crystals grown on self-assembled monolayers

DOE PAGES

Ihli, Johannes; Clark, Jesse N.; Côté, Alexander S.; ...

2016-06-15

Most of our knowledge of dislocation-mediated stress relaxation during epitaxial crystal growth comes from the study of inorganic heterostructures. In this study, we use Bragg coherent diffraction imaging to investigate a contrasting system, the epitaxial growth of calcite (CaCO 3) crystals on organic self-assembled monolayers, where these are widely used as a model for biomineralization processes. The calcite crystals are imaged to simultaneously visualize the crystal morphology and internal strain fields. Our data reveal that each crystal possesses a single dislocation loop that occupies a common position in every crystal. The loops exhibit entirely different geometries to misfit dislocations generatedmore » in conventional epitaxial thin films and are suggested to form in response to the stress field, arising from interfacial defects and the nanoscale roughness of the substrate. In conclusion, this work provides unique insight into how self-assembled monolayers control the growth of inorganic crystals and demonstrates important differences as compared with inorganic substrates.« less

Strain-relief by single dislocation loops in calcite crystals grown on self-assembled monolayers

PubMed Central

Ihli, Johannes; Clark, Jesse N.; Côté, Alexander S.; Kim, Yi-Yeoun; Schenk, Anna S.; Kulak, Alexander N.; Comyn, Timothy P.; Chammas, Oliver; Harder, Ross J.; Duffy, Dorothy M.; Robinson, Ian K.; Meldrum, Fiona C.

2016-01-01

Most of our knowledge of dislocation-mediated stress relaxation during epitaxial crystal growth comes from the study of inorganic heterostructures. Here we use Bragg coherent diffraction imaging to investigate a contrasting system, the epitaxial growth of calcite (CaCO3) crystals on organic self-assembled monolayers, where these are widely used as a model for biomineralization processes. The calcite crystals are imaged to simultaneously visualize the crystal morphology and internal strain fields. Our data reveal that each crystal possesses a single dislocation loop that occupies a common position in every crystal. The loops exhibit entirely different geometries to misfit dislocations generated in conventional epitaxial thin films and are suggested to form in response to the stress field, arising from interfacial defects and the nanoscale roughness of the substrate. This work provides unique insight into how self-assembled monolayers control the growth of inorganic crystals and demonstrates important differences as compared with inorganic substrates. PMID:27302863

A New Star-shaped Carbazole Derivative with Polyhedral Oligomeric Silsesquioxane Core: Crystal Structure and Unique Photoluminescence Property.

PubMed

Xu, Zixuan; Yu, Tianzhi; Zhao, Yuling; Zhang, Hui; Zhao, Guoyun; Li, Jianfeng; Chai, Lanqin

2016-01-01

A new inorganic–organic hybrid material based on polyhedral oligomeric silsesquioxane (POSS) capped with carbazolyl substituents, octakis[3-(carbazol-9-yl)propyldimethylsiloxy]-silsesquioxane (POSS-8Cz), was successfully synthesized and characterized. The X-ray crystal structure of POSS-8Cz were described. The photophysical properties of POSS-8Cz were investigated by using UV–vis,photoluminescence spectroscopic analysis. The hybrid material exhibits blue emission in the solution and the solid film.The morphology and thermal stablity properties were measured by X-ray diffraction (XRD) and TG-DTA analysis.

Epicuticular Wax Crystals of Wollemia nobilis: Morphology and Chemical Composition

PubMed Central

Dragota, Simona; Riederer, Markus

2007-01-01

Background and Aims The morphology of the epicuticular leaf waxes of Wollemia nobilis (Araucariaceae) was studied with special emphasis on the relationship between the microstructure of epicuticular wax crystals and their chemical composition. Wollemia nobilis is a unique coniferous tree of the family Araucariaceae and is of very high scientific value as it is the sole living representative of an ancient genus, which until 1994 was known only from fossils. Methods Scanning electron microscopy (SEM), gas chromatography (GC) combined with mass spectrometry (GC–MS) and nuclear magnetic resonance spectroscopy (NMR) were used for characterizing the morphology and the chemical structure of the epicuticular wax layer of W. nobilis needles. Key Results The main component of the leaf epicuticular wax of W. nobilis is nonacosan-10-ol. This secondary alcohol together with nonacosane diols is responsible for the tubular habit of the epicuticular wax crystals. Scanning electron micrographs revealed differences in the fine structure of adaxial and abaxial leaf surfaces that could be explained by gas chromatographic studies after selective mechanical removal of the waxes. Conclusions SEM investigations established the tubular crystalline microstructure of the epicuticular wax of W. nobilis leaves. GC–MS and NMR experiments showed that nonacosan-10-ol is the major constituent of the epicuticular wax of W. nobilis leaves. PMID:17611192

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.

A novel fabrication of Cu{sub 2}O@Cu{sub 7}S{sub 4} core-shell micro/nanocrystals from Cu{sub 2}O temples and enhanced photocatalytic activities

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

Li, Junqi, E-mail: sfmlab@163.com; Sun, Long; Yan, Ying

2016-08-15

Highlights: • The Cu{sub 2}O@Cu{sub 7}S{sub 4} core-shell crystals maintained the same morphology with template. • The crystals exhibit enhanced photocatalytic activity than the pure Cu{sub 2}O crystals. • The photocatalytic activity of different R crystals is diverse from each other. • A possible formation mechanism has been proposed. - Abstract: Uniform and monodispersed Cu{sub 2}O@Cu{sub 7}S{sub 4} core-shell micro/nanocrystals have been synthesized successfully at room temperature via a simple chemical etching reaction, using Cu{sub 2}O as sacrificial template. The structure and properties of the crystals were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM),more » X-ray photoelectron spectra (XPS). The photocatalytic activity of the Cu{sub 2}O@Cu{sub 7}S{sub 4} crystals was evaluated by photocatalytic decolorization of MeO (methyl orange) aqueous solution at ambient temperature under visible-light irradiation. The results show that the as-prepared Cu{sub 2}O@Cu{sub 7}S{sub 4} crystals revealed core-shell structure, which maintained the same morphology with corresponding template and were composed of cuboctahedron Cu{sub 7}S{sub 4} shell and active Cu{sub 2}O core. Due to the unique Cu{sub 2}O@Cu{sub 7}S{sub 4} core-shell structure, the crystals exhibit enhanced photocatalytic activity than that of the pure Cu{sub 2}O crystals, and the photocatalytic activity of different R crystals is diverse from each other. A possible formation mechanism has been proposed.« less

Morphology of single inhalable particle in the air polluted city of Shijiazhuang, China.

PubMed

Wang, Zanhong; Zhang, Lingzhi; Zhang, Yuliang; Zhao, Zhou; Zhang, Sumin

2008-01-01

In the typical air polluted city of Shijiazhuang, single inhalable particle samples in non-heating period, heating period, dust storm days, and snowy days were collected and detected by SEM/EDS (scanning electron microscopy and energy dispersive X-ray spectrometry). The particle morphology was characterized by the 6 shape clusters, which are: irregular square, agglomerate, sphere, floccule, column or stick, and unknown, by quantitative order. The irregular square particles are common in all kinds of samples; sphere particles are more, and column or stick are less in winter samples; in the wet deposit samples, agglomerate and floccule particles are not found. The surface of most particles is coarse with fractal edge, which can provide suitable chemical reaction bed in the polluted atmospheric environment. New formed calcium crystal is found to demonstrate the existence of neutralized reaction, explaining the reason for the high SO2 emission and low acid rain frequency in Shijiazhuang. The three sorts of surface patterns of spheres are smooth, semi-smooth, and coarse, corresponding to the element of Si-dominant, Si-Al-dominant, and Fe-dominant. The soot particle is present as floccule with average size around 10 microm, considerably larger than the former reported results, but wrapped or captured with other fine particles to make its appearance unique and enhance its toxicity potentially. The new formed calcium crystal, the 3 sorts of sphere surface patterns, and the unique soot appearance represent the single inhalable particle's morphology characteristics in Shijiazhuang City.

Crystallization, Crystal Orientation and Morphology of Poly(ethylene oxide) under 1D Defect-Free Nanoscale Confinement

NASA Astrophysics Data System (ADS)

Hsiao, Ming-Siao; Zheng, Joseph X.; van Horn, Ryan M.; Quirk, Roderic P.; Thomas, Edwin L.; Lotz, Bernard; Cheng, Stephen Z. D.

2009-03-01

One-dimensional (1-D) defect-free nanoscale confinement is created by growing single crystals of PS-b-PEO block copolymers in dilute solution. Those defect-free, 1-D confined lamellae having different PEO layer thicknesses in PS-b-PEO lamellar single crystals (or crystal mats) were used to study the polymer recrystallization and crystal orientation evolution as a function of recrystallization temperature (Trx) because the Tg^PS is larger than Tm^PEO in the PS-b-PEO single crystal. The results are summarized as follows. First, by the combination of electron diffraction and known PEO crystallography, the crystallization of PEO only takes place at Trx<-5^oC. Meanwhile a unique tilted PEO orientation is formed at Trx >-5^oC after self-seeding. The origin of the formation of tilted chains in the PEO crystal will be addressed. Second, from the analysis of 2D WAXD patterns of crystal mats, it is shown that the change in PEO c-axis orientation from homogeneous at low Trx to homeotropic at higher Trx transitions sharply, within 1^oC. The mechanism inducing this dramatic change in crystal orientation will be investigated in detail.

Morphology design of porous coordination polymer crystals by coordination modulation.

PubMed

Umemura, Ayako; Diring, Stéphane; Furukawa, Shuhei; Uehara, Hiromitsu; Tsuruoka, Takaaki; Kitagawa, Susumu

2011-10-05

The design of crystal morphology, or exposed crystal facets, has enabled the development (e.g., catalytic activities, material attributes, and oriented film formation) of porous coordination polymers (PCPs) without changing material compositions. However, because crystal growth mechanisms are not fully understood, control of crystal morphology still remains challenging. Herein, we report the morphology design of [Cu(3)(btc)(2)](n) (btc = benzene-1,3,5-tricarboxylate) by the coordination modulation method (modulator = n-dodecanoic acid or lauric acid). A morphological transition (octahedron-cuboctahedron-cube) in the [Cu(3)(btc)(2)](n) crystal was observed with an increase in concentration of the modulator. By suitably defining a coarse-grained standard unit of [Cu(3)(btc)(2)](n) as its cuboctahedron main pore and determining its attachment energy on crystal surfaces, Monte Carlo coarse-grain modeling revealed the population and orientation of carboxylates and elucidated an important role of the modulator in determining the <100>- and <111>-growth throughout the crystal growth process. This comprehension, in fact, successfully led to designed crystal morphologies with oriented growth on bare substrates. Because selective crystal orientations on the bare substrates were governed by crystal morphology, this contribution also casts a new light on the unexplored issue of the significance of morphology design of PCPs.

Nucleation and growth in alkaline zinc electrodeposition An Experimental and Theoretical study

NASA Astrophysics Data System (ADS)

Desai, Divyaraj

The current work seeks to investigate the nucleation and growth of zinc electrodeposition in alkaline electrolyte, which is of commercial interest to alkaline zinc batteries for energy storage. The morphology of zinc growth places a severe limitation on the typical cycle life of such batteries. The formation of mossy zinc leads to a progressive deterioration of battery performance while zinc dendrites are responsible for sudden catastrophic battery failure. The problems are identified as the nucleation-controlled formation of mossy zinc and the transport-limited formation of dendritic zinc. Consequently, this thesis work seeks to investigate and accurately simulate the conditions under which such morphologies are formed. The nucleation and early-stage growth of Zn electrodeposits is studied on carbon-coated TEM grids. At low overpotentials, the morphology develops by aggregation at two distinct length scales: ~5 nm diameter monocrystalline nanoclusters form ~50nm diameter polycrystalline aggregates, and second, the aggregates form a branched network. Epitaxial (0002) growth above a critical overpotential leads to the formation of hexagonal single-crystals. A kinetic model is provided using the rate equations of vapor solidification to simulate the evolution of the different morphologies. On solving these equations, we show that aggregation is attributed to cluster impingement and cluster diffusion while single-crystal formation is attributed to direct attachment. The formation of dendritic zinc is investigated using in-operando transmission X-ray microscopy which is a unique technique for imaging metal electrodeposits. The nucleation density of zinc nuclei is lowered using polyaniline films to cover the active nucleation sites. The effect of overpotential is investigated and the morphology shows beautiful in-operando formation of symmetric zinc crystals. A linear perturbation model was developed to predict the growth and formation of these crystals to first-order accuracy. Existing phase-field models of solidification and electrodeposition are used to simulate the growth and formation of individual zinc crystals. The driving force for solidification models (i.e. supersaturation) is reinterpreted in terms of overpotential under the assumption of a conductive electrolyte. The final morphologies are astonishingly similar to those observed in dynamical experiments. Further, the phase-field models obey the predictions of the linear perturbation analysis, which gives good credibility to the phase-field approach to simulate electrodeposition processes.

Crystal phase-based epitaxial growth of hybrid noble metal nanostructures on 4H/fcc Au nanowires

NASA Astrophysics Data System (ADS)

Lu, Qipeng; Wang, An-Liang; Gong, Yue; Hao, Wei; Cheng, Hongfei; Chen, Junze; Li, Bing; Yang, Nailiang; Niu, Wenxin; Wang, Jie; Yu, Yifu; Zhang, Xiao; Chen, Ye; Fan, Zhanxi; Wu, Xue-Jun; Chen, Jinping; Luo, Jun; Li, Shuzhou; Gu, Lin; Zhang, Hua

2018-03-01

Crystal-phase engineering offers opportunities for the rational design and synthesis of noble metal nanomaterials with unusual crystal phases that normally do not exist in bulk materials. However, it remains a challenge to use these materials as seeds to construct heterometallic nanostructures with desired crystal phases and morphologies for promising applications such as catalysis. Here, we report a strategy for the synthesis of binary and ternary hybrid noble metal nanostructures. Our synthesized crystal-phase heterostructured 4H/fcc Au nanowires enable the epitaxial growth of Ru nanorods on the 4H phase and fcc-twin boundary in Au nanowires, resulting in hybrid Au-Ru nanowires. Moreover, the method can be extended to the epitaxial growth of Rh, Ru-Rh and Ru-Pt nanorods on the 4H/fcc Au nanowires to form unique hybrid nanowires. Importantly, the Au-Ru hybrid nanowires with tunable compositions exhibit excellent electrocatalytic performance towards the hydrogen evolution reaction in alkaline media.

Self-assembly of red-blood-cell-like (NH4)[Fe2(OH)(PO4)2]·2H2O architectures from 2D nanoplates by sonochemical method.

PubMed

Wu, Kaipeng; Liu, Diwei; Tang, Yun

2018-01-01

Red-blood-cell-like (RBC-like) (NH 4 )[Fe 2 (OH)(PO 4 ) 2 ]·2H 2 O architectures assembled from 2D nanoplates are successfully synthesized via a facile sonochemical method. XRD measurement indicates that the as-prepared sample is well crystallized with a monoclinic structure. The morphology of the sample is characterized by SEM analysis, which shows that the (NH 4 )[Fe 2 (OH)(PO 4 ) 2 ]·2H 2 O particles exhibit a unique biconcave red blood cell morphology with an average diameter of 4um and thickness of 1.5um. The detailed time-dependent experiments are conducted to investigate the morphological evolution process. It reveals that the ultrasonic time is crucial to the morphology of the products, and the RBC-like (NH 4 )[Fe 2 (OH)(PO 4 ) 2 ]·2H 2 O proceeds in steps of crystallization, formation of thin plates, and the subsequent self-assembly. Compared to the available methods that are typically time-consuming and complicated, this smart sonochemical strategy proposed herein is efficient and simple. Moreover, these obtained special RBC-like architectures will be more fascinating for application in many areas. Copyright © 2017 Elsevier B.V. All rights reserved.

Two-Dimensional Magnesium Phosphate Nanosheets Form Highly Thixotropic Gels That Up-Regulate Bone Formation.

PubMed

Laurenti, Marco; Al Subaie, Ahmed; Abdallah, Mohamed-Nur; Cortes, Arthur R G; Ackerman, Jerome L; Vali, Hojatollah; Basu, Kaustuv; Zhang, Yu Ling; Murshed, Monzur; Strandman, Satu; Zhu, Julian; Makhoul, Nicholas; Barralet, Jake E; Tamimi, Faleh

2016-08-10

Hydrogels composed of two-dimensional (2D) nanomaterials have become an important alternative to replace traditional inorganic scaffolds for tissue engineering. Here, we describe a novel nanocrystalline material with 2D morphology that was synthesized by tuning the crystallization of the sodium-magnesium-phosphate system. We discovered that the sodium ion can regulate the precipitation of magnesium phosphate by interacting with the crystal's surface causing a preferential crystal growth that results in 2D morphology. The 2D nanomaterial gave rise to a physical hydrogel that presented extreme thixotropy, injectability, biocompatibility, bioresorption, and long-term stability. The nanocrystalline material was characterized in vitro and in vivo and we discovered that it presented unique biological properties. Magnesium phosphate nanosheets accelerated bone healing and osseointegration by enhancing collagen formation, osteoblasts differentiation, and osteoclasts proliferation through up-regulation of COL1A1, RunX2, ALP, OCN, and OPN. In summary, the 2D magnesium phosphate nanosheets could bring a paradigm shift in the field of minimally invasive orthopedic and craniofacial interventions because it is the only material available that can be injected through high gauge needles into bone defects in order to accelerate bone healing and osseointegration.

Efficient photodegradation of organic dye using anatase TiO2 plants as catalyst

NASA Astrophysics Data System (ADS)

Bahadur, Jitendra; Pal, Kaushik

2017-11-01

Anatase TiO2 hierarchical nanostructures with higher photocatalytic activity are of special importance in various applications. We have reported the synthesis of TiO2 as water chestnut plants like morphology via facile hydrothermal method, by using Titanium (IV) butoxide (TBOT) as a precursor solution. It is found that TiO2 nanoparticles work as seed and completely convert into water chestnut plants like structure or morphology, which are composed of crystallized anatase nanocrystals. X-ray diffraction spectra confirmed the presence of anatase phase of crystallized TiO2 plants (TPs). The average life time delay for generated charge carriers in TPs was calculated to be around 2.45 ns, which reflects slow recombination of charge carriers. The prepared TPs show excellent photocatalytic performance when applied in photo degradation of Rhodamine B organic dye. The unique features exhibited by TPs make them a promising candidate for vast potential applications in field such as solar cells, photocatalysis, supercapacitor, lithium ion batteries and some related fields.[Figure not available: see fulltext.

Infrared actuation-induced simultaneous reconfiguration of surface color and morphology for soft robotics.

PubMed

Banisadr, Seyedali; Chen, Jian

2017-12-13

Cephalopods, such as cuttlefish, demonstrate remarkable adaptability to the coloration and texture of their surroundings by modulating their skin color and surface morphology simultaneously, for the purpose of adaptive camouflage and signal communication. Inspired by this unique feature of cuttlefish skins, we present a general approach to remote-controlled, smart films that undergo simultaneous changes of surface color and morphology upon infrared (IR) actuation. The smart film has a reconfigurable laminated structure that comprises an IR-responsive nanocomposite actuator layer and a mechanochromic elastomeric photonic crystal layer. Upon global or localized IR irradiation, the actuator layer exhibits fast, large, and reversible strain in the irradiated region, which causes a synergistically coupled change in the shape of the laminated film and color of the mechanochromic elastomeric photonic crystal layer in the same region. Bending and twisting deformations can be created under IR irradiation, through modulating the strain direction in the actuator layer of the laminated film. Furthermore, the laminated film has been used in a remote-controlled inchworm walker that can directly couple a color-changing skin with the robotic movements. Such remote-controlled, smart films may open up new application possibilities in soft robotics and wearable devices.

Preliminary observations of the effect of solutal convection on crystal morphology

NASA Technical Reports Server (NTRS)

Broom, M. Beth H.; Witherow, William K.; Snyder, Robert S.; Carter, Daniel C.

1988-01-01

Studies to examine the effect of solutal convection on crystal morphology using sucrose as a model system were initiated. Aspect ratios, defined as the width of the 100-plane-oriented face over the width of the 001-plane-oriented face, were determined for oriented crystals which were grown with either the 001-oriented or the 100-oriented face perpendicular to the convective flow. The dependence of the crystal morphology on orientation is much greater for crystals grown with one face occluded than for crystals grown suspended in solution. Many factors appear to interact in a complex fashion to influence crystal morphology.

Kinetics-Driven Crystal Facets Evolution at the Tip of Nanowires: A New Implementation of the Ostwald-Lussac Law.

PubMed

Yin, Xin; Wang, Xudong

2016-11-09

Nanocrystal facets evolution is critical for designing nanomaterial morphology and controlling their properties. In this work, we report a unique high-energy crystal facets evolution phenomenon at the tips of wurtzite zinc oxide nanowires (NWs). As the zinc vapor supersaturation decreased at the NW deposition region, the NW tip facets evolved from the (0001) surface to the {101̅3} surface and subsequently to the {112̅2} surface and eventually back to the flat (0001) surface. A series of NW tip morphology was observed in accordance to the different combinations of exposed facets. Exposure of the high-energy facets was attributed to the fluctuation of the energy barriers for the formation of different crystal facets during the layer-by-layer growth of the NW tip. The energy barrier differences between these crystal facets were quantified from the surface area ratios as a function of supersaturation. On the basis of the experimental observation and kinetics analysis, we argue that at appropriate deposition conditions exposure of the crystal facets at NW growth front is not merely determined by the surface energy. Instead, the NW may choose to expose the facets with minimal formation energy barrier, which can be determined by the Ehrlich-Schwoebel barrier variation. This empirical law for the NW tip facet formation was in analogy to the Ostwald-Lussac law of phase transformation, which brings a new insight toward nanostructure design and controlled synthesis.

Crystal engineering of ibuprofen compounds: From molecule to crystal structure to morphology prediction by computational simulation and experimental study

NASA Astrophysics Data System (ADS)

Zhang, Min; Liang, Zuozhong; Wu, Fei; Chen, Jian-Feng; Xue, Chunyu; Zhao, Hong

2017-06-01

We selected the crystal structures of ibuprofen with seven common space groups (Cc, P21/c, P212121, P21, Pbca, Pna21, and Pbcn), which was generated from ibuprofen molecule by molecular simulation. The predicted crystal structures of ibuprofen with space group P21/c has the lowest total energy and the largest density, which is nearly indistinguishable with experimental result. In addition, the XRD patterns for predicted crystal structure are highly consistent with recrystallization from solvent of ibuprofen. That indicates that the simulation can accurately predict the crystal structure of ibuprofen from the molecule. Furthermore, based on this crystal structure, we predicted the crystal habit in vacuum using the attachment energy (AE) method and considered solvent effects in a systematic way using the modified attachment energy (MAE) model. The simulation can accurately construct a complete process from molecule to crystal structure to morphology prediction. Experimentally, we observed crystal morphologies in four different polarity solvents compounds (ethanol, acetonitrile, ethyl acetate, and toluene). We found that the aspect ratio decreases of crystal habits in this ibuprofen system were found to vary with increasing solvent relative polarity. Besides, the modified crystal morphologies are in good agreement with the observed experimental morphologies. Finally, this work may guide computer-aided design of the desirable crystal morphology.

Theoretical and experimental morphologies of 4-aminobenzophenone (ABP) crystals

NASA Astrophysics Data System (ADS)

Wang, Qingwu; Sheen, D. B.; Shepherd, E. E. A.; Sherwood, J. N.; Simpson, G. S.; Hammond, R. B.

1997-11-01

The lattice energy (Elatt), slice energies (Eslice) and attachment energies (Eatt) of the different habit faces of ABP crystals have been calculated using the computer program HABIT. On the basis of the attachment energies of different crystal faces, the morphology was defined as {1 0 0}, {0 0 1}, {1 1 0}, {11bar0} and {1 01bar}. To confirm this theoretical prediction, we have grown ABP films and ABP crystals from the vapour phase. In both cases, the morphologically most important face was defined as {1 0 0} face using X-ray diffraction techniques. The remaining faces of the vapour-grown crystals were defined using a projection method, while the crystallites in the films were morphologically analysed by means of atomic force microscopy (AFM). The experimental morphologies are basically in agreement with the computation. Deviations from the equilibrium morphology can be ascribed to departure from equilibrium conditions during growth. For completeness, the results are compared with those for crystals grown from solutions for which deviations in morphology from the theoretical predictions can be ascribed to interaction between the crystal faces and solvent molecules.

Mineral Biomarkers in Martian Meteorite Allan Hills 84001?

NASA Technical Reports Server (NTRS)

Thomas-Keprta, K. L.; Bazylinski, D. A.; Wentworth, S. J.; McKay, D. S.; Golden, D. C.; Gibson, E. K., Jr.; Romanek, C. S.

1998-01-01

The occurrence of fine-grained magnetite in the Fe-rich rims surrounding carbonate globules in the martian meteorite ALH84001, originally described in , have been proposed as fossil remains of primitive martian organisms. Here we report observations on size and shape distributions of magnetites from ALH84001 and compare them to biogenic and inorganic magnetite crystals of terrestrial origin. While some magnetite morphology is not unequivocally diagnostic for its biogenicity, such as cubodial forms of magnetite, which are common in inorganically formed magnetites, other morphologies of magnetite (parallel-epiped or elongated prismatic and arrowhead forms) are more likely signatures of biogenic activity. Some ALH 84001 magnetite particles described below have unique morphology and length-to-width ratios that are indistinguishable from a variety of terrestrial biogenic magnetite and distinct from all known inorganic forms of magnetite.

A molecular dynamics simulation of solvent effects on the crystal morphology of HMX.

PubMed

Duan, Xiaohui; Wei, Chunxue; Liu, Yonggang; Pei, Chonghua

2010-02-15

The solvent has a large effect on the crystal morphology of the organic explosive compound octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX, C(4)H(8)N(8)O(8)). The attachment energy calculations predict a growth morphology in vacuum dominated by (020), (011), (102 ), (111 ) and (100) crystal forms. Molecular dynamics simulations are performed for these crystal faces of HMX in contact with acetone solvent. A corrected attachment energy model, accounting for the surface chemistry and the associated topography (step structure) of the habit crystal plane, is applied to predict the morphological importance of a crystal surface in solvent. From the solvent-effected attachment energy calculations it follows that the (100) face becomes morphologically more important compared with that in vacuum, while the (020) and (102 ) are not visible at all. This agrees well with the observed experimental HMX morphology grown from the acetone solution.

Crystal morphology optimization of thiamine hydrochloride in solvent system: Experimental and molecular dynamics simulation studies

NASA Astrophysics Data System (ADS)

Yang, Yang; Han, Dandan; Du, Shichao; Wu, Songgu; Gong, Junbo

2018-01-01

Thiamine hydrochloride (THCL) was produced in methanol accompanied with agglomeration in industry, the plate like morphology of THCL in methanol was not deserve to have a good quality. Selecting a suitable solvent should be considered because solvent could be one of the essential factors to impact morphology. Methanol and methanol/ethyl acetate solvent (0.2 vol fraction of methanol) was selected as the solvent system in reactive crystallization of THCL. The experiment results show the THCL crystal morphology in methanol/ethyl acetate solvent system was granular and more regular than that in methanol. In order to explicate the different crystal morphology in different solvents, molecular dynamics (MD) simulation was introduced to simulate crystal morphology in different solvents. The attachment energy (AE) model was employed to investigate the morphology of THCL under vacuum conditions, methanol and methanol/ethyl acetate solvent conditions, respectively. The simulation crystal morphology was in a good agreement with that of experimented. The particle of THCL in methanol/ethyl acetate solvent has less tendency to agglomeration, and then it is favorable to the downstream process, such as filtration, storage and transportation.

3D visualization of additive occlusion and tunable full-spectrum fluorescence in calcite

PubMed Central

Green, David C.; Ihli, Johannes; Thornton, Paul D.; Holden, Mark A.; Marzec, Bartosz; Kim, Yi-Yeoun; Kulak, Alex N.; Levenstein, Mark A.; Tang, Chiu; Lynch, Christophe; Webb, Stephen E. D.; Tynan, Christopher J.; Meldrum, Fiona C.

2016-01-01

From biomineralization to synthesis, organic additives provide an effective means of controlling crystallization processes. There is growing evidence that these additives are often occluded within the crystal lattice. This promises an elegant means of creating nanocomposites and tuning physical properties. Here we use the incorporation of sulfonated fluorescent dyes to gain new understanding of additive occlusion in calcite (CaCO3), and to link morphological changes to occlusion mechanisms. We demonstrate that these additives are incorporated within specific zones, as defined by the growth conditions, and show how occlusion can govern changes in crystal shape. Fluorescence spectroscopy and lifetime imaging microscopy also show that the dyes experience unique local environments within different zones. Our strategy is then extended to simultaneously incorporate mixtures of dyes, whose fluorescence cascade creates calcite nanoparticles that fluoresce white. This offers a simple strategy for generating biocompatible and stable fluorescent nanoparticles whose output can be tuned as required. PMID:27857076

Single-crystalline chromium silicide nanowires and their physical properties.

PubMed

Hsu, Han-Fu; Tsai, Ping-Chen; Lu, Kuo-Chang

2015-01-01

In this work, chromium disilicide nanowires were synthesized by chemical vapor deposition (CVD) processes on Si (100) substrates with hydrous chromium chloride (CrCl3 · 6H2O) as precursors. Processing parameters, including the temperature of Si (100) substrates and precursors, the gas flow rate, the heating time, and the different flow gas of reactions were varied and studied; additionally, the physical properties of the chromium disilicide nanowires were measured. It was found that single-crystal CrSi2 nanowires with a unique morphology were grown at 700°C, while single-crystal Cr5Si3 nanowires were grown at 750°C in reducing gas atmosphere. The crystal structure and growth direction were identified, and the growth mechanism was proposed as well. This study with magnetism, photoluminescence, and field emission measurements demonstrates that CrSi2 nanowires are attractive choices for future applications in magnetic storage, photovoltaic, and field emitters.

Phase conversion from hexagonal CuS(y)Se(1-y) to cubic Cu(2-x)S(y)Se(1-y): composition variation, morphology evolution, optical tuning, and solar cell applications.

PubMed

Xu, Jun; Yang, Xia; Yang, Qingdan; Zhang, Wenjun; Lee, Chun-Sing

2014-09-24

In this work, we report a simple and low-temperature approach for the controllable synthesis of ternary Cu-S-Se alloys featuring tunable crystal structures, compositions, morphologies, and optical properties. Hexagonal CuS(y)Se(1-y) nanoplates and face centered cubic (fcc) Cu(2-x)S(y)Se(1-y) single-crystal-like stacked nanoplate assemblies are synthesized, and their phase conversion mechanism is well investigated. It is found that both copper content and chalcogen composition (S/Se atomic ratio) of the Cu-S-Se alloys are tunable during the phase conversion process. Formation of the unique single-crystal-like stacked nanoplate assemblies is resulted from oriented stacking coupled with the Ostwald ripening effect. Remarkably, optical tuning for continuous red shifts of both the band-gap absorption and the near-infrared localized surface plasmon resonance are achieved. Furthermore, the novel Cu-S-Se alloys are utilized for the first time as highly efficient counter electrodes (CEs) in quantum dot sensitized solar cells (QDSSCs), showing outstanding electrocatalytic activity for polysulfide electrolyte regeneration and yielding a 135% enhancement in power conversion efficiency (PCE) as compared to the noble metal Pt counter electrode.

Top-seeded solution growth and morphology change of RbTiOPO4:Ta single crystal

NASA Astrophysics Data System (ADS)

Li, Ziqing; Chen, Yang; Zhu, Pengfei; Ji, Nianjing; Duan, Xiulan; Jiang, Huaidong

2018-04-01

The RbTiOPO4:Ta single crystal with dimensions of 4 mm × 31 mm × 18 mm was successfully grown by Top Seeded Solution Growth Technique. It is concluded that the doping Ta element can strongly influence the growth and morphology of the RbTiOPO4 crystal. The evident morphology change of RbTiOPO4:Ta crystal with respect to RbTiOPO4 crystal has been observed and the (1 0 0) crystal face was more developed than any other crystal faces. The possible reasons of the morphology change were analyzed through experimental and theoretical methods. Several methods were tried to increase crystallographic a direction dimension of RbTiOPO4:Ta crystals. Finally, the RbTiOPO4:Ta single crystal with crystallographic a direction dimension up to 6 mm was obtained by using thicker seed crystal. This way makes it possible to get isometric RbTiOPO4:Ta crystals, which is beneficial for nonlinear optical applications due to larger area in x-y plane.

Optimization of crystallization conditions for biological macromolecules.

PubMed

McPherson, Alexander; Cudney, Bob

2014-11-01

For the successful X-ray structure determination of macromolecules, it is first necessary to identify, usually by matrix screening, conditions that yield some sort of crystals. Initial crystals are frequently microcrystals or clusters, and often have unfavorable morphologies or yield poor diffraction intensities. It is therefore generally necessary to improve upon these initial conditions in order to obtain better crystals of sufficient quality for X-ray data collection. Even when the initial samples are suitable, often marginally, refinement of conditions is recommended in order to obtain the highest quality crystals that can be grown. The quality of an X-ray structure determination is directly correlated with the size and the perfection of the crystalline samples; thus, refinement of conditions should always be a primary component of crystal growth. The improvement process is referred to as optimization, and it entails sequential, incremental changes in the chemical parameters that influence crystallization, such as pH, ionic strength and precipitant concentration, as well as physical parameters such as temperature, sample volume and overall methodology. It also includes the application of some unique procedures and approaches, and the addition of novel components such as detergents, ligands or other small molecules that may enhance nucleation or crystal development. Here, an attempt is made to provide guidance on how optimization might best be applied to crystal-growth problems, and what parameters and factors might most profitably be explored to accelerate and achieve success.

Optimization of crystallization conditions for biological macromolecules

PubMed Central

McPherson, Alexander; Cudney, Bob

2014-01-01

For the successful X-ray structure determination of macromolecules, it is first necessary to identify, usually by matrix screening, conditions that yield some sort of crystals. Initial crystals are frequently microcrystals or clusters, and often have unfavorable morphologies or yield poor diffraction intensities. It is therefore generally necessary to improve upon these initial conditions in order to obtain better crystals of sufficient quality for X-ray data collection. Even when the initial samples are suitable, often marginally, refinement of conditions is recommended in order to obtain the highest quality crystals that can be grown. The quality of an X-ray structure determination is directly correlated with the size and the perfection of the crystalline samples; thus, refinement of conditions should always be a primary component of crystal growth. The improvement process is referred to as optimization, and it entails sequential, incremental changes in the chemical parameters that influence crystallization, such as pH, ionic strength and precipitant concentration, as well as physical parameters such as temperature, sample volume and overall methodology. It also includes the application of some unique procedures and approaches, and the addition of novel components such as detergents, ligands or other small molecules that may enhance nucleation or crystal development. Here, an attempt is made to provide guidance on how optimization might best be applied to crystal-growth problems, and what parameters and factors might most profitably be explored to accelerate and achieve success. PMID:25372810

DNA-mediated engineering of multicomponent enzyme crystals

PubMed Central

Brodin, Jeffrey D.; Auyeung, Evelyn; Mirkin, Chad A.

2015-01-01

The ability to predictably control the coassembly of multiple nanoscale building blocks, especially those with disparate chemical and physical properties such as biomolecules and inorganic nanoparticles, has far-reaching implications in catalysis, sensing, and photonics, but a generalizable strategy for engineering specific contacts between these particles is an outstanding challenge. This is especially true in the case of proteins, where the types of possible interparticle interactions are numerous, diverse, and complex. Herein, we explore the concept of trading protein–protein interactions for DNA–DNA interactions to direct the assembly of two nucleic-acid–functionalized proteins with distinct surface chemistries into six unique lattices composed of catalytically active proteins, or of a combination of proteins and DNA-modified gold nanoparticles. The programmable nature of DNA–DNA interactions used in this strategy allows us to control the lattice symmetries and unit cell constants, as well as the compositions and habit, of the resulting crystals. This study provides a potentially generalizable strategy for constructing a unique class of materials that take advantage of the diverse morphologies, surface chemistries, and functionalities of proteins for assembling functional crystalline materials. PMID:25831510

Highly Luminescent 2D-Type Slab Crystals Based on a Molecular Charge-Transfer Complex as Promising Organic Light-Emitting Transistor Materials.

PubMed

Park, Sang Kyu; Kim, Jin Hong; Ohto, Tatsuhiko; Yamada, Ryo; Jones, Andrew O F; Whang, Dong Ryeol; Cho, Illhun; Oh, Sangyoon; Hong, Seung Hwa; Kwon, Ji Eon; Kim, Jong H; Olivier, Yoann; Fischer, Roland; Resel, Roland; Gierschner, Johannes; Tada, Hirokazu; Park, Soo Young

2017-09-01

A new 2:1 donor (D):acceptor (A) mixed-stacked charge-transfer (CT) cocrystal comprising isometrically structured dicyanodistyrylbenzene-based D and A molecules is designed and synthesized. Uniform 2D-type morphology is manifested by the exquisite interplay of intermolecular interactions. In addition to its appealing structural features, unique optoelectronic properties are unveiled. Exceptionally high photoluminescence quantum yield (Φ F ≈ 60%) is realized by non-negligible oscillator strength of the S 1 transition, and rigidified 2D-type structure. Moreover, this luminescent 2D-type CT crystal exhibits balanced ambipolar transport (µ h and µ e of ≈10 -4 cm 2 V -1 s -1 ). As a consequence of such unique optoelectronic characteristics, the first CT electroluminescence is demonstrated in a single active-layered organic light-emitting transistor (OLET) device. The external quantum efficiency of this OLET is as high as 1.5% to suggest a promising potential of luminescent mixed-stacked CT cocrystals in OLET applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DNA-mediated engineering of multicomponent enzyme crystals

DOE PAGES

Brodin, Jeffrey D.; Auyeung, Evelyn; Mirkin, Chad A.

2015-03-23

The ability to predictably control the coassembly of multiple nanoscale building blocks, especially those with disparate chemical and physical properties such as biomolecules and inorganic nanoparticles, has far-reaching implications in catalysis, sensing, and photonics, but a generalizable strategy for engineering specific contacts between these particles is an outstanding challenge. This is especially true in the case of proteins, where the types of possible interparticle interactions are numerous, diverse, and complex. In this paper, we explore the concept of trading protein–protein interactions for DNA–DNA interactions to direct the assembly of two nucleic-acid–functionalized proteins with distinct surface chemistries into six unique latticesmore » composed of catalytically active proteins, or of a combination of proteins and DNA-modified gold nanoparticles. The programmable nature of DNA–DNA interactions used in this strategy allows us to control the lattice symmetries and unit cell constants, as well as the compositions and habit, of the resulting crystals. Finally, this study provides a potentially generalizable strategy for constructing a unique class of materials that take advantage of the diverse morphologies, surface chemistries, and functionalities of proteins for assembling functional crystalline materials.« less

Study of Polymer Crystallization by Physical Vapor Deposition

NASA Astrophysics Data System (ADS)

Jeong, Hyuncheol

When a polymer is confined under the submicron length scale, confinement size and interfaces can significantly impact the crystallization kinetics and resulting morphology. The ability to tune the morphology of confined polymer systems is of critical importance for the development of high-performance polymer microelectronics. The wisdom from the research on confined crystallization suggests that it would be beneficial to have a processing route in which the crystallization of polymers is driven by interface and temperature effects at a nanometer-scale confinement. In practice, for atomic and small-molecular systems, physical vapor deposition (PVD) has been recognized as the most successful processing route for the precise control of the film structure at surface utilizing confinement effects. While standard PVD technologies are not generally applicable to the deposition of the chemically fragile macromolecules, the development of matrix-assisted pulsed laser evaporation (MAPLE) now enables the non-destructive PVD of high-molecular weight polymers. In this thesis work, we investigated the use of MAPLE for the precise control of the crystallization of polymer films at a molecular level. We also sought to decipher the rules governing the crystallization of confined polymers, by using MAPLE as a tool to form confined polymer systems onto substrates with a controlled temperature. We first explored the early stages of film growth and crystallization of poly(ethylene oxide) (PEO) at the substrate surface formed by MAPLE. The unique mechanism of film formation in MAPLE, the deposition of submicron-sized polymer droplets, allowed for the manifestation of confinement and substrate effects in the crystallization of MAPLE-deposited PEO. Furthermore, we also focused on the property of the amorphous PEO film formed by MAPLE, showing the dependence of polymer crystallization kinetics on the thermal history of the amorphous phase. Lastly, we probed how MAPLE processing affected the semi-crystalline structure in MAPLE-deposited polyethylene (PE) films. Depositing PE at various temperatures remarkably allowed for the tunability of the melting temperature and crystallinity of the PE films, thus manipulating the semi-crystalline structure. By comparing the structure of PE formed by different processing routes, i.e., MAPLE and melt-crystallization, we discussed how processing routes affect the development of semi-crystalline phase in polymer films.

Nacre biomineralisation: A review on the mechanisms of crystal nucleation.

PubMed

Nudelman, Fabio

2015-10-01

The wide diversity of biogenic minerals that is found in nature, each with its own morphology, mechanical properties and composition, is remarkable. In order to produce minerals that are optimally adapted for their function, biomineralisation usually occurs under strict cellular control. This control is exerted by specialised proteins and polysaccharides that assemble into a 3-dimensional organic matrix framework, forming a microenvironment where mineral deposition takes place. Molluscs are unique in that they use a striking variety of structural motifs to build their shells, each made of crystals with different morphologies and different calcium carbonate polymorphs. Much of want is known about mollusc shell formation comes from studies on the nacreous layer, or mother-of-pearl. In this review, we discuss two existing models on the nucleation of aragonite crystals during nacre formation: heteroepitaxial nucleation and mineral bridges. The heteroepitaxial nucleation model is based on the identification of chemical functional groups and aragonite-nucleating proteins at the centre of crystal imprints. It proposes that during nacre formation, each aragonite tablet nucleates independently on a nucleation site that is formed by acidic proteins and/or glycoproteins adsorbed on the chitin scaffold. The mineral bridges model is based on the identification of physical connections between the crystals in a stack, which results in a large number of crystals across several layers sharing the same crystallographic orientation. These observations suggest that there is one nucleation event per stack of tablets. Once the first crystal nucleates and reaches the top interlamellar matrix, it continues growing through pores, giving rise to the next layer of nacre, subsequently propagating into a stack. We compare both models and propose that they work in concert to control crystal nucleation in nacre. De novo crystal nucleation has to occur at least once per stack of aligned crystals, and is induced by nucleation sites. We suggest that further growth is controlled both by mineral bridges and nucleation sites. Finally, we discuss the role of amorphous calcium carbonate precursor in nacre formation. Copyright © 2015 Elsevier Ltd. All rights reserved.

Equilibria Configurations for Epitaxial Crystal Growth with Adatoms

NASA Astrophysics Data System (ADS)

Caroccia, Marco; Cristoferi, Riccardo; Dietrich, Laurent

2018-05-01

The behavior of a surface energy F}(E,u)} , where E is a set of finite perimeter and u\\in L^1(partial^{*} E, R_+) , is studied. These energies have been recently considered in the context of materials science to derive a new model in crystal growth that takes into account the effect of atoms, the freely diffusing on the surface (called adatoms), which are responsible for morphological evolution through an attachment and detachment process. Regular critical points, the existence and uniqueness of minimizers are discussed and the relaxation of F in a general setting under the L 1 convergence of sets and the vague convergence of measures is characterized. This is part of an ongoing project aimed at an analytical study of diffuse interface approximations of the associated evolution equations.

Application Of Empirical Phase Diagrams For Multidimensional Data Visualization Of High Throughput Microbatch Crystallization Experiments.

PubMed

Klijn, Marieke E; Hubbuch, Jürgen

2018-04-27

Protein phase diagrams are a tool to investigate cause and consequence of solution conditions on protein phase behavior. The effects are scored according to aggregation morphologies such as crystals or amorphous precipitates. Solution conditions affect morphological features, such as crystal size, as well as kinetic features, such as crystal growth time. Common used data visualization techniques include individual line graphs or symbols-based phase diagrams. These techniques have limitations in terms of handling large datasets, comprehensiveness or completeness. To eliminate these limitations, morphological and kinetic features obtained from crystallization images generated with high throughput microbatch experiments have been visualized with radar charts in combination with the empirical phase diagram (EPD) method. Morphological features (crystal size, shape, and number, as well as precipitate size) and kinetic features (crystal and precipitate onset and growth time) are extracted for 768 solutions with varying chicken egg white lysozyme concentration, salt type, ionic strength and pH. Image-based aggregation morphology and kinetic features were compiled into a single and easily interpretable figure, thereby showing that the EPD method can support high throughput crystallization experiments in its data amount as well as its data complexity. Copyright © 2018. Published by Elsevier Inc.

Crystal Growth and Dissolution of Methylammonium Lead Iodide Perovskite in Sequential Deposition: Correlation between Morphology Evolution and Photovoltaic Performance.

PubMed

Hsieh, Tsung-Yu; Huang, Chi-Kai; Su, Tzu-Sen; Hong, Cheng-You; Wei, Tzu-Chien

2017-03-15

Crystal morphology and structure are important for improving the organic-inorganic lead halide perovskite semiconductor property in optoelectronic, electronic, and photovoltaic devices. In particular, crystal growth and dissolution are two major phenomena in determining the morphology of methylammonium lead iodide perovskite in the sequential deposition method for fabricating a perovskite solar cell. In this report, the effect of immersion time in the second step, i.e., methlyammonium iodide immersion in the morphological, structural, optical, and photovoltaic evolution, is extensively investigated. Supported by experimental evidence, a five-staged, time-dependent evolution of the morphology of methylammonium lead iodide perovskite crystals is established and is well connected to the photovoltaic performance. This result is beneficial for engineering optimal time for methylammonium iodide immersion and converging the solar cell performance in the sequential deposition route. Meanwhile, our result suggests that large, well-faceted methylammonium lead iodide perovskite single crystal may be incubated by solution process. This offers a low cost route for synthesizing perovskite single crystal.

Surface structure of micro-diamond from ultrahigh-pressure felsic granulite, Bohemian Massif: AFM study of growth and resorption phenomena

NASA Astrophysics Data System (ADS)

Kotková, J.; Klapetek, P.

2012-04-01

Morphology, associated phases and retrogression phenomena of in-situ microdiamonds formed at extreme pressures in ultrahigh-pressure metamorphic terranes represent excellent tools to study character of diamond-forming media at great depths. Well-preserved microdiamonds discovered recently along with coesite in ultrahigh-pressure granulites of the north Bohemian crystalline basement, European Variscan belt (Kotková et al., 2011), provide unique material for such investigations. The diamonds are enclosed in major granulite phases, i.e. garnet both in felsic and intermediate lithologies and in kyanite in the felsic sample, as well as in zircon. Transmitted and reflected light microscopy of the felsic granulite sample, with peak mineral assemblage garnet, kyanite, feldspar and quartz, revealed presence of numerous, 5-20 μm-sized, perfectly preserved diamond crystals enclosed in kyanite grains. In contrast, diamonds within garnet are rare, can reach up to 30 μm in size, and graphite rims as well as polycrystalline graphite aggregates possibly representing complete diamond retrogression are common. We applied atomic force microscopy to study in-situ crystal morphology and surface microtopographic features, representing clues to the conditions and mechanisms of crystal formation as well as diamond resorption and retrogression. Both diamond enclosed in garnet and in kyanite of the felsic granulite occur exclusively as single crystals. The crystals have octahedral crystal shapes with straight but rounded edges and rounded corners. Concentric triangular terraces delimiting a flat triangular table on crystal scale and small micron-sized negatively oriented downward-pointing trigons developed on the octahedron crystal faces. Higher magnification reveals presence of discontinuous elongate hillocks oriented parallel to the octahedron face edge with positively oriented trigons. We suggest that the large-scale triangular terraces represent growth features. In contrast, the rounding of crystal edges and corners and development of negative trigons reflect diamond resorption. According to experimental works, such features are attributed to high temperature resorption, i.e. oxidation above ~ 950°C due to interaction with CO2 and/or H2O-bearing fluids (or fluid-bearing melts). Our results are consistent with presence of supercritical C-O-H fluid in the rocks in subduction zones documented from other ultrahigh-pressure metamorphic terranes, the resorption morphology corresponding rather to the interaction with water-rich than CO2-rich fluids. Kotková J., ÓBrien P., Ziemann M. (2011): Diamond and coesite discovered in Saxony-type granulite: Solution to the Variscan garnet peridotite enigma. Geology, 39, 7, 667-670.

Modelling morphology evolution during solidification of IPP in processing conditions

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

Pantani, R., E-mail: rpantani@unisa.it, E-mail: fedesantis@unisa.it, E-mail: vsperanza@unisa.it, E-mail: gtitomanlio@unisa.it; De Santis, F., E-mail: rpantani@unisa.it, E-mail: fedesantis@unisa.it, E-mail: vsperanza@unisa.it, E-mail: gtitomanlio@unisa.it; Speranza, V., E-mail: rpantani@unisa.it, E-mail: fedesantis@unisa.it, E-mail: vsperanza@unisa.it, E-mail: gtitomanlio@unisa.it

During polymer processing, crystallization takes place during or soon after flow. In most of cases, the flow field dramatically influences both the crystallization kinetics and the crystal morphology. On their turn, crystallinity and morphology affect product properties. Consequently, in the last decade, researchers tried to identify the main parameters determining crystallinity and morphology evolution during solidification In processing conditions. In this work, we present an approach to model flow-induced crystallization with the aim of predicting the morphology after processing. The approach is based on: interpretation of the FIC as the effect of molecular stretch on the thermodynamic crystallization temperature; modelingmore » the molecular stretch evolution by means of a model simple and easy to be implemented in polymer processing simulation codes; identification of the effect of flow on nucleation density and spherulites growth rate by means of simple experiments; determination of the condition under which fibers form instead of spherulites. Model predictions reproduce most of the features of final morphology observed in the samples after solidification.« less

Quantitative determination of zero-gravity effects on electronic materials processing germanium crystal growth with simultaneous interface demarcation. Experiment MA-060

NASA Technical Reports Server (NTRS)

Gatos, H. C.; Witt, A. F.

1977-01-01

Experiment MA-060 was designed to establish the crystal growth and segregation characteristics of a melt in a directional solidification configuration under near zero-g conditions. The interface demarcation technique was incorporated into the experiment since it constitutes a unique tool for recording the morphology of the growth rate throughout solidification, and for establishing an absolute time reference framework for all stages of the solidification process. An extensive study was performed of the germanium crystals grown during the Apollo-Soyuz Test Project mission. It was found that single crystal growth was achieved and that the interface demarcation functioned successfully. There was no indication that convection driven by thermal or surface tension gradients was present in the melt. The gallium segregation, in the absence of gravity, was found to be fundamentally different in its initial and its subsequent stages from that of the ground-based tests. None of the existing theoretical models for growth and segregation can account for the observed segregation behavior in the absence of gravity.

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.

Growth morphologies of wax in the presence of kinetic inhibitors

NASA Astrophysics Data System (ADS)

Tetervak, Alexander A.

Driven by the need to prevent crystallization of normal alkanes from diesel fuels in cold climates, the petroleum industry has developed additives to slow the growth of these crystals and alter their morphologies. Although the utility of these kinetic inhibitors has been well demonstrated in the field, few studies have directly monitored their effect at microscopic morphology, and the mechanisms by which they act remain poorly understood. Here we present a study of the effects of such additives on the crystallization of long-chain n-alkanes from solution. The additives change the growth morphology from plate-like crystals to a microcrystalline mesh. When we impose a front velocity by moving the sample through a temperature gradient, the mesh growth may form a macroscopic banded pattern and also exhibit a burst-crystallization behavior. In this study, we characterize these crystallization phenomena and also two growth models: a continuum model that demonstrates the essential behavior of the banded crystallization, and a simple qualitative cellular automata model that captures basics of the burst-crystallization process. Keywords: solidification; mesh crystallization; kinetic inhibitor; burst growth.

Synthesis, Crystal Structures and Properties of Ferrocenyl Bis-Amide Derivatives Yielded via the Ugi Four-Component Reaction.

PubMed

Zhao, Mei; Shao, Guang-Kui; Huang, Dan-Dan; Lv, Xue-Xin; Guo, Dian-Shun

2017-05-04

Ten ferrocenyl bis-amide derivatives were successfully synthesized via the Ugi four-component reaction by treating ferrocenecarboxylic acid with diverse aldehydes, amines, and isocyanides in methanol solution. Their chemical structures were fully characterized by IR, NMR, HR-MS, and X-ray diffraction analyses. They feature unique molecular morphologies and create a 14-membered ring motif in the centro-symmetric dimers generated in the solid state. Moreover, the electrochemical behavior of these ferrocenyl bis-amides was assessed by cyclic voltammetry.

Morphology and Kinetics of Growth of CaCO3 Precipitates Formed in Saline Water at 30°C

NASA Astrophysics Data System (ADS)

Sui, Xin; Wang, Baohui; Wu, Haiming

2018-02-01

The crystallization kinetics and morphology of CaCO3 crystals precipitated from the high salinity oilfield water were studied. The crystallization kinetics measurements show that nucleation and nuclei growth obey the first order reaction kinetics. The induction period of precipitation is extended in the high salinity solutions. Morphological studies show that impurity ions remain mostly in the solution phase instead of filling the CaCO3 crystal lattice. The morphology of CaCO3 precipitates can be changed from a smooth surface (calcite) to rough spheres (vaterite), and spindle rod bundles, or spherical, ellipsoid, flowers, plates and other shapes (aragonite).

Dilute condition corrosion behavior of glass-ceramic waste form

DOE PAGES

Crum, Jarrod V.; Neeway, James J.; Riley, Brian J.; ...

2016-08-11

Borosilicate glass-ceramics are being developed to immobilize high-level waste generated by aqueous reprocessing into a stable waste form. The corrosion behavior of this multiphase waste form is expected to be complicated by multiple phases and crystal-glass interfaces. A modified single-pass flow-through test was performed on polished monolithic coupons at a neutral pH (25 °C) and 90 °C for 33 d. The measured glass corrosion rates by micro analysis in the samples ranged from 0.019 to 0.29 g m -2 d -1 at a flow rate per surface area = 1.73 × 10 -6 m s -1. The crystal phases (oxyapatitemore » and Ca-rich powellite) corroded below quantifiable rates, by micro analysis. While, Ba-rich powellite corroded considerably in O10 sample. The corrosion rates of C1 and its replicate C20 were elevated an order of magnitude by mechanical stresses at crystal-glass interface caused by thermal expansion mismatch during cooling and unique morphology (oxyapatite clustering).« less

Dilute condition corrosion behavior of glass-ceramic waste form

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

Crum, Jarrod V.; Neeway, James J.; Riley, Brian J.

Borosilicate glass-ceramics are being developed to immobilize high-level waste generated by aqueous reprocessing into a stable waste form. The corrosion behavior of this multiphase waste form is expected to be complicated by multiple phases and crystal-glass interfaces. A modified single-pass flow-through test was performed on polished monolithic coupons at a neutral pH (25 °C) and 90 °C for 33 d. The measured glass corrosion rates by micro analysis in the samples ranged from 0.019 to 0.29 g m -2 d -1 at a flow rate per surface area = 1.73 × 10 -6 m s -1. The crystal phases (oxyapatitemore » and Ca-rich powellite) corroded below quantifiable rates, by micro analysis. While, Ba-rich powellite corroded considerably in O10 sample. The corrosion rates of C1 and its replicate C20 were elevated an order of magnitude by mechanical stresses at crystal-glass interface caused by thermal expansion mismatch during cooling and unique morphology (oxyapatite clustering).« less

Olefinic Thermoplastic Elastomer Gels: Combining Polymer Crystallization and Microphase Separation in a Selective Solvent

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

Armstrong, Daniel P.; Mineart, Kenneth P.; Lee, Byeongdu

Since selectively swollen thermoplastic elastomer gels (TPEGs) afford a wide range of beneficial properties that open new doors to developing elastomer-based technologies, in this study we examine the unique structure-property behavior of TPEGs composed of olefinic block copolymers (OBCs). Unlike their styrenic counterparts typically possessing two chemically different blocks, this class of multiblock copolymers consists of linear polyethylene hard blocks and poly(ethylene-co-α-octene) soft blocks, in which case, microphase separation between the hard and the soft blocks is accompanied by crystallization of the hard blocks. We prepare olefinic TPEGs (OTPEGs) through the incorporation of a primarily aliphatic oil that selectively swellsmore » the soft block and investigate the resultant morphological features through the use of polarized light microscopy and small-/wideangle X-ray scattering. These features are correlated with thermal and mechanical property measurements from calorimetry, rheology, and extensiometry to elucidate the roles of crystallization and self-assembly on gel characteristics and establish useful structure-property relationships.« less

Olefinic Thermoplastic Elastomer Gels: Combining Polymer Crystallization and Microphase Separation in a Selective Solvent

DOE PAGES

Armstrong, Daniel P.; Mineart, Kenneth P.; Lee, Byeongdu; ...

2016-11-01

Since selectively swollen thermoplastic elastomer gels (TPEGs) afford a wide range of beneficial properties that open new doors to developing elastomer-based technologies, in this study we examine the unique structure-property behavior of TPEGs composed of olefinic block copolymers (OBCs). Unlike their styrenic counterparts typically possessing two chemically different blocks, this class of multiblock copolymers consists of linear polyethylene hard blocks and poly(ethylene-co-α-octene) soft blocks, in which case, microphase separation between the hard and the soft blocks is accompanied by crystallization of the hard blocks. We prepare olefinic TPEGs (OTPEGs) through the incorporation of a primarily aliphatic oil that selectively swellsmore » the soft block and investigate the resultant morphological features through the use of polarized light microscopy and small-/wideangle X-ray scattering. These features are correlated with thermal and mechanical property measurements from calorimetry, rheology, and extensiometry to elucidate the roles of crystallization and self-assembly on gel characteristics and establish useful structure-property relationships.« less

Thermally induced crystallization kinetics of uncrosslinked and unfilled synthetic cis-1,4-polyisoprene rubber monitored by shear rheological tests

NASA Astrophysics Data System (ADS)

Yang, Wei; Hong, Daesun; Kim, Hyungsu; Kim, Byungsoo; Chang, Wenji V.

2016-11-01

This study demonstrates the unique capability of a shear rotational rheometer for studying the thermally induced crystallization (TIC) of uncrosslinked and unfilled cis-1,4-polyisoprene rubber (IR). At temperatures below -15°C, a crystallization phenomenon (TIC) occurred in a quasi-unstrained IR specimen. Such a distinguished phenomenon was determined from the steady and sharp changes of both tanδ and the modulus. The changing ratio of those parameters with time characterizes the crystallization rate, on which the effects of the compressive force magnitude, testing repeat, and temperature are studied. The crystallization rate was shown to depend less on the magnitude of normal force, but depended largely on the specimen's previous testing history. A specimen not fully recovered from the previous crystallized memory showed a faster rate than before. More cooling to -25°C increased the crystallization rate, but the slow crystallization helped increase the final crystallinity. The crystallization rate was further interpreted by the Avrami equation to propose the crystal structure, whose morphological feature was shown in agreement with the reported TEM and X-ray results. However, our study found a thermo-mechanically aged specimen showed a very different rheological behavior at the late stage of crystallization suggesting the crystalline metamorphosis. But this unexpected behavior turned out to be unrecoverable indicating a property failure due to material aging more plausibly. All these findings were successfully monitored by the rheometer. It is expected the well-organized rheometric measurements can sufficiently supplement some instrumental limitations of the traditional crystallization monitoring analyzers on soft materials.

Improving the diffraction of apoA-IV crystals through extreme dehydration.

PubMed

Deng, Xiaodi; Davidson, W Sean; Thompson, Thomas B

2012-01-01

Apolipoproteins are the protein component of high-density lipoproteins (HDL), which are necessary for mobilizing lipid-like molecules throughout the body. Apolipoproteins undergo self-association, especially at higher concentrations, making them difficult to crystallize. Here, the crystallization and diffraction of the core fragment of apolipoprotein A-IV (apoA-IV), consisting of residues 64-335, is presented. ApoA-IV(64-335) crystallized readily in a variety of hexagonal (P6) morphologies with similar unit-cell parameters, all containing a long axis of nearly 550 Å in length. Preliminary diffraction experiments with the different crystal morphologies all resulted in limited streaky diffraction to 3.5 Å resolution. Crystal dehydration was applied to the different morphologies with variable success and was also used as a quality indicator of crystal-growth conditions. The results show that the morphologies that withstood the most extreme dehydration conditions showed the greatest improvement in diffraction. One morphology in particular was able to withstand dehydration in 60% PEG 3350 for over 12 h, which resulted in well defined intensities to 2.7 Å resolution. These results suggest that the approach of integrating dehydration with variation in crystal-growth conditions might be a general technique to optimize diffraction. © 2012 International Union of Crystallography. All rights reserved.

Molecular basis of crystal morphology-dependent adhesion behavior of mefenamic acid during tableting.

PubMed

Waknis, Vrushali; Chu, Elza; Schlam, Roxana; Sidorenko, Alexander; Badawy, Sherif; Yin, Shawn; Narang, Ajit S

2014-01-01

The molecular basis of crystal surface adhesion leading to sticking was investigated by exploring the correlation of crystal adhesion to oxidized iron coated atomic force microscope (AFM) tips and bulk powder sticking behavior during tableting of two morphologically different crystals of a model drug, mefenamic acid (MA), to differences in their surface functional group orientation and energy. MA was recrystallized into two morphologies (plates and needles) of the same crystalline form. Crystal adhesion to oxidized iron coated AFM tips and bulk powder sticking to tablet punches was assessed using a direct compression formulation. Surface functional group orientation and energies on crystal faces were modeled using Accelrys Material Studio software. Needle-shaped morphology showed higher sticking tendency than plates despite similar particle size. This correlated with higher crystal surface adhesion of needle-shaped morphology to oxidized iron coated AFM probe tips, and greater surface energy and exposure of polar functional groups. Higher surface exposure of polar functional groups correlates with higher tendency to stick to metal surfaces and AFM tips, indicating involvement of specific polar interactions in the adhesion behavior. In addition, an AFM method is identified to prospectively assess the risk of sticking during the early stages of drug development.

A top-down approach to crystal engineering of a racemic Δ2-isoxazoline.

PubMed

Lombardo, Giuseppe M; Rescifina, Antonio; Chiacchio, Ugo; Bacchi, Alessia; Punzo, Francesco

2014-02-01

The crystal structure of racemic dimethyl (4RS,5RS)-3-(4-nitrophenyl)-4,5-dihydroisoxazole-4,5-dicarboxylate, C13H12N2O7, has been determined by single-crystal X-ray diffraction. By analysing the degree of growth of the morphologically important crystal faces, a ranking of the most relevant non-covalent interactions determining the crystal structure can be inferred. The morphological information is considered with an approach opposite to the conventional one: instead of searching inside the structure for the potential key interactions and using them to calculate the crystal habit, the observed crystal morphology is used to define the preferential lines of growth of the crystal, and then this information is interpreted by means of density functional theory (DFT) calculations. Comparison with the X-ray structure confirms the validity of the strategy, thus suggesting this top-down approach to be a useful tool for crystal engineering.

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.

Effect of pH on the morphology of kidney stones

NASA Astrophysics Data System (ADS)

Agarwal, Neelesh; Sova, Stacey; Singh, N. B.; Arnold, Brad; Choa, Fow-Sen; Cullum, Brian; Su, Ching-Hua

2016-05-01

The process for the formation of kidney stone is very complex phenomena and has some similarity to the crystal growth from a solution. It is very much dependent on the acidity pH of the fluids. This pH variation affects the content and amount of filtering residue and its morphology. In this study we have performed experiments using carbonate, oxides and urea to simulate and understand the morphologies of the residue filtered and coarsened in different conditions. We observed that different of morphologies of kidney stones can be explained on the basis of acidity and hydration conditions. At lower pH fat prism crystals are observed and as pH increases, long fat needle crystals with large aspect ratio are observed. The coarsening experiments showed further growth of crystals. The remelting experiments showed that during dissolution of kidney stones the joining material breaks first leaving the large faceted crystals undissolved when attempts are made to dissolve into small crystallites. However, the morphology did not change. It was also observed that impurities such as magnesium oxide (MgO) affect the morphology significantly.

Parallel computational and experimental studies of the morphological modification of calcium carbonate by cobalt

NASA Astrophysics Data System (ADS)

Braybrook, A. L.; Heywood, B. R.; Jackson, R. A.; Pitt, K.

2002-08-01

Crystal growth can be controlled by the incorporation of dopant ions into the lattice and yet the question of how such substituents affect the morphology has not been addressed. This paper describes the forms of calcite (CaCO 3) which arise when the growth assay is doped with cobalt. Distinct and specific morphological changes are observed; the calcite crystals adopt a morphology which is dominated by the {01.1} family of faces. These experimental studies paralleled the development of computational methods for the analysis of crystal habit as a function of dopant concentration. In this case, the predicted defect morphology also argued for the dominance of the (01.1) face in the growth form. The appearance of this face was related to the preferential segregation of the dopant ions to the crystal surface. This study confirms the evolution of a robust computational model for the analysis of calcite growth forms under a range of environmental conditions and presages the use of such tools for the predictive development of crystal morphologies in those applications where chemico-physical functionality is linked closely to a specific crystallographic form.

The osteopontin-controlled switching of calcium oxalate monohydrate morphologies in artificial urine provides insights into the formation of papillary kidney stones.

PubMed

Langdon, Aaron; Grohe, Bernd

2016-10-01

The protein osteopontin (OPN) plays an important role in preventing the formation of calcium oxalate monohydrate (COM) kidney stones. To gain insight into these mechanisms, crystallization was induced by addition of human kidney OPN to artificial urine (ionic strength comparable to urine; without citrate), and the OPN-COM interaction studied using a combination of scanning electron (SEM) and confocal microscopy. By SEM, we found that increasing OPN concentrations formed large monoclinic penetration twins (no protein added) and, at higher concentrations (1-, 2μg/ml OPN), super and hyper twins with crystal habits not found in previous studies. For instance, the hyper twins indicate well-facetted gearwheel-like habits with "teeth" developed in all crystallographic directions. At OPN concentrations ≥2μg/ml, a switching to small dumbbell-shaped COM habits with fine-textured surfaces occurred. Confocal microscopy of these dumbbells indicates protein incorporation in almost the entire crystal structure (in contrast to facetted COM), proposing a threshold concentration of ∼2μg/ml OPN for the facetted to the non-facetted habit transformation. Both the gearwheel-like and the dumbbell-shaped habit are again found side-by-side (presumably triggered by OPN concentration gradients within the sample) in in-vitro formed conglomerates, which resemble cross-sections of papillary kidney stones. The abrupt transformation from facetted to non-facetted habits and the unique compliance of the two in-vitro formed habits with the two main morphologies found in papillary kidney stones propose that OPN is a main effector in direct stone-forming processes. Moreover, stone structures which exhibit these two morphologies side-by-side might serve as a novel indicator for OPN concentrations surrounding those structures. Copyright © 2016 Elsevier B.V. All rights reserved.

Solvent selection for explaining the morphology of nitroguanidine crystal by molecular dynamics simulation

NASA Astrophysics Data System (ADS)

Song, Liang; Chen, Lizhen; Cao, Duanlin; Wang, Jianlong

2018-02-01

In this article, a method was performed to predict the morphology of needle-shaped crystals by analyzing the growth mechanisms for the various crystal faces. As an example, the crystal morphology of a nitroguanidine (NQ) was investigated via molecular dynamics simulations. The modified attachment energy (MEA) model was constructed by introducing surface chemistry terms and the relevant morphology of the habit crystal faces. The results indicate that the growth morphology of NQ in vacuum is dominated by {2 2 0}, {0 4 0}, {1 1 1}, {1 3 1} and {3 1 1} faces. The {2 2 0} and {0 4 0} faces are parallel to the elongation direction of the crystal, while the other faces are at the needle tips direction. The atoms or atomic groups exposed in crystal surface were used to analyze the relationship between structure and morphology. Compared to the surrounding faces, the needle tip faces have a large number of polar atoms or atomic groups. The needle tip faces have a high electronegativity on N, O atoms via molecular electrostatic potential (ESP) analysis. Furthermore, the protic solvent was used to reduce the attachment energy of the tip surfaces for achieving the purpose of inhibiting the growth of needle tips. Gamma-butyrolactone as the selected solvent inhibited effectively the growth of the needle tip faces. The predicted result is serviceable for the formation design.

Morphological, spectroscopic and thermal studies of samarium chloride coordinated single crystal grown by slow evaporation method

NASA Astrophysics Data System (ADS)

Slathia, Goldy; Raina, Bindu; Gupta, Rashmi; Bamzai, K. K.

2018-05-01

The synthesis of samarium chloride coordinated single crystal was carried out at room temperature by slow evaporation method. The crystal possesses a well defined hexagonal morphology with six symmetrically equivalent growth sectors separated by growth boundaries. The theoretical morphology has been established by structural approach using Bravaise-Friedele-Donnaye-Harker (BFDH) law. Fourier transform infra red spectroscopy was carried in order to study the geometry and structure of the crystal. The detailed thermogravimetric analysis elucidates the thermal stability of the complex.

Morphological analysis of GeTe in inline phase change switches

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

King, Matthew R., E-mail: matthew.king2@ngc.com; Department of Materials Science and Engineering, North Carolina State University, Raleigh, North Carolina 27695; El-Hinnawy, Nabil

2015-09-07

Crystallization and amorphization phenomena in indirectly heated phase change material-based devices were investigated. Scanning transmission electron microscopy was utilized to explore GeTe phase transition processes in the context of the unique inline phase change switch (IPCS) architecture. A monolithically integrated thin film heating element successfully converted GeTe to ON and OFF states. Device cycling prompted the formation of an active area which sustains the majority of structural changes during pulsing. A transition region on both sides of the active area consisting of polycrystalline GeTe and small nuclei (<15 nm) in an amorphous matrix was also observed. The switching mechanism, determined bymore » variations in pulsing parameters, was shown to be predominantly growth-driven. A preliminary model for crystallization and amorphization in IPCS devices is presented.« less

Controlling the Morphology of Side Chain Liquid Crystalline Block Copolymer Thin Films through Variations in Liquid Crystalline Content

PubMed Central

Verploegen, Eric; Zhang, Tejia; Jung, Yeon Sik; Ross, Caroline; Hammond, Paula T.

2009-01-01

In this paper we describe methods for manipulating the morphology of side-chain liquid crystalline block copolymers through variations in the liquid crystalline content. By systematically controlling the covalent attachment of side chain liquid crystals to a block copolymer (BCP) backbone, the morphology of both the liquid crystalline (LC) mesophase and the phase segregated BCP microstructures can be precisely manipulated. Increases in LC functionalization lead to stronger preferences for the anchoring of the LC mesophase relative to the substrate and the inter-material dividing surface (IMDS). By manipulating the strength of these interactions the arrangement and ordering of the ultrathin film block copolymer nanostructures can be controlled, yielding a range of morphologies that includes perpendicular and parallel cylinders, as well as both perpendicular and parallel lamellae. Additionally, we demonstrate the utilization of selective etching to create a nanoporous liquid crystalline polymer thin film. The unique control over the orientation and order of the self-assembled morphologies with respect to the substrate will allow for the custom design of thin films for specific nano-patterning applications without manipulation of the surface chemistry or the application of external fields. PMID:18763835

Controlling the morphology of side chain liquid crystalline block copolymer thin films through variations in liquid crystalline content.

PubMed

Verploegen, Eric; Zhang, Tejia; Jung, Yeon Sik; Ross, Caroline; Hammond, Paula T

2008-10-01

In this paper, we describe methods for manipulating the morphology of side-chain liquid crystalline block copolymers through variations in the liquid crystalline content. By systematically controlling the covalent attachment of side chain liquid crystals to a block copolymer (BCP) backbone, the morphology of both the liquid crystalline (LC) mesophase and the phase-segregated BCP microstructures can be precisely manipulated. Increases in LC functionalization lead to stronger preferences for the anchoring of the LC mesophase relative to the substrate and the intermaterial dividing surface. By manipulating the strength of these interactions, the arrangement and ordering of the ultrathin film block copolymer nanostructures can be controlled, yielding a range of morphologies that includes perpendicular and parallel cylinders, as well as both perpendicular and parallel lamellae. Additionally, we demonstrate the utilization of selective etching to create a nanoporous liquid crystalline polymer thin film. The unique control over the orientation and order of the self-assembled morphologies with respect to the substrate will allow for the custom design of thin films for specific nanopatterning applications without manipulation of the surface chemistry or the application of external fields.

Morphology and solubility of multiple crystal forms of Taka-amylase A

NASA Astrophysics Data System (ADS)

Ninomiya, Kumiko; Yamamoto, Tenyu; Oheda, Tadashi; Sato, Kiyotaka; Sazaki, Gen; Matsuura, Yoshiki

2001-01-01

An α-amylase originating from a mold Aspergillus oryzae, Taka-amylase A (Mr of 52 kDa, pI of 3.8), has been purified to an electrophoretically single band grade. Crystallization behaviors were investigated using ammonium sulfate and polyethleneglycol 8000 as precipitants. The variations in the morphology of the crystals obtained with changing crystallization parameters are described. Five apparently different crystal forms were obtained, and their morphology and crystallographic data have been determined. Solubility values of four typical forms were measured using a Michelson-type two-beam interferometer. The results of these experiments showed that this protein can be a potentially interesting and useful model for crystal growth study with a gram-amount availability of pure protein sample.

Factors affecting the morphology of isocitrate lyase crystals

NASA Technical Reports Server (NTRS)

Demattei, Robert C.; Feigelson, Robert S.; Weber, Patricia C.

1992-01-01

Isocitrate lyase crystals have been grown by the hanging drop vapor equilibration method in both 1-g and microgravity and by vapor equilibrium in small capillaries. The crystal morphologies obtained have ranged from dendritic to 'octagonal' prisms. Theoretical evaporation models have been applied to these growth regimes. The results of these analyses along with other experimental results, indicate the factors which must be controlled to produce good growth morphologies.

Mesoscale phase distribution in single particles of LiFePO4 following lithium deintercalation

PubMed Central

Boesenberg, Ulrike; Meirer, Florian; Liu, Yijin; Shukla, Alpesh K.; Dell’Anna, Rossana; Tyliszczak, Tolek; Chen, Guoying; Andrews, Joy C.; Richardson, Thomas J.; Kostecki, Robert; Cabana, Jordi

2013-01-01

The chemical phase distribution in hydrothermally grown micrometric single crystals LiFePO4 following partial chemical delithiation was investigated. Full field and scanning X-ray microscopy were combined with X-ray absorption spectroscopy at the Fe K- and O K-edges, respectively, to produce maps with high chemical and spatial resolution. The resulting information was compared to morphological insight into the mechanics of the transformation by scanning transmission electron microscopy. This study revealed the interplay at the mesocale between microstructure and phase distribution during the redox process, as morphological defects were found to kinetically determine the progress of the reaction. Lithium deintercalation was also found to induce severe mechanical damage in the crystals, presumably due to the lattice mismatch between LiFePO4 and FePO4. Our results lead to the conclusion that rational design of intercalation-based electrode materials, such as LiFePO4, with optimized utilization and life requires the tailoring of particles that minimize kinetic barriers and mechanical strain. Coupling TXM-XANES with TEM can provide unique insight into the behavior of electrode materials during operation, at scales spanning from nanoparticles to ensembles and complex architectures. PMID:23745016

Solvent effects on the crystal growth structure and morphology of the pharmaceutical dirithromycin

NASA Astrophysics Data System (ADS)

Wang, Yuan; Liang, Zuozhong

2017-12-01

Solvent effects on the crystal structure and morphology of pharmaceutical dirithromycin molecules were systematically investigated using both experimental crystallization and theoretical simulation. Dirithromycin is one of the new generation of macrolide antibiotics with two polymorphic forms (Form I and Form II) and many solvate forms. Herein, six solvates of the dirithromycin, including acetonitrile, acetonitrile/water, acetone, 1-propanol, N,N-dimethylformamide (DMF) and cyclohexane, were studied. Experimentally, we crystallized the dirithromycin molecules in different solvents by the solvent evaporating method and measured the crystal structures with the X-ray diffraction (XRD). We compared these crystal structures of dirithromycin solvates and analyzed the solvent property-determined structure evolution. The solvents have a strong interaction with the dirithromycin molecule due to the formation of inter-molecular interactions (such as the hydrogen bonding and close contacts (sum of vdW radii)). Theoretically, we calculated the ideal crystal habit based on the solvated structures with the attachment growth (AE) model. The predicted morphologies and aspect ratios of dirithromycin solvates agree well with the experimental results. This work could be helpful to better understand the structure and morphology evolution of solvates controlled by solvents and guide the crystallization of active pharmaceutical ingredients in the pharmaceutical industry.

A study of the solvent effect on the morphology of RDX crystal by molecular modeling method.

PubMed

Chen, Gang; Xia, Mingzhu; Lei, Wu; Wang, Fengyun; Gong, Xuedong

2013-12-01

Molecular dynamics simulations have been performed to investigate the effect of acetone solvent on the crystal morphology of RDX. The results show that the growth morphology of RDX crystal in vacuum is dominated by the (111), (020), (200), (002), and (210) faces using the BFDH laws, and (111) face is morphologically the most important. The analysis of surface structures of RDX crystal indicates that (020) face is non-polar, while (210), (111), (002), and (200) faces are polar among which (210) face has the strongest polarity. The interaction between acetone solvent and each RDX crystal face is different, and the order of binding energy on these surfaces is (210) > (111) > (002) > (200) > (020). The analysis of interactions among RDX and acetone molecules reveal that the system nonbond interactions are primary strong van der Waals and electrostatic interactions containing π-hole interactions, the weak hydrogen bond interactions are also existent. The effect of acetone on the growth of RDX crystal can be evaluated by comparing the binding energies of RDX crystalline faces. It can be predicted that compared to that in vacuum, in the process of RDX crystallization from acetone, the morphological importance of (210) face is increased more and (111) face is not the most important among RDX polar surfaces, while the non-polar (020) face probably disappears. The experimentally obtained RDX morphology grown from acetone is in agreement with the theoretical prediction.

A mimic study on effects of fluoride on tooth enamel structures

NASA Astrophysics Data System (ADS)

Ma, Guobin; Wang, Mu; Liu, Xiang Yang

2010-03-01

Tooth enamel is the hardest tissue in human body, and this superior mechanical property is contributed by its unique microstructures, i.e., oriented growth of rod-like apatite crystals into basic structural units called the prisms Fluoride (F^-) has been recognized to have significant effects on the physical and chemical properties of tooth enamel. However, the role of F^- on microstructures of apatite crystals is not well understood yet. Here we report a detailed investigation on the topic. Mimic in vitro growth of tooth enamel structures is performed at the biophysical conditions in simulated body fluids, using belt-like hydroxyapatite crystals as substrates It shows that F^- on the order of 0.1 mM will dramatically change the morphology of the grown crystals from irregular slabs to nano-needles, and the needles are aligned along the substrate with an average misorientation of ˜12 . Branched growth of bundles of nano-needles occurs with further increase of F^-, and finally, growth of highly porous structures as well as microspheres takes place when the F^- concentration exceeds 5 mM. In comparison with real tooth enamel structures, the relationship between enamel microstructures and tooth caries as well as fluorosis is discussed.

{112} Polar surfaces of copper(indium,gallium)selenide: Properties and effects on crystal growth

NASA Astrophysics Data System (ADS)

Liao, Dongxiang

Cu(In,Ga)Se2 (GIGS) are promising materials for thin film photovoltaic applications. This work studies the epitaxial growth of CIGS single crystal films on GaAs substrates of various orientations and characterizes the properties of the thin films. A surprising finding is the strong tendency of film surfaces to facet to {112} planes. The work attempted to establish the connections between the film morphology, the surface energies, the surface chemical compositions, and the reconstruction of polar surfaces. Using angle-resolved photoelectron emission spectroscopy, I found that there is a severe Cu depletion at the first 1-2 layer of the free surface of CuInSe2 and the surface is semiconducting. The results strongly support the model of a reconstructed non-stoichiometric polar surface and exclude the previously believed existence of a bulk second phase on the CIS surface. Unique features of the film morphology suggest that the properties and structure of the polar surfaces have great effects on the growth of the crystals, and probably on the incorporation of the large amount of point defects. Measured chemical composition profiles indicate that the Cu depletion observed on free CIGS surface remains at the CIGS/CdS heterojunction interface and Cd is incorporated into the surface of CIGS. It is proposed that this non-stoichiometric composition leads to charge imbalance at the interface and causes the type-inversion of the CIGS surface, which are favorable for the device performance.

On the development of two characteristically different crystal morphology in SiO(2)-MgO-Al (2)O (3)-K (2)O-B (2)O (3)-F glass-ceramic system.

PubMed

Roy, Shibayan; Basu, Bikramjit

2009-01-01

The present work demonstrates how crystals with two different characteristic morphologies can be formed in SiO(2)-MgO-Al(2)O(3)-K(2)O-B(2)O(3)-F glass-ceramic system by adopting two sets of heat treatment experiments. In our study, single stage heat treatment experiments were performed at 1,000 degrees C for varying holding time of 8-24 h with 4 h time interval and as a function of temperature in the range of 1,000-1,120 degrees C with 40 degrees C temperature interval. The constant heating rate of 10 degrees C/min was employed for both sets of experiments. The microstructural changes were investigated using Fourier transformed infrared spectroscopy (FT-IR), SEM-EDS and XRD. For temperature variation batches, the microstructure is characterized by interlocked, randomly oriented mica plates ('house-of-cards' morphology). An important and new observation of complex crystal morphology is made in the samples heat treated at 1,000 degrees C for varying holding times. Such morphology appears to be the results of composite spherulitic-dendritic like growth of mica rods radiating from a central nucleus. The possible mechanism for such characteristic crystal growth morphology is discussed with reference to a nucleation-growth kinetics based model. The activation energy for crystal nucleation and Avrami index are computed to be 388 kJ/mol and 1.3 respectively, assuming Johnson-Mehl-Avrami model of crystallization. Another important result is that a maximum of around 70% of spherulitic-dendritic like crystal morphology can be obtained after heat treatment at 1,000 degrees C for 24 h, while a lower amount (approximately 58%) of interlocked plate like mica crystals is formed after heat treatment at 1,040 degrees C for 4 h.

Polyethylene nano crystalsomes formed at a curved liquid/liquid interface.

PubMed

Wang, Wenda; Staub, Mark C; Zhou, Tian; Smith, Derrick M; Qi, Hao; Laird, Eric D; Cheng, Shan; Li, Christopher Y

2017-12-21

Crystallization is incommensurate with nanoscale curved space due to the lack of three dimensional translational symmetry of the latter. Herein, we report the formation of single-crystal-like, nanosized polyethylene (PE) capsules using a miniemulsion solution crystallization method. The miniemulsion was formed at elevated temperatures using PE organic solution as the oil phase and sodium dodecyl sulfate as the surfactant. Subsequently, cooling the system stepwisely for controlled crystallization led to the formation of hollow, nanosized PE crystalline capsules, which are named as crystalsomes since they mimic the classical self-assembled structures such as liposome, polymersome and colloidosome. We show that the formation of the nanosized PE crystalsomes is driven by controlled crystallization at the curved liquid/liquid interface of the miniemulson droplet. The morphology, structure and mechanical properties of the PE crystalsomes were characterized using scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and atomic force spectroscopy. Electron diffraction showed the single-crystal-like nature of the crystalsomes. The incommensurateness between the nanocurved interface and the crystalline packing led to reduced crystallinity and crystallite size of the PE crystalsome, as observed from the X-ray diffraction measurements. Moreover, directly quenching the emulsion below the spinodal line led to the formation of hierarchical porous PE crystalsomes due to the coupling of the PE crystallization and liquid/liquid phase separation. We anticipate that this unique crystalsome represents a new type of nanostructure that might be used as nanodrug carriers and ultrasound contrast agents.

“Skin-Core-Skin” Structure of Polymer Crystallization Investigated by Multiscale Simulation

PubMed Central

Ruan, Chunlei

2018-01-01

“Skin-core-skin” structure is a typical crystal morphology in injection products. Previous numerical works have rarely focused on crystal evolution; rather, they have mostly been based on the prediction of temperature distribution or crystallization kinetics. The aim of this work was to achieve the “skin-core-skin” structure and investigate the role of external flow and temperature fields on crystal morphology. Therefore, the multiscale algorithm was extended to the simulation of polymer crystallization in a pipe flow. The multiscale algorithm contains two parts: a collocated finite volume method at the macroscopic level and a morphological Monte Carlo method at the microscopic level. The SIMPLE (semi-implicit method for pressure linked equations) algorithm was used to calculate the polymeric model at the macroscopic level, while the Monte Carlo method with stochastic birth-growth process of spherulites and shish-kebabs was used at the microscopic level. Results show that our algorithm is valid to predict “skin-core-skin” structure, and the initial melt temperature and the maximum velocity of melt at the inlet mainly affects the morphology of shish-kebabs. PMID:29659516

Optimization and characterization of bulk hexagonal boron nitride single crystals grown by the nickel-chromium flux method

NASA Astrophysics Data System (ADS)

Hoffman, Tim

Hexagonal boron nitride (hBN) is a wide bandgap III-V semiconductor that has seen new interest due to the development of other III-V LED devices and the advent of graphene and other 2-D materials. For device applications, high quality, low defect density materials are needed. Several applications for hBN crystals are being investigated, including as a neutron detector and interference-less infrared-absorbing material. Isotopically enriched crystals were utilized for enhanced propagation of phonon modes. These applications exploit the unique physical, electronic and nanophotonics applications for bulk hBN crystals. In this study, bulk hBN crystals were grown by the flux method using a molten Ni-Cr solvent at high temperatures (1500°C) and atmospheric pressures. The effects of growth parameters, source materials, and gas environment on the crystals size, morphology and purity were established and controlled, and the reliability of the process was greatly improved. Single-crystal domains exceeding 1mm in width and 200microm in thickness were produced and transferred to handle substrates for analysis. Grain size dependence with respect to dwell temperature, cooling rate and cooling temperature were analyzed and modeled using response surface morphology. Most significantly, crystal grain width was predicted to increase linearly with dwell temperature, with single-crystal domains exceeding 2mm in at 1700°C. Isotopically enriched 10B and 11B hBN crystal were produced using a Ni-Cr-B flux method, and their properties investigated. 10B concentration was evaluated using SIMS and correlated to the shift in the Raman peak of the E2g mode. Crystals with enrichment of 99% 10B and >99% 11B were achieved, with corresponding Raman shift peaks at 1392.0 cm-1 and 1356.6 cm-1, respectively. Peak FWHM also decreased as isotopic enrichment approached 100%, with widths as low as 3.5 cm-1 achieved, compared to 8.0 cm-1 for natural abundance samples. Defect selective etching was performed using a molten NaOH-KOH etchant at 425°C-525°C, to quantify the quality of the crystals. Three etch pit shapes were identified and etch pit width was investigated as a function of temperature. Etch pit density and etch pit activation energy was estimated at 5x107 cm-2 and 60 kJ/mol, respectively. Screw and mixed-type dislocations were identified using diffraction-contrast TEM imaging.

A systematic examination of the morphogenesis of calcium carbonate in the presence of a double-hydrophilic block copolymer.

PubMed

Cölfen, H; Qi, L

2001-01-05

In this paper, a systematic study of the influence of various experimental parameters on the morphology and size of CaCO3 crystals after room-temperature crystallization from water in the presence of poly(ethylene glycol)-block-poly(methacrylic acid) (PEG-b-PMAA) is presented. The pH of the solution, the block copolymer concentration, and the ratio [polymer]/[CaCO3] turned out to be important parameters for the morphogenesis of CaCO3, whereas a moderate increase of the ionic strength (0.016 M) had no influence. Depending on the experimental conditions, the crystal morphologies can be tuned from calcite rhombohedra via rods, ellipsoids or dumbbells to spheres. A morphology map is presented which allows the prediction of the crystal morphology from a combination of pH, and CaCO3 and polymer concentration. Morphologies reported in literature for the same system but under different crystallization conditions agree well with the predictions from the morphology map. A closer examination of the growth of polycrystalline macroscopic CaCO3 spheres by TEM and time-resolved dynamic light scattering showed that CaCO3 macrocrystals are formed from strings of aggregated amorphous nanoparticles and then recrystallize as dumbbell-shaped or spherical calcite macrocrystal.

Sedimentology, stratigraphy, and depositional environment of the Crystal Geyser Dinosaur Quarry, east-central Utah

USGS Publications Warehouse

Suarez, M.B.; Suarez, C.A.; Kirkland, J.I.; Gonzalez, Luis A.; Grandstaff, D.E.; Terry, D.O.

2007-01-01

The Crystal Geyser Dinosaur Quarry, near Green River, Utah, is located at the base of the Lower Cretaceous (Barremian) Yellow Cat Member of the Cedar Mountain Formation. The quarry preserves a nearly monospecific accumulation of a new basal therizinosauroid, Falcarius utahensis. We used field descriptions and petrographic analysis to determine the depositional environment and development of the quarry strata. Results of these analyses suggest that the quarry represents multiple episodes of bone accumulation buried by spring and overbank flood deposits. Evidence for these previously undescribed spring deposits includes calcite macroscopic structures within the quarry strata - such as pisolites and travertine fragments - and calcite micromorphologies - including radial-fibrous, feather, and scandulitic dendrite morphologies and tufa clasts. At least two episodes of bone incorporation are preserved in the quarry based on their stratigraphic position and lithologic associations. The unique depositional setting in and around the Crystal Geyser Dinosaur Quarry appears to have been favorable for the preservation of vertebrate fossils and provides insight into early Cretaceous environments in North America. Copyright ?? 2007, SEPM (Society for Sedimentary Geology).

Magnetocaloric properties of distilled gadolinium: Effects of structural inhomogeneity and hydrogen impurity

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

Burkhanov, G. S.; Kolchugina, N. B.; Chzhan, V. B.

2014-06-16

High-purity Gd prepared by distillation is a structurally inhomogeneous system consisting of needle-shaped crystals of cross section 0.5–2.5 μm with near-c-axis orientation embedded in a matrix of nanosized (30–100 nm) grains. By measuring the magnetocaloric effect (MCE) directly, we find that the MCE values differ markedly for the plate-shaped samples cut out of a distillate along and perpendicular to the crystals. The effect of small controlled amounts of impurity (hydrogen) on the properties of distilled Gd is further studied. We observe opposite trends in the MCE response to hydrogen charging with respect to the crystal's orientation within the samples and discuss mechanismsmore » interrelating the unique structural morphology with the impurity behavior. As an overall assessment, the Curie temperatures of α-GdH{sub x} solid solutions increase from 291 K up to 294 K when increasing hydrogen concentration x from 0 to 0.15. Hydrogenation is found to broaden the ferromagnetic-to-paramagnetic phase transition. Hydrogen-containing specimens demonstrate reversibility of MCE at these temperatures.« less

High T c layered ferrielectric crystals by coherent spinodal decomposition

DOE PAGES

Susner, Michael A.; Belianinov, Alex; Borisevich, Albina Y.; ...

2015-11-13

Research in the rapidly-developing field of 2D-electronic materials has thus far been focused on metallic and semiconducting materials. However, complementary dielectric materials such as non-linear dielectrics are needed to enable realistic device architectures. Candidate materials require tunable dielectric properties and pathways for heterostructure assembly. Here we report on a family of cation-deficient transition metal thiophosphates whose unique chemistry makes them a viable prospect for these applications. In these materials, naturally occurring ferrielectric heterostructures composed of centrosymmetric In 4/3P 2S 6 and ferrielectrically-active CuInP 2S 6 are realized by controllable chemical phase separation in van-der-Waals bonded single crystals. CuInP 2S 6more » by itself is a layered ferrielectric with Tc just over room-temperature which rapidly decreases with homogenous doping. Surprisingly, in our composite materials, the ferrielectric Tc of the polar CuInP 2S 6 phase increases. This effect is enabled by unique spinodal decomposition that retains the overall van-der-Waals layered morphology of the crystal, but chemically separates CuInP 2S 6 and In 4/3P 2S 6 within each layer. The average spatial periodicity of the distinct chemical phases can be finely controlled by altering the composition and/or synthesis conditions. One intriguing prospect for such layered spinodal alloys is large volume synthesis of 2D in-plane heterostructures with periodically alternating polar and non-polar phases.« less

Amorphous photonic crystals with only short-range order.

PubMed

Shi, Lei; Zhang, Yafeng; Dong, Biqin; Zhan, Tianrong; Liu, Xiaohan; Zi, Jian

2013-10-04

Distinct from conventional photonic crystals with both short- and long-range order, amorphous photonic crystals that possess only short-range order show interesting optical responses owing to their unique structural features. Amorphous photonic crystals exhibit unique light scattering and transport, which lead to a variety of interesting phenomena such as isotropic photonic bandgaps or pseudogaps, noniridescent structural colors, and light localization. Recent experimental and theoretical advances in the study of amorphous photonic crystals are summarized, focusing on their unique optical properties, artificial fabrication, bionspiration, and potential applications. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Silver nanoplates with ground or metastable structures obtained from template-free two-phase aqueous/organic synthesis

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

Zhelev, Doncho V., E-mail: dontcho.jelev@nih.gov; Zheleva, Tsvetanka S.

2014-01-28

Silver has unique electrical, catalytic, and plasmonic characteristics and has been widely sought for fabrication of nanostructures. The properties of silver nanostructures are intimately coupled to the structure of silver crystals. Two crystal structures are known for silver: the stable (ground) state cubic face centered 3C-Ag structure and the metastable hexagonal 4H-Ag structure. Recently, Chackraborty et al. [J. Phys.: Condens. Matter 23, 325401 (2011)] discovered a low density, highly reactive metastable hexagonal 2H-Ag structure accessible during electrodeposition of silver nanowires in porous anodic alumina templates. This 2H-Ag structure has enhanced electrical and catalytic characteristics. In the present work we reportmore » template-free synthesis of silver nanoplates with the metastable 2H-Ag crystal structure, which appears together with the ground 3C-Ag and the metastable 4H-Ag structures in a two-phase solution synthesis with citric acid as the capping agent. The capacity of citric acid to stabilize both the stable and the metastable structures is explained by its preferential binding to the close packed facets of Ag crystals, which are the (111) planes for 3C-Ag and the (0001) planes for 4H-Ag and 2H-Ag. Nanoplate morphology and structure are characterized using scanning electron microscopy, X-ray diffraction, and transmission electron microscopy. The synthesized nanoplates have thickness from 15 to 17 nm and edge length from 1 to 10 μm. Transmission electron microscopy selected area electron diffraction is used to uniquely identify and distinguish between nanoplates with 2H-Ag or 4H-Ag or 3C-Ag structures.« less

Effect of silk sericin on morphology and structure of calcium carbonate crystal

NASA Astrophysics Data System (ADS)

Zhao, Rui-Bo; Han, Hua-Feng; Ding, Shao; Li, Ze-Hao; Kong, Xiang-Dong

2013-06-01

In this paper, silk sericin was employed to regulate the mineralization of calcium carbonate (CaCO3). CaCO3 composite particles were prepared by the precipitation reaction of sodium carbonate with calcium chloride solution in the presence of silk sericin. The as-prepared samples were collected at different reaction time to study the crystallization process of CaCO3 by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and X-ray diffraction (XRD). The results showed that silk sericin significantly affected the morphology and crystallographic polymorph of CaCO3. With increasing the reaction time, the crystal phase of CaCO3 transferred from calcite dominated to vaterite dominated mixtures, while the morphology of CaCO3 changed from disk-like calcite crystal to spherical vaterite crystal. These studies showed the potential of silk sericin used as a template molecule to control the growth of inorganic crystal.

Crystal growth, structure and morphology of hydrocortisone methanol solvate

NASA Astrophysics Data System (ADS)

Chen, Jianxin; Wang, Jiangkang; Zhang, Ying; Wu, Hong; Chen, Wei; Guo, Zhichao

2004-04-01

Hydrocortisone (HC), an important grucocorticoid, was crystallized from methanol solvent in the form of its methanol solvate. Its crystal structure belongs to orthorhombic, space group P2 12 12 1, with the unit cell parameters a=7.712(3) Å, b=14.392(5) Å, c=18.408(6) Å, Z=4. The methanol takes part in intermolecular hydrogen bonding, so if we change the solvent, the crystal habit of HC maybe different. The long parallelepiped morphology was also predicted by Cerius 2TM simulation program. The influence of intermolecular interaction was taken into account in the attachment energy model. The morphology calculation performed on the potential energy minimized model using a generic DREIDING 2.21 force field and developed minimization protocol with derived partial charges fits the experimental crystal shape well.

Entropy-driven crystal formation on highly strained substrates

PubMed Central

Savage, John R.; Hopp, Stefan F.; Ganapathy, Rajesh; Gerbode, Sharon J.; Heuer, Andreas; Cohen, Itai

2013-01-01

In heteroepitaxy, lattice mismatch between the deposited material and the underlying surface strongly affects nucleation and growth processes. The effect of mismatch is well studied in atoms with growth kinetics typically dominated by bond formation with interaction lengths on the order of one lattice spacing. In contrast, less is understood about how mismatch affects crystallization of larger particles, such as globular proteins and nanoparticles, where interparticle interaction energies are often comparable to thermal fluctuations and are short ranged, extending only a fraction of the particle size. Here, using colloidal experiments and simulations, we find particles with short-range attractive interactions form crystals on isotropically strained lattices with spacings significantly larger than the interaction length scale. By measuring the free-energy cost of dimer formation on monolayers of increasing uniaxial strain, we show the underlying mismatched substrate mediates an entropy-driven attractive interaction extending well beyond the interaction length scale. Remarkably, because this interaction arises from thermal fluctuations, lowering temperature causes such substrate-mediated attractive crystals to dissolve. Such counterintuitive results underscore the crucial role of entropy in heteroepitaxy in this technologically important regime. Ultimately, this entropic component of lattice mismatched crystal growth could be used to develop unique methods for heterogeneous nucleation and growth of single crystals for applications ranging from protein crystallization to controlling the assembly of nanoparticles into ordered, functional superstructures. In particular, the construction of substrates with spatially modulated strain profiles would exploit this effect to direct self-assembly, whereby nucleation sites and resulting crystal morphology can be controlled directly through modifications of the substrate. PMID:23690613

Chitosan-Assisted Crystallization and Film Forming of Perovskite Crystals through Biomineralization.

PubMed

Yang, Yang; Sun, Chen; Yip, Hin-Lap; Sun, Runcang; Wang, Xiaohui

2016-03-18

Biomimetic mineralization is a powerful approach for the synthesis of advanced composite materials with hierarchical organization and controlled structure. Herein, chitosan was introduced into a perovskite precursor solution as a biopolymer additive to control the crystallization and to improve the morphology and film-forming properties of a perovskite film by way of biomineralization. The biopolymer additive was able to control the size and morphology of the perovskite crystals and helped to form smooth films. The mechanism of chitosan-mediated nucleation and growth of the perovskite crystals was explored. As a possible application, the chitosan-perovskite composite film was introduced into a planar heterojunction solar cell and increased power conversion efficiency relative to that observed for the pristine perovskite film was achieved. The biomimetic mineralization method proposed in this study provides an alternative way of preparing perovskite crystals with well-controlled morphology and properties and extends the applications of perovskite crystals in photoelectronic fields, including planar-heterojunction solar cells. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preliminary morphological and X-ray diffraction studies of the crystals of the DNA cetyltrimethylammonium salt.

PubMed

Osica, V D; Pyatigorskaya, T L; Polyvtsev, O F; Dembo, A T; Kliya, M O; Vasilchenko, V N; Verkin, B I; Sukharevskya, B Y

1977-04-01

Double-stranded DNA molecules (molecular weight 2.5 X 10(5) - 5 X 10(5) daltons) have been crystallized from water-salt solutions as cetyltrimethylammonium salts (CTA-DNA). Variation of crystallization conditions results in a production of different types of CTA-DNA crystals: spherulits, dendrites, needle-shaped and faceted rhombic crystals, the latter beeing up to 0.3 mm on a side. X-ray diffraction data indicate that DNA molecules in the crystals form a hexagonal lattice which parameters vary slightly with the morphological type of the crystal. Comparison of the melting curves of the DNA preparation before and after crystallization suggests that DNA molecules are partially fractionated in the course of crystallization. Crystals of the CTA-DNA-proflavine complex have also been obtained.

Preliminary morphological and X-ray diffraction studies of the crystals of the DNA cetyltrimethylammonium salt.

PubMed Central

Osica, V D; Pyatigorskaya, T L; Polyvtsev, O F; Dembo, A T; Kliya, M O; Vasilchenko, V N; Verkin, B I; Sukharevskya, B Y

1977-01-01

Double-stranded DNA molecules (molecular weight 2.5 X 10(5) - 5 X 10(5) daltons) have been crystallized from water-salt solutions as cetyltrimethylammonium salts (CTA-DNA). Variation of crystallization conditions results in a production of different types of CTA-DNA crystals: spherulits, dendrites, needle-shaped and faceted rhombic crystals, the latter beeing up to 0.3 mm on a side. X-ray diffraction data indicate that DNA molecules in the crystals form a hexagonal lattice which parameters vary slightly with the morphological type of the crystal. Comparison of the melting curves of the DNA preparation before and after crystallization suggests that DNA molecules are partially fractionated in the course of crystallization. Crystals of the CTA-DNA-proflavine complex have also been obtained. Images PMID:866188

Effect of film thickness on morphological evolution in dewetting and crystallization of polystyrene/poly(ε-caprolactone) blend films.

PubMed

Ma, Meng; He, Zhoukun; Yang, Jinghui; Chen, Feng; Wang, Ke; Zhang, Qin; Deng, Hua; Fu, Qiang

2011-11-01

In this Article, the morphological evolution in the blend thin film of polystyrene (PS)/poly(ε-caprolactone) (PCL) was investigated via mainly AFM. It was found that an enriched two-layer structure with PS at the upper layer and PCL at the bottom layer was formed during spinning coating. By changing the solution concentration, different kinds of crystal morphologies, such as finger-like, dendritic, and spherulitic-like, could be obtained at the bottom PCL layer. These different initial states led to the morphological evolution processes to be quite different from each other, so the phase separation, dewetting, and crystalline morphology of PS/PCL blend films as a function of time were studied. It was interesting to find that the morphological evolution of PS at the upper layer was largely dependent on the film thickness. For the ultrathin (15 nm) blend film, a liquid-solid/liquid-liquid dewetting-wetting process was observed, forming ribbons that rupture into discrete circular PS islands on voronoi finger-like PCL crystal. For the thick (30 nm) blend film, the liquid-liquid dewetting of the upper PS layer from the underlying adsorbed PCL layer was found, forming interconnected rim structures that rupture into discrete circular PS islands embedded in the single lamellar PCL dendritic crystal due to Rayleigh instability. For the thicker (60 nm) blend film, a two-step liquid-liquid dewetting process with regular holes decorated with dendritic PCL crystal at early annealing stage and small holes decorated with spherulite-like PCL crystal among the early dewetting holes at later annealing stage was observed. The mechanism of this unusual morphological evolution process was discussed on the basis of the entropy effect and annealing-induced phase separation.

LiCoO2 Concaved Cuboctahedrons from Symmetry-Controlled Topological Reactions

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

Chen, H.; Wu, L.; Zhang, L.

2011-01-19

Morphology control of functional materials is generally performed by controlling the growth rates on selected orientations or faces. Here, we control particle morphology by 'crystal templating': by choosing appropriate precursor crystals and reaction conditions, we demonstrate that a material with rhombohedral symmetry - namely the layered, positive electrode material, LiCoO{sub 2} - can grow to form a quadruple-twinned crystal with overall cubic symmetry. The twinned crystals show an unusual, concaved-cuboctahedron morphology, with uniform particle sizes of 0.5-2 {micro}m. On the basis of a range of synthetic and analytical experiments, including solid-state NMR, X-ray powder diffraction analysis and HRTEM, we proposemore » that these twinned crystals form via selective dissolution and an ion-exchange reaction accompanied by oxidation of a parent crystal of CoO, a material with cubic symmetry. This template crystal serves to nucleate the growth of four LiCoO{sub 2} twin crystals and to convert a highly anisotropic, layered material into a pseudo-3-dimensional, isotropic material.« less

Growth Kinetics and Morphology of Barite Crystals Derived from Face-Specific Growth Rates

DOE PAGES

Godinho, Jose R. A.; Stack, Andrew G.

2015-03-30

Here we investigate the growth kinetics and morphology of barite (BaSO 4) crystals by measuring the growth rates of the (001), (210), (010), and (100) surfaces using vertical scanning interferometry. Solutions with saturation indices 1.1, 2.1, and 3.0 without additional electrolyte, in 0.7 M NaCl, or in 1.3 mM SrCl2 are investigated. Face-specific growth rates are inhibited in the SrCl 2 solution relative to a solution without electrolyte, except for (100). Contrarily, growth of all faces is promoted in the NaCl solution. The variation of face-specific rates is solution-specific, which leads to a. change of the crystal morphology and overallmore » growth rate of crystals. The measured face-specific growth rates are used to model the growth of single crystals. Modeled crystals have a morphology and size similar to those grown from solution. Based on the model the time dependence of surface area and growth rates is analyzed. Growth rates change with time due to surface area normalization for small crystals and large growth intervals. By extrapolating rates to crystals with large surfaces areas, time-independent growth rates are 0.783, 2.96, and 0.513 mmol∙m -2∙h -1, for saturation index 2.1 solutions without additional electrolyte, NaCl, and SrCl 2, respectively.« less

Growth Kinetics and Morphology of Barite Crystals Derived from Face-Specific Growth Rates

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

Godinho, Jose R. A.; Stack, Andrew G.

Here we investigate the growth kinetics and morphology of barite (BaSO 4) crystals by measuring the growth rates of the (001), (210), (010), and (100) surfaces using vertical scanning interferometry. Solutions with saturation indices 1.1, 2.1, and 3.0 without additional electrolyte, in 0.7 M NaCl, or in 1.3 mM SrCl2 are investigated. Face-specific growth rates are inhibited in the SrCl 2 solution relative to a solution without electrolyte, except for (100). Contrarily, growth of all faces is promoted in the NaCl solution. The variation of face-specific rates is solution-specific, which leads to a. change of the crystal morphology and overallmore » growth rate of crystals. The measured face-specific growth rates are used to model the growth of single crystals. Modeled crystals have a morphology and size similar to those grown from solution. Based on the model the time dependence of surface area and growth rates is analyzed. Growth rates change with time due to surface area normalization for small crystals and large growth intervals. By extrapolating rates to crystals with large surfaces areas, time-independent growth rates are 0.783, 2.96, and 0.513 mmol∙m -2∙h -1, for saturation index 2.1 solutions without additional electrolyte, NaCl, and SrCl 2, respectively.« less

Deformational characteristics of thermoplastic elastomers

NASA Astrophysics Data System (ADS)

Indukuri, Kishore K.

This thesis focuses primarily on the structure-property relationships of poly (styrene-ethylene-butylene-styrene) triblock copolymer TPEs. First evidence for strain-induced crystallization occurring in certain SEBS block copolymers has been established using unique techniques like deformation calorimetry, combined in-situ small angle X-ray and wide angle X-ray diffraction (SAXD/WAXD). Also the ramifications of such strain-induced crystallization on the mechanical properties like cyclic hysteresis, stress relaxation/creep retention of these SEBS systems have been studied. In addition, the structural changes in the morphology of these systems on deformation have been investigated using combined SAXD/WAXD setup. Small angle X-ray diffraction probed the changes at the nano-scale of polystyrene (PS) cylinders, while wide angle X-ray diffraction probed the changes at molecular length scales of the amorphous/crystalline domains of the elastomeric mid-block in these systems. New structural features at both these length scales have been observed and incorporated into the overall deformation mechanisms of the material. Continuous processing techniques like extrusion have been used to obtain ultra long-range order and orientation in these SEBS systems. Thus well ordered crystal like hexagonal packing of cylinders, where in each element in this hexagonal lattice can be individually addressed without any grain boundaries can be realized using these robust techniques. The effect of long-range order/orientation on the mechanical properties has been studied. In addition, these well ordered systems serve as model systems for evaluating deformation mechanisms of these SEBS systems, where the relative contributions of each of the phases can be estimated. EPDM/i-PP thermoplastic vulcanizates (TPVs) have micron size scale phase separated morphologies of EPDM rubber dispersed in a semicrystalline i-PP matrix as a result of the dynamic vulcanization process. Confocal microscopy studies, along with scanning electron microscopy (SEM) studies show that the morphology of these EPDM/i-PP systems resembles a microcellular "filled" foam in which i-PP occupies the strut regions and EPDM the inner core. Based on this, an analytical model has been developed that takes into account composition information, molecular weight, cure state and morphology into account.

Lattice Boltzmann Simulation of Kinetic Isotope Effect During Snow Crystal Formation

NASA Astrophysics Data System (ADS)

Lu, G.; Depaolo, D. J.; Kang, Q.; Zhang, D.

2007-12-01

The isotopic composition of precipitation, especially that of snow, plays a special role in the global hydrological cycle and in reconstruction of past climates using polar ice cores. The fractionation of the major water isotope species (HHO, HDO, HHO-18) during ice crystal formation is critical to understanding the global distribution of isotopes in precipitation. Ice crystal growth in clouds is traditionally treated with a spherically-symmetric steady state diffusion model, with semi-empirical modifications added to account for ventilation and for complex crystal morphology. Although it is known that crystal growth rate, which depends largely on the degree of vapor over- saturation, determines crystal morphology, there are no quantitative models that relate morphology to the vapor saturation factor. Since kinetic (vapor phase diffusion-controlled) isotopic fractionation also depends on growth rate, there should be direct relationships between vapor saturation, crystal morphology, and crystal isotopic composition. We use a 2D lattice Boltzmann model to simulate diffusion-controlled ice crystal growth from vapor- oversaturated air. In the model, crystals grow solely according to the diffusive fluxes just above the crystal surfaces, and hence crystal morphology arises from the initial and boundary conditions in the model and does not need to be specified a priori. Crystal growth patterns can be varied between random growth and deterministic growth (along the maximum concentration gradient for example). The input parameters needed are the isotope- dependent vapor deposition rate constant (k) and the water vapor diffusivity in air (D). The values of both k and D can be computed from kinetic theory, and there are also experimentally determined values of D. The deduced values of k are uncertain to the extent that the condensation coefficient for ice is uncertain. The ratio D/k is a length (order 1 micron) that determines the minimum scale of dendritic growth features and allows us to scale the numerical calculations to atmospheric conditions. Our calculations confirm that the crystal/vapor isotopic fractionation approaches the equilibrium value, and the crystals are compact (circular in 2D) as the saturation factor approaches unity (S= 1.0). However, few natural crystals form under such conditions. At higher oversaturation (e.g. S = 1.2), dendritic crystals of millimeter size develop on timescales appropriate to cloud processes, and kinetic effects control isotopic fractionation. Fractionation factors for dendritic crystals are similar to those predicted by the spherical diffusion model, but the model also gives estimates of crystal heterogeneity. Dendritic crystals are constrained to be relatively large, with dimension much greater than about 20D/k. The most difficult aspect of the modeling is to account for the large density difference between air and ice, which requires us to use a fictitious higher density for the vapor-oversaturated air and scale the crystal growth time accordingly. An approach using a larger scale simulation and the domain decomposition method can provide a vapor flux for a nested smaller scale calculation. The results clarify the controls on crystal growth, and the relationships between saturation state, growth rate, crystal morphology and isotopic fractionation.

Structure and engineering of celluloses.

PubMed

Pérez, Serge; Samain, Daniel

2010-01-01

This chapter collates the developments and conclusions of many of the extensive studies that have been conducted on cellulose, with particular emphasis on the structural and morphological features while not ignoring the most recent results derived from the elucidation of unique biosynthetic pathways. The presentation of structural and morphological data gathered together in this chapter follows the historical development of our knowledge of the different structural levels of cellulose and its various organizational levels. These levels concern features such as chain conformation, chain polarity, chain association, crystal polarity, and microfibril structure and organization. This chapter provides some historical landmarks related to the evolution of concepts in the field of biopolymer science, which parallel the developments of novel methods for characterization of complex macromolecular structures. The elucidation of the different structural levels of organization opens the way to relating structure to function and properties. The chemical and biochemical methods that have been developed to dissolve and further modify cellulose chains are briefly covered. Particular emphasis is given to the facets of topochemistry and topoenzymology where the morphological features play a key role in determining unique physicochemical properties. A final chapter addresses what might be considered tomorrow's goal in amplifying the economic importance of cellulose in the context of sustainable development. Selected examples illustrate the types of result that can be obtained when cellulose fibers are no longer viewed as inert substrates, and when the polyhydroxyl nature of their surfaces, as well as their entire structural complexity, are taken into account. Copyright © 2010 Elsevier Inc. All rights reserved.

Interlinked multiphase Fe-doped MnO2 nanostructures: a novel design for enhanced pseudocapacitive performance

NASA Astrophysics Data System (ADS)

Wang, Ziya; Wang, Fengping; Li, Yan; Hu, Jianlin; Lu, Yanzhen; Xu, Mei

2016-03-01

Structure designing and morphology control can lead to high performance pseudocapacitive materials for supercapacitors. In this work, we have designed interlinked multiphase Fe-doped MnO2 nanostructures (α-MnO2/R-MnO2/ε-MnO2) to enhance the electrochemical properties by a facile method. These hierarchical hollow microspheres assembled by interconnected nanoflakes, and with plenty of porous nanorods radiating from the spherical shells were hydrothermally obtained. The supercapacitor electrode prepared from the unique construction exhibits outstanding specific capacitance of 267.0 F g-1 even under a high mass loading (~5 mg cm-2). Obviously improved performances compared to pure MnO2 are also demonstrated with a good rate capability, high energy density (1.30 mW h cm-3) and excellent cycling stability of 100% capacitance retention after 2000 cycles at 2 A g-1. The synergistic effects of alternative crystal structures, appropriate crystallinity and optimal morphology are identified to be responsible for the observations. This rational multiphase composite strategy provides a promising idea for materials scientists to design and prepare scalable electrode materials for energy storage devices.Structure designing and morphology control can lead to high performance pseudocapacitive materials for supercapacitors. In this work, we have designed interlinked multiphase Fe-doped MnO2 nanostructures (α-MnO2/R-MnO2/ε-MnO2) to enhance the electrochemical properties by a facile method. These hierarchical hollow microspheres assembled by interconnected nanoflakes, and with plenty of porous nanorods radiating from the spherical shells were hydrothermally obtained. The supercapacitor electrode prepared from the unique construction exhibits outstanding specific capacitance of 267.0 F g-1 even under a high mass loading (~5 mg cm-2). Obviously improved performances compared to pure MnO2 are also demonstrated with a good rate capability, high energy density (1.30 mW h cm-3) and excellent cycling stability of 100% capacitance retention after 2000 cycles at 2 A g-1. The synergistic effects of alternative crystal structures, appropriate crystallinity and optimal morphology are identified to be responsible for the observations. This rational multiphase composite strategy provides a promising idea for materials scientists to design and prepare scalable electrode materials for energy storage devices. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr08857g

An Investigation into the Effects of Additives on Crystal Characteristics and Impact Sensitivity of RDX

NASA Astrophysics Data System (ADS)

Wang, Dong-Xu; Chen, Shu-Sen; Li, Yan-Yue; Yang, Jia-Yun; Wei, Tian-Yu; Jin, Shao-Hua

2014-07-01

Additives are one of the most important factors that greatly affect the crystal characteristics of the high energy compound hexahydro-1,3,5-trinitro-1,3,5-s-triazine (RDX, C3H6N6O6) and they have an influence on impact sensitivity. In this article, a growth morphology method was applied to obtain the crystal habit of RDX in a vacuum as well as the morphologically important faces, and molecular dynamics simulations were applied to calculate the interaction energy between these crystal faces and additive molecules for prediction of the additive-effect crystal habits of RDX. On this basis, crystal characteristics including crystal morphology, aspect ratio, and total surface charge were investigated. Then the particle size and surface electrostatic voltage of the samples from recrystallization were analyzed experimentally. The impact sensitivity test indicated that acrylamide, which could enhance the regularity and degree of sphericity of RDX crystals and effectively reduce the surface static electricity of RDX, was successful in reducing the impact sensitivity of RDX as an additive for crystallization. The above experimental results were in good agreement with the conclusions based on the theoretical calculations.

Correlation of lattice defects and thermal processing in the crystallization of titania nanotube arrays

NASA Astrophysics Data System (ADS)

Hosseinpour, Pegah M.; Yung, Daniel; Panaitescu, Eugen; Heiman, Don; Menon, Latika; Budil, David; Lewis, Laura H.

2014-12-01

Titania nanotubes have the potential to be employed in a wide range of energy-related applications such as solar energy-harvesting devices and hydrogen production. As the functionality of titania nanostructures is critically affected by their morphology and crystallinity, it is necessary to understand and control these factors in order to engineer useful materials for green applications. In this study, electrochemically-synthesized titania nanotube arrays were thermally processed in inert and reducing environments to isolate the role of post-synthesis processing conditions on the crystallization behavior, electronic structure and morphology development in titania nanotubes, correlated with the nanotube functionality. Structural and calorimetric studies revealed that as-synthesized amorphous nanotubes crystallize to form the anatase structure in a three-stage process that is facilitated by the creation of structural defects. It is concluded that processing in a reducing gas atmosphere versus in an inert environment provides a larger unit cell volume and a higher concentration of Ti3+ associated with oxygen vacancies, thereby reducing the activation energy of crystallization. Further, post-synthesis annealing in either reducing or inert atmospheres produces pronounced morphological changes, confirming that the nanotube arrays thermally transform into a porous morphology consisting of a fragmented tubular architecture surrounded by a network of connected nanoparticles. This study links explicit data concerning morphology, crystallization and defects, and shows that the annealing gas environment determines the details of the crystal structure, the electronic structure and the morphology of titania nanotubes. These factors, in turn, impact the charge transport and consequently the functionality of these nanotubes as photocatalysts.

Effects of surface stability on the morphological transformation of metals and metal oxides as investigated by first-principles calculations.

PubMed

Andrés, Juan; Gracia, Lourdes; Gouveia, Amanda Fernandes; Ferrer, Mateus Meneghetti; Longo, Elson

2015-10-09

Morphology is a key property of materials. Owing to their precise structure and morphology, crystals and nanocrystals provide excellent model systems for joint experimental and theoretical investigations into surface-related properties. Faceted polyhedral crystals and nanocrystals expose well-defined crystallographic planes depending on the synthesis method, which allow for thoughtful investigations into structure-reactivity relationships under practical conditions. This feature article introduces recent work, based on the combined use of experimental findings and first-principles calculations, to provide deeper knowledge of the electronic, structural, and energetic properties controlling the morphology and the transformation mechanisms of different metals and metal oxides: Ag, anatase TiO2, BaZrO3, and α-Ag2WO4. According to the Wulff theorem, the equilibrium shapes of these systems are obtained from the values of their respective surface energies. These investigations are useful to gain further understanding of how to achieve morphological control of complex three-dimensional crystals by tuning the ratio of the surface energy values of the different facets. This strategy allows the prediction of possible morphologies for a crystal and/or nanocrystal by controlling the relative values of surface energies.

Morphology and formation mechanism in precipitation of calcite induced by Curvibacter lanceolatus strain HJ-1

NASA Astrophysics Data System (ADS)

Zhang, Chonghong; Li, Fuchun; Lv, Jiejie

2017-11-01

Precipitation of calcium carbobate induced by microbial activities is common occurrence in controlled solution, but the formation mechanism and morphology in precipitation of calcite in solution systems is unclear, and the role of microbes is disputed. Here, culture experiment was performed for 50 days using the Curvibacter lanceolatus strain HJ-1 in a M2 culture medium, and the phase composition and morphology of the precipitates were characterized by the X-ray diffraction (XRD), Fourier transform infrared (FT-IR), and scanning electron microscopy (SEM) techniques. We show that the precipitation processes in our experiment lead to unusual morphologies of crystals corresponding to different growth stages, and the morphologies of the precipitated crystal aggregates ranging from the main rod-, cross-, star-, cauliflower-like morphologies to spherulitic structure. The complex and unusual morphologies of the precipitated calcite by strain HJ-1 may provide a reference point for better understanding the biomineralization mechanism of calcite, moreover, morphological transition of minerals revealed that the multi-ply crystals-aggregation mechanism for calcite growth in crystallisation media.

Crystal morphology modification by the addition of tailor-made stereocontrolled poly(N-isopropyl acrylamide).

PubMed

Munk, Tommy; Baldursdottir, Stefania; Hietala, Sami; Rades, Thomas; Kapp, Sebastian; Nuopponen, Markus; Kalliomäki, Katriina; Tenhu, Heikki; Rantanen, Jukka

2012-07-02

The use of additives in crystallization of pharmaceuticals is known to influence the particulate properties critically affecting downstream processing and the final product performance. Desired functionality can be build into these materials, e.g. via optimized synthesis of a polymeric additive. One such additive is the thermosensitive polymer poly(N-isopropyl acrylamide) (PNIPAM). The use of PNIPAM as a crystallization additive provides a possibility to affect viscosity at separation temperatures and nucleation and growth rates at higher temperatures. In this study, novel PNIPAM derivatives consisting of both isotactic-rich and atactic blocks were used as additives in evaporative crystallization of a model compound, nitrofurantoin (NF). Special attention was paid to possible interactions between NF and PNIPAM and the aggregation state of PNIPAM as a function of temperature and solvent composition. Optical light microscopy and Raman and FTIR spectroscopy were used to investigate the structure of the NF crystals and possible interaction with PNIPAM. A drastic change in the growth mechanism of nitrofurantoin crystals as monohydrate form II (NFMH-II) was observed in the presence of PNIPAM; the morphology of crystals changed from needle to dendritic shape. Additionally, the amphiphilic nature of PNIPAM increased the solubility of nitrofurantoin in water. PNIPAMs with varying molecular weights and stereoregularities resulted in similar changes in the crystal habit of the drug regardless of whether the polymer was aggregated or not. However, with increased additive concentration slower nucleation and growth rates of the crystals were observed. Heating of the crystallization medium resulted in phase separation of the PNIPAM. The phase separation had an influence on the achieved crystal morphology resulting in fewer, visually larger and more irregular dendritic crystals. No proof of hydrogen bond formation between PNIPAM and NF was observed, and the suggested mechanism for the observed dendritic morphology is related to the steric hindrance phenomenon. PNIPAM can be used as a crystallization additive with an obvious effect on the growth of NF crystals.

Cells Recognize and Prefer Bone-like Hydroxyapatite: Biochemical Understanding of Ultrathin Mineral Platelets in Bone.

PubMed

Liu, Cuilian; Zhai, Halei; Zhang, Zhisen; Li, Yaling; Xu, Xurong; Tang, Ruikang

2016-11-09

Hydroxyapatite (HAP) nanocrystallites in all types of bones are distinguished by their ultrathin characteristics, which are uniaxially oriented with fibrillar collagen to uniquely expose the (100) faces. We speculate that living organisms prefer the specific crystal morphology and orientation of HAP because of the interactions between cells and crystals at the mineral-cell interface. Here, bone-like platy HAP (p-HAP) and two different rod-like HAPs were synthesized to investigate the ultrathin mineral modulating effect on cell bioactivity and bone generation. Cell viability and osteogenic differentiation of mesenchymal stem cells (MSCs) were significantly promoted by the platy HAP with (100) faces compared to rod-like HAPs with (001) faces as the dominant crystal orientation, which indicated that MSCs can recognize the crystal face and prefer the (100) HAP faces. This face-specific preference is dependent on the selective adsorption of fibronectin (FN), a plasma protein that plays a central role in cell adhesion, on the HAP surface. This selective adsorption is further confirmed by molecule dynamics (MD) simulation. Our results demonstrate that it is an intelligent choice for cells to use ultrathin HAP with a large (100) face as a basic building block in the hierarchical structure of bone, which is crucial to the promotion of MSCs osteoinductions during bone formation.

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

Boppana, Venkata Bharat Ram; Hould, Nathan D.; Lobo, Raul F., E-mail: lobo@udel.ed

We report the first instance of a hydrothermal synthesis of zinc germanate (Zn{sub 2}GeO{sub 4}) nano-materials having a variety of morphologies and photochemical properties in surfactant, template and catalyst-free conditions. A systematic variation of synthesis conditions and detailed characterization using X-ray diffraction, ultraviolet-visible diffuse reflectance spectroscopy, Raman spectroscopy, electron microscopy, X-ray photoelectron spectroscopy and small angle X-ray scattering led to a better understanding of the growth of these particles from solution. At 140 {sup o}C, the zinc germanate particle morphology changes with pH from flower-shaped at pH 6.0, to poly-disperse nano-rods at pH 10 when the Zn to Ge ratiomore » in the synthesis solution is 2. When the Zn to Ge ratio is reduced to 1.25, mono-disperse nano-rods could be prepared at pH 7.5. Nanorod formation is also independent of the addition of cetyltrimethylammonium bromide (CTAB), in contrast to previous reports. Photocatalytic tests show that Zn{sub 2}GeO{sub 4} nano-rods (by weight) and flower shaped (by surface area) are the most active for methylene blue dye degradation among the synthesized zinc germanate materials. -- Graphical abstract: Zinc germanate materials were synthesized possessing unique morphologies dependent on the hydrothermal synthesis conditions in the absence of surfactant, catalyst or template. These novel materials are characterized and evaluated for their photocatalytic activities. Display Omitted highlights: > Zinc germanate synthesized hydrothermally (surfactant free) with unique morphologies. > Flower-shaped, nano-rods, globular particles obtained dependent on synthesis pH. > At 140 {sup o}C, they possess the rhombohedral crystal irrespective of synthesis conditions. > They are photocatalytically active for the degradation of methylene blue. > Potential applications could be photocatalytic water splitting and CO{sub 2} reduction.« less

Synthesis and Properties of Nanoparticle Forms Saponite Clay, Cancrinite Zeolite and Phase Mixtures Thereof.

PubMed

Shao, Hua; Pinnavaia, Thomas J

2010-09-01

The low-temperature synthesis (90°C) of nanoparticle forms of a pure phase smectic clay (saponite) and zeolite (cancrinite) is reported, along with phase mixtures thereof. A synthesis gel corresponding to the Si:Al:Mg unit cell composition of saponite (3.6:0.40:3.0) and a NaOH/Si ratio of 1.39 affords the pure phase clay with disordered nanolayer stacking. Progressive increases in the NaOH/Si ratio up to a value of 8.33 results in the co-crystallization of first garronite and then cancrinite zeolites with nanolath morphology. The resulting phase mixtures exhibit a compound particulate structure of intertwined saponite nanolayers and cancrinite nanolaths that cannot be formed through physical mixing of the pure phase end members. Under magnesium-free conditions, pure phase cancrinite nanocrystals are formed. The Si/Al ratio of the reaction mixture affects the particle morphology as well as the chemical composition of the cancrinite zeolite. Ordinarily, cancrinite crystallizes with a Si/Al ratio of 1.0, but a silicon-rich form of the zeolite (Si/Al=1.25) is crystallized at low temperature from a silica rich synthesis gel, as evidenced by (29)Si NMR spectroscopy and XEDS-TEM. Owing to the exceptionally high external surface areas of the pure phase clay (875 m(2)/g) and zeolite end members (8.9 - 40 m(2)/g), as well as their unique mixed phase composites (124 - 329 m(2)/g), these synthetic derivatives are promising model nanoparticles for studies of the bioavailability of poly-aromatic hydrocarbons immobilized in silicate bearing sediments and soils.

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.

Morphological stability of sapphire crystallization front

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

Baranov, V. V., E-mail: baranov.isc@gmail.com; Nizhankovskyi, S. V.

2016-03-15

The main factors and specificity of growth conditions for sapphire and Ti:sapphire crystals, which affect the morphological stability of the crystal–melt interface, have been investigated with allowance for the concentration and radiative melt supercooling. It is shown that the critical sapphire growth rate is determined to a great extent by the optical transparency of the melt and the mixing conditions near the crystallization front.

Factors influencing gypsum crystal morphology within a flue gas desulfurization vessel

NASA Astrophysics Data System (ADS)

Lewis, Kinsey M.

Flue gas desulfurization (FGD) is utilized by the coal--powered generating industry to safely eliminate sulfur dioxide. A FGD vessel (scrubber) synthetically creates gypsum crystals by combining limestone (CaCO3), SO2 flue gas, water and oxygen resulting in crystalline gypsum (CaSO4 · 2H2O), which can be sold for an economic return. Flat disk--like crystals, opposed to rod--like crystals, are hard to dewater, lowering economic return. The objectives were to investigate the cause of varying morphologies, understand the environment of precipitation, as well as identify correlations between operating conditions and resulting unfavorable gypsum crystal growth. Results show evidence supporting airborne impurities due to the onsite coal pile, the abundance and size of CaCO 3 and high Ca:SO4 ratios within the scrubber as possible factors controlling gypsum crystal morphology. In conclusion, regularly purging the system and incorporating a filter on the air intake valve will provide an economic byproduct avoiding costly landfill deposits.

Effects of cyclic structure inhibitors on the morphology and growth of tetrahydrofuran hydrate crystals

NASA Astrophysics Data System (ADS)

Li, Sijia; Wang, Yanhong; Lang, Xuemei; Fan, Shuanshi

2013-08-01

Morphology and growth of hydrate crystals with cyclic structure inhibitors at a hydrate-liquid interface were directly observed through a microscopic manipulating apparatus. Tetrahydrofuran (THF) hydrate was employed as an objective. The effects of four kind of cyclic structure inhibitors, polyvinylpyrrolidone (PVP), poly(N-vinyl-2-pyrrolidone-co-2-vinyl pyridine) (PVPP), poly(2-vinyl pyridine-co-N-vinylcaprolactam) (PVPC) and poly(N-vinylcaprolactam) (PVCap), were investigated. Morphological patterns between each hydrate crystal growth from hydrate-liquid interface into droplet were found differ significantly. Lamellar structure growth of hydrate crystal was observed without inhibitor, while with PVP was featheriness-like, PVPP was like long dendritic crystal, PVPC was Mimosa pudica leaf-like and PVCap was like weeds. The growth rate of hydrate crystal without inhibitor was 0.00498 mm3/s, while with PVPP, PVPC and PVCap, were 0.00339 mm3/s, 0.00350 mm3/s, 0.00386 mm3/s and 0.00426 mm3/s, respectively. Cyclic structure inhibitors can decrease the growth rate, degree of reduction in growth rate of hydrate crystals decrease with the increase of cylinder number.

Phase-field crystal simulation facet and branch crystal growth

NASA Astrophysics Data System (ADS)

Chen, Zhi; Wang, Zhaoyang; Gu, Xinrui; Chen, Yufei; Hao, Limei; de Wit, Jos; Jin, Kexin

2018-05-01

Phase-field crystal model with one mode is introduced to describe morphological transition. The relationship between growth morphology and smooth density distribution was investigated. The results indicate that the pattern selection of dendrite growth is caused by the competition between interface energy anisotropy and interface kinetic anisotropy based on the 2D phase diagram. When the calculation time increases, the crystal grows to secondary dendrite at the dimensionless undercooling equal to - 0.4. Moreover, when noise is introduced in the growth progress, the symmetry is broken in the growth mode, and there becomes irregular fractal-like growth morphology. Furthermore, the single crystal shape develops into polycrystalline when the noise amplitude is large enough. When the dimensionless undercooling is less than - 0.3, the noise has a significant effect on the growth shape. In addition, the growth velocity of crystal near to liquid phase line is slow, while the shape far away from the liquid adapts to fast growth. Based on the simulation results, the method was proved to be effective, and it can easily obtain different crystal shapes by choosing the different points in 2D phase diagram.

Time-Lapse, in Situ Imaging of Ice Crystal Growth Using Confocal Microscopy

PubMed Central

2016-01-01

Ice crystals nucleate and grow when a water solution is cooled below its freezing point. The growth velocities and morphologies of the ice crystals depend on many parameters, such as the temperature of ice growth, the melting temperature, and the interactions of solutes with the growing crystals. Three types of morphologies may appear: dendritic, cellular (or fingerlike), or the faceted equilibrium form. Understanding and controlling which type of morphology is formed is essential in several domains, from biology to geophysics and materials science. Obtaining, in situ, three dimensional observations without introducing artifacts due to the experimental technique is nevertheless challenging. Here we show how we can use laser scanning confocal microscopy to follow in real-time the growth of smoothed and faceted ice crystals in zirconium acetate solutions. Both qualitative and quantitative observations can be made. In particular, we can precisely measure the lateral growth velocity of the crystals, a measure otherwise difficult to obtain. Such observations should help us understand the influence of the parameters that control the growth of ice crystals in various systems. PMID:27917410

Time-Lapse, in Situ Imaging of Ice Crystal Growth Using Confocal Microscopy.

PubMed

Marcellini, Moreno; Noirjean, Cecile; Dedovets, Dmytro; Maria, Juliette; Deville, Sylvain

2016-11-30

Ice crystals nucleate and grow when a water solution is cooled below its freezing point. The growth velocities and morphologies of the ice crystals depend on many parameters, such as the temperature of ice growth, the melting temperature, and the interactions of solutes with the growing crystals. Three types of morphologies may appear: dendritic, cellular (or fingerlike), or the faceted equilibrium form. Understanding and controlling which type of morphology is formed is essential in several domains, from biology to geophysics and materials science. Obtaining, in situ, three dimensional observations without introducing artifacts due to the experimental technique is nevertheless challenging. Here we show how we can use laser scanning confocal microscopy to follow in real-time the growth of smoothed and faceted ice crystals in zirconium acetate solutions. Both qualitative and quantitative observations can be made. In particular, we can precisely measure the lateral growth velocity of the crystals, a measure otherwise difficult to obtain. Such observations should help us understand the influence of the parameters that control the growth of ice crystals in various systems.

Morphological stability and kinetics in crystal growth from vapors

NASA Technical Reports Server (NTRS)

Rosenberger, Franz

1990-01-01

The following topics are discussed: (1) microscopy image storage and processing system; (2) growth kinetics and morphology study with carbon tetrabromide; (3) photothermal deflection vapor growth setup; (4) bridgman growth of iodine single crystals; (5) vapor concentration distribution measurement during growth; and (6) Monte Carlo modeling of anisotropic growth kinetics and morphology. A collection of presentations and publications of these results are presented.

Extracellular matrix protein in calcified endoskeleton: a potential additive for crystal growth and design

NASA Astrophysics Data System (ADS)

Azizur Rahman, M.; Fujimura, Hiroyuki; Shinjo, Ryuichi; Oomori, Tamotsu

2011-06-01

In this study, we demonstrate a key function of extracellular matrix proteins (ECMPs) on seed crystals, which are isolated from calcified endoskeletons of soft coral and contain only CaCO 3 without any living cells. This is the first report that an ECMP protein extracted from a marine organism could potentially influence in modifying the surface of a substrate for designing materials via crystallization. We previously studied with the ECMPs from a different type of soft coral ( Sinularia polydactyla) without introducing any seed crystals in the process , which showed different results. Thus, crystallization on the seed in the presence of ECMPs of present species is an important first step toward linking function to individual proteins from soft coral. For understanding this interesting phenomenon, in vitro crystallization was initiated in a supersaturated solution on seed particles of calcite (1 0 4) with and without ECMPs. No change in the crystal growth shape occurred without ECMPs present during the crystallization process. However, with ECMPs, the morphology and phase of the crystals in the crystallization process changed dramatically. Upon completion of crystallization with ECMPs, an attractive crystal morphology was found. Scanning electron microscopy (SEM) was utilized to observe the crystal morphologies on the seeds surface. The mineral phases of crystals nucleated by ECMPs on the seeds surface were examined by Raman spectroscopy. Although 50 mM Mg 2+ is influential in making aragonite in the crystallization process, the ECMPs significantly made calcite crystals even when 50 mM Mg 2+ was present in the process. Crystallization with the ECMP additive seems to be a technically attractive strategy to generate assembled micro crystals that could be used in crystals growth and design in the Pharmaceutical and biotechnology industries.

Amelogenin-assisted ex vivo remineralization of human enamel: effects of supersaturation degree and fluoride concentration

PubMed Central

Fan, Yuwei; Nelson, James R.; Alvarez, Jason R.; Hagan, Joseph; Berrier, Allison; Xu, Xiaoming

2011-01-01

The formation of organized nanocrystals that resemble enamel is crucial for successful enamel remineralization. Calcium, phosphate and fluoride ions and amelogenin are important ingredients for the formation of organized hydroxyapatite (HAP) crystals in vitro. However, the effects of these remineralization agents on the enamel crystal morphology have not been thoroughly studied. The objective of this study was to investigate the effects of fluoride ions, supersaturation degree and amelogenin on the crystal morphology and organization of ex vivo remineralized human enamel. Extracted third molars were sliced thin and acid-etched to provide the enamel surface for immersion in different remineralization solutions. The crystal morphology and mineral phase of the remineralized enamel surface were analyzed by FE-SEM, ATR-FTIR and XRD. The concentration of fluoride and supersaturation degree of hydroxyapatite had significant effects on the crystal morphology and crystal organization, which varied from plate-like loose crystals to rod-like densely packed nanocrystal arrays. Densely packed arrays of fluoridated hydroxyapatite nanorods were observed under the following conditions: σ(HAP) = 10.2±2.0 with fluoride 1.5±0.5 mg/L and amelogenin 40±10 µg/mL, pH 6.8±0.4. A phase diagram summarized the conditions that form dense or loose hydroxyapatite nanocrystal structures. This study provides the basis for the development of novel dental materials for caries management. PMID:21256987

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 of Skeletal Diamonds from Graphite and Natural Coal in Presence of Hydrous Fluids at P=8 GPa and T=1400-1500° C

NASA Astrophysics Data System (ADS)

Dobrzhinetskaya, L. F.; Renfro, A. P.; Green, H. W.

2001-12-01

Most metamorphic microdiamonds from crustal UHP rocks of the Kokchetav massive, Kazakhstan are characterized by skeletal-hopper crystals, cuboid-like crystals with cavities "healed over" by graphite, rose-like crystals, and other imperfect morphologies. According to the classical theory of crystal growth at thermodynamic equilibrium, only shapes with a minimum surface energy are stable. Thus imperfect crystallographic forms of most metamorphic diamonds formally may be interpreted as metastable while the presence of other high pressure phases associated with diamond indicates that the rocks have been subjected to UHP metamorphism within the diamond stability field. The classical theory also says that a skeletal-hopper crystal is one that develops under conditions of rapid growth, a high degree of supersaturation and in the presence of impurities. In contrast to these observations, most experiments on diamond synthesis at high P (5-7.7 GPa) and T (1250 - 1900° C) from graphite (Wang et al., 1999; Hong et al., 1999; Yamaoka et al., 2000) and carbonate material (Pal'anov et al., 1999; Sokol et al.,2000) in presence of fluid phase produced perfect octahedral and cube-octahedral diamond crystals. Advanced analytical research on metamorphic diamonds and their inclusions has demonstrated that they were crystallized from a multicomponent COH-rich supercritical fluid phase, the composition of which suggests intermixture of crustal and mantle components (de Corte et al., 1999; Dobrzhinetskaya et al., 2001, Stockhert et al., 2001). We have recently synthesized imperfect diamond crystals (skeletal-hopper morphologies with effect of etching of the diamond surfaces) from graphite and natural coal + 2% Mg(OH)2 as a source for fluid phase. Conditions of experiments are: P=8-8.5 GPa, T=1400-1500° C, t=14 to 136 hours. Our experimental data are in a good agreement with similar experiments conducted by Kanda et al. (1984) who showed that with increasing water content of the system, the morphology of diamond crystals changes progressively from octahedra to crystals with elements of dodecahedra to hollow/hopper and skeletal morphologies. We hypothesize that imperfect morphologies of metamorphic diamonds are due to the presence of OH in the system.

NASA research Program: The roles of fluid motion and other transport phenomena in the morphology of materials

NASA Technical Reports Server (NTRS)

Saville, D. A.

1988-01-01

The influence of transport phenomena on the morphology of crystalline materials was investigated. Two problems were studied: the effects of convection on the crystallization of pure materials, and the crystallization of proteins from solution.

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?

Dislocation, crystallite size distribution and lattice strain of magnesium oxide nanoparticles

NASA Astrophysics Data System (ADS)

Sutapa, I. W.; Wahid Wahab, Abdul; Taba, P.; Nafie, N. L.

2018-03-01

The oxide of magnesium nanoparticles synthesized using sol-gel method and analysis of the structural properties was conducted. The functional groups of nanoparticles has been analysed by Fourier Transform Infrared Spectroscopy (FT-IR). Dislocations, average size of crystal, strain, stress, the energy density of crystal, crystallite size distribution and morphologies of the crystals were determined based on X-ray diffraction profile analysis. The morphological of the crystal was analysed based on the image resulted from SEM analysis. The crystallite size distribution was calculated with the contention that the particle size has a normal logarithmic form. The most orientations of crystal were determined based on the textural crystal from diffraction data of X-ray diffraction profile analysis. FT-IR results showed the stretching vibration mode of the Mg-O-Mg in the range of 400.11-525 cm-1 as a broad band. The average size crystal of nanoparticles resulted is 9.21 mm with dislocation value of crystal is 0.012 nm-2. The strains, stress, the energy density of crystal are 1.5 x 10-4 37.31 MPa; 0.72 MPa respectively. The highest texture coefficient value of the crystal is 0.98. This result is supported by morphological analysis using SEM which shows most of the regular cubic-shaped crystals. The synthesis method is suitable for simple and cost-effective synthesis model of MgO nanoparticles.

In Situ TEM and AFM Investigation of Morphological Controls during the Growth of Single Crystal BaWO 4

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

Liu, Lili; Zhang, Shuai; Bowden, Mark E.

Barium tungstate (BaWO 4) is a widely investigated inorganic optical material due to its attractive emission properties. Because those properties strongly depend on crystal structure and morphology, numerous approaches to controlling growth have been pursued. However, an understanding of the growth mechanisms that lead to the wide range of morphologies obtained to date is largely lacking, and most attempts to develop that understanding have been based on post-growth analyses. Significantly, such analyses have led to the conclusion that certain BaWO 4 crystal morphologies result from a nonclassical growth process of oriented attachment. In this work, we systematically varied the morphologymore » of BaWO 4 crystals by adjusting the relative concentrations of solute, water, and ethanol. We then explored the growth mechanism leading to the observed range of morphologies through in situ TEM and in situ AFM. We find that even the most complex BaWO 4 morphologies occur through purely classical growth mechanisms largely controlled by the content of solute and ethanol. The latter acts as an impurity to poison growth at low concentrations and low solute levels, but leads to development of growth instabilities and eventual dendritic growth at high alcohol and moderate solute concentrations by driving up the supersaturation. These findings also highlight the necessity of in situ experiments to interpret ex situ observations of crystal growth and decipher the controlling mechanisms.« less

Design of unique composites based on aromatic thermosetting copolyesters

NASA Astrophysics Data System (ADS)

Parkar, Zeba

Aromatic thermosetting copolyester (ATSP) has promise in high-temperature applications. It can be employed as a bulk polymer, as a coating and as a matrix for carbon fiber composites (ATSP/C composites). This work focuses on the applications of high performance ATSP/C composites. The morphology of the ATSP matrix in the presence of carbon fiber was studied. The effect of liquid crystalline character of starting oligomers used to prepare ATSP on the final crystal structure of the ATSP/C composite was evaluated. Matrices obtained by crosslinking of both liquid crystalline oligomers (ATSP2) and non-liquid crystalline oligomers (ATSP1) tend to crystallize in presence of carbon fibers. The crystallite size of ATSP2 is 4 times that of ATSP1. Composites made from ATSP2 yield tougher matrices compared to those made from ATSP1. Thus toughened matrices could be achieved without incorporating any additives by just changing the morphology of the final polymer. The flammability characteristics of ATSP were also studied. The limiting oxygen index (LOI) of bulk ATSP was found to be 40% whereas that of ATSP/C composites is estimated to be 85%. Thus, ATSP shows potential to be used as a flame resistant material, and also as an aerospace reentry shield. Mechanical properties of the ATSP/C composite were characterized. ATSP was observed to bond strongly with reinforcing carbon fibers. The tensile strength, modulus and shear modulus were comparable to those of conventionally used high temperature epoxy resins. ATSP shows a unique capability for healing of interlaminar cracks on application of heat and pressure, via the Interchain Transesterification Reaction (ITR). ITR can also be used for reduction in void volume and healing of microcracks. Thus, ATSP resin systems provide a unique intrinsic repair mechanism compared to any other thermosetting systems in use today. Preliminary studies on measurement of residual stresses for ATSP/C composites indicate that the stresses induced are much lower than that in epoxy/C composites. Thermal fatigue testing suggests that ATSP shows better resistance to microcracking compared to epoxy resins.

Lattice Boltzmann Simulation of Water Isotope Fractionation During Growth of Ice Crystals in Clouds

NASA Astrophysics Data System (ADS)

Lu, G.; Depaolo, D.; Kang, Q.; Zhang, D.

2006-12-01

The isotopic composition of precipitation, especially that of snow, plays a special role in the global hydrological cycle and in reconstruction of past climates using polar ice cores. The fractionation of the major water isotope species (HHO, HDO, HHO-18) during ice crystal formation is critical to understanding the global distribution of isotopes in precipitation. Ice crystal growth in clouds is traditionally treated with a spherically- symmetric steady state diffusion model, with semi-empirical modifications added to account for ventilation and for complex crystal morphology. Although it is known that crystal growth rate, which depends largely on the degree of vapor over-saturation, determines crystal morphology, there are no existing quantitative models that directly relate morphology to the vapor saturation factor. Since kinetic (vapor phase diffusion-controlled) isotopic fractionation also depends on growth rate, there should be a direct relationship between vapor saturation, crystal morphology, and crystal isotopic composition. We use a 2D Lattice-Boltzmann model to simulate diffusion-controlled ice crystal growth from vapor- oversaturated air. In the model, crystals grow solely according to the diffusive fluxes just above the crystal surfaces, and hence crystal morphology arises from the initial and boundary conditions in the model and does not need to be specified a priori. The input parameters needed are the isotope-dependent vapor deposition rate constant (k) and the water vapor diffusivity in air (D). The values of both k and D can be computed from kinetic theory, and there are also experimentally determined values of D. The deduced values of k are uncertain to the extent that the sticking coefficient (or accommodation coefficient) for ice is uncertain. The ratio D/k is a length that determines the minimum scale of dendritic growth features and allows us to scale the numerical calculations to atmospheric conditions using a dimensionless Damkohler number: Da = kh/D, where h is the width of the 2D calculation domain. Varying the nondimensional Da in the model is equivalent to varying the scale (h) in the model. Our calculations confirm that the crystal/vapor isotopic fractionation approaches the equilibrium value, and the crystals are compact (circular in 2D) as the saturation factor approaches unity (S= 1.0). At higher oversaturation (e.g. S = 1.2), dendritic crystals of millimeter size develop on timescales appropriate to cloud processes, the isotopic fractionations are dominated by kinetic effects, and similar to those predicted by the spherical diffusion model. Dendritic crystals are constrained to be relatively large, with dimension much greater than D/k. The most difficult aspect of the modeling is to account for the large density difference between air and ice, which requires us to use a fictitious higher density for the vapor-oversaturated air and scale the crystal growth time accordingly. A different approach, using a larger scale simulation to derive boundary conditions for a nested smaller scale calculation is in progress. The results to date clarify the controls on dendritic crystal growth, the relationships between saturation state, growth rate, crystal morphology and isotopic fractionation, and provide limits on the value of the accommodation coefficient.

Controlled synthesis of BiVO{sub 4} with multiple morphologies via an ethylenediamine-assisted hydrothermal method

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

Qi, Xuemei, E-mail: qixuemei@shiep.edu.cn; School of Environmental and Chemical Engineering, Shanghai University of Electric Power, Shanghai 200090; Zhu, Xinyuan

2014-11-15

Graphical abstract: BiVO{sub 4} samples with various morphologies were synthesized via a simple ethylenediamine (EN) assisted hydrothermal route. One of the mixed crystal phase with spherical and porous morphology showed excellent photocatalytic activity and about 90% Rhodamine B was degraded after 140 min visible light irradiation. - Highlights: • BiVO{sub 4} samples with various morphologies were synthesized by hydrothermal method. • Ethylenediamine mainly acts as alkaline source to adjust pH values of precursor. • BiVO{sub 4} with spherical morphology has excellent photocatalytic activity. - Abstract: In this work, BiVO{sub 4} particles with different crystal structures and morphologies including hexahedral, sphericalmore » porous and hyperbranched ones were fabricated in the presence of ethylenediamine by hydrothermal process. The as-fabricated samples were well characterized by X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, Raman spectroscopy and ultraviolet–visible absorption spectroscopy. The results showed that the morphology and crystal structure of BiVO{sub 4} particles could be well controlled by only changing the ethylenediamine content in the deionized water solution. Photocatalytic activity of the samples was evaluated by the degradation of Rhodamine B under visible-light irradiation. It was shown that BiVO{sub 4} sample with spherical porous morphology and mixed crystal phase exhibited the best photocatalytic performance after optimizing the ethylenediamine content. The best degradation ratio of Rhodamine B could reach about 87% after 140 min visible-light irradiation.« less

Occurrence and characterisation of calcium oxalate crystals in stems and fruits of Hylocereus costaricensis and Selenicereus megalanthus (Cactaceae: Hylocereeae).

PubMed

Viñas, María; Jiménez, Víctor M

2016-10-01

Detailed description about occurrence of calcium oxalate (CaOx) crystals in the edible vine cactus species Hylocereus costaricensis and Selenicereus megalanthus is scarce. Therefore, we evaluated and characterized the presence, morphology and composition of CaOx crystals in both species. Crystals were isolated from greenhouse and in vitro vegetative stems, and from ripe fruit peels and pulp by enzymatic digestion and density centrifugation and quantified with a haemocytometer. Morphologies were studied using scanning electron microscopy, elemental composition with energy-dispersive X-ray spectroscopy and salt composition with X-ray powder diffraction. Analyses conducted confirmed that isolated crystals were exclusively composed by CaOx, both mono- and dihydrated. Highest crystal contents were measured in greenhouse stems, followed by the fruit peels. While very few crystals were quantified in in vitro plants, they were not detected in the fruit pulp at all, which is of advantage for its human consumption and could be linked to mechanisms of seed dispersal through animals. Different crystal morphologies were observed, sometimes varying between genotypes and tissues analysed. This is the first work known to the authors with a detailed characterization of CaOx crystals in vine cacti. Copyright © 2016 Elsevier Ltd. All rights reserved.

Flow-induced crystallization in isotactic polypropylene

NASA Astrophysics Data System (ADS)

Hamad, Fawzi Ghassan

Brief intervals of strong flow stretch chains in a semicrystalline polymer melt, which results in an increase in the nuclei number density and a transformation of the crystal structure. This flow-induced crystallization (FIC) phenomenon is explored in this study using highly isotactic polypropylene (iPP) samples. Using one synthesized and five commercial linear isotactic polypropylene samples, we investigate the FIC behavior by imposing shear onto these samples in a rotational rheometer. Equipped with a good temperature control and flexible shear protocol, we apply different temperature and flow conditions. The magnitude of the FIC effect varies with basic processing parameters (shear rate, specific work, crystallization temperature, and shearing temperature) and material properties (totalistic, molecular weight distribution, and particle concentration in the polymer). The scope of this study is to systematically investigate the influences of these parameters on FIC. The FIC effects that are investigated in this dissertation are: crystallization kinetics, persistence time of flow-induced nuclei, and crystal morphology. The crystallization time was measured in the rheometer by monitoring the onset of crystallization after quenching samples sheared above Tm. These samples were subsequently used to study their flow-induced nuclei persistence time and crystal morphology. The lifetime of flow-induced nuclei was determined by measuring the time required to return from FIC back to quiescent crystallization using a differential scanning calorimeter. The crystal morphology was imaged using polarized optical microscopy and atomic force microscopy. We investigated the influence of specific work on the three FIC characteristics, and found three regimes that are separated by the critical work ( Wc) and the saturation work (Wsat) thresholds. Below the critical work threshold, the morphology is composed of mostly spherulite crystals, which keep a constant volume, and a small fraction of rice grain (anisotropic) crystals. The number of rice grain crystals increases with specific work, speeding up the crystallization time of the semicrystalline polymer. At critical work, spherulite formation stops, and the morphology consists only of rice grain structures. This morphology allows the sample to crystallize at higher temperatures when cooling at 5 C/min, with the sheared sample crystallizing at 129C compared to the unsheared sample at 113C. . Shearing isotactic polypropylene at higher temperatures reduced the FIC effect after subsequent quenching. Generally speaking, shearing at higher temperatures results in slower crystallization, but surprisingly, the influence of temperature is rather weak. Flow-induced crystallization persists even when shear is applied well above the equilibrium melting temperature (187C), finally weakening above the Hoffman-Weeks temperature (210C). This is likely due to the long lifetime of flow- induced precursors (crystallize to form rice grains), which remain stable at temperatures below 210C and only start to disappear slowly in prolonged annealing at temperatures above 210C (diminishing the FIC effect). Tacticity was found to govern the maximum nuclei number density in sheared samples; samples with lower isotactic content show a stronger FIC effect. Similarly, it was found that the concentration of particulates (mainly catalyst residue) are crucially important to FIC, samples with lower amounts of particles lowering the FIC nuclei number density. Data shows that the rate at which the crystallization time changes correlates with the prominence of the high molecular weight tail. A sample with a higher molecular weight tail in its distribution exhibits a faster change in crystallization time as a function of specific work. Similarly, increasing the molecular weight of the added component in a blend induces a larger change in the FIC behavior. (Abstract shortened by ProQuest.).

Crystal morphology of sunflower wax in soybean oil organogel

USDA-ARS?s Scientific Manuscript database

While sunflower wax has been recognized as an excellent organogelator for edible oil, the detailed morphology of sunflower wax crystals formed in an edible oil organogel has not been fully understood. In this study, polarized light microscopy, phase contrast microscopy, scanning electron microscopy ...

Method for estimating the morphological significance of simple forms of crystals from X-ray data

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

Treivus, E. B., E-mail: sbobr1@bk.ru

2010-09-15

When developing V.I. Mikheev and I.I. Shafranovskii's method for estimating the morphological significance of faces of different simple forms from X-ray reflection intensities, a way to approximately evaluate the morphological significance of simple forms on crystals from the structure amplitudes of the corresponding atomic planes is proposed. The potential for this approach is demonstrated by the examples of marcasite and zircon.

Morphological study on small molecule acceptor-based organic solar cells with efficiencies beyond 7% (Presentation Recording)

NASA Astrophysics Data System (ADS)

Ma, Wei; Yan, He

2015-10-01

Despite the essential role of fullerenes in achieving best-performance organic solar cells (OSCs), fullerene acceptors have several drawbacks including poor light absorption, high-cost production and purification. For this reason, small molecule acceptor (SMA)-based OSCs have attracted much attention due to the easy tunability of electronic and optical properties of SMA materials. In this study, polymers with temperature dependent aggregation behaviors are combined with various small molecule acceptor materials, which lead to impressive power conversion efficiencies of up to 7.3%. The morphological and aggregation properties of the polymer:small molecule blends are studied in details. It is found that the temperature-dependent aggregation behavior of polymers allows for the processing of the polymer solutions at moderately elevated temperature, and more importantly, controlled aggregation and strong crystallization of the polymer during the film cooling and drying process. This results in a well-controlled and near-ideal polymer:small molecule morphology that is controlled by polymer aggregation during warm casting and thus insensitive to the choice of small molecules. As a result, several cases of highly efficient (PCE between 6-7.3%) SMA OSCs are achieved. The second part of this presentation will describe the morphology of a new small molecule acceptor with a unique 3D structure. The relationship between molecular structure and morphology is revealed.

High-quality multilayer graphene on an insulator formed by diffusion controlled Ni-induced layer exchange

NASA Astrophysics Data System (ADS)

Murata, H.; Saitoh, N.; Yoshizawa, N.; Suemasu, T.; Toko, K.

2017-12-01

The Ni-induced layer-exchange growth of amorphous carbon is a unique method used to fabricate uniform multilayer graphene (MLG) directly on an insulator. To improve the crystal quality of MLG, we prepare AlOx or SiO2 interlayers between amorphous C and Ni layers, which control the extent of diffusion of C atoms into the Ni layer. The growth morphology and Raman spectra observed from MLG formed by layer exchange strongly depend on the material type and thickness of the interlayers; a 1-nm-thick AlOx interlayer is found to be ideal for use in experiments. Transmission electron microscopy and electron energy-loss spectra reveal that the crystal quality of the resulting MLG is much higher than that of a sample without an interlayer. The grain size reaches a few μm, leading to an electrical conductivity of 1290 S/cm. The grain size and the electrical conductivity are the highest among MLG synthesized using a solid-phase reaction including metal-induced crystallization. The direct synthesis of uniform, high-quality MLG on arbitrary substrates will pave the way for advanced electronic devices integrated with carbon materials.

Hierarchical domain structure of lead-free piezoelectric (Na{sub 1/2} Bi{sub 1/2})TiO{sub 3}-(K{sub 1/2} Bi{sub 1/2})TiO{sub 3} single crystals

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

Luo, Chengtao, E-mail: lchentao@vt.edu; Wang, Yaojin; Ge, Wenwei

2016-05-07

We report a unique hierarchical domain structure in single crystals of (Na{sub 1/2}Bi{sub 1/2})TiO{sub 3}-xat. %(K{sub 1/2}Bi{sub 1/2})TiO{sub 3} for x = 5 and 8 by transmission electron microscopy (TEM). A high density of polar nano-domains with a lamellar morphology was found, which were self-assembled into a quadrant-like configuration, which then assembled into conventional ferroelectric macro-domains. Studies by high resolution TEM revealed that the polar lamellar regions contained a coexistence of in-phase and anti-phase oxygen octahedral tilt regions of a few nanometers in size. Domain frustration over multiple length scales may play an important role in the stabilization of the hierarchy, andmore » in reducing the piezoelectric response of this Pb-free piezoelectric solid solution.« less

Crystal Growth of ZnSe and Related Ternary Compound Semiconductors by Vapor Transport

NASA Technical Reports Server (NTRS)

Su, Ching-Hua; Brebrick, R. F.; Burger, A.; Dudley, M.; Matyi, R.; Ramachandran, N.; Sha, Yi-Gao; Volz, M.; Shih, Hung-Dah

1999-01-01

Complete and systematic ground-based experimental and theoretical analyses on the Physical Vapor Transport (PVT) of ZnSe and related ternary compound semiconductors have been performed. The analyses included thermodynamics, mass flux, heat treatment of starting material, crystal growth, partial pressure measurements, optical interferometry, chemical analyses, photoluminescence, microscopy, x-ray diffraction and topography as well as theoretical, analytical and numerical analyses. The experimental results showed the influence of gravity orientation on the characteristics of: (1) the morphology of the as-grown crystals as well as the as-grown surface morphology of ZnSe and Cr doped ZnSe crystals; (2) the distribution of impurities and defects in ZnSe grown crystals; and (3) the axial segregation in ZnSeTe grown crystals.

The polymorphic weddellite crystals in three species of Cephalocereus (Cactaceae).

PubMed

Bárcenas-Argüello, María-Luisa; Gutiérrez-Castorena, Ma C-del-Carmen; Terrazas, Teresa

2015-10-01

Mineral inclusions in plant cells are genetically regulated, have an ecological function and are used as taxonomic characters. In Cactaceae, crystals in epidermal and cortical tissues have been reported; however, few studies have conducted chemical and morphological analyses on these crystals, and even fewer have reported non-mineral calcium to determine its systematic value. Cephalocereus apicicephalium, C. totolapensis and C. nizandensis are Cactaceae species endemic to the Isthmus of Tehuantepec, Mexico with abundant epidermal prismatic crystals. In the present study, we characterize the mineral cell inclusions, including their chemical composition and their morphology, for three species of Cephalocereus. Crystals of healthy branches of the three species were isolated and studied. The crystals were identified by X-ray diffraction (XRD), their morphology was described using a petrographic and scanning electron microscope (SEM), and their elemental composition was measured with Energy Dispersive X-ray (EDXAR). The three species synthesized weddellite with different degrees of hydration depending on the species. The optical properties of calcium oxalate crystals were different from the core, which was calcium carbonate. We observed a large diversity of predominantly spherical forms with SEM. EDXAR analysis detected different concentrations of Ca and significant amounts of elements, such as Si, Mg, Na, K, Cl, and Fe, which may be related to the edaphic environment of these cacti. The occurrence of weddellite is novel for the genus according to previous reports. The morphological diversity of the crystals may be related to their elemental composition and may be a source of phylogenetic characters. Copyright © 2015 Elsevier Ltd. All rights reserved.

Morphology of a highly asymmetric double crystallizable poly(ɛ-caprolactone-b-ethylene oxide) block copolymer

NASA Astrophysics Data System (ADS)

Li, Liangbin; Meng, Fenghua; Zhong, Zhiyuan; Byelov, Dmytro; de Jeu, Wim H.; Feijen, Jan

2007-01-01

The morphology of a highly asymmetric double crystallizable poly(ɛ-caprolactone-b-ethylene oxide) (PCL-b-PEO) block copolymer has been studied with in situ simultaneously small and wide-angle x-ray scattering as well as atomic force microscopy. The molecular masses Mn of the PCL and PEO blocks are 24 000 and 5800, respectively. X-ray scattering and rheological measurements indicate that no microphase separation occurs in the melt. Decreasing the temperature simultaneously triggers off a crystallization of PCL and microphase separation between the PCL and PEO blocks. Coupling and competition between microphase separation and crystallization results in a morphology of PEO spheres surrounded by PCL partially crystallized in lamella. Further decreasing temperature induces the crystallization of PEO spheres, which have a preferred orientation due to the confinements from hard PCL crystalline lamella and from soft amorphous PCL segments in different sides. The final morphology of this highly asymmetric block copolymer is similar to the granular morphology reported for syndiotactic polypropylene and other (co-) polymers. This implies a similar underlying mechanism of coupling and competition of various phase transitions, which is worth further exploration.

Formation of different micro-morphologies from VO2 and ZnO crystallization using macro-porous silicon substrates

NASA Astrophysics Data System (ADS)

Salazar-Kuri, U.; Antúnez, E. E.; Estevez, J. O.; Olive-Méndez, Sion F.; Silva-González, N. R.; Agarwal, V.

2017-05-01

Square-shaped macropores produced by electrochemical anodization of n- and p-type Si wafers have been used as centers of nucleation to crystallize VO2 and ZnO. Substrate roughness dependent formation of different morphologies is revealed in the form of squared particles, spheres, bars and ribbons in the case of VO2 and hexagonal piles and spheres in the case of ZnO, have been observed.The presence of nano-/micro-metric crystals was studied through field emission scanning electron microscopy and energy dispersive X-ray spectroscopy mapping. Crystal structure of metal oxides was confirmed by micro-Raman spectroscopy. The growth of the different morphologies has been explained in terms of the surface free energy of a bare Si/SiO2 substrate and its modification originated from the roughness of the surface and of the walls of the porous substrates. This energy plays a crucial role on the minimization of the required energy to induce heterogeneous nucleation and crystal growth. Present work strengthens and provides an experimental evidence of roughness dependent metal oxide crystal growth with well-defined habits from pore corners and rough sides of the pore walls, similar to already reported protein crystals.

Crystal structure and habit of dirithromycin acetone solvate: A combined experimental and simulative study

NASA Astrophysics Data System (ADS)

Yi, Qinhua; Chen, Jianfeng; Le, Yuan; Wang, Jiexin; Xue, Chunyu; Zhao, Hong

2013-06-01

Dirithromycin (DIR) was crystallized from acetone solvent in the form of an acetone solvate. Its crystal structure belongs to monoclinic, space group P21, with the unit cell parameters a=14.688(3) Å, b=11.6120(12) Å, c=14.9129(12) Å, β=94.794(10)°, and Z=2. Results of X-ray diffraction (XRD) and thermogravimetry-differential scanning calorimetry (TG-DSC) indicated that the solvent molecules could enter the crystal lattice and thus the solvate is formed. The molecular dynamics (MD) simulation method was applied to study the solvent effect. It revealed that the relative growth rates of the main crystal habit faces changed a lot, which made the most morphologically important habit face shift from (001) face to (100) face due to polar groups or atoms exposure and hence a large solvent interaction. The prism habit predicted by a modified attachment energy (AE) model agreed well with the observed experimental morphology grown from the acetone solution. This prediction method may help for a solvent selection to improve the morphology in the drug crystallization process.

Morphology and networks of sunflower wax crystals in organogel

USDA-ARS?s Scientific Manuscript database

Plant waxes are considered as promising alternatives to unhealthy solid fats such as trans fats and saturated fats in structured food products including margarines and spreads. Sunflower wax is of a great interest due to its strong gelling ability. Morphology of sunflower wax crystals formed in soyb...

Macroporous Semiconductors

PubMed Central

Föll, Helmut; Leisner, Malte; Cojocaru, Ala; Carstensen, Jürgen

2010-01-01

Pores in single crystalline semiconductors come in many forms (e.g., pore sizes from 2 nm to > 10 µm; morphologies from perfect pore crystal to fractal) and exhibit many unique properties directly or as nanocompounds if the pores are filled. The various kinds of pores obtained in semiconductors like Ge, Si, III-V, and II-VI compound semiconductors are systematically reviewed, emphasizing macropores. Essentials of pore formation mechanisms will be discussed, focusing on differences and some open questions but in particular on common properties. Possible applications of porous semiconductors, including for example high explosives, high efficiency electrodes for Li ion batteries, drug delivery systems, solar cells, thermoelectric elements and many novel electronic, optical or sensor devices, will be introduced and discussed.

Coordinated Stem and NanoSIMS Analysis of Enstatite Whiskers in Interplanetary Dust Particles

NASA Technical Reports Server (NTRS)

Nakamura-Messenger, K.; Messenger, Scott; Keller, L. P.

2009-01-01

Enstatite whiskers (less than 10 micrometer length, less than 200 nanometer width) occur in chondritic-porous interplanetary dust particles (CP IDPs), an Antarctic micrometeorite and a comet 81P/Wild-2 sample. The whiskers are typically elongated along the [100] axis and contain axial screw dislocations, while those in terrestrial rocks and meteorites are elongated along [001]. The unique crystal morphologies and microstructures are consistent with the enstatite whiskers condensing above approximately 1300 K in a low-pressure nebular or circumstellar gas. To constrain the site of enstatite whisker formation, we carried out coordinated mineralogical, chemical and oxygen isotope measurements on enstatite whiskers in a CP IDP.

The Effect of Additives on the Early Stages of Growth of Calcite Single Crystals

PubMed Central

Freeman, Colin L.; Gong, Xiuqing; Levenstein, Mark A.; Wang, Yunwei; Kulak, Alexander; Anduix‐Canto, Clara; Lee, Phillip A.; Li, Shunbo; Chen, Li; Christenson, Hugo K.

2017-01-01

Abstract As crystallization processes are often rapid, it can be difficult to monitor their growth mechanisms. In this study, we made use of the fact that crystallization proceeds more slowly in small volumes than in bulk solution to investigate the effects of the soluble additives Mg2+ and poly(styrene sulfonate) (PSS) on the early stages of growth of calcite crystals. Using a “Crystal Hotel” microfluidic device to provide well‐defined, nanoliter volumes, we observed that calcite crystals form via an amorphous precursor phase. Surprisingly, the first calcite crystals formed are perfect rhombohedra, and the soluble additives have no influence on the morphology until the crystals reach sizes of 0.1–0.5 μm for Mg2+ and 1–2 μm for PSS. The crystals then continue to grow to develop morphologies characteristic of these additives. These results can be rationalized by considering additive binding to kink sites, which is consistent with crystal growth by a classical mechanism. PMID:28767197

Calcium oxalate crystal growth modification; investigations with confocal Raman microscopy

NASA Astrophysics Data System (ADS)

McMulkin, Calum J.; Massi, Massimiliano; Jones, Franca

2017-06-01

Confocal Raman Microscopy (CRM) in combination with a photophysical investigation has been employed to give insight into the interaction between calcium oxalate monohydrate (COM) and a series of tetrazole containing crystal growth modifier's (CGM's), in conjunction with characterisation of morphological changes using scanning electron and optical microscopy. The tetrazole CGM's were found to interact by surface adsorption with minimal morphological changes to the COM crystals however, significant interactions via chemisorption were observed; it was discovered that the chemisorption is sufficiently strong for aggregation of the tetrazole species to occur within the crystal during crystallisation.

Effects of crystal-melt interfacial energy anisotropy on dendritic morphology and growth kinetics

NASA Technical Reports Server (NTRS)

Glicksman, M. E.; Singh, N. B.

1989-01-01

Morphological and kinetic studies of succinonitrile, a BCC crystal with a low (0.5 percent) anisotropy and pivalic acid, and FCC crystal with relatively large (5 percent) anisotropy in solid-liquid interfacial energy, show clearly that anisotropy in the solid-liquid interfacial energy does not affect the tip radius-velocity relationship, but has a profound influence on the tip region and the rate of amplification of branching waves. Anisotropy of the solid-liquid interfacial energy may be one of the key factors by which the microstructural characteristics of cast structures reflect individual material behavior, especially crystal symmetry.

The influence of growth environment on the crystallization of nortriptyline hydrochloride, a tricyclic antidepressant

NASA Astrophysics Data System (ADS)

MacCalman, M. L.; Roberts, K. J.; Hendriksen, B. A.

1993-03-01

The preparation of the nortriptyline hydrochloride, an important pharmaceutical product, by crystallization from both alcohol and aqueous solutions is presented. At low temperatures this material shows a higher solubility in absolute alcohol compared to aqueous solutions in a trend which reverses at higher temperatures. Examination of crystals prepared from alcohol solutions reveal essentially a needle-like crystal habit which is in excellent agreement with morphological predictions based on the bulk crystallographic structure. In contrast crystals prepared from aqueous solution at high temperatures reveal a particulate structure dominated by heavily agglomerated crystallites with plate-like morphology. When this material is crystallized at the lower temperatures, where the solubility curve is steep, X-ray and thermal analysis appear to show that crystallization results in a new polymorphic structure associated with a less agglomerated product.

Retraction of cold drawn polyethylene: the influence of lamellar thickeness and density

NASA Technical Reports Server (NTRS)

Falender, J. R.; Hansen, D.

1971-01-01

The role of crystal morphology in the retraction of oriented, linear polyethylene was studied utilizing samples crystallized under conditions controlled to vary, separately, lamellar crystal thickness and density. Samples were oriented in a simple shear deformation to a strain of 4.0 prior to measuring retraction tendency in creep and relaxation type tests. Characterizations of specimens were made using wide and small angle X-ray techniques. The specific morphological variations were chosen to test the hypothesis that a long range elastic restoring force can originate in conjunction with deformation of lamellar crystals and the consequent increase in lamellar crystal surface area and surface free energy. The results support this hypothesis.

Retraction of cold-drawn polyethylene - Influence of lamellar thickness and density.

NASA Technical Reports Server (NTRS)

Falender, J. R.; Hansen, D.

1972-01-01

The role of crystal morphology in the retraction of oriented linear polyethylene was studied utilizing samples crystallized under conditions controlled to vary, separately, lamellar crystal thickness and density. Samples were oriented in a simple shear deformation to a strain of 4.0 prior to measuring retraction tendency in creep- and relaxation-type tests. Characterizations of specimens were made using wide- and small-angle x-ray techniques. The specific morphological variations were chosen to test the hypothesis that a long-range elastic restoring force can originate in conjunction with deformation of lamellar crystals and the consequent increase in lamellar crystal surface area and surface free energy. The results support this hypothesis.

Growth Temperature Dependence of Morphology of GaN Single Crystals in the Na-Li-Ca Flux Method

NASA Astrophysics Data System (ADS)

Wu, Xi; Hao, Hangfei; Li, Zhenrong; Fan, Shiji; Xu, Zhuo

2018-02-01

In this paper, the effect of growth temperature on the morphology and transparency of the GaN crystals obtained by the Li-Ca-added Na Flux method was studied. Addition of Li-Ca was attempted to control the growth habit and further improve transparency of GaN crystals. The samples with wurtzite structure of GaN were confirmed by the x-ray powder diffraction analysis. GaN single crystal with maximum size of about 6 mm was grown at 750°C. As the growth temperature was increased from 700°C to 850°C, the morphology of the crystals changed from pyramid to prism, and their surfaces became smooth. It was found that high growth temperature was beneficial to obtain a transparent crystal, but the evaporation of sodium would suppress its further growth. The E 2 (high) mode in the Raman spectra was at 568 cm-1, and the full-width at half-maximum values of this peak for the crystals obtained at 700°C, 750°C, 800°C, and 850°C were 7.5 cm-1, 10.3 cm-1, 4.4 cm-1, and 4.0 cm-1, respectively. It indicates that all the crystals are stress free and the transparent crystal grown at high temperature has high structural quality or low impurity concentrations.

Nanoparticle induced piezoelectric, super toughened, radiation resistant, multi-functional nanohybrids.

PubMed

Tiwari, Vimal K; Shripathi, T; Lalla, N P; Maiti, Pralay

2012-01-07

We have developed multifunctional nanohybrids of poly(vinylidene fluoride-co-chlorotrifluoroethylene) (CTFE) with a small percentage of surface modified inorganic layered silicate showing dramatic improvement in toughness, radiation resistant and piezoelectric properties vis-à-vis pristine polymer. Massive intercalation (d(001) 1.8 → 3.9 nm) of polymer inside the nanoclay galleries and unique crystallization behavior of the fluoropolymer on the surface of individual silicate layer has been reported. Toughness in the nanohybrid increases more than three orders of magnitude as compared to pure CTFE. High energy radiation (80 MeV Si(+7)) causes chain session, amorphization and creates olefinic bonds in the pure polymer while the nanohybrids are radiation resistant at a similar dose. Nanoclay induces the metastable piezoelectric β-phase in CTFE, suitable for sensor and actuator application. Molecular level changes after irradiation and controlled morphology for smart membrane have been confirmed by using spectroscopy, sol-gel technique, surface morphology studies and in situ residual gas analysis.

Surfactant-Free Shape Control of Gold Nanoparticles Enabled by Unified Theoretical Framework of Nanocrystal Synthesis.

PubMed

Wall, Matthew A; Harmsen, Stefan; Pal, Soumik; Zhang, Lihua; Arianna, Gianluca; Lombardi, John R; Drain, Charles Michael; Kircher, Moritz F

2017-06-01

Gold nanoparticles have unique properties that are highly dependent on their shape and size. Synthetic methods that enable precise control over nanoparticle morphology currently require shape-directing agents such as surfactants or polymers that force growth in a particular direction by adsorbing to specific crystal facets. These auxiliary reagents passivate the nanoparticles' surface, and thus decrease their performance in applications like catalysis and surface-enhanced Raman scattering. Here, a surfactant- and polymer-free approach to achieving high-performance gold nanoparticles is reported. A theoretical framework to elucidate the growth mechanism of nanoparticles in surfactant-free media is developed and it is applied to identify strategies for shape-controlled syntheses. Using the results of the analyses, a simple, green-chemistry synthesis of the four most commonly used morphologies: nanostars, nanospheres, nanorods, and nanoplates is designed. The nanoparticles synthesized by this method outperform analogous particles with surfactant and polymer coatings in both catalysis and surface-enhanced Raman scattering. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Revealing the planar chemistry of two-dimensional heterostructures at the atomic level.

PubMed

Chou, Harry; Ismach, Ariel; Ghosh, Rudresh; Ruoff, Rodney S; Dolocan, Andrei

2015-06-23

Two-dimensional (2D) atomic crystals and their heterostructures are an intense area of study owing to their unique properties that result from structural planar confinement. Intrinsically, the performance of a planar vertical device is linked to the quality of its 2D components and their interfaces, therefore requiring characterization tools that can reveal both its planar chemistry and morphology. Here, we propose a characterization methodology combining (micro-) Raman spectroscopy, atomic force microscopy and time-of-flight secondary ion mass spectrometry to provide structural information, morphology and planar chemical composition at virtually the atomic level, aimed specifically at studying 2D vertical heterostructures. As an example system, a graphene-on-h-BN heterostructure is analysed to reveal, with an unprecedented level of detail, the subtle chemistry and interactions within its layer structure that can be assigned to specific fabrication steps. Such detailed chemical information is of crucial importance for the complete integration of 2D heterostructures into functional devices.

Layered double hydroxide-based nanomaterials as highly efficient catalysts and adsorbents.

PubMed

Li, Changming; Wei, Min; Evans, David G; Duan, Xue

2014-11-01

Layered double hydroxides (LDHs) are a class of anion clays consisting of brucite-like host layers and interlayer anions, which have attracted increasing interest in the fields of catalysis/adsorption. By virtue of the versatility in composition, morphology, and architecture of LDH materials, as well as their unique structural properties (intercalation, topological transformation, and self-assembly with other functional materials), LDHs display great potential in the design and fabrication of nanomaterials applied in photocatalysis, heterogeneous catalysis, and adsorption/separation processes. Taking advantage of the structural merits and various control synthesis strategies of LDHs, the active center structure (e.g., crystal facets, defects, geometric and electronic states, etc.) and macro-nano morphology can be facilely manipulated for specific catalytic/adsorbent processes with largely enhanced performances. In this review, the latest advancements in the design and preparation of LDH-based functional nanomaterials for sustainable development in catalysis and adsorption are summarized. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dissolution and mechanical behaviors of recrystallized carbamazepine from alcohol solution in the presence of additives

NASA Astrophysics Data System (ADS)

Nokhodchi, A.; Bolourtchian, N.; Dinarvand, R.

2005-02-01

Carbamazepine (CBZ) crystals were grown from pure ethanol solutions containing various additives (PEG 4000, PVP K30 or Tween 80). Physical characteristics of the crystals were studied for the morphology of crystals using scanning electron microscope, for the identification of polymorphism by X-ray powder diffraction (XRPD) and FT-IR, and for thermodynamic properties using differential scanning calorimetery (DSC). The dissolution behaviour of various carbamazepine crystals was also studied by dissolution apparatus II at pH 7.4 containing 1% sodium lauryl sulphate (SLS). The scanning electron micrograph (SEM) studies showed that the presence of the additives in the solutions growth medium affected the morphology and size of carbamazepine crystals. SEMs of untreated and treated carbamazepine crystals obtained from alcohol containing PEG 4000, PVP K30 or Tween 80 showed that the crystal shape of untreated carbamazepine is flaky or thin plate-like, whereas the crystals obtained from alcohol containing no additive, PEG 4000, PVP K30 or Tween 80 are polyhedral prismatic, block-shaped, polyhedral or hexagonal, respectively. XRPD, FT-IR and DSC results showed that the untreated CBZ was form III and recrystallization of CBZ in the absence or presence of the additives did not cause any polymorphic changes. The results showed that the higher dissolution rate and compact strength were observed for the crystals obtained in the presence of PVP K30. The presence of the additives in crystallization medium alters crystal morphology of carbamazepine, but only the samples crystallized in the presence of PVP K30 showed an improvement in dissolution rate and tensile strength.

Automated preparation method for colloidal crystal arrays of monodisperse and binary colloid mixtures by contact printing with a pintool plotter.

PubMed

Burkert, Klaus; Neumann, Thomas; Wang, Jianjun; Jonas, Ulrich; Knoll, Wolfgang; Ottleben, Holger

2007-03-13

Photonic crystals and photonic band gap materials with periodic variation of the dielectric constant in the submicrometer range exhibit unique optical properties such as opalescence, optical stop bands, and photonic band gaps. As such, they represent attractive materials for the active elements in sensor arrays. Colloidal crystals, which are 3D gratings leading to Bragg diffraction, are one potential precursor of such optical materials. They have gained particular interest in many technological areas as a result of their specific properties and ease of fabrication. Although basic techniques for the preparation of regular patterns of colloidal crystals on structured substrates by self-assembly of mesoscopic particles are known, the efficient fabrication of colloidal crystal arrays by simple contact printing has not yet been reported. In this article, we present a spotting technique used to produce a microarray comprising up to 9600 single addressable sensor fields of colloidal crystal structures with dimensions down to 100 mum on a microfabricated substrate in different formats. Both monodisperse colloidal crystals and binary colloidal crystal systems were prepared by contact printing of polystyrene particles in aqueous suspension. The array morphology was characterized by optical light microscopy and scanning electron microscopy, which revealed regularly ordered crystalline structures for both systems. In the case of binary crystals, the influence of the concentration ratio of the large and small particles in the printing suspension on the obtained crystal structure was investigated. The optical properties of the colloidal crystal arrays were characterized by reflection spectroscopy. To examine the stop bands of the colloidal crystal arrays in a high-throughput fashion, an optical setup based on a CCD camera was realized that allowed the simultaneous readout of all of the reflection spectra of several thousand sensor fields per array in parallel. In agreement with Bragg's relation, the investigated arrays exhibited strong opalescence and stop bands in the expected wavelength range, confirming the successful formation of highly ordered colloidal crystals. Furthermore, a narrow distribution of wavelength-dependent stop bands across the sensor array was achieved, demonstrating the capability of producing highly reproducible crystal spots by the contact printing method with a pintool plotter.

Microfluidic approach toward continuous and ultrafast synthesis of metal-organic framework crystals and hetero structures in confined microdroplets.

PubMed

Faustini, Marco; Kim, Jun; Jeong, Guan-Young; Kim, Jin Yeong; Moon, Hoi Ri; Ahn, Wha-Seung; Kim, Dong-Pyo

2013-10-02

Herein, we report a novel nanoliter droplet-based microfluidic strategy for continuous and ultrafast synthesis of metal-organic framework (MOF) crystals and MOF heterostructures. Representative MOF structures, such as HKUST-1, MOF-5, IRMOF-3, and UiO-66, were synthesized within a few minutes via solvothermal reactions with substantially faster kinetics in comparison to the conventional batch processes. The approach was successfully extended to the preparation of a demanding Ru3BTC2 structure that requires high-pressure hydrothermal synthesis conditions. Finally, three different types of core-shell MOF composites, i.e., Co3BTC2@Ni3BTC2, MOF-5@diCH3-MOF-5, and Fe3O4@ZIF-8, were synthesized by exploiting a unique two-step integrated microfluidic synthesis scheme in a continuous-flow mode. The synthesized MOF crystals were characterized by X-ray diffraction, scanning electron microscopy, and BET surface area measurements. In comparison with bare MOF-5, MOF-5@diCH3-MOF-5 showed enhanced structural stability in the presence of moisture, and the catalytic performance of Fe3O4@ZIF-8 was examined using Knoevenagel condensation as a probe reaction. The microfluidic strategy allowed continuous fabrication of high-quality MOF crystals and composites exhibiting distinct morphological characteristics in a time-efficient manner and represents a viable alternative to the time-consuming and multistep MOF synthesis processes.

Semi-crystalline morphologies of linear and cyclic poly(ɛ-caprolactones) in the diffusion-limited film thickness regime

NASA Astrophysics Data System (ADS)

Kelly, Giovanni; Bergeson, Amelia; Haque, Farihah; Grayson, Scott; Albert, Julie

Thin and ultrathin films of semi-crystalline polymers have been studied for decades due to their far-reaching applications including opto-electronic materials and biological studies of drug delivery and cell adhesion. This body of work has focused on every aspect of crystallization, from the fundamental thermodynamics and kinetics of crystal growth to methods for affecting crystalline morphologies via blending with other polymers. Due to significant synthetic challenges, one area where progress has lagged behind is the study of non-linear architectures, especially ring polymers. However, pioneering work by polymer chemists around the world has closed that gap, and we are beginning to observe important differences between ring and linear polymers in bulk materials. As a complement to those advances, this work aims to compare the morphologies of linear and cyclic poly(ɛ-caprolactones) (PCL) observed in heavily-confined ultrathin films where crystal growth is diffusion-limited. Understanding how confinement effects alter morphology will provide invaluable insight into differences in crystal growth as a function of molecular architecture.

Self-assembled Tunable Photonic Hyper-crystals

DTIC Science & Technology

2014-07-16

a cobalt nanoparticle-based ferrofluid. Unique spectral properties of photonic hyper-crystals lead to extreme sensitivity of the material to...monolayer coatings of cobalt nanoparticles, which should find numerous applications in biological and chemical sensing. 2 Approved for public release...assembly of photonic hyper crystals has been achieved by application of external magnetic field to a cobalt nanoparticle based ferrofluid. Unique spectral

Sharp Morphological Transitions from Nanoscale Mixed-Anchoring Patterns in Confined Nematic Liquid Crystals

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

Armas-Pérez, Julio C.; Li, Xiao; Martínez-González, José A.

Liquid crystals are known to be particularly sensitive to orientational cues provided at surfaces or interfaces. In this work, we explore theoretically, computationally, and experimentally the behavior of liquid crystals on isolated nanoscale patterns with controlled anchoring characteristics at small length scales. The orientation of the liquid crystal is controlled through the use of chemically patterned polymer brushes that are tethered to a surface. This system can be engineered with remarkable precision, and the central question addressed here is whether a characteristic length scale exists at which information encoded on a surface is no longer registered by a liquid crystal.more » To do so, we adopt a tensorial description of the free energy of the hybrid liquidcrystal surface system, and we investigate its morphology in a systematic manner. For long and narrow surface stripes, it is found that the liquid crystal follows the instructions provided by the pattern down to 100 nm widths. This is accomplished through the creation of line defects that travel along the sides of the stripes. We show that a "sharp" morphological transition occurs from a uniform undistorted alignment to a dual uniform/splay-bend morphology. The theoretical and numerical predictions advanced here are confirmed by experimental observations. Our combined analysis suggests that nanoscale patterns can be used to manipulate the orientation of liquid crystals at a fraction of the energetic cost that is involved in traditional liquid crystal-based devices. The insights presented in this work have the potential to provide a new fabrication platform to assemble low power bistable devices, which could be reconfigured upon application of small external fields.« less

Morphology effect on the light scattering and dynamic response of polymer network liquid crystal phase modulator.

PubMed

Xiangjie, Zhao; Cangli, Liu; Jiazhu, Duan; Jiancheng, Zeng; Dayong, Zhang; Yongquan, Luo

2014-06-16

Polymer network liquid crystal (PNLC) was one of the most potential liquid crystal for submillisecond response phase modulation, which was possible to be applied in submillisecond response phase only spatial light modulator. But until now the light scattering when liquid crystal director was reoriented by external electric field limited its phase modulation application. Dynamic response of phase change when high voltage was applied was also not elucidated. The mechanism that determines the light scattering was studied by analyzing the polymer network morphology by SEM method. Samples were prepared by varying the polymerization temperature, UV curing intensity and polymerization time. The morphology effect on the dynamic response of phase change was studied, in which high voltage was usually applied and electro-striction effect was often induced. The experimental results indicate that the polymer network morphology was mainly characterized by cross linked single fibrils, cross linked fibril bundles or even both. Although the formation of fibril bundle usually induced large light scattering, such a polymer network could endure higher voltage. In contrast, although the formation of cross linked single fibrils induced small light scattering, such a polymer network cannot endure higher voltage. There is a tradeoff between the light scattering and high voltage endurance. The electro-optical properties such as threshold voltage and response time were taken to verify our conclusion. For future application, the monomer molecular structure, the liquid crystal solvent and the polymerization conditions should be optimized to generate optimal polymer network morphology.

Schismatoglottis and Apoballis (Araceae: Schismatoglottideae): A new example for the significance of pollen morphology in Araceae systematics

PubMed Central

Ulrich, Silvia; Hesse, Michael; Bröderbauer, David; Wong, Sin Yeng; Boyce, Peter C.

2016-01-01

Pollen characters in Araceae accord well with recent DNA-based phylogenies, and here we provide a new example of “compass needle” quality in Araceae on the basis of two closely related genera, Schismatoglottis and Apoballis. All investigated Schismatoglottis pollen is psilate (smooth pollen surface) with calcium crystals covering the pollen surface. By contrast, pollen of species transferred to recently resurrected Apoballis (Apoballis acuminatissima and A. mutata) is distinctively echinate (spiny). A unique layer covers the endexine of Schismatoglottis, and the whole pollen surface of Apoballis. Our findings strongly suggest that “Schismatoglottis” species with echinate pollen fall into the genus Apoballis. Moreover, all schismatoglottid taxa perform spathe movements during anthesis to control the movement of pollinators. The spathe movements of Apoballis acuminatissima clearly differ from those known in Schismatoglottis species, and indeed are so far unique for the entire family. This, together with differences in floral odour is strongly suggestive of differences in pollination ecology between the genera Schismatoglottis and Apoballis. PMID:28904408

Role of scanning electron microscopy in identifying drugs used in medical practice.

PubMed

Fazil Marickar, Y M; Sylaja, N; Koshy, Peter

2009-10-01

Several plant preparations are administered for treatment of stone disease without scientific basis. This paper presents the results of in vitro and animal experimental studies using scanning electron microscopy (SEM) in the identification of the therapeutic properties of trial drugs in medicine. In the first set of the study, urinary crystals namely calcium oxalate monohydrate and calcium oxalate dehydrate were grown in six sets of Hane's tubes in silica gel medium. Trial drugs namely scoparia dulcis Lynn, musa sapiens and dolicos biflorus were incorporated in the gel medium to identify the dopant effect of the trial drugs on the size and extent of crystal column growth. The changes in morphology of crystals were studied using SEM. In the second set, six male Wistar rats each were calculogenised by administering sodium oxalate and ethylene glycol and diabetised using streptozotocin. The SEM changes of calculogenisation were studied. The rats were administered trial drugs before calculogenisation or after. The kidneys of the rats studied under the scanning electron microscope showed changes in tissue morphology and crystal deposition produced by calculogenisation and alterations produced by addition of trial drugs. The trial drugs produced changes in the pattern of crystal growth and in the crystal morphology of both calcium oxalate monohydrate and calcium oxalate dihydrate grown in vitro. Elemental distribution analysis showed that the crystal purity was not altered by the trial drugs. Scoparia dulcis Lynn was found to be the most effective anticalculogenic agent. Musa sapiens and dolicos biflorus were found to have no significant effect in inhibiting crystal growth. The kidneys of rats on calculogenisation showed different grades of crystals in the glomerulus and interstitial tissues, extrusion of the crystals into the tubular lumen, collodisation and tissue inflammatory cell infiltration. Scoparia dulcis Lynn exhibited maximum protector effect against the changes of calculogenisation. Musa sapiens and dolicos biflorus had only minimal effect in preventing crystal deposition, inflammatory cell infiltration and other changes of calculogenisation. SEM was found to be effective in assessing the effect of drugs on crystal growth morphology and tissue histology.

From crystal morphology to molecular and scale crystallography

NASA Astrophysics Data System (ADS)

Janner, A.; Janssen, T.

2015-08-01

A number of topics, ranging from morphology of aperiodic crystals to indexed enclosing forms of axial-symmetric proteins, nucleic acids and viruses, have been selected among those investigated by the authors in 50 years of research. The basic symmetries involved in fields like superspace, molecular and scale crystallography, are considered from a personal point of view in their time evolution. A number of specific subjects follow, chosen among a few highlights and presented according to the experience of the authors: snow crystals, calaverite {{AuTe}}2, the incommensurately modulated crystals {{Rb}}2{{ZnBr}}4, {[{N}{({{CH}}3)}4]}2{{ZnCl}}4 and the mitochondrial ferritin.

Rapid crystallization and morphological adjustment of zeolite ZSM-5 in nonionic emulsions

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

Zhang Ying, E-mail: yingzh1977@163.co; Jin Chao; Research Institute of Petroleum Processing, Beijing 100083

2011-01-15

Zeolite ZSM-5 was synthesized for the first time in a nonionic emulsion composed of polyoxyethylated alkylphenol, butanol, cyclohexane and tetraethylammonium hydroxide (TEAOH)-containing zeolite synthesis mixture. The crystallization kinetics in the emulsion was investigated and the ZSM-5 product was characterized in detail by XRD, SEM, FT-IR, TG, N{sub 2} adsorption and CHN analysis techniques. Compared with the conventionally hydrothermal synthesis with the same structure directing agent TEAOH, the emulsion system allows rapid crystallization of ZSM-5. The ZSM-5 product exhibits unusual agglomerated structure and possesses larger specific surface area. The FT-IR, TG results plus CHN analysis show the encapsulation of a tracemore » of emulsion components in the emulsion ZSM-5. Control experiments show the emulsion system exerts the crystallization induction and morphological adjustment effects mainly during the aging period. The effects are tentatively attributed to the confined space domains, surfactant-water interaction as well as surfactant-growing crystals interaction existing in the emulsion. -- Graphical abstract: The nonionic emulsion synthesis allows rapid crystallization and morphological adjustment of zeolite ZSM-5 compared with the conventional hydrothermal synthesis. Display Omitted« 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.

Delaminated sodium nonatitanate and a method for producing delaminated sodium nonatitanate

DOEpatents

Nyman, May D.

2016-02-02

A hydrothermal synthesis method of making a delaminated titanate is disclosed. The delaminated titanate has a unique structure or morphology. The delaminated titanate is first formed by forming at a low temperature a layered sodium nonatitanate (SNT), which may be referred to as layered sodium titanate. The layered SNT has a unique morphology. The layered SNT is then synthesized into a delaminated titanate having a unique morphology.

Protein crystal growth in low gravity

NASA Technical Reports Server (NTRS)

Feigelson, Robert S.

1993-01-01

This Final Technical Report for NASA Grant NAG8-774 covers the period from April 27, 1989 through December 31, 1992. It covers five main topics: fluid flow studies, the influence of growth conditions on the morphology of isocitrate lyase crystals, control of nucleation, the growth of lysozyme by the temperature gradient method and graphoepitaxy of protein crystals. The section on fluid flow discusses the limits of detectability in the Schlieren imaging of fluid flows around protein crystals. The isocitrate lyase study compares crystals grown terrestrially under a variety of conditions with those grown in space. The controlling factor governing the morphology of the crystals is the supersaturation. The lack of flow in the interface between the drop and the atmosphere in microgravity causes protein precipitation in the boundary layer and a lowering of the supersaturation in the drop. This lowered supersaturation leads to improved crystal morphology. Preliminary experiments with lysozyme indicated that localized temperature gradients could be used to nucleate crystals in a controlled manner. An apparatus (thermonucleator) was designed to study the controlled nucleation of protein crystals. This apparatus has been used to nucleate crystals of materials with both normal (ice-water, Rochelle salt and lysozyme) and retrograde (horse serum albumin and alpha chymotrypsinogen A) solubility. These studies have lead to the design of an new apparatus that small and more compatible with use in microgravity. Lysozyme crystals were grown by transporting nutrient from a source (lysozyme powder) to the crystal in a temperature gradient. The influence of path length and cross section on the growth rate was demonstrated. This technique can be combined with the thermonucleator to control both nucleation and growth. Graphoepitaxy utilizes a patterned substrate to orient growing crystals. In this study, silicon substrates with 10 micron grooves were used to grow crystals of catalase, lysozyme and canavalin. In all cases, the crystals grew oriented to the substrate. The supersaturation needed for nucleation and growth was lower on the patterned substrates. In some cases, isolated, large crystals were grown.

Verb Selection and Past-Tense Morphology: Crystal's Criteria Revisited

ERIC Educational Resources Information Center

Weiler, Brian

2013-01-01

Research findings concerning verb-level influences on past-tense morphology carry implications for the careful selection of treatment targets. Using 6 of the broad criteria for "good verbs to choose" proposed by D. Crystal (1985) more than 25 years ago as a framework, this article summarizes some of the more recent research with a nod…

Elastic Organic Crystals of a Fluorescent π-Conjugated Molecule.

PubMed

Hayashi, Shotaro; Koizumi, Toshio

2016-02-18

An elastic organic crystal of a π-conjugated molecule has been fabricated. A large fluorescent single crystal of 1,4-bis[2-(4-methylthienyl)]-2,3,5,6-tetrafluorobenzene (over 1 cm long) exhibited a fibril lamella morphology based on slip-stacked molecular wires, and it was found to be a remarkably elastic crystalline material. The straight crystal was capable of bending more than 180° under applied stress and then quickly reverted to its original shape upon relaxation. In addition, the fluorescence quantum yield of the crystal was about twice that of the compound in THF solution. Mechanical bending-relaxation resulted in reversible change of the morphology and fluorescence. This research offers a more general approach to flexible crystals as a promising new family of organic semiconducting materials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Crystallization of Chicken Egg White Lysozyme from Assorted Sulfate Salts

NASA Technical Reports Server (NTRS)

Forsythe, Elizabeth L.; Snell, Edward H.; Malone, Christine C.; Pusey, Marc L.

1998-01-01

Chicken egg white lysozyme has been found to crystallize from ammonium, sodium, potassium, rubidium, magnesium, and manganese sulfates at acidic and basic pH, with protein concentrations from 60 to 190 mg/ml. Four different crystal morphologies have been obtained, depending upon the temperature, protein concentration, and precipitating salt employed, Crystals grown at 15 C were generally tetragonal, with space group P43212. Crystallization at 20 C typically resulted in the formation of orthorhombic crystals, space group P21212 1. The tetragonal much less than orthorhombic morphology transition appeared to be a function of both the temperature and protein concentration, occurring between 15 and 20 C and between 100 and 125 mg/ml protein concentration. Crystallization from 0.8 -1.2M magnesium sulfate at pH 7.6 - 8.0 gave a hexagonal (trigonal) crystal form, space group P3121, which diffracted to 2.8 A. Ammonium sulfate was also found to result in a monoclinic form, space group C2. Small twinned monoclinic crystals of approx. 0.2 mm on edge were grown by dialysis followed by seeded sitting drop crystallization.

Tuning calcite morphology and growth acceleration by a rational design of highly stable protein-mimetics

NASA Astrophysics Data System (ADS)

Chen, Chun-Long; Qi, Jiahui; Tao, Jinhui; Zuckermann, Ronald N.; Deyoreo, James J.

2014-09-01

In nature, proteins play a significant role in biomineral formation. One of the ultimate goals of bioinspired materials science is to develop highly stable synthetic molecules that mimic the function of these natural proteins by controlling crystal formation. Here, we demonstrate that both the morphology and the degree of acceleration or inhibition observed during growth of calcite in the presence of peptoids can be rationally tuned by balancing the electrostatic and hydrophobic interactions, with hydrophobic interactions playing the dominant role. While either strong electrostatic or hydrophobic interactions inhibit growth and reduces expression of the {104} faces, correlations between peptoid-crystal binding energies and observed changes in calcite growth indicate moderate electrostatic interactions allow peptoids to weakly adsorb while moderate hydrophobic interactions cause disruption of surface-adsorbed water layers, leading to growth acceleration with retained expression of the {104} faces. This study provides fundamental principles for designing peptoids as crystallization promoters, and offers a straightforward screening method based on macroscopic crystal morphology. Because peptoids are sequence-specific, highly stable, and easily synthesized, peptoid-enhanced crystallization offers a broad range of potential applications.

Crystal morphology variation in inkjet-printed organic materials

NASA Astrophysics Data System (ADS)

Ihnen, Andrew C.; Petrock, Anne M.; Chou, Tsengming; Samuels, Phillip J.; Fuchs, Brian E.; Lee, Woo Y.

2011-11-01

The recent commercialization of piezoelectric-based drop-on-demand inkjet printers provides an additive processing platform for producing and micropatterning organic crystal structures. We report an inkjet printing approach where macro- and nano-scale energetic composites composed of cyclotrimethylenetrinitramine (RDX) crystals dispersed in a cellulose acetate butyrate (CAB) matrix are produced by direct phase transformation from organic solvent-based all-liquid inks. The characterization of printed composites illustrates distinct morphological changes dependent on ink deposition parameters. When 10 pL ink droplets rapidly formed a liquid pool, a coffee ring structure containing dendritic RDX crystals was produced. By increasing the substrate temperature, and consequently the evaporation rate of the pooled ink, the coffee ring structure was mitigated and shorter dendrites from up to ∼1 to 0.2 mm with closer arm spacing from ∼15 to 1 μm were produced. When the nucleation and growth of RDX and CAB were confined within the evaporating droplets, a granular structure containing nanoscale RDX crystals was produced. The results suggest that evaporation rate and microfluidic droplet confinement can effectively be used to tailor the morphology of inkjet-printed energetic composites.

Tuning calcite morphology and growth acceleration by a rational design of highly stable protein-mimetics

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

Chen, Chunlong; Qi, Jiahui; Tao, Jinhui

2014-09-05

In nature, proteins play a significant role in biomineral formation. One of the ultimate goals of bioinspired materials science is to develop highly stable synthetic molecules that mimic the function of these natural proteins by controlling crystal formation. Here, we demonstrate that both the morphology and the degree of acceleration or inhibition observed during growth of calcite in the presence of peptoids can be rationally tuned by balancing the electrostatic interactions (EI) and hydrophobic interactions (HI), with HI playing the dominant role. While either strong EI or HI inhibit growth and suppress (104) face expression, correlations between peptoid-crystal binding energiesmore » and observed changes in calcite growth indicate moderate EI allow peptoids to weakly adsorb while moderate HI cause disruption of surface-adsorbed water layers, leading to growth acceleration with retained expression of (104) faces. This study provides fundamental principles for designing peptoids as crystallization promoters, and offers a straightforward screening method based on macroscopic crystal morphology. Because peptoids are sequence-specific, highly stable, and easily synthesized, peptoid-enhanced crystallization offers a broad range of potential applications.« less

Controlling Crystal Microstructure to Minimize Loss in Polymer Dielectrics

NASA Astrophysics Data System (ADS)

Miranda, Daniel; Iacob, Ciprian; Zhang, Shihai; Runt, James

Polymer dielectric films are of great importance for high performance capacitors. For these films it is critical to reduce dielectric loss, as it diminishes efficiency and contributes to waste heat generation during device operation. Here, a model semi-crystalline polymer, poly(ethylene naphthalate) (PEN), was used to examine how morphological factors inhibit chain relaxations responsible for loss. This was achieved by manipulating the extent of crystallization and the crystalline microstructure through a combination of annealing and uniaxial drawing, and investigating their effects on dielectric performance. Varying crystallization conditions influenced the dynamic Tg and extent of rigid amorphous fraction formation, but had a limited effect on loss magnitude. Film orientation however greatly reduced loss, through strain-induced crystallization and development of oriented amorphous mesophasic regions. Post-drawing annealing conditions were capable of further refining the crystal microstructure and, in turn, the dielectric properties. These findings demonstrate that semi-crystalline polymer morphology has a very strong influence on amorphous chain relaxations, and understanding how processing conditions affect morphology is critical to the rational design of polymer dielectrics. Office of Naval Research.

Tuning calcite morphology and growth acceleration by a rational design of highly stable protein-mimetics

PubMed Central

Chen, Chun-Long; Qi, Jiahui; Tao, Jinhui; Zuckermann, Ronald N.; DeYoreo, James J.

2014-01-01

In nature, proteins play a significant role in biomineral formation. One of the ultimate goals of bioinspired materials science is to develop highly stable synthetic molecules that mimic the function of these natural proteins by controlling crystal formation. Here, we demonstrate that both the morphology and the degree of acceleration or inhibition observed during growth of calcite in the presence of peptoids can be rationally tuned by balancing the electrostatic and hydrophobic interactions, with hydrophobic interactions playing the dominant role. While either strong electrostatic or hydrophobic interactions inhibit growth and reduces expression of the {104} faces, correlations between peptoid-crystal binding energies and observed changes in calcite growth indicate moderate electrostatic interactions allow peptoids to weakly adsorb while moderate hydrophobic interactions cause disruption of surface-adsorbed water layers, leading to growth acceleration with retained expression of the {104} faces. This study provides fundamental principles for designing peptoids as crystallization promoters, and offers a straightforward screening method based on macroscopic crystal morphology. Because peptoids are sequence-specific, highly stable, and easily synthesized, peptoid-enhanced crystallization offers a broad range of potential applications. PMID:25189418

Biomimetic synthesis of struvite with biogenic morphology and implication for pathological biomineralization

NASA Astrophysics Data System (ADS)

Li, Han; Yao, Qi-Zhi; Wang, Yu-Ying; Li, Yi-Liang; Zhou, Gen-Tao

2015-01-01

Recent studies have found that certain urinary proteins can efficiently inhibit stone formation. These discoveries are significant for developing effective therapies for stone disease, but the inhibition mechanism of crystallization remains elusive. In the present study, polyaspartic acid (PASP) was employed as a model peptide to investigate the effect of urinary proteins on the crystallization and morphological evolution of struvite. The results demonstrate that selective adsorption/binding of PASP onto the {010} and {101} faces of struvite crystals results in arrowhead-shaped morphology, which further evolves into X-shaped and unusual tabular structures with time. Noticeably, these morphologies are reminiscent of biogenic struvite morphology. Concentration-dependent experiments show that PASP can inhibit struvite growth and the inhibitory capacity increases with increasing PASP concentration, whereas aspartic acid monomers do not show a significant effect. Considering that PASP is a structural and functional analogue of the subdomains of aspartic acid-rich proteins, our results reveal that aspartic acid-rich proteins play a key role in regulating biogenic struvite morphology, and aspartic acid residues contribute to the inhibitory capacity of urinary proteins. The potential implications of PASP for developing therapeutic agents for urinary stone disease is also discussed.

Biomimetic synthesis of struvite with biogenic morphology and implication for pathological biomineralization.

PubMed

Li, Han; Yao, Qi-Zhi; Wang, Yu-Ying; Li, Yi-Liang; Zhou, Gen-Tao

2015-01-16

Recent studies have found that certain urinary proteins can efficiently inhibit stone formation. These discoveries are significant for developing effective therapies for stone disease, but the inhibition mechanism of crystallization remains elusive. In the present study, polyaspartic acid (PASP) was employed as a model peptide to investigate the effect of urinary proteins on the crystallization and morphological evolution of struvite. The results demonstrate that selective adsorption/binding of PASP onto the {010} and {101} faces of struvite crystals results in arrowhead-shaped morphology, which further evolves into X-shaped and unusual tabular structures with time. Noticeably, these morphologies are reminiscent of biogenic struvite morphology. Concentration-dependent experiments show that PASP can inhibit struvite growth and the inhibitory capacity increases with increasing PASP concentration, whereas aspartic acid monomers do not show a significant effect. Considering that PASP is a structural and functional analogue of the subdomains of aspartic acid-rich proteins, our results reveal that aspartic acid-rich proteins play a key role in regulating biogenic struvite morphology, and aspartic acid residues contribute to the inhibitory capacity of urinary proteins. The potential implications of PASP for developing therapeutic agents for urinary stone disease is also discussed.

The Contributions of Phonological and Morphological Awareness to Literacy Skills In the Adult Basic Education Population

PubMed Central

Fracasso, Lucille E.; Bangs, Kathryn; Binder, Katherine S.

2014-01-01

The Adult Basic Education (ABE) population consists of a wide range of abilities with needs that may be unique to this set of learners. The purpose of this study was to better understand the relative contributions of phonological decoding and morphological awareness to spelling, vocabulary, and comprehension across a sample of ABE students. In this study, phonological decoding was a unique predictor of spelling ability, listening comprehension and reading comprehension. We also found that morphological awareness was a unique predictor of spelling ability, vocabulary, and listening comprehension. Morphological awareness indirectly contributed to reading comprehension through vocabulary. These findings suggest the need for morphological interventions for this group of learners. PMID:24935886

Containerless protein crystal growth method

NASA Technical Reports Server (NTRS)

Rhim, Won-Kyu; Chung, Sang K.

1991-01-01

A method of growing protein crystals from levitated drops is introduced and unique features of containerless approach in 1-g and micro-G laboratories are discussed. Electrostatic multidrop levitation system which is capable of simultaneous four drop levitation is described. A method of controlling protein saturation level in a programmed way is introduced and discussed. Finally, some of the unique features of containerless approach of protein crystal growth in space are discussed and summarized.

Morphological Diversity in Crystal Growth of l-Ascorbic Acid Dissolved in Methanol

NASA Astrophysics Data System (ADS)

Ito, Miho; Izui, Machiko; Yamazaki, Yoshihiro; Matsushita, Mitsugu

2003-06-01

Morphological diagram with respect to crystal growth of l-ascorbic acid (C6H8O6; so-called vitamin C) from methanol solution on a flat glass dish is presented. Varying humidity and initial concentration of l-ascorbic acid in methanol solution, the following three distinct kinds of growing patterns have been observed: homogeneous disk, concentric ring and dendrite. In addition, in higher concentration clearly faceted small single crystals grow in any humidity less than 90%. Crossovers from one pattern to another were observed, too.

Crystallization kinetics in Si-1 at%Sn during rapid solidification in undercooled melt

NASA Astrophysics Data System (ADS)

Kuribayashi, K.; Ozawa, S.; Nagayama, K.; Inatomi, Y.

2017-06-01

In order to elucidate the cause of the morphological transition of crystals growing in an undercooled melt of semiconducting materials, we carried out the containerless solidification of undoped Si and Si-1 at%Sn using a CO2 laser-equipped electromagnetic levitator (EML). The crystallization of these materials was successfully achieved under controlled undercooling. The relation between the shape of growing crystals and the degree of undercooling in Si-1 at%Sn was similar to that in undoped Si; that is, plate-like needle crystals were observed at low undercooling, whereas at medium and high undercooling the shape of growing crystals changed to massive dendrites. The grain-size of as-solidified samples of Si-1 at%Sn was remarkably small compared with that of undoped Si. The surface morphologies of samples solidified by dropping the melt onto a chill plate of mirror-polished silicon consisted of typical twin-related <110> dendrites. On the other hand, samples that were dropped from the undercooled state consisted of twin-free <100> dendrites. The nucleation rate of two-dimensional nuclei calculated on the basis of two mechanisms, which are the twin-plane re-entrant edge mechanism and the twin-free mechanism, suggested that the morphological transition to twin-free <100> dendrites from twin-related <110> dendrites occurs when the degree of undercooling becomes larger than the critical value. These results indicate that the cause of the morphological transition of Si growing in the undercooled melt is not the roughening transition of the crystal-melt interface but the transition of the nucleation kinetics to the twin-free mechanism from the twin-related mechanism.

Effect of Interaction of the Temperature Field and Supersaturation on the Morphology of the Solid-Vapor Interface in Crystal Growth by Physical Vapor Transport

NASA Technical Reports Server (NTRS)

Grasza, K.; Palosz, W.; Curreri, Peter A. (Technical Monitor)

2002-01-01

An in-situ study of the morphology of the solid-vapor interface during iodine crystal growth was done. The conditions for terrace growth, flat faces formation and retraction, competition between sources of steps, formation of protrusions, surface roughening, and defect overgrowth are demonstrated and discussed.

Fox-7 for Insensitive Boosters

DTIC Science & Technology

2010-08-01

cavitation , and therefore nucleation, to occur at each frequency. As well as producing ultrasound at different frequencies, the method of delivery of...processing techniques using ultrasound , designed to optimise FOX-7 crystal size and morphology to improve booster formulations, and results from these...7 booster formulations. Also included are particle processing techniques using ultrasound , designed to optimise FOX-7 crystal size and morphology

MOCVD Growth and Characterization of n-type Zinc Oxide Thin Films

NASA Astrophysics Data System (ADS)

Ben-Yaacov, Tammy

In the past decade, there has been widespread effort in the development of zinc oxide as a II-V1 semiconductor material. ZnO has potential advantages in optoelectronip device applications due to its unique electrical and optical properties. What stands out among these properties is its wide direct bandgap of 3.37 eV and its high electrical conductivity and transparency in the visible and near-UV regions of the spectrum. ZnO can be grown heteroepitaxially on GaN under near lattice-matched conditions and homoepitaxially as well, as high-quality bulk ZnO substrates are commercially available. This dissertation focuses on the development of the growth of high-quality, single crystal n-type ZnO films, control of n-type conductivity, as well as its application as a transparent contact material in GaN-based devices. The first part of this dissertation is an extensive heteroepitaxial and homoepitaxial growth study presenting the properties of ZnO(0001) layers grown on GaN(0001) templates and ZnO(0001) substrates. We show that deposition on GaN requires a two-step growth technique involving the growth of a low temperature nucleation layer before growing a high temperature epitaxial layer in order to obtain smooth ZnO films with excellent crystal quality and step-flow surface morphology. We obtained homoepitaxial ZnO(0001) films of structural quality and surface morphology that is comparable to the as-received substrates, and showed that a high growth temperature (≥1000°C) is needed in order to achieve step-flow growth mode. We performed n-type doping experiments, and established the conditions for which Indium effectively controls the n-type conductivity of ZnO films grown on GaN(0001) templates. A peak carrier concentration of 3.22x 10 19cm-3 and minimum sheet resistance of 97 O/square was achieved, while simultaneously maintaining good morphology and crystal quality. Finally, we present In-doped ZnO films implemented as p-contacts for GaN-based solar cells and LEDs, and we investigate the n-ZnO/p-GaN interface. We show that ZnO has potential as an effective p-contact for these devices, and determine properties that still need improvement in order for ZnO to compete with other contact materials. We also compare the device performance to metal-contacted devices. In summary, this thesis describes the growth of ZnO(0001) films by MOCVD, the progress in developing ZnO material with excellent surface morphology, high crystal quality, and controllable n-type doping, as well as its application to GaN-based optoelectronic devices as a p-contact material.

Precipitation and growth of barite within hydrothermal vent deposits from the Endeavour Segment, Juan de Fuca Ridge

NASA Astrophysics Data System (ADS)

Jamieson, John William; Hannington, Mark D.; Tivey, Margaret K.; Hansteen, Thor; Williamson, Nicole M.-B.; Stewart, Margaret; Fietzke, Jan; Butterfield, David; Frische, Matthias; Allen, Leigh; Cousens, Brian; Langer, Julia

2016-01-01

Hydrothermal vent deposits form on the seafloor as a result of cooling and mixing of hot hydrothermal fluids with cold seawater. Amongst the major sulfide and sulfate minerals that are preserved at vent sites, barite (BaSO4) is unique because it requires the direct mixing of Ba-rich hydrothermal fluid with sulfate-rich seawater in order for precipitation to occur. Because of its extremely low solubility, barite crystals preserve geochemical fingerprints associated with conditions of formation. Here, we present data from petrographic and geochemical analyses of hydrothermal barite from the Endeavour Segment of the Juan de Fuca Ridge, northeast Pacific Ocean, in order to determine the physical and chemical conditions under which barite precipitates within seafloor hydrothermal vent systems. Petrographic analyses of 22 barite-rich samples show a range of barite crystal morphologies: dendritic and acicular barite forms near the exterior vent walls, whereas larger bladed and tabular crystals occur within the interior of chimneys. A two component mixing model based on Sr concentrations and 87Sr/86Sr of both seawater and hydrothermal fluid, combined with 87Sr/86Sr data from whole rock and laser-ablation ICP-MS analyses of barite crystals indicate that barite precipitates from mixtures containing as low as 17% and as high as 88% hydrothermal fluid component, relative to seawater. Geochemical modelling of the relationship between aqueous species concentrations and degree of fluid mixing indicates that Ba2+ availability is the dominant control on mineral saturation. Observations combined with model results support that dendritic barite forms from fluids of less than 40% hydrothermal component and with a saturation index greater than ∼0.6, whereas more euhedral crystals form at lower levels of supersaturation associated with greater contributions of hydrothermal fluid. Fluid inclusions within barite indicate formation temperatures of between ∼120 °C and 240 °C during barite crystallization. The comparison of fluid inclusion formation temperatures to modelled mixing temperatures indicates that conductive cooling of the vent fluid accounts for 60-120 °C reduction in fluid temperature. Strontium zonation within individual barite crystals records fluctuations in the amount of conductive cooling within chimney walls that may result from cyclical oscillations in hydrothermal fluid flux. Barite chemistry and morphology can be used as a reliable indicator for past conditions of mineralization within both extinct seafloor hydrothermal deposits and ancient land-based volcanogenic massive sulfide deposits.

Single Crystals Grown Under Unconstrained Conditions

NASA Astrophysics Data System (ADS)

Sunagawa, Ichiro

Based on detailed investigations on morphology (evolution and variation in external forms), surface microtopography of crystal faces (spirals and etch figures), internal morphology (growth sectors, growth banding and associated impurity partitioning) and perfection (dislocations and other lattice defects) in single crystals, we can deduce how and by what mechanism the crystal grew and experienced fluctuation in growth parameters through its growth and post-growth history under unconstrained condition. The information is useful not only in finding appropriate way to growing highly perfect and homogeneous single crystals, but also in deciphering letters sent from the depth of the Earth and the Space. It is also useful in discriminating synthetic from natural gemstones. In this chapter, available methods to obtain molecular information are briefly summarized, and actual examples to demonstrate the importance of this type of investigations are selected from both natural minerals (diamond, quartz, hematite, corundum, beryl, phlogopite) and synthetic crystals (SiC, diamond, corundum, beryl).

Rates and processes of crystal growth in the system anorthite-albite. [magmatic liquids in igneous rock formation

NASA Technical Reports Server (NTRS)

Kirkpatrick, R. J.; Klein, L.; Uhlmann, D. R.; Hays, J. F.

1979-01-01

The growth rates and interface morphologies of crystals of synthetic compositions in the anorthite (CaAl2Si2O8)-albite (NaAlSi3O8) plagioclase feldspar system are measured in an investigation of the crystallization of igneous rocks. Mixed plagioclase glasses with compositions of 75% and 50% anorthite were observed using the microscope heating technique as they crystallized at temperatures near the liquidus, and 75%, 50% and 20% anorthite crystals were treated by resistance heating and observed at greater degrees of undercooling. Growth rates were found to be independent of time and to decrease with increasing albite content, ranging from 0.5 to 2 x 10 to the -5th cm/min. The crystal morphologies for all compositions are faceted near the liquidus and become progressively skeletal, dendritic and fibrillar with increasing undercooling.

Regulation of calcite crystal morphology by intracrystalline acidic proteins and glycoproteins.

PubMed

Albeck, S; Addadi, I; Weiner, S

1996-01-01

Many biologically formed calcite crystals contain intracrystalline macromolecules. The ways in which they interact with growing calcite crystals were evaluated by monitoring changes in the morphology of calcite crystals grown in vitro in their presence. Macromolecules were extracted from within isolated prisms from the prismatic layer of the shell of the mollusk Atrina rigida and from spines of the sea urchin Paracentrotus lividus. Two modes of interaction were identified; the interaction of highly acidic proteins with calcite planes perpendicular to the c crystallographic axis and the interaction of glycoproteins with planes roughly parallel to the c axis. By different preparative procedures we demonstrated that the polysaccharide moieties of the sea urchin spine glycoproteins are directly involved in the latter mode of interactions. We suggest that organisms utilize the abilities of these macromolecules to interact in different ways with calcite crystals, and in so doing fine-tune aspects of the control of crystal growth in vivo.

Morphology of growth of Bi2Sr2CaCu2O8 single crystals

NASA Astrophysics Data System (ADS)

Indenbom, M. V.; van der Beek, C. J.; Berseth, V.; Wolf, Th.; Berger, H.; Benoit, W.

1996-12-01

A good correlation of twins on the basal surface of flux-grown Bi2Sr2CaCu2Ox (BSCCO) single crystals with surface. growth steps is observed, the b-axis being perpendicular to the steps and, thus, parallel to the growth direction. It is found that mono-twin BSCCO single crystals produced by the travelling solvent floating zone method also grow preferentially along b, i.e. nearly perpendicularly to the boule axis, contrary to the common belief. This new understanding of the morphology of growth explains the nature of major defects in these crystals, which considerably change their measured superconducting properties, in a different way.

The Effects of Crystal Phase and Particle Morphology of Calcium Phosphates on Proliferation and Differentiation of Human Mesenchymal Stromal Cells.

PubMed

Danoux, Charlène; Pereira, Daniel; Döbelin, Nicola; Stähli, Christoph; Barralet, Jake; van Blitterswijk, Clemens; Habibovic, Pamela

2016-07-01

Calcium phosphate (CaP) ceramics are extensively used for bone regeneration; however, their clinical performance is still considered inferior to that of patient's own bone. To improve the performance of CaP bone graft substitutes, it is important to understand the effects of their individual properties on a biological response. The aim of this study is to investigate the effects of the crystal phase and particle morphology on the behavior of human mesenchymal stromal cells (hMSCs). To study the effect of the crystal phase, brushite, monetite, and octacalcium phosphate (OCP) are produced by controlling the precipitation conditions. Brushite and monetite are produced as plate-shaped and as needle-shaped particles, to further investigate the effect of particle morphology. Proliferation of hMSCs is inhibited on OCP as compared to brushite and monetite in either morphology. Brushite needles consistently show the lowest expression of most osteogenic markers, whereas the expression on OCP is in general high. There is a trend toward a higher expression of the osteogenic markers on plate-shaped than on needle-shaped particles for both brushite and monetite. Within the limits of CaP precipitation, these data indicate the effect of both crystal phase and particle morphology of CaPs on the behavior of hMSCs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Composition and automated crystal orientation mapping of rapid solidification products in hypoeutectic Al-4 at.%Cu alloys

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

Zweiacker, K. W.; Liu, Can; Gordillo, M. A.

Rmore » apid solidification can produce metastable phases and unusual microstructure modifications in multi-component alloys during additive manufacturing or laser beam welding. Composition and phase mapping by transmission electron microscopy have been used in this paper to characterize the morphologically distinct zones developing in hypoeutectic Al-4 at.% Cu alloy after pulsed laser melting for different crystal growth rate regimes. Deviations of the compositions of the alloy phases from equilibrium predictions and unique orientation relationships between the solidification transformation products have been determined. Specifically, for the columnar growth zone at solidification rates of 0.8 m s - 1 < v < v a = 1.8 m s - 1 , two distinct orientation relationships were established between the concomitantly forming non-equilibrium phases, supersaturated α-Al solid solution and the discontinuously distributed α-Al 2Cu-based θ'-phase, which can be described as {110} θ ∥ {001} α, [001] θ ∥ [110] α and {001} θ ∥ {001} α, [100] θ ∥ [100] α. These orientation relationships permit formation of coherent interphase interfaces with low interfacial free energy. Finally, this endows a kinetic advantage to the thermodynamically less stable θ'-Al 2Cu phase relative to the more stable equilibrium θ-Al 2Cu phase during formation of the morphologically modified eutectic of the columnar growth zone grains, since repeated nucleation is required to establish the discontinuous distribution of θ'-Al 2Cu phase.« less

Composition and automated crystal orientation mapping of rapid solidification products in hypoeutectic Al-4 at.%Cu alloys

DOE PAGES

Zweiacker, K. W.; Liu, Can; Gordillo, M. A.; ...

2017-12-05

Rmore » apid solidification can produce metastable phases and unusual microstructure modifications in multi-component alloys during additive manufacturing or laser beam welding. Composition and phase mapping by transmission electron microscopy have been used in this paper to characterize the morphologically distinct zones developing in hypoeutectic Al-4 at.% Cu alloy after pulsed laser melting for different crystal growth rate regimes. Deviations of the compositions of the alloy phases from equilibrium predictions and unique orientation relationships between the solidification transformation products have been determined. Specifically, for the columnar growth zone at solidification rates of 0.8 m s - 1 < v < v a = 1.8 m s - 1 , two distinct orientation relationships were established between the concomitantly forming non-equilibrium phases, supersaturated α-Al solid solution and the discontinuously distributed α-Al 2Cu-based θ'-phase, which can be described as {110} θ ∥ {001} α, [001] θ ∥ [110] α and {001} θ ∥ {001} α, [100] θ ∥ [100] α. These orientation relationships permit formation of coherent interphase interfaces with low interfacial free energy. Finally, this endows a kinetic advantage to the thermodynamically less stable θ'-Al 2Cu phase relative to the more stable equilibrium θ-Al 2Cu phase during formation of the morphologically modified eutectic of the columnar growth zone grains, since repeated nucleation is required to establish the discontinuous distribution of θ'-Al 2Cu phase.« less

Effect of crystals and fibrous network polymer additives on cellular morphology of microcellular foams

NASA Astrophysics Data System (ADS)

Miyamoto, Ryoma; Utano, Tatsumi; Yasuhara, Shunya; Ishihara, Shota; Ohshima, Masahiro

2015-05-01

In this study, the core-back foam injection molding was used for preparing microcelluar polypropylene (PP) foam with either a 1,3:2,4 bis-O-(4-methylbenzylidene)-D-sorbitol gelling agent (Gel-all MD) or a fibros network polymer additive (Metablen 3000). Both agent and addiive could effectively control the celluar morphology in foams but somehow different ways. In course of cooling the polymer with Gel-all MD in the mold caity, the agent enhanced the crystal nucleation and resulted in the large number of small crystals. The crystals acted as effective bubble nucleation agent in foaming process. Thus, the agent reduced the cell size and increased the cell density, drastically. Furthermore, the small crystals provided an inhomogenuity to the expanding cell wall and produced the high open cell content with nano-scale fibril structure. Gell-all as well as Metablene 3000 formed a gel-like fibrous network in melt. The network increased the elongational viscosity and tended to prevent the cell wall from breaking up. The foaming temperature window was widened by the presence of the network. Especially, the temperature window where the macro-fibrous structure was formed was expanded to the higher temperature. The effects of crystal nucleating agent and PTFE on crystals' size and number, viscoelsticity, rheological propreties of PP and cellular morphology were compared and thorougly investigated.

Influence of diffusion and convective transport on dendritic growth in dilute alloys

NASA Technical Reports Server (NTRS)

Glicksman, M. E.; Singh, N. B.; Chopra, M.

1982-01-01

Experimentation has been carried out in which the kinetics and morphology of dendritic growth were measured as a function of thermal supercooling, solute concentration, and spatial orientation of the dendritic growth axis. The crystal growth system studied is succinonitrile, NC(CH2)2CN, with additions of argon (up to 0.1 mole percent). This system is especially useful as a model for alloy studies because kinetic data are available for high purity (7-9's) succinonitrile. The influence of the solute, at fixed thermal supercooling, is to increase the growth velocity and correspondingly decrease intrinsic crystal dimensions. Morphological measurements are described in detail relating tip size, perturbation wavelength, supercooling, and solute concentration. The analysis of these effects based on morphological stability theory is also discussed, and experiments permitting the separation of convective and diffusive heat transport during crystal growth of succinonitrile are described. The studies underscore the importance of gravitationally-induced buoyancy effects on crystal growth.

Face-by-face growth of sucrose crystals from aqueous solutions in the presence of raffinose—II: Growth morphology and segregation

NASA Astrophysics Data System (ADS)

Sgualdino, G.; Aquilano, D.; Pastero, L.; Vaccari, G.

2007-10-01

Raffinose segregation into sucrose crystals is experimentally determined along with the modifications of the quantitative sucrose growth morphology, which are in turn related to the different growth conditions. ( Craff, σ) morphodromes nicely represent the conflict between the supersaturation and the raffinose concentration in the solution on the growth morphology, while the overall segregation rate is nearly proportional to the linear overall crystal growth rate. Chernov and Burton-Prim-Slichter models, checked to fit our keff and ln(keff-1-1) coefficients as a function of the supersaturation and of the mean linear overall growth rate, do not allow to know whether the segregation occurs either by a process dominated by surface integration, or by additive transfer dominated by volume diffusion within the boundary layer. The distribution of segregated raffinose strictly depends on the { h k l} growth sectors and doped crystals contain deformed lattice zones, as it comes out from X-ray powder diagrams.

Fast growth with crystal splitting of morphology-controllable Bi2S3 flowers on TiO2 nanotube arrays

NASA Astrophysics Data System (ADS)

Yang, L. X.; Ding, Y. B.; Luo, S. L.; Luo, Y.; Deng, F.; Li, Y.

2013-03-01

Bi2S3 crystals with flower-like morphologies are deposited on TiO2 nanotube arrays (NTs) by applying the cathodic pulse electrodeposition (PED) technique at 120 °C in 20 s. The highly oriented TiO2 NTs/Ti serving as substrate has high surface energy which is favorable for Gibbs free energy decreasing in nucleation process. Numerous boundaries between NTs are nucleation sites for atomic clusters, resulting in a fast nucleation velocity. Effective and fast heterogeneous nucleation initiates a thermodynamic control growth model and finally leads to the fast formation of highly crystallized Bi2S3 with a typical splitting property. Ethylene glycol (EG) was introduced into the electrolytes to inhibit the typical growth along the c axis ([0 0 1] plane) and facilitate the growth along the ab plane, producing Bi2S3 crystals with variable morphologies from sheaves to flowers by increasing EG contents.

Modeling variability in dendritic ice crystal backscattering cross sections at millimeter wavelengths using a modified Rayleigh-Gans theory

NASA Astrophysics Data System (ADS)

Lu, Yinghui; Clothiaux, Eugene E.; Aydin, Kültegin; Botta, Giovanni; Verlinde, Johannes

2013-12-01

Using the Generalized Multi-particle Mie-method (GMM), Botta et al. (in this issue) [7] created a database of backscattering cross sections for 412 different ice crystal dendrites at X-, Ka- and W-band wavelengths for different incident angles. The Rayleigh-Gans theory, which accounts for interference effects but ignores interactions between different parts of an ice crystal, explains much, but not all, of the variability in the database of backscattering cross sections. Differences between it and the GMM range from -3.5 dB to +2.5 dB and are highly dependent on the incident angle. To explain the residual variability a physically intuitive iterative method was developed to estimate the internal electric field within an ice crystal that accounts for interactions between the neighboring regions within it. After modifying the Rayleigh-Gans theory using this estimated internal electric field, the difference between the estimated backscattering cross sections and those from the GMM method decreased to within 0.5 dB for most of the ice crystals. The largest percentage differences occur when the form factor from the Rayleigh-Gans theory is close to zero. Both interference effects and neighbor interactions are sensitive to the morphology of ice crystals. Improvements in ice-microphysical models are necessary to predict or diagnose internal structures within ice crystals to aid in more accurate interpretation of radar returns. Observations of the morphology of ice crystals are, in turn, necessary to guide the development of such ice-microphysical models and to better understand the statistical properties of ice crystal morphologies in different environmental conditions.

Morphology and the Strength of Intermolecular Contact in Protein Crystals

NASA Technical Reports Server (NTRS)

Matsuura, Yoshiki; Chernov, Alexander A.

2002-01-01

The strengths of intermolecular contacts (macrobonds) in four lysozyme crystals were estimated based on the strengths of individual intermolecular interatomic interaction pairs. The periodic bond chain of these macrobonds accounts for the morphology of protein crystals as shown previously. Further in this paper, the surface area of contact, polar coordinate representation of contact site, Coulombic contribution on the macrobond strength, and the surface energy of the crystal have been evaluated. Comparing location of intermolecular contacts in different polymorphic crystal modifications, we show that these contacts can form a wide variety of patches on the molecular surface. The patches are located practically everywhere on this surface except for the concave active site. The contacts frequently include water molecules, with specific intermolecular hydrogen-bonds on the background of non-specific attractive interactions. The strengths of macrobonds are also compared to those of other protein complex systems. Making use of the contact strengths and taking into account bond hydration we also estimated crystal-water interfacial energies for different crystal faces.

Comparison study of morphology and crystallization behavior of polyethylene and poly(ethylene oxide) on single-walled carbon nanotubes.

PubMed

Zheng, Xiaoli; Xu, Qun

2010-07-29

In this work, we provided a comparison study of morphology and crystallization behavior of polyethylene (PE) and poly(ethylene oxide) (PEO) on single-walled carbon nanotubes (SWNTs) with assistance of supercritical CO(2). The resulting polymer/SWNT nanohybrids were characterized by transmission electron microscopy, scanning electron microscopy, Fourier transform infrared spectroscopy, Raman spectra, wide-angle X-ray diffraction, and differential scanning calorimetry. SWNT small bundles were decorated by PE lamellar crystals, forming nanohybrid "shish-kebab" (NHSK) structure, whereas SWNTs were only wrapped by a thin amorphous polymer coating in the case of PEO. The varying morphologies of the nanohybrids were found to depend on the molecular conformation and the interactions between polymer chains and SWNTs. Nonisothermal experiments showed that SWNTs provided heterogeneous nucleation sites for PE crystallization, while the NHSK structure hindered polymer chain diffusion and crystal growth. Also, SWNTs played antinucleation effect on PEO. In addition, the formation mechanism analysis indicated that PE chains preferred to form a homogeneous coating along the tube axis before proceeding to kebab crystal growth. The purpose of this work is to enlarge the area of theoretical understanding of introducing precisely hierarchical structures on carbon nanotubes, which are important for functional design in nanodevice applications.

A facile chemical conversion synthesis of Sb2S3 nanotubes and the visible light-driven photocatalytic activities

PubMed Central

2012-01-01

We report a simple chemical conversion and cation exchange technique to realize the synthesis of Sb2S3 nanotubes at a low temperature of 90°C. The successful chemical conversion from ZnS nanotubes to Sb2S3 ones benefits from the large difference in solubility between ZnS and Sb2S3. The as-grown Sb2S3 nanotubes have been transformed from a weak crystallization to a polycrystalline structure via successive annealing. In addition to the detailed structural, morphological, and optical investigation of the yielded Sb2S3 nanotubes before and after annealing, we have shown high photocatalytic activities of Sb2S3 nanotubes for methyl orange degradation under visible light irradiation. This approach offers an effective control of the composition and structure of Sb2S3 nanomaterials, facilitates the production at a relatively low reaction temperature without the need of organics, templates, or crystal seeds, and can be extended to the synthesis of hollow structures with various compositions and shapes for unique properties. PMID:22448960

Toward the Fabrication of Advanced Nanofiltration Membranes by Controlling Morphologies and Mesochannel Orientations of Hexagonal Lyotropic Liquid Crystals.

PubMed

Wang, Guang; Garvey, Christopher J; Zhao, Han; Huang, Kang; Kong, Lingxue

2017-07-21

Water scarcity has been recognized as one of the major threats to human activity, and, therefore, water purification technologies are increasingly drawing attention worldwide. Nanofiltration (NF) membrane technology has been proven to be an efficient and cost-effective way in terms of the size and continuity of the nanostructure. Using a template based on hexagonal lyotropic liquid crystals (LLCs) and partitioning monomer units within this structure for subsequent photo-polymerisation presents a unique path for the fabrication of NF membranes, potentially producing pores of uniform size, ranging from 1 to 5 nm, and large surface areas. The subsequent orientation of this pore network in a direction normal to a flat polymer film that provides ideal transport properties associated with continuous pores running through the membrane has been achieved by the orientation of hexagonal LLCs through various strategies. This review presents the current progresses on the strategies for structure retention from a hexagonal LLCs template and the up-to-date techniques used for the reorientation of mesochanels for continuity through the whole membrane.

The Contributions of Phonological and Morphological Awareness to Literacy Skills in the Adult Basic Education Population.

PubMed

Fracasso, Lucille E; Bangs, Kathryn; Binder, Katherine S

2016-01-01

The Adult Basic Education (ABE) population consists of a wide range of abilities with needs that may be unique to this set of learners. The purpose of this study was to better understand the relative contributions of phonological decoding and morphological awareness to spelling, vocabulary, and comprehension across a sample of ABE students. In this study, phonological decoding was a unique predictor of spelling ability, listening comprehension, and reading comprehension. We also found that morphological awareness was a unique predictor of spelling ability, vocabulary, and listening comprehension. Morphological awareness indirectly contributed to reading comprehension through vocabulary. These findings suggest the need for morphological interventions for this group of learners. © Hammill Institute on Disabilities 2014.

Bio-inspired routes for synthesizing efficient nanoscale platinum electrocatalysts

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

Cha, Jennifer N.; Wang, Joseph

2014-08-31

The overall objective of the proposed research is to use fundamental advances in bionanotechnology to design powerful platinum nanocrystal electrocatalysts for fuel cell applications. The new economically-viable, environmentally-friendly, bottom-up biochemical synthetic strategy will produce platinum nanocrystals with tailored size, shape and crystal orientation, hence leading to a maximum electrochemical reactivity. There are five specific aims to the proposed bio-inspired strategy for synthesizing efficient electrocatalytic platinum nanocrystals: (1) isolate peptides that both selectively bind particular crystal faces of platinum and promote the nucleation and growth of particular nanocrystal morphologies, (2) pattern nanoscale 2-dimensional arrays of platinum nucleating peptides from DNA scaffolds,more » (3) investigate the combined use of substrate patterned peptides and soluble peptides on nanocrystal morphology and growth (4) synthesize platinum crystals on planar and large-area carbon electrode supports, and (5) perform detailed characterization of the electrocatalytic behavior as a function of catalyst size, shape and morphology. Project Description and Impact: This bio-inspired collaborative research effort will address key challenges in designing powerful electrocatalysts for fuel cell applications by employing nucleic acid scaffolds in combination with peptides to perform specific, environmentally-friendly, simultaneous bottom-up biochemical synthesis and patterned assembly of highly uniform and efficient platinum nanocrystal catalysts. Bulk synthesis of nanoparticles usually produces a range of sizes, accessible catalytic sites, crystal morphologies, and orientations, all of which lead to inconsistent catalytic activities. In contrast, biological systems routinely demonstrate exquisite control over inorganic syntheses at neutral pH and ambient temperature and pressures. Because the orientation and arrangement of the templating biomolecules can be precisely controlled, the nanocrystals boast a defined shape, morphology, orientation and size and are synthesized at benign reaction conditions. Adapting the methods of biomineralization towards the synthesis of platinum nanocrystals will allow effective control at a molecular level of the synthesis of highly active metal electrocatalysts, with readily tailored properties, through tuning of the biochemical inputs. The proposed research will incorporate many facets of biomineralization by: (1) isolating peptides that selectively bind particular crystal faces of platinum (2) isolating peptides that promote the nucleation and growth of particular nanocrystal morphologies (3) using two-dimensional DNA scaffolds to control the spatial orientation and density of the platinum nucleating peptides, and (4) combining bio-templating and soluble peptides to control crystal nucleation, orientation, and morphology. The resulting platinum nanocrystals will be evaluated for their electrocatalytic behavior (on common carbon supports) to determine their optimal size, morphology and crystal structure. We expect that such rational biochemical design will lead to highly uniform and efficient platinum nanocrystal catalysts for fuel cell applications.« less

Investigation of the unique degradation phenomenon observed in CsSrBr3: Eu 5% scintillator crystals

NASA Astrophysics Data System (ADS)

Gokhale, S. S.; Loyd, M.; Stand, L.; Lindsey, A.; Swider, S.; Zhuravleva, M.; Melcher, C. L.

2016-10-01

CsSrBr3: Eu 5% is a promising compound scintillator for radiation detection and imaging applications. Light output and energy resolution measured for a crystal of volume 5×5×5 mm3 were 55,000±2000 ph/MeV and 5.6% at 662 keV respectively which is a significant improvement over previous reports. The hygroscopicity of the compound and the tendency of the scintillator crystals to degrade when exposed to the atmosphere necessitate the proper encapsulation of the crystals. It was observed that unlike other hygroscopic scintillator crystals CsSrBr3 undergoes a unique degradation while encapsulated in mineral oil. The light output of the crystal decreases over time, but there is no visually observed physical degradation of the crystal. This degradation is a reversible process wherein a degraded crystal can be subjected to annealing in vacuum in order to restore its original performance.

Size- and morphology-controllable synthesis of MIL-96 (Al) by hydrolysis and coordination modulation of dual aluminium source and ligand systems.

PubMed

Liu, Dandan; Liu, Yunqi; Dai, Fangna; Zhao, Jinchong; Yang, Kang; Liu, Chenguang

2015-10-07

In this paper, an efficient method to fabricate Al-based metal organic framework (Al-MOF) MIL-96 crystals with controllable size and morphology, by mixing other forms of reactants to replace the coordination modulators or capping agents, is presented. The size and morphology of the MIL-96 crystals can be selectively varied by simply altering the ratio of dual reactants via their hydrolysis reaction. All the samples were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), Fourier Transform Infrared (FT-IR) spectroscopy, thermogravimetric analysis (TGA) and nitrogen sorption. Then based on the BFDH theory, a mechanism for the impact of hydrolysis of reactants on the crystal size and morphology is presented and discussed. We also evaluated the performance of these MOFs as sorbents for capturing CO2, and they all show enhanced adsorption properties compared with the bulk material, displaying high adsorption capacities on CO2 at atmospheric pressure and ambient temperature.

Interfacial Interaction in Anodic Aluminum Oxide Templates Modifies Morphology, Surface Area, and Crystallization of Polyamide-6 Nanofibers.

PubMed

Xue, Junhui; Xu, Yizhuang; Jin, Zhaoxia

2016-03-08

Here, we demonstrated that, when the precipitation process of polyamide-6 (PA6) solution happens in cylindrical channels of an anodized aluminum oxide membrane (AAO), interface interactions between a solid surface, solvent, non-solvent, and PA6 will influence the obtained polymer nanostructures, resulting in complex morphologies, increased surface area, and crystallization changes. With the enhancing interaction of PA6 and the AAO surface, the morphology of PA6 nanostructures changes from solid nanofibers, mesoporous, to bamboo-like, while at the same time, metastable γ-phase domains increase in these PA6 nanostructures. Brunauer-Emmett-Teller (BET) surface areas of solid, bamboo-like, and mesoporous PA6 nanofibers rise from 16, 20.9, to 25 m(2)/g. This study shows that interfacial interaction in AAO template fabrication can be used in manipulating the morphology and crystallization of one-dimensional polymer nanostructures. It also provides us a simple and novel method to create porous PA6 nanofibers with a large surface area.

MnO2 prepared by hydrothermal method and electrochemical performance as anode for lithium-ion battery.

PubMed

Feng, Lili; Xuan, Zhewen; Zhao, Hongbo; Bai, Yang; Guo, Junming; Su, Chang-Wei; Chen, Xiaokai

2014-01-01

Two α-MnO2 crystals with caddice-clew-like and urchin-like morphologies are prepared by the hydrothermal method, and their structure and electrochemical performance are characterized by scanning electron microscope (SEM), X-ray diffraction (XRD), galvanostatic cell cycling, cyclic voltammetry, and electrochemical impedance spectroscopy (EIS). The morphology of the MnO2 prepared under acidic condition is urchin-like, while the one prepared under neutral condition is caddice-clew-like. The identical crystalline phase of MnO2 crystals is essential to evaluate the relationship between electrochemical performances and morphologies for lithium-ion battery application. In this study, urchin-like α-MnO2 crystals with compact structure have better electrochemical performance due to the higher specific capacity and lower impedance. We find that the relationship between electrochemical performance and morphology is different when MnO2 material used as electrochemical supercapacitor or as anode of lithium-ion battery. For lithium-ion battery application, urchin-like MnO2 material has better electrochemical performance.

Control of Orientation and Morphology of Crystals Grown Under Organic Templates

NASA Astrophysics Data System (ADS)

Stripe, Benjamin

Living creatures demonstrate an extraordinary ability to both grow and control the growth of inorganic crystals. These biominerals are found almost everywhere in nature from simple plants and plankton to our own teeth and bones. A great deal of research has been focused on how living creatures are able to achieve such control over the shape, size, orientation, and arrangement of these biominerals. Many studies have been done demonstrating the effects the presence of organic molecules can have on the morphology of nucleating inorganic crystals. These studies have led to the use of ordered arrays of biological molecules as templates to select the orientation of the crystals. Such experiments have had amazing success cataloging monolayers, orientations and morphologies of crystals grown beneath them. However, despite several decades of work, the exact mechanisms by which the orientation and morphology of crystals is selected by organic templates are still not known. The present study attempts to explain the complex interactions that take place at the template surface and decide the orientations and morphologies of the crystals that nucleate there. To do this, scanning electron microscopy (SEM), grazing incidence x-ray diffraction (GID), and x-ray reflectivity have been used to probe the templates and nucleating crystals in situ. The experiments described here seek to move beyond the well-studied two-component systems. In many of these two-component systems a single template and a single type of crystal are grown, and often many claims and comparisons are made about monolayer charge, crystal surface energies, stereochemical recognition, and lattice matches. However, almost all of the claims and comparisons are between systems that are different enough that assumptions about relative charge, strain, recognition, and lattice dynamics are either unfounded or poorly supported. To bridge this gap in the comparison of these different two-component systems the studies presented here are tunable three-component systems. These experiments allow for either continuously adjusting the template by means of two miscible monolayers or adjusting the growing crystals by incorporation of secondary ions. In either case, the idea is the same: we can more accurately compare two-component systems and isolate the controlling factor in the selection of orientation and morphology of the nucleating crystals. The results of these studies have shown that there is a complex interplay of charge, lattice parameters and kinetics. Despite this, we have been able to show that well-oriented growth of single non-dendritic crystals is limited to a fairly small range of surface charges and relative growth kinetics. Within this range, variations in the growing crystals can be seen based on changes in the average lattice parameters despite there being no evidence of direct epitaxy. Theories have evolved around the idea of stereochemical matching between the template and nucleating surface. These theories correlate the template molecular tilt to the orientation relative to the nucleation plane. However, these theories are not supported by the results presented in this manuscript. The data presented in this manuscript are suggestive of far more complex interfacial interactions involving an intermediary amorphous precursor, or possible networks of hydrated or hydrogen bonded ions than has been suggested in previous studies. Excitingly, it appears to be possible to control the selection of orientation using these multicomponent systems despite the complex interactions at the surface.

Preparation and characterization of superfine ammonium perchlorate (AP) crystals through ceramic membrane anti-solvent crystallization

NASA Astrophysics Data System (ADS)

Ma, Zhenye; Li, Cheng; Wu, Rujun; Chen, Rizhi; Gu, Zhenggui

2009-10-01

In this paper, a novel ceramic membrane anti-solvent crystallization (CMASC) method was proposed for the safe and rapid preparation ammonium perchlorate (AP) crystals, in which the acetone and ethyl acetate were chosen as solvent and anti-solvent, respectively. Comparing with the conventional liquid anti-solvent crystallization (LASC), CMASC which successfully introduces ceramic membrane with regular pore structure to the LASC as feeding medium, is favorable to control the rate of feeding rate and, therefore, to obtain size and morphology controllable AP. Several kinds of micro-sized AP particles with different morphology were obtained including polyhedral-like, quadrate-like to rod-like. The effect of processing parameters on the crystal size and shape of AP crystals such as volume ratio of anti-solvent to solvent, feeding pressure and crystallization temperature were investigated. It is found that higher volume ratio of anti-solvent to solvent, higher feeding pressure and higher temperature result in smaller particle size. Scaning electron microscopy (SEM) and X-ray diffraction (XRD) were used to characterize the resulting AP crystals. The nucleation and growth kinetic of the resulting AP crystals were also discussed.

Hydrogen-bond coordination in organic crystal structures: statistics, predictions and applications.

PubMed

Galek, Peter T A; Chisholm, James A; Pidcock, Elna; Wood, Peter A

2014-02-01

Statistical models to predict the number of hydrogen bonds that might be formed by any donor or acceptor atom in a crystal structure have been derived using organic structures in the Cambridge Structural Database. This hydrogen-bond coordination behaviour has been uniquely defined for more than 70 unique atom types, and has led to the development of a methodology to construct hypothetical hydrogen-bond arrangements. Comparing the constructed hydrogen-bond arrangements with known crystal structures shows promise in the assessment of structural stability, and some initial examples of industrially relevant polymorphs, co-crystals and hydrates are described.

Melt growth of organic 4-(2-Phenylisopropyl) phenol single crystal and its structural, thermal, dielectric permittivity and optical properties

NASA Astrophysics Data System (ADS)

Sadhasivam, S.; Rajesh, N. P.

2017-12-01

A nonlinear optical (NLO) organic crystal 4-(2-Phenylisopropyl) phenol has been grown by a top seeded melt growth technique. The melt growth kinetics of solid-liquid (molten) interface and facets formation in melt growth were studied. The melt grown crystal has the (001), (00 1 bar),(110)(1 bar 1 bar 0) ,(1 bar 20),(1 2 bar 0),(2 bar 10) and(2 1 bar 0) different morphological face. The morphological characteristics of melt grown crystal helps to better infer the kinetic influence of melt and hone growth of organic material. The rhombohedral lattice cell parameters were measured by single crystal X-ray diffraction. 4-(2-Phenylisopropyl) phenol crystallizes in space group of R 3 bar . Thermal study shows that solid to liquid transition occurring at 350 K and decomposes at 597 K. The grown crystal was optically transparent in the wavelength range of 300-1100 nm. The low dielectric constant (9-11) was measured in the [001] of 4-(2-Phenylisopropyl) phenol crystal.

Controlling ZIF-67 crystals formation through various cobalt sources in aqueous solution

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

Guo, Xiangli; Jiangsu Key Laboratory of Advanced Metallic Materials, Nanjing 211189; Xing, Tiantian

2016-03-15

Zeolitic imidazolate frameworks ZIF-67 were prepared under hydrothermal (120 °C) and non-hydrothermal (room temperature) from various cobalt sources and 2-methylimidazolate (Hmim) in aqueous solution within 30 min. The particle size and morphology were found to be related to the reactivity of the cobalt salt, Hmim/Co{sup 2+} molar ratios and experimental condition. Using Co(NO{sub 3}){sub 2} as cobalt source, small-sized ZIF-67 crystals with agglomeration were formed. For CoCl{sub 2}, small-sized rhombic dodecahedron were obtained. While large-sized crystals of rhombic dodecahedron structure were obtained from CoSO{sub 4} and Co(OAc){sub 2}. Under hydrothermal condition, the size of ZIF-67 crystals tended to be moremore » uniform and the morphology were more regular comparing to non-hydrothermal condition. This study provides a simple way to control the size and morphology of ZIF-67 crystals prepared in aqueous solution. - Graphical abstract: Zeolitic imidazolate frameworks ZIF-67 were prepared under hydrothermal (120 °C) and non-hydrothermal (room temperature) from four different cobalt sources (Co(NO{sub 3}){sub 2}, CoCl{sub 2}, CoSO{sub 4} and Co(OAc){sub 2}) in aqueous solution within 30 min. The particle size and morphology were found to be related to the reactivity of the cobalt salt, Hmim/Co{sup 2+} molar ratios and experimental condition. - Highlights: • The particle size and morphology were determined by the reactivity of cobalt salt. • ZIF-67 could be prepared from CoSO{sub 4} and Co(OAc){sub 2} at Hmim/Co{sup 2+} molar ratio of 10. • Uniform and regular particles were obtained under hydrothermal condition.« less

Synthesis and Characterization of a New Co-Crystal Explosive with High Energy and Good Sensitivity

NASA Astrophysics Data System (ADS)

Gao, Han; Jiang, Wei; Liu, Jie; Hao, Gazi; Xiao, Lei; Ke, Xiang; Chen, Teng

2017-10-01

A new energetic co-crystal consisting of one of the most powerful explosive molecules 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) and the military explosive cyclotrimethylenetrinitramine (RDX) was prepared with a simple solvent evaporation method. Scanning electron microscopy (SEM) revealed the morphology of the bar-shaped product, which differed greatly from the morphology of the individual components. Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, X-ray diffraction spectrum (XRD), and differential scanning calorimetry (DSC) proved the formation of the co-crystal at the molecular level. The result of mechanical sensitivity test indicated the sensitivity was effectively reduced compared to raw CL-20. Finally, a possible crystallization mechanism was discussed.

Additive-mediated electrochemical synthesis of platelike copper crystals for methanol electrooxidation.

PubMed

Venkatasubramanian, Rajesh; He, Jibao; Johnson, Michael W; Stern, Ilan; Kim, Dae Ho; Pesika, Noshir S

2013-10-29

A room-temperature electrochemical approach to synthesizing anisotropic platelike copper microcrystals and nanocrystals in the presence of potassium bromide is presented. Morphological and elemental characterization was performed using SEM, TEM, and XRD to confirm the anisotropic morphology and crystal structure of the synthesized copper particles. A possible mechanism for explaining the anisotropic crystal growth is proposed on the basis of the preferential adsorption of bromide ions to selective crystal faces. The shape-dependent electrocatalytic property of copper particles is demonstrated by its enhanced catalytic activity for methanol oxidation. Further development of such anisotropic copper particles localized on an electrode surface will lead us to find a suitable alternative for noble metal-based electrocatalysts for the methanol oxidation reaction relevant to fuel cells.

Biomimetic synthesis of calcium carbonate with different morphologies and polymorphs in the presence of bovine serum albumin and soluble starch.

PubMed

Liu, Yuxi; Chen, Yuping; Huang, Xuechen; Wu, Gang

2017-10-01

Calcium carbonate has been synthesized by the reaction of Na 2 CO 3 and CaCl 2 in the presence of bovine serum albumin (BSA) and soluble starch. Effects of various bovine serum albumin (BSA) and soluble starch on the polymorph and morphology of CaCO 3 crystals were investigated. Crystallization of vaterite is favored in the presence of BSA and soluble starch, respectively, while calcite is favored in the presence of a mixture of BSA and soluble starch. The morphologies of CaCO 3 particles in the presence of mixture of BSA and soluble starch are mainly rod-like, suggesting that the BSA, soluble and their assemblies play key roles in stabilizing and directing the CaCO 3 crystal growth. Copyright © 2017. Published by Elsevier B.V.

Synthesis of Mesoporous α-Fe2O3 Nanoparticles by Non-ionic Soft Template and Their Applications to Heavy Oil Upgrading

NASA Astrophysics Data System (ADS)

Park, Chulwoo; Jung, Jinhwan; Lee, Chul Wee; Cho, Joungmo

2016-12-01

This paper reports the synthetic route of 3-D network shape α-Fe2O3 from aqueous solutions of iron precursor using a non-ionic polymeric soft-template, Pluronic P123. During the synthesis of α-Fe2O3, particle sizes, crystal phases and morphologies were significantly influenced by pH, concentrations of precursor and template. The unique shape of worm-like hematite was obtained only when a starting solution was prepared by a weakly basic pH condition and a very specific composition of constituents. The synthesized nanocrystal at this condition had a narrow pore size distribution and high surface area compared to the bulk α-Fe2O3 or the one synthesized from lower pH conditions. The hydrocracking performance was tested over the synthesized iron oxide catalysts with different morphologies. The worm-like shape of iron oxide showed a superior performance, including overall yield of liquid fuel product and coke formation, over the hydrocracking of heavy petroleum oil.

Synthesis of Mesoporous α-Fe2O3 Nanoparticles by Non-ionic Soft Template and Their Applications to Heavy Oil Upgrading

PubMed Central

Park, Chulwoo; Jung, Jinhwan; Lee, Chul Wee; Cho, Joungmo

2016-01-01

This paper reports the synthetic route of 3-D network shape α-Fe2O3 from aqueous solutions of iron precursor using a non-ionic polymeric soft-template, Pluronic P123. During the synthesis of α-Fe2O3, particle sizes, crystal phases and morphologies were significantly influenced by pH, concentrations of precursor and template. The unique shape of worm-like hematite was obtained only when a starting solution was prepared by a weakly basic pH condition and a very specific composition of constituents. The synthesized nanocrystal at this condition had a narrow pore size distribution and high surface area compared to the bulk α-Fe2O3 or the one synthesized from lower pH conditions. The hydrocracking performance was tested over the synthesized iron oxide catalysts with different morphologies. The worm-like shape of iron oxide showed a superior performance, including overall yield of liquid fuel product and coke formation, over the hydrocracking of heavy petroleum oil. PMID:27966663

Synthesis of Mesoporous α-Fe2O3 Nanoparticles by Non-ionic Soft Template and Their Applications to Heavy Oil Upgrading.

PubMed

Park, Chulwoo; Jung, Jinhwan; Lee, Chul Wee; Cho, Joungmo

2016-12-14

This paper reports the synthetic route of 3-D network shape α-Fe 2 O 3 from aqueous solutions of iron precursor using a non-ionic polymeric soft-template, Pluronic P123. During the synthesis of α-Fe 2 O 3 , particle sizes, crystal phases and morphologies were significantly influenced by pH, concentrations of precursor and template. The unique shape of worm-like hematite was obtained only when a starting solution was prepared by a weakly basic pH condition and a very specific composition of constituents. The synthesized nanocrystal at this condition had a narrow pore size distribution and high surface area compared to the bulk α-Fe 2 O 3 or the one synthesized from lower pH conditions. The hydrocracking performance was tested over the synthesized iron oxide catalysts with different morphologies. The worm-like shape of iron oxide showed a superior performance, including overall yield of liquid fuel product and coke formation, over the hydrocracking of heavy petroleum oil.

Solvothermal synthesis and surface chemistry to control the size and morphology of nanoquartz

DOE PAGES

Sochalski-Kolbus, Lindsay M.; Wang, Hsiu-Wen; Rondinone, Adam Justin; ...

2015-09-29

In this paper, we report a solvothermal synthesis method that allows the crystallization of quartz to occur at a relatively low temperature of 300°C in the form of isolated nanosized euhedral crystals. Transmission electron microscopy (TEM) and small area electron diffraction (SAED) were used to confirm the phases present and their particle sizes, morphologies, and crystallinity of the products. In conclusion, the results show that it is possible to control the size and morphology of the nanoquartz from rough nanospheres to nanorods using fluoride, which templates the nanocrystals and moderates growth.

Relationships between the morphology and thermoresponsive behavior in micro/nanostructured thermosetting matrixes containing a 4'-(hexyloxy)-4-biphenylcarbonitrile liquid crystal.

PubMed

Tercjak, Agnieszka; Mondragon, Iñaki

2008-10-07

Meso/nanostructured thermoresponsive thermosetting materials based on an epoxy resin modified with two different molecular weight amphiphilic poly(styrene- block-ethylene oxide) block copolymers (PSEO) and a low molecular weight liquid crystal, 4'-(hexyloxy)-4-biphenylcarbonitrile (HOBC), were investigated. A strong influence of the addition of PSEO on the morphology generated in HOBC--(diglicydyl ether of bisphenol A epoxy resin/ m-xylylenediamine) was detected, especially in the case of the addition of PSEO block copolymers with a higher PEO-block content and a lower molecular weight. The morphologies generated in the ternary systems also influenced the thermoresponsive behavior of the HOBC separated phase provoked by applying an external field, such as a temperature gradient and an electrical field. Thermal analysis of the investigated materials allowed for a better understanding of the relationships between generated morphology/thermo-optical properties/PSEO:HOBC ratio, and HOBC content. Controlling the relationship between the morphology and thermoresponsive behavior in micro/nanostructured thermosetting materials based on a 4'-(hexyloxy)-4-biphenylcarbonitrile liquid crystal allows the development of materials which can find application in thermo- and in some cases electroresponsive devices, with a high contrast ratio between transparent and opaque states.

Tailoring Graphene Morphology and Orientation on Cu(100), Cu(110), and Cu(111)

NASA Astrophysics Data System (ADS)

Jacobberger, Robert; Arnold, Michael

2013-03-01

Graphene CVD on Cu is phenomenologically complex, yielding diverse crystal morphologies, such as lobes, dendrites, stars, and hexagons, of various orientations. We present a comprehensive study of the evolution of these morphologies as a function of Cu surface orientation, pressure, H2:CH4, and nucleation density. Growth was studied on ultra-smooth, epitaxial Cu films inside Cu enclosures to minimize factors that normally complicate growth. With low H2:CH4, Mullins-Sekerka instabilities propagate to form dendrites, indicating transport limited growth. In LPCVD, the dendrites extend hundreds of microns in the 100, 111, and 110 directions on Cu(100), (110), and (111) and are perturbed by twin boundaries. In APCVD, multiple preferred dendrite orientations exist. With increasing H2:CH4, the dendritic nature of growth is suppressed. In LPCVD, square, rectangle, and hexagon crystals form on Cu(100), (110) and (111), reflecting the Cu crystallography. In APCVD, the morphology becomes hexagonal on each surface. If given ample time, every growth regime yields high-quality monolayers with D:G Raman ratio <0.1. The understanding gained here provides a framework to rationally tailor the graphene crystal morphology and orientation.

Morphology of diesel soot residuals from supercooled water droplets and ice crystals: Implications for optical properties

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

China, Swarup; Kulkarni, Gourihar; Scarnato, Barbara V.

Freshly emitted soot particles are fractal-like aggregates, but atmospheric processing often transforms their morphology. Morphology of soot particles plays an important role in determining their optical properties, life cycle and hence their effect on Earth’s radiative balance. However, little is known about the morphology of soot particles that participated in cold cloud processes. Here we report results from laboratory experiments that simulate cold cloud processing of diesel soot particles by allowing them to form supercooled droplets and ice crystals at -20 and -40°C, respectively. Electron microscopy revealed that soot residuals from ice crystals were more compact (roundness~0.55) than those frommore » supercooled droplets (roundness ~0.45), while nascent soot particles were the least compact (roundness~0.41). Optical simulations using the discrete dipole approximation showed that the more compact structure enhances soot single scattering albedo by a factor up to 1.4, thereby reducing the top-of-the-atmosphere direct radiative forcing by ~63%. Lastly, these results underscore that climate models should consider the morphological evolution of soot particles due to cold cloud processing to improve the estimate of direct radiative forcing of soot.« less

Morphology of diesel soot residuals from supercooled water droplets and ice crystals: Implications for optical properties

DOE PAGES

China, Swarup; Kulkarni, Gourihar; Scarnato, Barbara V.; ...

2015-11-01

Freshly emitted soot particles are fractal-like aggregates, but atmospheric processing often transforms their morphology. Morphology of soot particles plays an important role in determining their optical properties, life cycle and hence their effect on Earth’s radiative balance. However, little is known about the morphology of soot particles that participated in cold cloud processes. Here we report results from laboratory experiments that simulate cold cloud processing of diesel soot particles by allowing them to form supercooled droplets and ice crystals at -20 and -40°C, respectively. Electron microscopy revealed that soot residuals from ice crystals were more compact (roundness~0.55) than those frommore » supercooled droplets (roundness ~0.45), while nascent soot particles were the least compact (roundness~0.41). Optical simulations using the discrete dipole approximation showed that the more compact structure enhances soot single scattering albedo by a factor up to 1.4, thereby reducing the top-of-the-atmosphere direct radiative forcing by ~63%. Lastly, these results underscore that climate models should consider the morphological evolution of soot particles due to cold cloud processing to improve the estimate of direct radiative forcing of soot.« less

Seed-Mediated Growth of Gold Nanocrystals: Changes to the Crystallinity or Morphology as Induced by the Treatment of Seeds with a Sulfur Species

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

Zheng, Yiqun; Luo, Ming; Tao, Jing

We report our observation of changes to the crystallinity or morphology during seed-mediated growth of Au nanocrystals. When single-crystal Au seeds with a spherical or rod-like shape were treated with a chemical species such as S₂O₃²⁻ ions, twin defects were developed during the growth process to generate multiply twinned nanostructures. X-ray photoelectron spectroscopy analysis indicated that the S₂O₃²⁻ ions were chemisorbed on the surfaces of the seeds during the treatment. The chemisorbed S₂O₃²⁻ ions somehow influenced the crystallization of Au atoms added onto the surface during a growth process, leading to the formation of twin defects. In contrast to themore » spherical and rod-like Au seeds, the single-crystal structure was retained to generate a concave morphology when single-crystal Au seeds with a cubic or octahedral shape were used for a similar treatment and then seed-mediated growth. The different outcomes are likely related to the difference in spatial distribution of S₂O₃²⁻ ions chemisorbed on the surface of a seed. This approach based on surface modification is potentially extendable to other noble metals for engineering the crystallinity and morphology of nanocrystals formed via seed-mediated growth.« less

Seed-Mediated Growth of Gold Nanocrystals: Changes to the Crystallinity or Morphology as Induced by the Treatment of Seeds with a Sulfur Species

DOE PAGES

Zheng, Yiqun; Luo, Ming; Tao, Jing; ...

2014-12-11

We report our observation of changes to the crystallinity or morphology during seed-mediated growth of Au nanocrystals. When single-crystal Au seeds with a spherical or rod-like shape were treated with a chemical species such as S₂O₃²⁻ ions, twin defects were developed during the growth process to generate multiply twinned nanostructures. X-ray photoelectron spectroscopy analysis indicated that the S₂O₃²⁻ ions were chemisorbed on the surfaces of the seeds during the treatment. The chemisorbed S₂O₃²⁻ ions somehow influenced the crystallization of Au atoms added onto the surface during a growth process, leading to the formation of twin defects. In contrast to themore » spherical and rod-like Au seeds, the single-crystal structure was retained to generate a concave morphology when single-crystal Au seeds with a cubic or octahedral shape were used for a similar treatment and then seed-mediated growth. The different outcomes are likely related to the difference in spatial distribution of S₂O₃²⁻ ions chemisorbed on the surface of a seed. This approach based on surface modification is potentially extendable to other noble metals for engineering the crystallinity and morphology of nanocrystals formed via seed-mediated growth.« less

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

Lin, Xiaomei; Lv, Xin; Wang, Limin

Graphical abstract: - Highlights: • Effect of CTAB on the morphology and crystallization of MnFe{sub 2}O{sub 4}. • The lowest coercivity of MnFe{sub 2}O{sub 4} polyhedron is 11.9 Oe. • MnFe{sub 2}O{sub 4} as anode for LIB shows good reversible capacity and cycle performances. - Abstract: The uniform different morphologies MnFe{sub 2}O{sub 4}, including cube, truncated cube, polyhedron and octahedron, were successfully synthesized via a solvothermal route using cetyltrimethylammonium bromide. The results of control experiments revealed that the concentration of cetyltrimethylammonium bromide was an important factor, which affected the morphology and crystallization of MnFe{sub 2}O{sub 4} submicro-crystals. All the preparedmore » samples exhibited soft-magnetic behavior at room temperature. Especially, the coercivity of MnFe{sub 2}O{sub 4} polyhedron with 200 nm diameter was 11.9 Oe, which was among the lowest values reported so far. Moreover, MnFe{sub 2}O{sub 4} submicro-crystals with special morphologies demonstrated higher reversible capacity (about 1000 mAh g{sup −1}) and different cycle performances. After 50 cycles, polyhedron structure remained 428 mAh/g. The MnFe{sub 2}O{sub 4} would have a potential application as anode material for lithium ion batteries.« less

Anatase TiO2 single crystals with dominant {0 0 1} facets: Synthesis, shape-control mechanism and photocatalytic activity

NASA Astrophysics Data System (ADS)

Tong, Huifen; Zhou, Yingying; Chang, Gang; Li, Pai; Zhu, Ruizhi; He, Yunbin

2018-06-01

Anatase TiO2 micro-crystals with 51% surface exposing highly active {0 0 1} facets are prepared by hydrothermal synthesis using TiF4 as Ti resource and HF as morphology control agent. In addition, anatase TiO2 single crystals exposing large {0 0 1} crystal facets are facilely synthesized with "green" NaF plus HCl replacing HF for the morphology control. A series of comparative experiments are carried out for separately studying the effects of F- and H+ concentrations on the growth of TiO2 crystals, which have not been understood very much in depth so far. The results indicate that both F- and H+ synergistically affect the synthesis of truncated anatase octahedrons, where F- is preferentially adsorbed on the {0 0 1} facets resulting in lateral growth of these facets and H+ adjusts the growth rate of anatase TiO2 along different orientations by tuning the hydrolysis rate. Based on this information, anatase TiO2 single crystals with small size (1.3 μm) and large exposure of {0 0 1} facets (45%) are successfully prepared under optimal conditions ([H+]/[F-] = 20:1). Photocatalytic activities of the as-prepared products toward methylene blue photo-degradation are further tested. It is revealed that both crystal size and percentage of {0 0 1} facets are decisive for the photocatalytic performance, and the crystals with a small size (1.3 μm) and large exposure of {0 0 1} facets (45%) are catalytically most active. This work has clarified the main factors that control the growth process and morphology of anatase TiO2 single crystals for achieving superior photocatalytic properties.

Growth and characterization of new semiorganic nonlinear optical and piezoelectric lithium sulfate monohydrate oxalate single crystals

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

Yadav, Harsh; Sinha, Nidhi; Kumar, Binay, E-mail: b3kumar69@yahoo.co.in

2015-04-15

Highlights: • A new semiorganic single crystal of LSO grown by slow evaporation technique. • Morphological studies of the LSO crystal deduced by BFDH law. • In the UV–vis spectrum wide transparent region and large band gap were found. • SHG is equal to KDP crystal and d{sub 33} was found to be equal to 6pC/N. • Grown crystal belongs to softer category. - Abstract: New semiorganic crystal of lithium sulfate monohydrate oxalate (LSO) for nonlinear application was synthesized by controlled slow evaporation method. The growth rate of various planes of the grown crystal was estimated by morphological study. Singlemore » crystal XRD analysis confirmed that the crystal belongs to triclinic lattice with space group P1. High transparency (∼95%) with large band gap (4.57 eV) was analyzed by UV–vis studies. FTIR and Raman spectroscopy were used to identify various functional groups present in the LSO crystal. SHG efficiency was found to be equal to the KDP crystal. Thermal stability (up to 117.54 °C) and melting point (242 °C) of the crystal were studied by TG-DTA. In dielectric measurements, the value of dielectric constant decreases with increase in frequency. Hardness studies confirmed soft nature of crystals. The piezoelectric coefficient was found to be 6pC/N along [0 0 1].« less

Placement of molecules in (not out of) the cell

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

Dauter, Zbigniew, E-mail: dauter@anl.gov

2013-01-01

The importance of presenting macromolecular structures in unified, standard ways is discussed. To uniquely describe a crystal structure, it is sufficient to specify the crystal unit cell and symmetry, and describe the unique structural motif which is repeated by the space-group symmetry throughout the whole crystal. It is somewhat arbitrary how such a unique motif can be defined and positioned with respect to the unit-cell origin. As a result of such freedom, some isomorphous structures are presented in the Protein Data Bank in different locations and appear as if they have different atomic coordinates, despite being completely equivalent structurally. Thismore » may easily confuse those users of the PDB who are less familiar with crystallographic symmetry transformations. It would therefore be beneficial for the community of PDB users to introduce standard rules for locating crystal structures of macromolecules in the unit cells of various space groups.« less

Secondary Crystal Growth on a Cracked Hydrotalcite-Based Film Synthesized by the Sol-Gel Method.

PubMed

Lee, Wooyoung; Lee, Chan Hyun; Lee, Ki Bong

2016-05-02

The sol-gel synthesis method is an attractive technology for the fabrication of ceramic films due to its preparation simplicity and ease of varying the metal composition. However, this technique presents some limitations in relation to the film thickness. Notably, when the film thickness exceeds the critical limit, large tensile stresses occur, resulting in a cracked morphology. In this study, a secondary crystal growth method was introduced as a post-treatment process for Mg/Al hydrotalcite-based films synthesized by the sol-gel method, which typically present a cracked morphology. The cracked hydrotalcite-based film was hydrothermally treated for the secondary growth of hydrotalcite crystals. In the resulting film, hydrotalcite grew with a vertical orientation, and the gaps formed during the sol-gel synthesis were filled with hydrotalcite after the crystal growth. The secondary crystal growth method provides a new solution for cracked ceramic films synthesized by the sol-gel method.

Illusory spirals and loops in crystal growth

PubMed Central

Shtukenberg, Alexander G.; Zhu, Zina; Bhandari, Misha; Song, Pengcheng; Kahr, Bart; Ward, Michael D.

2013-01-01

The theory of dislocation-controlled crystal growth identifies a continuous spiral step with an emergent lattice displacement on a crystal surface; a mechanistic corollary is that closely spaced, oppositely winding spirals merge to form concentric loops. In situ atomic force microscopy of step propagation on pathological l-cystine crystals did indeed show spirals and islands with step heights of one lattice displacement. We show by analysis of the rates of growth of smaller steps only one molecule high that the major morphological spirals and loops are actually consequences of the bunching of the smaller steps. The morphology of the bunched steps actually inverts the predictions of the theory: Spirals arise from pairs of dislocations, loops from single dislocations. Only through numerical simulation of the growth is it revealed how normal growth of anisotropic layers of molecules within the highly symmetrical crystals can conspire to create features in apparent violation of the classic theory. PMID:24101507

Fracture of single crystals of the nickel-base superalloy PWA 1480E in helium at 22 C

NASA Technical Reports Server (NTRS)

Chen, P. S.; Wilcox, R. C.

1991-01-01

The fracture behavior and deformation of He-charged (at 22 C) single crystals of PWA 1480E Ni-base superalloy were investigated using SEM and TEM techniques to observe the behavior of tensile fractures in notched single crystals with seven different crystal growth orientations: 100-line, 110-line, 111-line, 013-line, 112-line, 123-line, and 223-line. To identify the cleavage plane orientation, a stereoscopic technique, combined with the use of planar gamma-prime morphologies, was applied. It was found that gamma-prime particles were orderly and closely aligned with edges along the 100-line, 010-line, and 001-line-oriented directions of the gamma matrix. Different crystal growth orientations were found not to affect the morphology of gamma-prime particles. The accumulation of dislocations around gamma/gamma-prime interfaces formed strong barriers to subsequent dislocation movement and was the primary strengthening mechanism at room temperature.

Two-dimensional and three-dimensional evaluation of the deformation relief

NASA Astrophysics Data System (ADS)

Alfyorova, E. A.; Lychagin, D. V.

2017-12-01

This work presents the experimental results concerning the research of the morphology of the face-centered cubic single crystal surface after compression deformation. Our aim is to identify the method of forming a quasiperiodic profile of single crystals with different crystal geometrical orientation and quantitative description of deformation structures. A set of modern methods such as optical and confocal microscopy is applied to determine the morphology of surface parameters. The results show that octahedral slip is an integral part of the formation of the quasiperiodic profile surface starting with initial strain. The similarity of the formation process of the surface profile at different scale levels is given. The size of consistent deformation regions is found. This is 45 µm for slip lines ([001]-single crystal) and 30 µm for mesobands ([110]-single crystal). The possibility of using two- and three-dimensional roughness parameters to describe the deformation structures was shown.

Anion Exchange in II-VI Semiconducting Nanostructures via Atomic Templating.

PubMed

Agarwal, Rahul; Krook, Nadia M; Ren, Ming-Liang; Tan, Liang Z; Liu, Wenjing; Rappe, Andrew M; Agarwal, Ritesh

2018-03-14

Controlled chemical transformation of nanostructures is a promising technique to obtain precisely designed novel materials, which are difficult to synthesize otherwise. We report high-temperature vapor-phase anion-exchange reactions to chemically transform II-VI semiconductor nanostructures (100-300 nm length scale) while retaining the single crystallinity, crystal structure, morphology, and even defect distribution of the parent material via atomic templating. The concept of atomic templating is employed to obtain kinetically controlled, thermodynamically metastable structural phases such as zincblende CdSe and CdS from zincblende CdTe upon complete chemical replacement of Te with Se or S. The underlying transformation mechanisms are explained through first-principles density functional theory calculations. Atomic templating is a unique path to independently tune materials' phase and composition at the nanoscale, allowing the synthesis of novel materials.

Spatiotemporal chaos near the onset of cellular growth during thin-film solidification of a binary alloy

NASA Technical Reports Server (NTRS)

Lee, J. T. C.; Tsiveriotis, K.; Brown, R. A.

1992-01-01

Thin-film solidification experiments with a succinonitrile-acetone alloy are used to observe the long time-scale dynamics of cellular crystal growth at growth rates only slightly above the critical value VC = Vc(lambda sub c) for the onset of morphological instability. Under these conditions only very small amplitude cells are observed with wavelengths near the value predicted by linear stability theory lambda = lambda sub c. At long times, microstructures with wavelengths significantly finer than lambda suc c form by nucleation at defects across the interface. These interfaces do not have a unique microstructure, but seem to exhibit spatiotemporal chaos on a long time scale caused by the continual birth and death of cells by tip splitting and cell annihilation in grooves.

Analysis of dispersion relation in three-dimensional single gyroid

NASA Astrophysics Data System (ADS)

Jheng, Pei-Lun; Hung, Yu-Chueh

2016-03-01

Gyroid is a type of three-dimensional chiral structures and has been found in many insect species. Besides the photonic crystal properties exhibited by gyroid structures, the chirality and gyroid network morphology also provide unique opportunities for manipulating propagation of light. In this work, we present studies based on finite-difference time domain (FDTD) method for analyzing the dispersion relation characteristics of dielectric single gyroid (SG) metamaterials. The band structures, transmission spectrum, dispersion surfaces, equifrequency contours (EFCs) of SG metamaterials are examined. Some interesting wave guiding characteristics, such as negative refraction and collimation, are presented and discussed. We also show how these optical properties are predicted by analyzing the EFCs at different frequencies. These results are crucial for the design of functional devices at optical frequencies based on dielectric single gyroid metamaterials.

In situ synthesis of TiO2(B) nanotube/nanoparticle composite anode materials for lithium ion batteries.

PubMed

Liu, Xiang; Sun, Qian; Ng, Alan M C; Djurišić, Aleksandra B; Xie, Maohai; Liao, Changzhong; Shih, Kaimin; Vranješ, Mila; Nedeljković, Jovan M; Deng, Zhaofeng

2015-10-23

Titania nanotubes were prepared by a simple hydrothermal route. Their electrochemical performance has been examined in detail and compared to TiO2(B) nanoparticles, TiO2 anatase and P25 titania nanoparticles. The cycling and rate performance of TiO2 nanotubes is superior to both types of nanoparticles, and it can be further improved by an in situ titanium precursor treatment, which results in the formation of TiO2 nanoparticles on/between the nanotubes. The obtained specific capacity after 200 cycles at 0.2 A g(-1) charge/discharge rate remained above 130 mAh g(-1). The enhanced lithium storage properties of these samples can be attributed to their unique morphology and crystal structure.

Ice Shaping Properties, Similar to That of Antifreeze Proteins, of a Zirconium Acetate Complex

PubMed Central

Deville, Sylvain; Viazzi, Céline; Leloup, Jérôme; Lasalle, Audrey; Guizard, Christian; Maire, Eric; Adrien, Jérôme; Gremillard, Laurent

2011-01-01

The control of the growth morphologies of ice crystals is a critical issue in fields as diverse as biomineralization, medicine, biology, civil or food engineering. Such control can be achieved through the ice-shaping properties of specific compounds. The development of synthetic ice-shaping compounds is inspired by the natural occurrence of such properties exhibited by antifreeze proteins. We reveal how a particular zirconium acetate complex is exhibiting ice-shaping properties very similar to that of antifreeze proteins, albeit being a radically different compound. We use these properties as a bioinspired approach to template unique faceted pores in cellular materials. These results suggest that ice-structuring properties are not exclusive to long organic molecules and should broaden the field of investigations and applications of such substances. PMID:22028886

Mineralogy and Organic Geochemistry of Acid Sulfate Environments from Valles Caldera, New Mexico: Habitability, Weathering and Biosignatures

NASA Astrophysics Data System (ADS)

Vogel, M. B.; Des Marais, D. J.; Jahnke, L. L.; Kubo, M.

2009-12-01

We report on the mineralogy, organic preservation potential and habitability of sulfate deposits in acid sulfate volcanic settings at Valles Caldera, New Mexico. Fumaroles and acidic springs are potential analogs for aqueous environments on Mars and may offer insights into habitability of sulfate deposits such as those at Meridiani Planum. Sulfates recently detected on Mars are posited to have formed from fluids derived from basaltic weathering and igneous volatile input, ultimately precipitating from acidic brines subjected to desiccation and freeze-thaw cycles (McClennan and Grotzinger, 2008). Key issues concerning martian sulfate deposits are their relationship to aqueous clay deposits, and whether or not specific sulfates deposits represent former habitable environments (see Soderblum and Bell, 2008; Tosca et al., 2008). Modern terrestrial volcanic fumaroles and hot springs precipitate various Ca-, Mg- and Fe- sulfates along with clays, and can help clarify whether certain acid sulfate mineral assemblages reflect habitable environments. Valles caldera is a resurgent caldera last active in the Pleistocene (1.4 - 1.0 Ma) that hosts several active fumaroles and over 40 geothermal exploration wells (see Goff, 2009). Fumaroles and associated mudpots and springs at Valles range from pH < 1 to 3, and affect argillic alteration upon rhylolitic tuffs and sedimentary deposits (Charles et al., 1986). We identified assemblages containing gypsum, quartz, Al-sulfates, elemental sulfur, clays and other minerals using XRD and SEM-EDS. Our previous research has shown that sulfates from different marine depositional environments display textural and morphological traits that are indicative of biological influence, or specific conditions in the depositional environments (Vogel et al., 2009). Gypsum crystals that develop in the presence of microbial biofilms in marine environments may have distorted crystal morphologies, biofilm - associated dissolution features, and accessory carbonate minerals. Gypsum from Valles Caldera fumaroles develops in the absence of microbial biofilms and differs from biologically influenced marine gypsum in terms of is highly prismatic morphology, lack of texture, and association with clays, and other sulfates. Studies of Valles gypsum crystals therefore support the uniqueness of the putative morphological biosignatures in marine gypsum. We also assayed organic matter from fumarole encrustations to understand how low pH and sulfate content may discriminate against or enhance preservation of specific classes of organic compounds in acid sulfate environments. Similar to gypsiferous marine environments, organics are characterized by abundant organosulfur complexes. Long chain alkanes (> nC22) are abundant from acid sulfate environments. As with hypersaline marine depositional environments, sulfidation appears to be a major diagenetic pathway for organic matter in acid sulfate environments.

Flow-Directed Crystallization for Printed Electronics.

PubMed

Qu, Ge; Kwok, Justin J; Diao, Ying

2016-12-20

The solution printability of organic semiconductors (OSCs) represents a distinct advantage for materials processing, enabling low-cost, high-throughput, and energy-efficient manufacturing with new form factors that are flexible, stretchable, and transparent. While the electronic performance of OSCs is not comparable to that of crystalline silicon, the solution processability of OSCs allows them to complement silicon by tackling challenging aspects for conventional photolithography, such as large-area electronics manufacturing. Despite this, controlling the highly nonequilibrium morphology evolution during OSC printing remains a challenge, hindering the achievement of high electronic device performance and the elucidation of structure-property relationships. Many elegant morphological control methodologies have been developed in recent years including molecular design and novel processing approaches, but few have utilized fluid flow to control morphology in OSC thin films. In this Account, we discuss flow-directed crystallization as an effective strategy for controlling the crystallization kinetics during printing of small molecule and polymer semiconductors. Introducing the concept of flow-directed crystallization to the field of printed electronics is inspired by recent advances in pharmaceutical manufacturing and flow processing of flexible-chain polymers. Although flow-induced crystallization is well studied in these areas, previous findings may not apply directly to the field of printed electronics where the molecular structures (i.e., rigid π-conjugated backbone decorated with flexible side chains) and the intermolecular interactions (i.e., π-π interactions, quadrupole interactions) of OSCs differ substantially from those of pharmaceuticals or flexible-chain polymers. Another critical difference is the important role of solvent evaporation in open systems, which defines the flow characteristics and determines the crystallization kinetics and pathways. In other words, flow-induced crystallization is intimately coupled with the mass transport processes driven by solvent evaporation during printing. In this Account, we will highlight these distinctions of flow-directed crystallization for printed electronics. In the context of solution printing of OSCs, the key issue that flow-directed crystallization addresses is the kinetics mismatch between crystallization and various transport processes during printing. We show that engineering fluid flows can tune the kinetics of OSC crystallization by expediting the nucleation and crystal growth processes, significantly enhancing thin film morphology and device performance. For small molecule semiconductors, nucleation can be enhanced and patterned by directing the evaporative flux via contact line engineering, and defective crystal growth can be alleviated by enhancing mass transport to yield significantly improved coherence length and reduced grain boundaries. For conjugated polymers, extensional and shear flow can expedite nucleation through flow-induced conformation change, facilitating the control of microphase separation, degree of crystallinity, domain alignment, and percolation. Although the nascent concept of flow-directed solution printing has not yet been widely adopted in the field of printed electronics, we anticipate that it can serve as a platform technology in the near future for improving device performance and for systematically tuning thin film morphology to construct structure-property relationships. From a fundamental perspective, it is imperative to develop a better understanding of the effects of fluid flow and mass transport on OSC crystallization as these processes are ubiquitous across all solution processing techniques and can critically impact charge transport properties.

Sodium chloride crystallization from thin liquid sheets, thick layers, and sessile drops in microgravity

NASA Astrophysics Data System (ADS)

Fontana, Pietro; Pettit, Donald; Cristoforetti, Samantha

2015-10-01

Crystallization from aqueous sodium chloride solutions as thin liquid sheets, 0.2-0.7 mm thick, with two free surfaces supported by a wire frame, thick liquid layers, 4-6 mm thick, with two free surfaces supported by metal frame, and hemispherical sessile drops, 20-32 mm diameter, supported by a flat polycarbonate surface or an initially flat gelatin film, were carried out under microgravity on the International Space Station (ISS). Different crystal morphologies resulted based on the fluid geometry: tabular hoppers, hopper cubes, circular [111]-oriented crystals, and dendrites. The addition of polyethylene glycol (PEG-3350) inhibited the hopper growth resulting in flat-faced surfaces. In sessile drops, 1-4 mm tabular hopper crystals formed on the free surface and moved to the fixed contact line at the support (polycarbonate or gelatin) self-assembling into a shell. Ring formation created by sessile drop evaporation to dryness was observed but with crystals 100 times larger than particles in terrestrially formed coffee rings. No hopper pyramids formed. By choosing solution geometries offered by microgravity, we found it was possible to selectively grow crystals of preferred morphologies.

Growth of InAs NWs with controlled morphology by CVD

NASA Astrophysics Data System (ADS)

Huang, Y. S.; Li, M.; Wang, J.; Xing, Y.; Xu, H. Q.

2017-06-01

We report on the growth of single crystal InAs NWs on Si/SiOx substrates by chemical vapor deposition (CVD). By adjusting growth parameters, the diameters, morphology, length and the proportion of superlattice ZB InAs NWs (NWs) can be controlled on a Si/SiOx substrate. Our work provides a low-cost route to grow and phase-engineer single crystal InAs NWs for a wide range of potential applications.

Photonic Crystal Geometry for Organic Solar Cells

NASA Astrophysics Data System (ADS)

Samulski, Edward; Lopez, Rene; Ko, Doo-Hyun; Tumbleston, John

2010-03-01

Efficient absorption of light calls for thicker PV active layers whereas carrier transport always benefits from thinner ones, and this dichotomy is at the heart of an efficiency/cost conundrum that has kept solar energy expensive relative to fossil fuels. We report a 2-D, photonic crystal morphology that enhances the efficiency of organic photovoltaic cells relative to conventional planar cells.[1] The morphology is developed by patterning an organic photoactive bulk heterojunction blend using PRINT a process that lends itself to large area fabrication of nanostructures.[2] The photonic crystal cell morphology increases photocurrents generally, and particularly through the excitation of resonant modes near the band edge of the organic PV material. [1] Ko, D.-H.; Tumbleston, J. R.; Zhang, L.; Williams, S.; DeSimone, J. M.; Rene, L.; Samulski, E. T. Nano Lett. 2009, 9, 2742--2746. [2] Hampton et al. Adv. Mater. 2008, 20, 2667.

Layered double hydroxide using hydrothermal treatment: morphology evolution, intercalation and release kinetics of diclofenac sodium

NASA Astrophysics Data System (ADS)

Joy, Mathew; Iyengar, Srividhya J.; Chakraborty, Jui; Ghosh, Swapankumar

2017-12-01

The present work demonstrates the possibilities of hydrothermal transformation of Zn-Al layered double hydroxide (LDH) nanostructure by varying the synthetic conditions. The manipulation in washing step before hydrothermal treatment allows control over crystal morphologies, size and stability of their aqueous solutions. We examined the crystal growth process in the presence and the absence of extra ions during hydrothermal treatment and its dependence on the drug (diclofenac sodium (Dic-Na)) loading and release processes. Hexagonal plate-like crystals show sustained release with ˜90% of the drug from the matrix in a week, suggesting the applicability of LDH nanohybrids in sustained drug delivery systems. The fits to the release kinetics data indicated the drug release as a diffusion-controlled release process. LDH with rod-like morphology shows excellent colloidal stability in aqueous suspension, as studied by photon correlation spectroscopy.

Amelogenin Affects Brushite Crystal Morphology and Promotes Its Phase Transformation to Monetite

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

Ren, Dongni; Ruan, Qichao; Tao, Jinhui

2016-09-07

Amelogenin protein is involved in organized apatite crystallization during enamel formation. Brushite (CaHPO4·2H2O), which is one of the precursors for hydroxyapatite in in vitro mineralization, has been used for fabrication of biomaterials for hard tissue repair. In order to explore its potential application in biomimetic material synthesis, we studied the influence of amelogenin on brushite morphology and phase transformation to monetite. Our results show that amelogenin can adsorb onto surface of brushite, leading to the formation of layered structures on the (010) face. Amelogenin promoted the phase transformation of brushite into monetite (CaHPO4) in the dry state, presumably by interactingmore » with crystalline water layers in brushite unit cell. Changes to the crystal morphology by amelogenin continued even after the phase transformation to monetite forming an organized nanotextured structure of nano-sticks resembling the bundle structure in enamel.« less

MnO2 prepared by hydrothermal method and electrochemical performance as anode for lithium-ion battery

PubMed Central

2014-01-01

Two α-MnO2 crystals with caddice-clew-like and urchin-like morphologies are prepared by the hydrothermal method, and their structure and electrochemical performance are characterized by scanning electron microscope (SEM), X-ray diffraction (XRD), galvanostatic cell cycling, cyclic voltammetry, and electrochemical impedance spectroscopy (EIS). The morphology of the MnO2 prepared under acidic condition is urchin-like, while the one prepared under neutral condition is caddice-clew-like. The identical crystalline phase of MnO2 crystals is essential to evaluate the relationship between electrochemical performances and morphologies for lithium-ion battery application. In this study, urchin-like α-MnO2 crystals with compact structure have better electrochemical performance due to the higher specific capacity and lower impedance. We find that the relationship between electrochemical performance and morphology is different when MnO2 material used as electrochemical supercapacitor or as anode of lithium-ion battery. For lithium-ion battery application, urchin-like MnO2 material has better electrochemical performance. PMID:24982603

Morphological Evolution of Nanocluster Aggregates and Single Crystals in Alkaline Zinc Electrodeposition

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

Desai, D; Turney, DE; Anantharaman, B

2014-04-24

The morphology of Zn electrodeposits is studied on carbon-coated transmission electron microscopy grids. At low over-potentials (eta = -50 mV), the morphology develops by aggregation at two distinct length scales: similar to 5 nm diameter monocrystalline nanoclusters form similar to 50 nm diameter polycrystalline aggregates, and the aggregates form a branched network. Epitaxial (00 (0) over bar2) growth above an overpotential of vertical bar eta(c)vertical bar > 125 mV leads to the formation of hexagonal single crystals up to 2 mu m in diameter. Potentiostatic current transients were used to calculate the nucleation rate from Scharifker et al.'s model. Themore » exp(eta) dependence of the nucleation rates indicates that atomistic nucleation theory explains the nucleation process better than Volmer-Weber theory. A kinetic model is provided using the rate equations of vapor solidification to simulate the evolution of the different morphologies. On solving these equations, we show that aggregation is attributed to cluster impingement and cluster diffusion while single-crystal formation is attributed to direct attachment.« less

Protein crystal growth in low gravity

NASA Technical Reports Server (NTRS)

Feigelson, Robert S.

1991-01-01

The objective of this research is to study the effect of low gravity on the growth of protein crystals and those parameters which will affect growth and crystal quality. The application of graphoepitaxy (artificial epitaxy) to proteins is detailed. The development of a method for the control of nucleation is discussed. The factor affecting the morphology of isocitrate lyase crystals is presented.

Use of moments of momentum to predict the crystal habit in potassium hydrogen phthalate

NASA Technical Reports Server (NTRS)

Barber, Patrick G.; Petty, John T.

1990-01-01

A relatively simple calculation of the moments of momentum predicts the morphological order of crystal faces for potassium hydrogen phthalate. The effects on the habit caused by the addition of monomeric, dimeric, and larger aggregates during crystal growth are considered. The first six of the seven observed crystal faces are predicted with this method.

Phosphate recovery through struvite-family crystals precipitated in the presence of citric acid: mineralogical phase and morphology evaluation.

PubMed

Perwitasari, D S; Edahwati, L; Sutiyono, S; Muryanto, S; Jamari, J; Bayuseno, A P

2017-11-01

Precipitation strategy of struvite-family crystals is presented in this paper to recover phosphate and potassium from a synthetic wastewater in the presence of citric acid at elevated temperature. The crystal-forming solutions were prepared from crystals of MgCl 2 and NH 4 H 2 PO 4 with a molar ratio of 1:1:1 for Mg +2 , [Formula: see text], and [Formula: see text], and the citric acid (C 6 H 8 O 7 ) was prepared (1.00 and 20.00 ppm) from citric acid crystals. The Rietveld analysis of X-ray powder diffraction pattern confirmed a mixed product of struvite, struvite-(K), and newberyite crystallized at 30°C in the absence of citric acid. In the presence of citric acid at 30° and 40°C, an abundance of struvite and struvite-(K) were observed. A minute impurity of sylvite and potassium peroxide was unexpectedly found in certain precipitates. The crystal solids have irregular flake-shaped morphology, as shown by scanning electron microscopy micrograph. All parameters (citric acid, temperature, pH, Mg/P, and N/P) were deliberately arranged to control struvite-family crystals precipitation.

Reversible shear-induced crystallization above equilibrium freezing temperature in a lyotropic surfactant system

PubMed Central

Rathee, Vikram; Krishnaswamy, Rema; Pal, Antara; Raghunathan, V. A.; Impéror-Clerc, Marianne; Pansu, Brigitte; Sood, A. K.

2013-01-01

We demonstrate a unique shear-induced crystallization phenomenon above the equilibrium freezing temperature in weakly swollen isotropic and lamellar mesophases with bilayers formed in a cationic-anionic mixed surfactant system. Synchrotron rheological X-ray diffraction study reveals the crystallization transition to be reversible under shear (i.e., on stopping the shear, the nonequilibrium crystalline phase melts back to the equilibrium mesophase). This is different from the shear-driven crystallization below , which is irreversible. Rheological optical observations show that the growth of the crystalline phase occurs through a preordering of the phase to an phase induced by shear flow, before the nucleation of the phase. Shear diagram of the phase constructed in the parameter space of shear rate vs. temperature exhibits and transitions above the equilibrium crystallization temperature , in addition to the irreversible shear-driven nucleation of in the phase below . In addition to revealing a unique class of nonequilibrium phase transition, the present study urges a unique approach toward understanding shear-induced phenomena in concentrated mesophases of mixed amphiphilic systems. PMID:23986497

Shear-induced enhancements of crystallization kinetics and morphological transformation for long chain branched polylactides with different branching degrees

PubMed Central

Wang, Junyang; Bai, Jing; Zhang, Yaqiong; Fang, Huagao; Wang, Zhigang

2016-01-01

The effects of long chain branching (LCB) degree on the shear-induced isothermal crystallization kinetics of a series of LCB polylactides (LCB PLAs) have been investigated by using rotational rheometer, polarized optical microscopy (POM) and scanning electron microscopy (SEM). Dynamic viscoelastic properties obtained by small-amplitude oscillatory shear (SAOS) tests indicate that LCB PLAs show more broadened relaxation time spectra with increasing LCB degree. Upon a pre-shear at the shear rate of 1 s−1 LCB PLAs show much faster crystallization kinetics than linear PLA and the crystallization kinetics is enhanced with increasing LCB degree. By modeling the system as a suspension the quantitative evaluation of nucleation density can be derived from rheological experiments. The nucleation density is greatly enhanced with increasing LCB degree and a saturation in shear time is observed. Crystalline morphologies for LCB PLAs observed by POM and SEM demonstrate the enhancement of nucleation density with increasing LCB degree and a transformation from spherulitic to orientated crystalline morphologies. The observation can be ascribed to longer relaxation time of the longest macromolecular chains and broadened, complex relaxation behaviors due to the introduction of LCB into PLA, which is essential in stabilizing the orientated crystal nuclei after pre-shear. PMID:27246803

The inhibition of tetrahydrofuran clathrate-hydrate formation with antifreeze protein

NASA Astrophysics Data System (ADS)

Zeng, H.; Wilson, L. D.; Walker, V. K.; Ripmeester, J. A.

2003-01-01

The effect of Type I fish antifreeze protein (AFP) from the winter flounder, Pleuronectes americanus (Walbaum), (WfAFP) on the formation of tetrahydrofuran (THF) clathrate hydrate was studied by observing changes in THF crystal morphology and determining the induction time for nucleation. AFP retarded THF clathrate-hydrate growth at the tested temperatures and modified the THF clathrate-hydrate crystal morphology from octahedral to plate-like. AFP appears to be even more effective than the kinetic inhibitor, polyvinylpyrrolidone (PVP). Recombinant AFP from an insect, a spruce budworm, Choristoneura fumiferana (Clem.), moth, (Cf) was also tested for inhibition activity by observation of the THF-hydrate-crystal-growth habit. Like WfAFP, CfAFP appeared to show adsorption on multiple THF-hydrate-crystal faces. A protein with no antifreeze activity, cytochrome C, was used as a control and it neither changed the morphology of the THF clathrate-hydrate crystals, nor retarded the formation of the hydrate. Preliminary experiments on the inhibition activity of WfAFP on a natural gas hydrate assessed induction time and the amount of propane gas consumed. Similar to the observations for THF, the data indicated that WfAFP inhibited propane-hydrate growth. Taken together, these results support our hypothesis that AFPs can inhibit clathrate-hydrate growth and as well, offer promise for the understanding of the inhibition mechanism.

g-Tensor determination from single-crystal ESR data

NASA Astrophysics Data System (ADS)

Byrn, Marianne P.; Strouse, Charles E.

A general method is presented for extraction of the g tensor from single-crystal electron spin resonance data. This method does not depend on knowledge of crystal morphology or on the presence of crystallographic symmetry. The g values are obtained from rotations around three arbitrarily chosen but accurately known axes.

Modelling the growth of feather crystals

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

Wood, H.J.; Hunt, J.D.; Evans, P.V.

1997-02-01

An existing numerical model of dendritic growth has been adapted to model the growth of twinned columnar dendrites (feather crystals) in a binary aluminium alloy, Examination of the effect of dendrite tip angle on growth has led to an hypothesis regarding the stability of a pointed tip morphology in these crystals.

Synthesis and structural characterization of nano-hydroxyapatite biomaterials prepared by microwave processing

NASA Astrophysics Data System (ADS)

Ramli, Rosmamuhamadani; Arawi, Ainaa Zafirah Omar; Talari, Mahesh Kumar; Mahat, Mohd Muzamir; Jais, Umi Sarah

2012-07-01

Synthetic hydroxyapatite, (HA, Ca10(PO4)6(OH)2), is an attractive and widely utilized bio-ceramic material for orthopedic and dental implants because of its close resemblance of native tooth and bone crystal structure. Synthetic HA exhibits excellent osteoconductive properties. Osteoconductivity means the ability to provide the appropriate scaffold or template for bone formation. Calcium phosphate biomaterials [(HA), tri-calcium phosphate (TCP) and biphasic calcium phosphate (HA/TCP)] with appropriate three-dimensional geometry are able to bind and concentrate endogenous bone morphogenetic proteins in circulation, and may become osteoinductive and can be effective carriers of bone cell seeds. This HA can be used in bio-implants as well as drug delivery application due to the unique properties of HA. Biomaterials synthesized from the natural species like mussel shells have additional benefits such as high purity, less expensive and high bio compatibility. In this project, HA-nanoparticles of different crystallite size were prepared by microwave synthesis of precursors. High purity CaO was extracted from the natural mussel shells for the synthesis of nano HA. Dried nano HA powders were analyzed using X-Ray Diffraction (XRD) technique for the determination of crystal structure and impurity content. Scanning Electron Microscopic (SEM) investigation was employed for the morphological investigation of nano HA powders. From the results obtained, it was concluded that by altering the irradiation time, nano HA powders of different crystallite sizes and morphologies could be produced. Crystallite sizes calculated from the XRD patterns are found to be in the range of 10-55 nm depending on the irradiation time.

Template-Directed Crystallization of High Energy Materials

DTIC Science & Technology

2014-04-01

objectives of this grant were to (a) examine the solution crystallization of RDX , HMX and CL-20 from a variety of solvents, withdetailed analysis of...crystal nucleation templates and (c) to assess the growth of RDX , HMX and CL-20 on these templates. High explosives, crystallization, RDX , CL-20...crystallization of RDX , HMX and CL-20 from a variety of solvents, with detailed analysis of their phase, size, and morphological properties; (b) to

Improvement of physicomechanical properties of carbamazepine by recrystallization at different pH values.

PubMed

Javadzadeh, Yousef; Mohammadi, Ameneh; Khoei, Nazaninossadat Seyed; Nokhodchi, Ali

2009-06-01

The morphology of crystals has an appreciable impact role on the physicochemical properties of drugs. Drug properties such as flowability, dissolution, hardness and bioavailability may be affected by crystallinity behaviours of drugs. The objective of this study was to achieve an improved physicomechanical property of carbamazepine powder through recrystallization from aqueous solutions at different pH values. For this purpose, carbamazapine was recrystallized from aqueous solutions at different pH values (1, 7, 11). The morphology of crystals was investigated using scanning electron microscopy; X-ray powder diffraction (XRPD) was used to identify polymorphism; thermodynamic properties were analyzed using differential scanning calorimetery (DSC). Dissolution rate was determined using USP dissolution apparatus. Mechanical behavior of recrystallized carbamazepine powders was investigated by making tablets under different compaction pressure and measuring their hardness. SEM studies showed that the carbamazepine crystallization in different media affected the morphology and size of carbamazepine crystals. The shape of carbamazepine crystals changed from flaky or thin plate-like to needle shape. XRPD and DSC results ruled out any crystallinity changes occurring due to the temperature during recrystallization procedure or pH of crystallization media. The crushing strength of tablets indicated that all of the recrystallized carbamazepine samples had better compactiblity than the original carbamazepine powder. In vitro dissolution studies of carbamazepine samples showed a higher dissolution rate for carbamazepine crystals obtained from media with pH 11 and 1. Carbamazepine particles recrystallized from aqueous solutions of different pH values (all media) appeared to have superior mechanical properties to those of the original carbamazepine sample.

In vitro studies reveal antiurolithic effect of Terminalia arjuna using quantitative morphological information from computerized microscopy.

PubMed

Mittal, A; Tandon, S; Singla, S K; Tandon, C

2015-01-01

For most cases, urolithiasis is a condition where excessive oxalate is present in the urine. Many reports have documented free radical generation followed by hyperoxaluria as a consequence of which calcium oxalate (CaOx) deposition occurs in the kidney tissue. The present study is aimed to exam the antilithiatic potency of the aqueous extract (AE) of Terminalia arjuna (T. arjuna). The antilithiatic activity of Terminalia arjuna was investigated in vitro nucleation, aggregation and growth of the CaOx crystals as well as the morphology of CaOx crystals using the inbuilt software 'Image-Pro Plus 7.0' of Olympus upright microscope (BX53). Antioxidant activity of AE of Terminalia arjuna bark was also determined in vitro. Terminalia arjuna extract exhibited a concentration dependent inhibition of nucleation and aggregation of CaOx crystals. The AE of Terminalia arjuna bark also inhibited the growth of CaOx crystals. At the same time, the AE also modified the morphology of CaOx crystals from hexagonal to spherical shape with increasing concentrations of AE and reduced the dimensions such as area, perimeter, length and width of CaOx crystals in a dose dependent manner. Also, the Terminalia arjuna AE scavenged the DPPH (2, 2-diphenyl-1-picrylhydrazyl) radicals with an IC50 at 13.1µg/mL. The study suggests that Terminalia arjuna bark has the potential to scavenge DPPH radicals and inhibit CaOx crystallization in vitro. In the light of these studies, Terminalia arjuna can be regarded as a promising candidate from natural plant sources of antilithiatic and antioxidant activity with high value.

Optical trapping assembling of clusters and nanoparticles in solution by CW and femtosecond lasers

NASA Astrophysics Data System (ADS)

Masuhara, Hiroshi; Sugiyama, Teruki; Yuyama, Ken-ichi; Usman, Anwar

2015-02-01

Laser trapping of molecular systems in solution is classified into three cases: JUST TRAPPING, EXTENDED TRAPPING, and NUCLEATION and GROWTH. The nucleation in amino acid solutions depends on where the 1064-nm CW trapping laser is focused, and crystallization and liquid-liquid phase separation are induced by laser trapping at the solution/air surface and the solution/glass interface, respectively. Laser trapping crystallization is achieved even in unsaturated solution, on which unique controls of crystallization are made possible. Crystal size is arbitrarily controlled by tuning laser power for a plate-like anhydrous crystal of l-phenylalanine. The α- or γ-crystal polymorph of glycine is selectively prepared by changing laser power and polarization. Further efficient trapping of nanoparticles and their following ejection induced by femtosecond laser pulses are introduced as unique trapping phenomena and finally future perspective is presented.

Quantitative control of CaCO3 growth on quartz crystal microbalance sensors as a signal amplification method.

PubMed

Wu, Congcong; Sun, Zhaomei; Liu, Li-Shang

2017-07-10

The surface crystallization of CaCO 3 on gold was monitored by a quartz crystal microbalance (QCM). Quantitative control of the grown crystals was realized by adjusting the ratio of two functional groups, -N(CH 3 ) 3 and -COOH, on SAMs. Crystals with uniform size, morphology and polymorphism were obtained. The amount of crystals formed was found to increase with an increase in the -COOH group. The proposed quantitative control of crystallization can be an effective mass amplification strategy for QCM to enhance its assay sensitivity.

Morphological Awareness and Children's Writing: Accuracy, Error, and Invention

PubMed Central

McCutchen, Deborah; Stull, Sara

2014-01-01

This study examined the relationship between children's morphological awareness and their ability to produce accurate morphological derivations in writing. Fifth-grade U.S. students (n = 175) completed two writing tasks that invited or required morphological manipulation of words. We examined both accuracy and error, specifically errors in spelling and errors of the sort we termed morphological inventions, which entailed inappropriate, novel pairings of stems and suffixes. Regressions were used to determine the relationship between morphological awareness, morphological accuracy, and spelling accuracy, as well as between morphological awareness and morphological inventions. Linear regressions revealed that morphological awareness uniquely predicted children's generation of accurate morphological derivations, regardless of whether or not accurate spelling was required. A logistic regression indicated that morphological awareness was also uniquely predictive of morphological invention, with higher morphological awareness increasing the probability of morphological invention. These findings suggest that morphological knowledge may not only assist children with spelling during writing, but may also assist with word production via generative experimentation with morphological rules during sentence generation. Implications are discussed for the development of children's morphological knowledge and relationships with writing. PMID:25663748

Banded Spherulitic Morphology in Blends of Poly(propylene fumarate) and Poly( -caprolactone) and Interaction with MC3T3-E1 Cells

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

Wang, Kan; Jesse, Stephen; Wang, Shanfeng

2012-01-01

The thermal properties, morphological development, crystallization behavior, and miscibility of semicrystalline PCL and its 25, 50, and 75 wt% blends with amorphous PPF in spin-coated thin films crystallized at various crystallization temperatures (T{sub c}) from 25 to 52 C are investigated. The surface roughness of PPF/PCL ({phi}{sub PCL} = 75%) films increases with increasing T{sub c} and consequently the adsorption of serum proteins is also increased. No significant variance is found in surface hydrophilicity or in mouse MC3T3-E1 cell attachment, spreading, and proliferation on PPF/PCL ({phi}{sub PCL} = 75%) films crystallized isothermally at 25, 37, and 45 C, because ofmore » low ridge height, nonuniformity in structures, and PPF surface segregation« less

Morphological Features of Diamond Crystals Dissolved in Fe0.7S0.3 Melt at 4 GPa and 1400°C

NASA Astrophysics Data System (ADS)

Sonin, V. M.; Zhimulev, E. I.; Pomazanskiy, B. S.; Zemnuhov, A. L.; Chepurov, A. A.; Afanasiev, V. P.; Chepurov, A. I.

2018-01-01

An experimental study of the dissolution of natural and synthetic diamonds in a sulfur-bearing iron melt (Fe0.7S0.3) with high P-T parameters (4 GPa, 1400°C) was performed. The results demonstrated that under these conditions, octahedral crystals with flat faces and rounded tetrahexahedral diamond crystals are transformed into rounded octahedroids, which have morphological characteristics similar to those of natural diamonds from kimberlite. It was suggested that, taking into account the complex history of individual natural diamond crystals, including the dissolution stages, sulfur-bearing metal melts up to sulfide melts were not only diamond-forming media during the early evolution of the Earth, but also natural solvents of diamond in the mantle environment before the formation of kimberlitic melts.

Investigations into the mechanical and physical behavior of thermoplastic elastomers

NASA Astrophysics Data System (ADS)

Wright, Kathryn Janelle

This thesis describes investigations into the physical and mechanical characteristics of two commercial thermoplastic elastomer (TPE) systems. Both systems studied exhibit elastomeric behavior similar to more traditional crosslinked elastomers; however, in these TPEs non-conventional polymer architectures and morphologies are used to produce their elastomeric behavior. The two TPEs of interest are ethylene-propylene random copolymers and dynamically vulcanized blends of ethylene-propylene-diene monomer (EPDM) and isotactic polypropylene (iPP). Very few studies have examined the mechanical behavior of these materials in terms of their composition and morphology. As such, the primary goal of this research is to both qualitatively and quantitatively understand the influence of composition and morphology on mechanical behavior. In additional very little information is available that compares their performance with that of crosslinked elastomers. As a result, the secondary goal is to qualitatively compare the mechanical responses of these TPEs with that of their more traditional counterparts. The ethylene-propylene copolymers studied have very high comonomer contents and exhibit slow crystallization kinetics. Their morphology consists of nanoscale crystallites embedded in an amorphous rubbery matrix. These crystallites act as physical crosslinks that allow for elasticity. Slow crystallization causes subsequent changes in mechanical behavior that take place over days and even weeks. Physical responses (e.g., density, crystallization kinetics, and crystal structure) of five copolymer compositions are investigated. Mechanical responses (e.g., stiffness, ductility, yielding, and reversibility) are also examined. Finally, the influence of morphology on deformation is studied using in situ analytical techniques. The EPDM/iPP blends are dynamically vulcanized which produces a complex morphology consisting of chemically crosslinked EPDM domains embedded within a semicrystalline iPP matrix. Six compositions are investigated as a function of three parameters: major volume fraction, iPP molecular weight, and EPDM cure state. The influence of these parameters on morphology and resulting mechanical behavior is examined. This work culminates in the development of a morphological model to describe the steady-state reversibility of these EPDM/iPP blends. The model is then evaluated in terms of composition and cure state.

Biomimetic Photonic Crystals based on Diatom Algae Frustules

NASA Astrophysics Data System (ADS)

Mishler, Jonathan; Alverson, Andrew; Herzog, Joseph

2015-03-01

Diatom algae are unicellular, photosynthetic microorganisms with a unique external shell known as a frustule. Frustules, which are composed of amorphous silica, exhibit a unique periodic nano-patterning, distinguishing diatoms from other types of phytoplankton. Diatoms have been studied for their distinctive optical properties due to their resemblance of photonic crystals. In this regard, diatoms are not only considered for their applications as photonic crystals, but also for their use as biomimetic templates for artificially fabricated photonic crystals. Through the examination and measurement of the physical characteristics of many scanning electron microscope (SEM) images of diatom frustules, a biomimetic photonic crystal derived from diatom frustules can be recreated and modeled with the finite element method. In this approach, the average geometries of the diatom frustules are used to recreate a 2-dimensional photonic crystal, after which the electric field distribution and optical transmission through the photonic crystal are both measured. The optical transmission is then compared to the transmission spectra of a regular hexagonal photonic crystal, revealing the effects of diatom geometry on their optical properties. Finally, the dimensions of the photonic crystal are parametrically swept, allowing for further control over the transmission of light through the photonic crystal.

Selective crystallization of calcium salts by poly(acrylate)-grafted chitosan.

PubMed

Neira-Carrillo, Andrónico; Yazdani-Pedram, Mehrdad; Retuert, Jaime; Diaz-Dosque, Mario; Gallois, Sebastien; Arias, José L

2005-06-01

The biopolymer chitosan was chemically modified by grafting polyacrylamide or polyacrylic acid in a homogeneous aqueous phase using potassium persulfate (KPS) as redox initiator system in the presence of N,N-methylene-bis-acrylamide as a crosslinking agent. The influence of the grafted chitosan on calcium salts crystallization in vitro was studied using the sitting-drop method. By using polyacrylamide grafted chitosan as substrate, rosette-like CaSO4 crystals were observed. This was originated by the presence of sulfate coming from the initiator KPS. By comparing crystallization on pure chitosan and on grafted chitosan, a dramatic influence of the grafted polymer on the crystalline habit of both salts was observed. Substrates prepared by combining sulfate with chitosan or sulfate with polyacrylamide did not produce similar CaSO4 morphologies. Moreover, small spheres or donut-shaped CaCO3 crystals on polyacrylic acid grafted chitosan were generated. The particular morphology of CaCO3 crystals depends also on other synthetic parameters such as the molecular weight of the chitosan sample and the KPS concentration.

Chondroitin sulfate template-mediated biomimetic synthesis of nano-flake hydroxyapatite

NASA Astrophysics Data System (ADS)

He, Dan; Xiao, Xiufeng; Liu, Fang; Liu, Rongfang

2008-11-01

By Ca(NO 3) 2·4H 2O and (NH 4) 3PO 4·3H 2O as reagents and chondroitin sulfate (ChS) as a template, nano-flake hydroxyapatite (HA) is synthesized using a biomimetic method according to the biomineralization theory. HA crystals obtained are characterized in crystalline phase, microstructure, chemical composition and morphology by X-ray diffraction (XRD), Fourier transform infrared spectroscope (FTIR), transmission electron microscopy (TEM) and elemental analysis respectively. UV-vis spectrum is adopted to investigate interactions between functional groups ChS and HA. The results show that HA crystal nucleation and growth take place in chemical interactions between HA crystals and ChS as a template. And elemental analysis indicates that obtained HA contains a small amount of ChS. Furthermore, ChS concentration significantly affects the morphology of HA crystals. Staple-fiber-like HA crystals can be obtained at a low concentration in ChS, and flake-like HA crystals synthesized at a high concentration (≥0.5 wt.%) of ChS as a template.

Solvent effects and polymorphic transformation of organic nonlinear optical crystal L-pyroglutamic acid in solution growth processes . I. Solvent effects and growth morphology

NASA Astrophysics Data System (ADS)

Wang, W. S.; Aggarwal, M. D.; Choi, J.; Gebre, T.; Shields, Angela D.; Penn, Benjamin G.; Frazier, Donald O.

1999-03-01

Single crystals of a new promising nonlinear optical material for the tunable UV harmonic generation, L-pyroglutamic acid 60×20×20 mm 3 in size were obtained from aqueous solution by using the temperature-lowering method. Solubility of L-pyroglutamic acid in different solvents was measured. The single crystals showed different morphological characteristics and growth rate in different solvents with different crystallographic orientations. Methanol or ethanol solutions yielded needle-like crystals. In mixed solution such as methanol/H 2O or ethanol/ H 2O plate-like crystals with a thickness in the direction [0 1 0] were observed. The water as a good solvent, however, produced long prism-like crystals. The two polymorphs of L-pyroglutamic acid (α and β phases) were found for the first time. The growth shapes of α-phase is mainly a prism and β phases is a rhombic plate.The growth rate of α and β phases is mainly a function of the supersaturation of the L-pyroglutamic acid in solution.

Ca2+ transport and signalling in enamel cells

PubMed Central

Nurbaeva, Meerim K.; Eckstein, Miriam; Feske, Stefan

2016-01-01

Abstract Dental enamel is one of the most remarkable examples of matrix‐mediated biomineralization. Enamel crystals form de novo in a rich extracellular environment in a stage‐dependent manner producing complex microstructural patterns that are visually stunning. This process is orchestrated by specialized epithelial cells known as ameloblasts which themselves undergo striking morphological changes, switching function from a secretory role to a cell primarily engaged in ionic transport. Ameloblasts are supported by a host of cell types which combined represent the enamel organ. Fully mineralized enamel is the hardest tissue found in vertebrates owing its properties partly to the unique mixture of ionic species represented and their highly organized assembly in the crystal lattice. Among the main elements found in enamel, Ca2+ is the most abundant ion, yet how ameloblasts modulate Ca2+ dynamics remains poorly known. This review describes previously proposed models for passive and active Ca2+ transport, the intracellular Ca2+ buffering systems expressed in ameloblasts and provides an up‐dated view of current models concerning Ca2+ influx and extrusion mechanisms, where most of the recent advances have been made. We also advance a new model for Ca2+ transport by the enamel organ. PMID:27510811

Modulation of polyepoxysuccinic acid on crystallization of calcium oxalate

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

Zhang, Yanqing; Tang, Yongming, E-mail: tangym@njtech.edu.cn; Xu, Jinqiu

The influence of polyepoxysuccinic acid (PESA) on the phase composition and crystal morphology of calcium oxalate was investigated in this paper. It was found that the presence of PESA inhibited the growth of the monoclinic calcium oxalate monohydrate (COM) crystal and promoted the nucleation of the tetragonal calcium oxalate dihydrate (COD). In addition, with the increase in PESA concentration, the aggregation of COD crystals was reduced but the particle size was increased. Under the conditions of low calcium-to-oxalate ratio and high CaOx concentration, PESA could not effectively stabilize the formation of COD. Based on molecular dynamic simulations, the adsorption ofmore » PESA on CaOx crystal faces was confirmed. - Graphical abstract: Introduction of PESA into crystallization solutions promotes the formation of calcium oxalate dehydrate and modifies the morphology of crystals. - Highlights: • PESA induces the formation of COD at low supersaturation. • Establishment of Ca-rich surface augments the adsorption of PESA. • At Ca/Ox=0.5 PESA cannot induce the formation of COD compared with Ca/Ox=2. • Interaction of PESA with COM faces is stronger than that with COD faces.« less

Single crystal fibers for high power lasers

NASA Astrophysics Data System (ADS)

Kim, W.; Florea, C.; Baker, C.; Gibson, D.; Shaw, L. B.; Bowman, S.; O'Connor, S.; Villalobos, G.; Bayya, S.; Aggarwal, I. D.; Sanghera, J. S.

2012-11-01

In this paper, we present our recent results in developing cladded-single crystal fibers for high power single frequency fiber lasers significantly exceeding the capabilities of existing silica fiber based lasers. This fiber laser would not only exploit the advantages of crystals, namely their high temperature stability, high thermal conductivity, superior environmental ruggedness, high propensity for rare earth ion doping and low nonlinearity, but will also provide the benefits from an optical fiber geometry to enable better thermal management thereby enabling the potential for high laser power output in short lengths. Single crystal fiber cores with diameters as small as 35μm have been drawn using high purity rare earth doped ceramic or single crystal feed rods by Laser Heated Pedestal Growth (LHPG) process. The mechanical, optical and morphological properties of these fibers have been characterized. The fibers are very flexible and show good overall uniformity. We also measured the optical loss as well as the non-radiative loss of the doped crystal fibers and the results show that the fibers have excellent optical and morphological quality. The gain coefficient of the crystal fiber matches the low quantum defect laser model and it is a good indication of the high quality of the fibers.

Morphology of poly-p-xylylene crystallized during polymerization.

NASA Technical Reports Server (NTRS)

Kubo, S.; Wunderlich, B.

1971-01-01

The morphology of as-polymerized poly-p-xylylene grown between -17 and 30 C is found to consist of lame llar alpha crystals oriented with the (010) plane parallel to the support surface. The crystallinity decreases with decreasing polymerization temperature. Spherulitic and nonspherulitic portions of the polymer film consist of folded chain lamellas with the chain axis parallel to the support surface. The results were obtained by small- and wide-angle X-ray measurements, electron and optical microscopy, and differential thermal analysis.

Probability and surprisal in auditory comprehension of morphologically complex words.

PubMed

Balling, Laura Winther; Baayen, R Harald

2012-10-01

Two auditory lexical decision experiments document for morphologically complex words two points at which the probability of a target word given the evidence shifts dramatically. The first point is reached when morphologically unrelated competitors are no longer compatible with the evidence. Adapting terminology from Marslen-Wilson (1984), we refer to this as the word's initial uniqueness point (UP1). The second point is the complex uniqueness point (CUP) introduced by Balling and Baayen (2008), at which morphologically related competitors become incompatible with the input. Later initial as well as complex uniqueness points predict longer response latencies. We argue that the effects of these uniqueness points arise due to the large surprisal (Levy, 2008) carried by the phonemes at these uniqueness points, and provide independent evidence that how cumulative surprisal builds up in the course of the word co-determines response latencies. The presence of effects of surprisal, both at the initial uniqueness point of complex words, and cumulatively throughout the word, challenges the Shortlist B model of Norris and McQueen (2008), and suggests that a Bayesian approach to auditory comprehension requires complementation from information theory in order to do justice to the cognitive cost of updating probability distributions over lexical candidates. Copyright © 2012 Elsevier B.V. All rights reserved.

Efficiency enhancement of perovskite solar cells using structural and morphological improvement of CH3NH3PbI3 absorber layers

NASA Astrophysics Data System (ADS)

Alidaei, Maryam; Izadifard, Morteza; Ghazi, Mohammad E.; Ahmadi, Vahid

2018-01-01

Perovskite solar cells have been heavily investigated due to their unique properties such as high power conversion efficiency (PCE), low-cost fabrication by solution processes, high diffusion length, large absorption coefficient, and direct and tunable band gap. PCE of perovskite devices is strongly dependent on the absorber layer properties such as morphology, crystallinity, and compactness, which are required to be optimized. In this work, the CH3NH3PbI3 (170-480 nm) absorber layers with various methylammonium iodine (MAI) concentrations (7, 10, 20 and 40 mg ml-1) and perovskite solar cells with the fluorine-doped tin oxide (400 nm)/C-TiO2 (30 nm)/Meso-TiO2 (400 nm)/CH3NH3PbI3 (170-480 nm)/P3HT (30 nm)/Au (100 nm) structure were fabricated. A two-step solution process was used for deposition of the CH3NH3PbI3 absorber layers. The morphology, crystal structure, and optical properties of the perovskite layer grown on glass and also the photovoltaic properties of the fabricated solar cells were studied. The results obtained showed that by controlling the deposition conditions, due to the reduction in charge recombination, PCE enhancement of the perovskite solar cell (up to 11.6%) was accessible.

Structural development and kinetic analysis of PbTiO3 powders processed at low-temperature via new sol-gel approach

NASA Astrophysics Data System (ADS)

Bel-Hadj-Tahar, Radhouane; Abboud, Mohamed

2018-04-01

The synthesis of crystalline lead titanate powder by a generic low-temperature sol-gel approach is developed. Acetoin was added as ligand, instead of the commonly used alkanolamines, to ensure total dissolution of the precursor compounds. The feasibility of the acetoin-Ti isopropoxide complex as a new precursor of PbTiO3 perovskite particles via sol-gel method has been demonstrated. No excess lead has been introduced. Nanometric PbTiO3 crystallites have been formed at 400 °C under atmospheric pressure from titanium isopropoxide and lead acetate in alcoholic solution by remarkably low activation energy of crystallization process of 90 kJ mol-1. The powders show tetragonal lattice and dendritic morphology. In addition to the effect of heat-treatment temperature, time, and atmosphere, the sol chemistry particularly influenced the phase composition, particle size, and particle morphology. The use of different ligands significantly modified powder morphology. The extent of the crystallization was quantitatively evaluated by differential thermal analysis and analyzed by Johnson-Mehl-Avrami approach. The crystallization followed two rate regimes depending on the interval of the crystallized fraction.

Calcite precipitates in Slovenian bottled waters.

PubMed

Stanič, Tamara Ferjan; Miler, Miloš; Brenčič, Mihael; Gosar, Mateja

2017-06-01

Storage of bottled waters in varying ambient conditions affects its characteristics. Different storage conditions cause changes in the initial chemical composition of bottled water which lead to the occurrence of precipitates with various morphologies. In order to assess the relationship between water composition, storage conditions and precipitate morphology, a study of four brands of Slovenian bottled water stored in PET bottles was carried out. Chemical analyses of the main ions and measurements of the physical properties of water samples were performed before and after storage of water samples at different ambient conditions. SEM/EDS analysis of precipitates was performed after elapsed storage time. The results show that the presence of Mg 2+ , SO 4 2- , SiO 2 , Al, Mn and other impurities such as K + , Na + , Ba and Sr in the water controlled precipitate morphology by inhibiting crystal growth and leading to elongated rhombohedral calcite crystal forms which exhibit furrowed surfaces and calcite rosettes. Different storage conditions, however, affected the number of crystallization nuclei and size of calcite crystals. Hollow calcite spheres composed of cleavage rhombohedrons formed in the water with variable storage conditions by a combination of evaporation and precipitation of water droplets during high temperatures or by the bubble templating method.

Experimental and theoretical study to explain the morphology of CaMoO4 crystals

NASA Astrophysics Data System (ADS)

Oliveira, F. K. F.; Oliveira, M. C.; Gracia, L.; Tranquilin, R. L.; Paskocimas, C. A.; Motta, F. V.; Longo, E.; Andrés, J.; Bomio, M. R. D.

2018-03-01

CaMoO4 crystals were prepared by a controlled co-precipitation method and processed in a domestic microwave-assisted hydrothermal system with two different surfactants (ethyl 4-dimethylaminobenzoate and 1,2,4,5-benzenetetracarboxylic dianhydride). The corresponding structures were characterized by X-ray diffraction and Rietveld refinement techniques, Fourier transform infrared spectroscopy, ultraviolet-visible absorption spectroscopy, and photoluminescence measurements. Field emission scanning electron microscopy was used to investigate the morphology of the as-synthesized aggregates. The structure, the surface stability of the (001), (112), (100), (110), (101), and (111) surfaces of CaMoO4, and their morphological transformations were investigated through systematic first-principles calculations within the density functional theory method at the B3LYP level. Analysis of the surface structures showed that the electronic properties were associated with the presence of undercoordinated [CaOx] (x = 5 and 6) and [MoOy] (y = 4 and 3) clusters. The relative surfaces energies were tuned to predict a complete map of the morphologies available through a Wulff construction approach. The results reveal that the experimental and theoretical morphologies obtained coincide when the surface energies of the (001) and (101) surfaces increase, while the surface energy of the (100) facet decreases simultaneously. The results provide a comprehensive catalog of the morphologies most likely to be present under realistic conditions, and will serve as a starting point for future studies on the surface chemistry of CaMoO4 crystals.

Crystal fibers for high power lasers

NASA Astrophysics Data System (ADS)

Kim, W.; Florea, C.; Gibson, D.; Peele, J.; Askins, C.; Shaw, B.; Bowman, S.; O'Connor, S.; Bayya, S.; Aggarwal, I.; Sanghera, J. S.

2013-02-01

In this paper, we present our recent progress in developing single crystal fibers for high power single frequency fiber lasers. The optical, spectral and morphological properties as well as the loss and gain measured from these crystal fibers drawn by Laser Heated Pedestal Growth (LHPG) system are also discussed. Results on application of various cladding materials on the crystal core and the methods of fiber end-face polishing are also presented.

Precipitation of thin-film organic single crystals by a novel crystal growth method using electrospray and ionic liquid film

NASA Astrophysics Data System (ADS)

Ueda, Hiroyuki; Takeuchi, Keita; Kikuchi, Akihiko

2018-04-01

We report an organic single crystal growth technique, which uses a nonvolatile liquid thin film as a crystal growth field and supplies fine droplets containing solute from the surface of the liquid thin film uniformly and continuously by electrospray deposition. Here, we investigated the relationships between the solute concentration of the supplied solution and the morphology and size of precipitated crystals for four types of fluorescent organic low molecule material [tris(8-hydroxyquinoline)aluminum (Alq3), 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (PBD), N,N‧-bis(3-methylphenyl)-N,N‧-diphenylbenzidine (TPD), and N,N-bis(naphthalene-1-yl)-N,N-diphenyl-benzidine (NPB)] using an ionic liquid as the nonvolatile liquid. As the concentration of the supplied solution decreased, the morphology of precipitated crystals changed from dendritic or leaf shape to platelike one. At the solution concentration of 0.1 mg/ml, relatively large platelike single crystals with a diagonal length of over 100 µm were obtained for all types of material. In the experiment using ionic liquid and dioctyl sebacate as nonvolatile liquids, it was confirmed that there is a clear positive correlation between the maximum volume of the precipitated single crystal and the solubility of solute under the same solution supply conditions.

Magnetic spherical cores partly coated with periodic mesoporous organosilica single crystals.

PubMed

Li, Jing; Wei, Yong; Li, Wei; Deng, Yonghui; Zhao, Dongyuan

2012-03-07

Core-shell structured materials are of special significance in various applications. Until now, most reported core-shell structures have polycrystalline or amorphous coatings as their shell layers, with popular morphologies of microspheres or quasi-spheres. However, the single crystals, either mesoscale or atomic ones, are still rarely reported as shell layers. If single crystals can be coated on core materials, it would result in a range of new type core-shell structures with various morphologies, and probably more potential applications. In this work, we demonstrate that periodic mesoporous organosilica (PMO) single crystals can partly grow on magnetic microspheres to form incomplete Fe(3)O(4)@nSiO(2)@PMO core-shell materials in aqueous solution, which indeed is the first illustration that mesoporous single-crystal materials can be used as shell layers for preparation of core-shell materials. The achieved materials have advantages of high specific surface areas, good magnetic responses, embedded functional groups and cubic mesopore channels, which might provide them with various application conveniences. We suppose the partial growth is largely decided by the competition between growing tendency of single crystals and the resistances to this tendency. In principle, other single crystals, including a range of atomic single crystals, such as zeolites, are able to be developed into such core-shell structures.

Novel lithium titanate-graphene hybrid containing two graphene conductive frameworks for lithium-ion battery with excellent electrochemical performance

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

Ruiyi, Li; Tengyuan, Chen; Beibei, Sun

Graphical abstract: We developed a new Novel lithium titanate-graphene nanohybrid containing two graphene conductive frameworks. The unique architecture creates fast electron transfer and rapid mass transport of electrolyte. The hybrid electrode provides excellent electrochemical performances for lithium-ion batteries, including high specific capacity, outstanding rate capability and intriguing cycling stability. - Highlights: • We reported a new LTO-graphene nanohybrid containing two graphene conductive frameworks. • One graphene framework greatly improves the electrical conductivity of LTO crystal. • Another graphene framework enhances electrical conductivity of between LTO crystals and electrolyte transport. • The unique architecture creates big tap density, ultrafast electron transfermore » and rapid mass transport. • The hybrid electrode provides excellent electrochemical performance for lithium-ion batteries. - ABSTRACT: The paper reported the synthesis of lithium titanate(LTO)-graphene hybrid containing two graphene conductive frameworks (G@LTO@G). Tetrabutyl titanate and graphene were dispersed in tertbutanol and heated to reflux state by microwave irradiation. Followed by adding lithium acetate to produce LTO precursor/graphene (p-LTO/G). The resulting p-LTO/G offers homogeneous morphology and ultra small size. All graphene sheets were buried in the spherical agglomerates composed of primitive particles through the second agglomeration. The p-LTO/G was calcined to LTO@graphene (LTO@G). To obtain G@LTO@G, the LTO@G was further hybridized with graphene. The as-prepared G@LTO@G shows well-defined three-dimensional structure and hierarchical porous distribution. Its unique architecture creates big tap density, fast electron transfer and rapid electrolyte transport. As a result, the G@LTO@G provides high specific capacity (175.2 mA h g{sup −1} and 293.5 mA cm{sup −3}), outstanding rate capability (155.7 mAh g{sup −1} at 10C) and intriguing cycling stability (97.2% capacity retention at 5C after 1000 cycles)« less

Micromechanical models for the stiffness and strength of UHMWPE macrofibrils

NASA Astrophysics Data System (ADS)

Dong, Hai; Wang, Zheliang; O'Connor, Thomas C.; Azoug, Aurelie; Robbins, Mark O.; Nguyen, Thao D.

2018-07-01

Ultrahigh molecular weight polyethylene (UHMWPE) fibers have a complex hierarchical structure that at the micron-scale is composed of oriented chain crystals, lamellar crystals, and amorphous domains organized into macrofibrils. We developed a computational micromechanical modeling study of the effects of the morphological structure and constituent material properties on the deformation mechanisms, stiffness and strength of the UHMWPE macrofibrils. Specifically, we developed four representative volume elements, which differed in the arrangement and orientation of the lamellar crystals, to describe the various macrofibrillar microstructures observed in recent experiments. The stiffness and strength of the crystals were determined from molecular dynamic simulations of a pure PE crystal. A finite deformation crystal plasticity model was used to describe the crystals and an isotropic viscoplastic model was used for the amorphous phase. The results show that yielding in UHMWPE macrofibrils under axial tension is dominated by the slip in the oriented crystals, while yielding under transverse compression and shear is dominated by slips in both the oriented and lamellar crystals. The results also show that the axial modulus and strength are mainly determined by the volume fraction of the oriented crystals and are insensitive to the arrangements of the lamellar crystals when the modulus of the amorphous phase is significantly smaller than that of the crystals. In contrast, the arrangement and size of the lamellar crystals have a significant effect on the stiffness and strength under transverse compression and shear. These findings can provide a guide for new materials and processing design to improve the properties of UHMWPE fibers by controlling the macrofibrillar morphologies.

Recent results and new hardware developments for protein crystal growth in microactivity

NASA Technical Reports Server (NTRS)

Delucas, L. J.; Long, M. M.; Moore, K. M.; Smith, C.; Carson, M.; Narayana, S. V. L.; Carter, D.; Clark, A. D., Jr.; Nanni, R. G.; Ding, J.

1993-01-01

Protein crystal growth experiments have been performed on 16 space shuttle missions since April, 1985. The initial experiments utilized vapor diffusion crystallization techniques similar to those used in laboratories for earth-based experiments. More recent experiments have utilized temperature induced crystallization as an alternative method for growing high quality protein crystals in microgravity. Results from both vapor diffusion and temperature induced crystallization experiments indicate that proteins grown in microgravity may be larger, display more uniform morphologies, and yield diffraction data to significantly higher resolutions than the best crystals of these proteins grown on earth.

Cloning, expression, purification, crystallization and preliminary X-ray crystallographic investigations of a unique editing domain from archaebacteria.

PubMed

Dwivedi, Shweta; Kruparani, Shobha P; Sankaranarayanan, Rajan

2004-09-01

Threonyl-tRNA synthetase (ThrRS) faces a crucial double-discrimination problem during the translation of genetic code. Most ThrRSs from the archaeal kingdom possess a unique editing domain that differs from those of eubacteria and eukaryotes. In order to understand the structural basis of the editing mechanism in archaea, the editing module of ThrRS from Pyrococcus abyssi comprising of the first 183 amino-acid residues was cloned, expressed, purified and crystallized. The crystals belong to the trigonal space group P3(1(2))21, with one molecule in the asymmetric unit.

Capillarity creates single-crystal calcite nanowires from amorphous calcium carbonate.

PubMed

Kim, Yi-Yeoun; Hetherington, Nicola B J; Noel, Elizabeth H; Kröger, Roland; Charnock, John M; Christenson, Hugo K; Meldrum, Fiona C

2011-12-23

Single-crystal calcite nanowires are formed by crystallization of morphologically equivalent amorphous calcium carbonate (ACC) particles within the pores of track etch membranes. The polyaspartic acid stabilized ACC is drawn into the membrane pores by capillary action, and the single-crystal nature of the nanowires is attributed to the limited contact of the intramembrane ACC particle with the bulk solution. The reaction environment then supports transformation to a single-crystal product. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Molecular-Scale Structural Controls on Nanoscale Growth Processes: Step-Specific Regulation of Biomineral Morphology

NASA Astrophysics Data System (ADS)

Dove, P. M.; Davis, K. J.; De Yoreo, J. J.; Orme, C. A.

2001-12-01

Deciphering the complex strategies by which organisms produce nanocrystalline materials with exquisite morphologies is central to understanding biomineralizing systems. One control on the morphology of biogenic nanoparticles is the specific interactions of their surfaces with the organic functional groups provided by the organism and the various inorganic species present in the ambient environment. It is now possible to directly probe the microscopic structural controls on crystal morphology by making quantitative measurements of the dynamic processes occurring at the mineral-water interface. These observations can provide crucial information concerning the actual mechanisms of growth that is otherwise unobtainable through macroscopic techniques. Here we use in situ molecular-scale observations of step dynamics and growth hillock morphology to directly resolve roles of principal impurities in regulating calcite surface morphologies. We show that the interactions of certain inorganic as well as organic impurities with the calcite surface are dependent upon the molecular-scale structures of step-edges. These interactions can assume a primary role in directing crystal morphology. In calcite growth experiments containing magnesium, we show that growth hillock structures become modified owing to the preferential inhibition of step motion along directions approximately parallel to the [010]. Compositional analyses have shown that Mg incorporates at different levels into the two types of nonequivalent steps, which meet at the hillock corner parallel to [010]. A simple calculation of the strain caused by this difference indicates that we should expect a significant retardation at this corner, in agreement with the observed development of [010] steps. If the low-energy step-risers produced by these [010] steps is perpendicular to the c-axis as seems likely from crystallographic considerations, this effect provides a plausible mechanism for the elongated calcite crystal habits found in natural environments that contain magnesium. In a separate study, step-specific interactions are also found between chiral aspartate molecules and the calcite surface. The L and D- aspartate enantiomers exhibit structure preferences for the different types of step-risers on the calcite surface. These site-specific interactions result in the transfer of asymmetry from the organic molecule to the crystal surface through the formation of chiral growth hillocks and surface morphologies. These studies yield direct experimental insight into the molecular-scale structural controls on nanocrystal morphology in biomineralizing systems.

Late Diagenetic Cements in the Murray Formation, Gale Crater, Mars: Implications for Postdepositional Fluid Flow

NASA Astrophysics Data System (ADS)

Kah, L. C.; Kronyak, R. E.; Van Beek, J.; Nachon, M.; Mangold, N.; Thompson, L. M.; Wiens, R. C.; Grotzinger, J. P.; Schieber, J.

2015-12-01

The Murray formation in its type section at Pahrump Hills, consists of approximately 14 meters of recessive-weathering mudstone interbedded with decimeter-scale cross-bedded sandstone in the upper portions of the exposed section. Mudstone textures vary from massive, to poorly laminated, to well laminated. Unusual 3-dimensional crystal clusters and dendrites occur in the lowermost part of the section and are erosionally resistant with respect to the host rock. Crystal clusters consist of elongate lathes that occur within individual blocks of the fractured substrate. Individual lathes show tabular morphologies with a pseudo-rectangular cross-section and the three dimensional morphology of the crystal clusters cross-cut host rock lamination with little or no deformation. Dendritic structures are typically larger and show predominantly planar growth aligned with bedding planes. Individual lathes within the dendrites are elongate and pseudo-rectangular in cross-section. Unlike crystal clusters, dendritic morphologies appear to nucleate at bedrock fractures and near mineralized veins. Here we show evidence that crystal clusters and dendrites are post-depositional, potentially burial diagenetic features. Association of features with through-going fractures suggests that fractures may have been a primary transport pathway for ions responsible for dendrite growth. Even where dendrites do not occur, enhanced cementation suggests that fluids permeated the rock matrix. We suggest that growth of clusters proceeded as inter-particle crystal growth, wherein mineral growth within inter-particle spaces resulted in cementation and porosity loss, with little further effect on the rock matrix. Crystal clusters and dendrites are most likely to form when mineral saturation states are highest, for instance with initial intrusion of fracture-borne fluids and mixing with ambient pore fluids, and thus emphasize the importance of fractures in ion transport during late diagenesis.

In vitro studies reveal antiurolithic effect of Terminalia arjuna using quantitative morphological information from computerized microscopy

PubMed Central

Mittal, A.; Tandon, S.; Singla, S.K.; Tandon, C.

2015-01-01

ABSTRACT Purpose: For most cases, urolithiasis is a condition where excessive oxalate is present in the urine. Many reports have documented free radical generation followed by hyperoxaluria as a consequence of which calcium oxalate (CaOx) deposition occurs in the kidney tissue. The present study is aimed to exam the antilithiatic potency of the aqueous extract (AE) of Terminalia arjuna (T. arjuna). Materials and Methods: The antilithiatic activity of Terminalia arjuna was investigated in vitro nucleation, aggregation and growth of the CaOx crystals as well as the morphology of CaOx crystals using the inbuilt software ‘Image-Pro Plus 7.0’ of Olympus upright microscope (BX53). Antioxidant activity of AE of Terminalia arjuna bark was also determined in vitro. Results: Terminalia arjuna extract exhibited a concentration dependent inhibition of nucleation and aggregation of CaOx crystals. The AE of Terminalia arjuna bark also inhibited the growth of CaOx crystals. At the same time, the AE also modified the morphology of CaOx crystals from hexagonal to spherical shape with increasing concentrations of AE and reduced the dimensions such as area, perimeter, length and width of CaOx crystals in a dose dependent manner. Also, the Terminalia arjuna AE scavenged the DPPH (2, 2-diphenyl-1-picrylhydrazyl) radicals with an IC50 at 13.1µg/mL. Conclusions: The study suggests that Terminalia arjuna bark has the potential to scavenge DPPH radicals and inhibit CaOx crystallization in vitro. In the light of these studies, Terminalia arjuna can be regarded as a promising candidate from natural plant sources of antilithiatic and antioxidant activity with high value. PMID:26689519

Morphology and orientation of β-BaB{sub 2}O{sub 4} crystals patterned by laser in the inside of samarium barium borate glass

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

Nishii, Akihito; Shinozaki, Kenji; Honma, Tsuyoshi

Nonlinear optical β-BaB{sub 2}O{sub 4} crystal lines (β-BBO) were patterned in the inside of 8Sm{sub 2}O{sub 3}–42BaO–50B{sub 2}O{sub 3} glass by irradiations of continuous-wave Yb:YVO{sub 4} lasers with a wavelength of 1080 nm (power: P=0.8–1.0 W, scanning speed: S=0.2–2.5 μm/s), in which the laser focal position was moved gradually from the surface to the inside. The morphology, size, and orientation of β-BBO crystals were examined from polarization optical microscope and birefringence imaging observations. It was demonstrated that c-axis oriented β-BBO crystals with long lengths (e.g., 20 mm) were patterned in the inside of the glass. The morphology of β-BBO inmore » the cross-section of lines was a rectangular shape with rounded corners, and the volume of β-BBO formed increased with increasing laser power and with decreasing laser scanning speed. The maximum depth in the inside from the surface for β-BBO patterning increased with increasing laser power, e.g., D{sub max}∼100 μm at P=0.8 W, D{sub max}∼170 μm at P=0.9 W, and D{sub max}∼200 μm at P=1 W. The present study proposes that the laser-induced crystallization opens a new door for applied engineering in glassy solids. - Graphical abstract: This figure shows the POM photographs for β-BaB{sub 2}O{sub 4} crystal lines patterned by cw Yb:YVO{sub 4} fiber laser irradiations with a laser power of P=0.8 W and a laser scanning speed S=2 μm/s in the glass. The laser focal point was moved gradually from the surface into the inside. The results shown in Fig. 1 demonstrate that it is possible to pattern highly oriented β-BaB{sub 2}O{sub 4} crystals even in the inside of glasses. - Highlights: • β-BaB{sub 2}O{sub 4} crystal lines were patterned in the inside of a glass by lasers. • Laser focal position was moved gradually from the surface to the inside. • Birefringence imaging was observed. • Morphology, size, and orientation of crystals were clarified. • Crystal lines with long lengths (e.g., 20 mm) were patterned at the depth of 200 μm.« less

Crystal-melt interface mobility in bcc Fe: Linking molecular dynamics to phase-field and phase-field crystal modeling

NASA Astrophysics Data System (ADS)

Guerdane, M.; Berghoff, M.

2018-04-01

By combining molecular dynamics (MD) simulations with phase-field (PF) and phase-field crystal (PFC) modeling we study collision-controlled growth kinetics from the melt for pure Fe. The MD/PF comparison shows, on the one hand, that the PF model can be properly designed to reproduce quantitatively different aspects of the growth kinetics and anisotropy of planar and curved solid-liquid interfaces. On the other hand, this comparison demonstrates the ability of classical MD simulations to predict morphology and dynamics of moving curved interfaces up to a length scale of about 0.15 μ m . After mapping the MD model to the PF one, the latter permits to analyze the separate contribution of different anisotropies to the interface morphology. The MD/PFC agreement regarding the growth anisotropy and morphology extends the trend already observed for the here used PFC model in describing structural and elastic properties of bcc Fe.

Synthesis of barium and strontium carbonate crystals with unusual morphologies using an organic additive

NASA Astrophysics Data System (ADS)

Chen, Long; Jiang, Jizhong; Bao, Zuben; Pan, Jian; Xu, Weibing; Zhou, Lili; Wu, Zhigang; Chen, Xu

2013-12-01

In this paper, strontium carbonate (SrCO3) and barium carbonate (BaCO3) crystals were synthesized in the presence of an organic additive-hexamethylenetetramine (HMT) using two CO2 sources. Scanning electron microscopy and X-ray powder diffractometry were used to characterize the products. The results showed that the morphologies of orthorhombic strontianite SrCO3 transformed from branch-like to flower-like, and to capsicum-like at last, while the morphologies of BaCO3 change from fiber-like to branchlike, and to rod-like finally with an increase of the molar ratio HMT/Sr2+ and HMT/Ba2+ from 0.2 to 10 using ammonium carbonate as CO2 source. When using diethyl carbonate instead of ammonium carbonate as CO2 source, SrCO3 flowers aggregated by rods and BaCO3 shuttles were formed. The possible formation mechanisms of SrCO3 and BaCO3 crystals obtained in different conditions were also discussed.

Comparative analysis of surface wax in mature fruits between Satsuma mandarin (Citrus unshiu) and 'Newhall' navel orange (Citrus sinensis) from the perspective of crystal morphology, chemical composition and key gene expression.

PubMed

Wang, Jinqiu; Hao, Haohao; Liu, Runsheng; Ma, Qiaoli; Xu, Juan; Chen, Feng; Cheng, Yunjiang; Deng, Xiuxin

2014-06-15

Surface wax of mature Satsuma mandarin (Citrus unshiu) and 'Newhall' navel orange (Citrus sinensis) was analysed by crystal morphology, chemical composition, and gene expression levels. The epicuticular and total waxes of both citrus cultivars were mostly composed of aldehydes, alkanes, fatty acids and primary alcohols. The epicuticular wax accounted for 80% of the total wax in the Newhall fruits and was higher than that in the Satsuma fruits. Scanning electron microscopy showed that larger and more wax platelets were deposited on the surface of Newhall fruits than on the Satsuma fruits. Moreover, the expression levels of genes involved in the wax formation were consistent with the biochemical and crystal morphological analyses. These diversities of fruit wax between the two cultivars may contribute to the differences of fruit postharvest storage properties, which can provide important information for the production of synthetic wax for citrus fruits. Copyright © 2013 Elsevier Ltd. All rights reserved.

Bioleaching of incineration fly ash by Aspergillus niger - precipitation of metallic salt crystals and morphological alteration of the fungus.

PubMed

Xu, Tong-Jiang; Ramanathan, Thulasya; Ting, Yen-Peng

2014-09-01

This study examines the bioleaching of municipal solid waste incineration fly ash by Aspergillus niger , and its effect on the fungal morphology, the fate of the ash particles, and the precipitation of metallic salt crystals during bioleaching. The fungal morphology was significantly affected during one-step and two-step bioleaching; scanning electron microscopy revealed that bioleaching caused distortion of the fungal hyphae (with up to 10 μm hyphae diameter) and a swollen pellet structure. In the absence of the fly ash, the fungi showed a linear structure (with 2-4 μm hyphae diameter). Energy-dispersive X-ray spectroscopy and X-ray diffraction confirmed the precipitation of calcium oxalate hydrate crystals at the surface of hyphae in both one-step and two-step bioleaching. Calcium oxalate precipitation affects bioleaching via the weakening of the fly ash, thus facilitating the release of other tightly bound metals in the matrix.

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.

Form follows function: morphological diversification and alternative trapping strategies in carnivorous Nepenthes pitcher plants.

PubMed

Bauer, Ulrike; Clemente, C J; Renner, T; Federle, W

2012-01-01

Carnivorous plants of the genus Nepenthes have evolved a striking diversity of pitcher traps that rely on specialized slippery surfaces for prey capture. With a comparative study of trap morphology, we show that Nepenthes pitcher plants have evolved specific adaptations for the use of either one of two distinct trapping mechanisms: slippery wax crystals on the inner pitcher wall and 'insect aquaplaning' on the wet upper rim (peristome). Species without wax crystals had wider peristomes with a longer inward slope. Ancestral state reconstructions identified wax crystal layers and narrow, symmetrical peristomes as ancestral, indicating that wax crystals have been reduced or lost multiple times independently. Our results complement recent reports of nutrient source specializations in Nepenthes and suggest that these specializations may have driven speciation and rapid diversification in this genus. © 2011 The Authors. Journal of Evolutionary Biology © 2011 European Society For Evolutionary Biology.

Control of morphology and crystal purity of InP nanowires by variation of phosphine flux during selective area MOMBE

NASA Astrophysics Data System (ADS)

Kelrich, A.; Dubrovskii, V. G.; Calahorra, Y.; Cohen, S.; Ritter, D.

2015-02-01

We present experimental results showing how the growth rate, morphology and crystal structure of Au-catalyzed InP nanowires (NWs) fabricated by selective area metal organic molecular beam epitaxy can be tuned by the growth parameters: temperature and phosphine flux. The InP NWs with 20-65 nm diameters are grown at temperatures of 420 and 480 °C with the PH3 flow varying from 1 to 9 sccm. The NW tapering is suppressed at a higher temperature, while pure wurtzite crystal structure is preferred at higher phosphine flows. Therefore, by combining high temperature and high phosphine flux, we are able to fabricate non-tapered and stacking fault-free InP NWs with the quality that other methods rarely achieve. We also develop a model for NW growth and crystal structure which explains fairly well the observed experimental tendencies.

Crystal growth from the vapor phase experiment MA-085

NASA Technical Reports Server (NTRS)

Wiedemeir, H.; Sadeek, H.; Klaessig, F. C.; Norek, M.

1976-01-01

Three vapor transport experiments on multicomponent systems were performed during the Apollo Soyuz mission to determine the effects of microgravity forces on crystal morphology and mass transport rates. The mixed systems used germanium selenide, tellurium, germanium tetraiodide (transport agent), germanium monosulfide, germanium tetrachloride (transport agent), and argon (inert atmosphere). The materials were enclosed in evacuated sealed ampoules of fused silica and were transported in a temperature gradient of the multipurpose electric furnace onboard the Apollo Soyuz spacecraft. Preliminary evaluation of 2 systems shows improved quality of space grown crystals in terms of growth morphology and bulk perfection. This conclusion is based on a direct comparison of space grown and ground based crystals by means of X-ray diffraction, microscopic, and chemical etching techniques. The observation of greater mass transport rates than predicted for a microgravity environment by existing vapor transport models indicates the existence of nongravity caused transport effects in a reactive solid/gas phase system.

Investigation of Y/SBA Composite Molecular Sieves Morphology Control and Catalytic Performance for n-Pentane Aromatization

PubMed Central

Shi, Chun-Wei; Wu, Wen-Yuan; Li, Shuai; Bian, Xue; Zhao, Shan-lin; Pei, Ming-Yuan

2016-01-01

Using Y molecular sieve as the core, Y/SBA-15 composite molecular sieves were prepared by different crystallization methods in the paper. The growth process and morphologies of the composite molecular sieves were controlled by adjusting the synthesis factors. The structures and acidity of two kinds of composite molecular sieves were characterized by X-ray diffraction (XRD), N2 adsorption/desorption, transmission electron microscopy (TEM), and NH3-TPD. The catalysis performances of the composite molecular sieves were investigated in the aromatization reaction of n-pentane. The results indicated that the desired core-shell composite molecular sieves were obtained when the crystallization conditions were 36 hours, 100 °C and secondary crystallization. The aromatization results showed that core-shell composite molecular sieves had better selectivity for producing high application value xylenes compared to mixed-crystal composite molecular sieves. PMID:27029526

Microstructural control over soluble pentacene deposited by capillary pen printing for organic electronics.

PubMed

Lee, Wi Hyoung; Min, Honggi; Park, Namwoo; Lee, Junghwi; Seo, Eunsuk; Kang, Boseok; Cho, Kilwon; Lee, Hwa Sung

2013-08-28

Research into printing techniques has received special attention for the commercialization of cost-efficient organic electronics. Here, we have developed a capillary pen printing technique to realize a large-area pattern array of organic transistors and systematically investigated self-organization behavior of printed soluble organic semiconductor ink. The capillary pen-printed deposits of organic semiconductor, 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS_PEN), was well-optimized in terms of morphological and microstructural properties by using ink with mixed solvents of chlorobenzene (CB) and 1,2-dichlorobenzene (DCB). Especially, a 1:1 solvent ratio results in the best transistor performances. This result is attributed to the unique evaporation characteristics of the TIPS_PEN deposits where fast evaporation of CB induces a morphological evolution at the initial printed position, and the remaining DCB with slow evaporation rate offers a favorable crystal evolution at the pinned position. Finally, a large-area transistor array was facilely fabricated by drawing organic electrodes and active layers with a versatile capillary pen. Our approach provides an efficient printing technique for fabricating large-area arrays of organic electronics and further suggests a methodology to enhance their performances by microstructural control of the printed organic semiconducting deposits.

Interlinked multiphase Fe-doped MnO2 nanostructures: a novel design for enhanced pseudocapacitive performance.

PubMed

Wang, Ziya; Wang, Fengping; Li, Yan; Hu, Jianlin; Lu, Yanzhen; Xu, Mei

2016-04-07

Structure designing and morphology control can lead to high performance pseudocapacitive materials for supercapacitors. In this work, we have designed interlinked multiphase Fe-doped MnO2 nanostructures (α-MnO2/R-MnO2/ε-MnO2) to enhance the electrochemical properties by a facile method. These hierarchical hollow microspheres assembled by interconnected nanoflakes, and with plenty of porous nanorods radiating from the spherical shells were hydrothermally obtained. The supercapacitor electrode prepared from the unique construction exhibits outstanding specific capacitance of 267.0 F g(-1) even under a high mass loading (∼5 mg cm(-2)). Obviously improved performances compared to pure MnO2 are also demonstrated with a good rate capability, high energy density (1.30 mW h cm(-3)) and excellent cycling stability of 100% capacitance retention after 2000 cycles at 2 A g(-1). The synergistic effects of alternative crystal structures, appropriate crystallinity and optimal morphology are identified to be responsible for the observations. This rational multiphase composite strategy provides a promising idea for materials scientists to design and prepare scalable electrode materials for energy storage devices.

Thin film solar cells grown by organic vapor phase deposition

NASA Astrophysics Data System (ADS)

Yang, Fan

Organic solar cells have the potential to provide low-cost photovoltaic devices as a clean and renewable energy resource. In this thesis, we focus on understanding the energy conversion process in organic solar cells, and improving the power conversion efficiencies via controlled growth of organic nanostructures. First, we explain the unique optical and electrical properties of organic materials used for photovoltaics, and the excitonic energy conversion process in donor-acceptor heterojunction solar cells that place several limiting factors of their power conversion efficiency. Then, strategies for improving exciton diffusion and carrier collection are analyzed using dynamical Monte Carlo models for several nanostructure morphologies. Organic vapor phase deposition is used for controlling materials crystallization and film morphology. We improve the exciton diffusion efficiency while maintaining good carrier conduction in a bulk heterojunction solar cell. Further efficiency improvement is obtained in a novel nanocrystalline network structure with a thick absorbing layer, leading to the demonstration of an organic solar cell with 4.6% efficiency. In addition, solar cells using simultaneously active heterojunctions with broad spectral response are presented. We also analyze the efficiency limits of single and multiple junction organic solar cells, and discuss the challenges facing their practical implementations.

Anomalous Growth Rate of Ag Nanocrystals Revealed by in situ STEM

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

Ge, Mingyuan; Lu, Ming; Chu, Yong

In situ microscopy of colloidal nanocrystal growth offers a unique opportunity to acquire direct and straightforward data for assessing classical growth models. For this study, we observe the growth trajectories of individual Ag nanoparticles in solution using in situ scanning transmission electron microscopy. For the first time, we provide experimental evidence of growth rates of Ag nanoparticles in the presence of Pt in solution that are significantly faster than predicted by Lifshitz-Slyozov-Wagner theory. We attribute these observed anomalous growth rates to the synergistic effects of the catalytic properties of Pt and the electron beam itself. Transiently reduced Pt atoms servemore » as active sites for Ag ions to grow, thereby playing a key role in controlling the growth kinetics. Electron beam illumination greatly increases the local concentration of free radicals, thereby strongly influencing particle growth rate and the resulting particle morphology. Through a systematic investigation, we demonstrate the feasibility of utilizing these synergistic effects for controlling the growth rates and particle morphologies at the nanoscale. Our findings not only expand the current scope of crystal growth theory, but may also lead to a broader scientific application of nanocrystal synthesis.« less

Anomalous Growth Rate of Ag Nanocrystals Revealed by in situ STEM

DOE PAGES

Ge, Mingyuan; Lu, Ming; Chu, Yong; ...

2017-11-27

In situ microscopy of colloidal nanocrystal growth offers a unique opportunity to acquire direct and straightforward data for assessing classical growth models. For this study, we observe the growth trajectories of individual Ag nanoparticles in solution using in situ scanning transmission electron microscopy. For the first time, we provide experimental evidence of growth rates of Ag nanoparticles in the presence of Pt in solution that are significantly faster than predicted by Lifshitz-Slyozov-Wagner theory. We attribute these observed anomalous growth rates to the synergistic effects of the catalytic properties of Pt and the electron beam itself. Transiently reduced Pt atoms servemore » as active sites for Ag ions to grow, thereby playing a key role in controlling the growth kinetics. Electron beam illumination greatly increases the local concentration of free radicals, thereby strongly influencing particle growth rate and the resulting particle morphology. Through a systematic investigation, we demonstrate the feasibility of utilizing these synergistic effects for controlling the growth rates and particle morphologies at the nanoscale. Our findings not only expand the current scope of crystal growth theory, but may also lead to a broader scientific application of nanocrystal synthesis.« less

Morphology, stoichiometry, and crystal structure control via post-annealing for Pt-ZnO nanograin Schottky barrier interfaces

NASA Astrophysics Data System (ADS)

Chan, Yuet Ching; Yu, Jerry; Ho, Derek

2018-06-01

Nanointerfaces have attracted intensive research effort for advanced electronics due to their unique and tunable semiconducting properties made possible by metal-contacted oxide structures at the nanoscale. Although much work has been on the adjustment of fabrication parameters to achieve high-quality interfaces, little work has experimentally obtained the various correlations between material parameters and Schottky barrier electronic properties to accurately probe the underlying phenomenon. In this work, we investigate the control of Pt-ZnO nanograin interfaces properties by thermal annealing. Specifically, we quantitatively analyze the correlation between material parameters (such as surface morphology, crystallographic structure, and stoichiometry) and Schottky diode parameters (Schottky barrier height, ideality factor, and contact resistance). Results revealed strong dependencies of Schottky barrier characteristics on oxygen vacancies, surface roughness, grain density, d-spacing, and crystallite size. I-V-T data shows that annealing at 600 °C produces a nanograin based interface with the most rectifying diode characteristics. These dependencies, which have not been previously reported holistically, highlight the close relationship between material properties and Schottky barrier characteristics, and are instrumental for the performance optimization of nanostructured metal-semiconductor interfaces in advanced electronic devices.

Smectic C liquid crystal growth through surface orientation by ZnxCd1-xSe thin films

NASA Astrophysics Data System (ADS)

Katranchev, B.; Petrov, M.; Bineva, I.; Levi, Z.; Mineva, M.

2012-12-01

A smectic C liquid crystal (LC) texture, consisting of distinct local single crystals (DLSCs) was grown using predefined orientation of ternary nanocrystalline thin films of ZnxCd1-xSe. The surface morphology and orientation features of the ZnxCd1-xSe films were investigated by AFM measurements and micro-texture polarization analysis. The ZnxCd1-xSe surface causes a substantial enlargement of the smectic C DLSCs and induction of a surface bistable state. The specific character of the morphology of this coating leads to the decrease of the corresponding anchoring energy. Two new chiral states, not typical for this LC were indicated. The physical mechanism providing these new effects is presented.

The occurence of uric acids and the growth morphology of the anhydrous monoclinic modification : C 5H 4N 4O 3

NASA Astrophysics Data System (ADS)

Rinaudo, C.; Boistelle, R.

1980-07-01

Anhydrous and hydrated uric acid crystals which frequently occur in human urolithiasis have been grown from pure aqueous solutions at 25 and 37°C. The appearance domain of either modification is given as a function of initial uric acid concentration at pH values ranging from 3.0 to 5.5. The present paper mostly deals with the anhydrous phase and it is shown that its experimental and theoretical growth morphologies are in agreement, the crystals exhibiting the {100}, {210}, {121}, {001} and {201} forms. Crystal habit depends on supersaturation; {100} has always the largest extension at low supersaturation {121} develops to the detriment of {210}, {001} and {201}.

Single crystal structure analyses of scheelite-powellite CaW1-xMoxO4 solidsolutions and unique occurrence in Jisyakuyama skarn deposits

NASA Astrophysics Data System (ADS)

Yamashita, K.; Yoshiasa, A.; Miyazaki, H.; Tokuda, M.; Tobase, T.; Isobe, H.; Nishiyama, T.; Sugiyama, K.; Miyawaki, R.

2017-12-01

Jisyakuyama skarn deposit, Fukuchi, Fukuoka, Japan, shows a simple occurrenceformed by penetration of hot water into limestone cracks. A unique occurrence of scheelite-powellite CaW1-xMoxO4 minerals is observed in the skarn deposit. Many syntheticexperiments for scheelite-powellite solid solutions have been reported as research onfluorescent materials. In this system it is known that a complete continuous solid solution isformed even at room temperature. In this study, we have carried out the chemical analyses,crystal structural refinements and detail description of occurrence on scheelite-powelliteminerals. We have also attempted synthesis of single crystal of solid solution in a widecomposition range. The chemical compositions were determined by JEOL scanningelectron microscope and EDS, INCA system. We have performed the crystal structurerefinements of the scheelite-powellite CaW1-xMoxO4 solid solutions (x=0.0-1.0) byRIGAKU single-crystal structure analysis system RAPID. The R and S values are around0.0s and 1.03. As the result of structural refinements of natural products and many solidsolutions, we confirm that most large natural single crystals have compositions at bothendmembers, and large solid solution crystals are rare. The lattice constants, interatomicdistances and other crystallographic parameters for the solid solution change uniquely withcomposition and it was confirmed as a continuous solid solution. Single crystals of scheeliteendmember + powellite endmember + solid solution with various compositions form anaggregate in the deposit (Figure 1). Crystal shapes of powellite and scheelite arehypidiomorphic and allotriomorphic, respectively. Many solid solution crystals areaccompanied by scheelite endmember and a compositional gap is observed betweenpowellite and solid-solution crystals. The presence of several penetration solutions withsignificantly different W and Mo contents may be assumed. This research can be expectedto lead to giving restrictive conditions to elucidate the mineralization process. Figure1. Scheelite + Powellite + solid solution aggregate

Polymer-directed crystallization of atorvastatin.

PubMed

Choi, Hyemin; Lee, Hyeseung; Lee, Min Kyung; Lee, Jonghwi

2012-08-01

Living organisms secrete minerals composed of peptides and proteins, resulting in "mesocrystals" of three-dimensional-assembled composite structures. Recently, this biomimetic polymer-directed crystallization technique has been widely applied to inorganic materials, although it has seldom been used with drugs. In this study, the technique was applied to the drowning-out crystallization of atorvastatin using various polymers. Nucleation and growth at optimized conditions successfully produced composite crystals with significant polymer contents and unusual characteristics. Atorvastatin composite crystals containing polyethylene glycol, polyacrylic acid, polyethylene imine, and chitosan showed a markedly decreased melting point and heat of fusion, improved stability, and sustained-release patterns. The use of hydroxypropyl cellulose yielded a unique combination of enhanced in vitro release and improved drug stability under a forced degradation condition. The formation hypothesis of unique mesocrystal structures was strongly supported by an X-ray diffraction pattern and substantial melting point reduction. This polymer-directed crystallization technique offers a novel and effective way, different from the solid dispersion approach, to engineer the release, stability, and processability of drug crystals. Copyright © 2012 Wiley Periodicals, Inc.

Investigating the Influence of Temperature on the Kaolinite-Base Synthesis of Zeolite and Urease Immobilization for the Potential Fabrication of Electrochemical Urea Biosensors.

PubMed

Anderson, David Ebo; Balapangu, Srinivasan; Fleischer, Heidimarie N A; Viade, Ruth A; Krampa, Francis D; Kanyong, Prosper; Awandare, Gordon A; Tiburu, Elvis K

2017-08-08

Temperature-dependent zeolite synthesis has revealed a unique surface morphology, surface area and pore size which influence the immobilization of urease on gold electrode supports for biosensor fabrication. XRD characterization has identified zeolite X (Na) at all crystallization temperatures tested. However, N₂ adsorption and desorption results showed a pore size and pore volume of zeolite X (Na) 60 °C, zeolite X (Na) 70 °C and zeolite X (Na) 90 °C to range from 1.92 nm to 2.45 nm and 0.012 cm³/g to 0.061 cm³/g, respectively, with no significant differences. The specific surface area of zeolite X (Na) at 60, 70 and 90 °C was 64 m²/g, 67 m²/g and 113 m²/g, respectively. The pore size, specific surface area and pore volumes of zeolite X (Na) 80 °C and zeolite X (Na) 100 °C were dramatically increased to 4.21 nm, 295 m²/g, 0.762 cm³/g and 4.92 nm, 389 m²/g, 0.837 cm³/g, in that order. The analytical performance of adsorbed urease on zeolite X (Na) surface was also investigated using cyclic voltammetry measurements, and the results showed distinct cathodic and anodic peaks by zeolite X (Na) 80 °C and zeolite X (Na) 100 °C. These zeolites' molar conductance was measured as a function of urea concentration and gave an average polynomial regression fit of 0.948. The findings in this study suggest that certain physicochemical properties, such as crystallization temperature and pH, are critical parameters for improving the morphological properties of zeolites synthesized from natural sources for various biomedical applications.

Investigating the Influence of Temperature on the Kaolinite-Base Synthesis of Zeolite and Urease Immobilization for the Potential Fabrication of Electrochemical Urea Biosensors

PubMed Central

Anderson, David Ebo; Balapangu, Srinivasan; Fleischer, Heidimarie N. A.; Viade, Ruth A.; Awandare, Gordon A.; Tiburu, Elvis K.

2017-01-01

Temperature-dependent zeolite synthesis has revealed a unique surface morphology, surface area and pore size which influence the immobilization of urease on gold electrode supports for biosensor fabrication. XRD characterization has identified zeolite X (Na) at all crystallization temperatures tested. However, N2 adsorption and desorption results showed a pore size and pore volume of zeolite X (Na) 60 °C, zeolite X (Na) 70 °C and zeolite X (Na) 90 °C to range from 1.92 nm to 2.45 nm and 0.012 cm3/g to 0.061 cm3/g, respectively, with no significant differences. The specific surface area of zeolite X (Na) at 60, 70 and 90 °C was 64 m2/g, 67 m2/g and 113 m2/g, respectively. The pore size, specific surface area and pore volumes of zeolite X (Na) 80 °C and zeolite X (Na) 100 °C were dramatically increased to 4.21 nm, 295 m2/g, 0.762 cm3/g and 4.92 nm, 389 m2/g, 0.837 cm3/g, in that order. The analytical performance of adsorbed urease on zeolite X (Na) surface was also investigated using cyclic voltammetry measurements, and the results showed distinct cathodic and anodic peaks by zeolite X (Na) 80 °C and zeolite X (Na) 100 °C. These zeolites’ molar conductance was measured as a function of urea concentration and gave an average polynomial regression fit of 0.948. The findings in this study suggest that certain physicochemical properties, such as crystallization temperature and pH, are critical parameters for improving the morphological properties of zeolites synthesized from natural sources for various biomedical applications. PMID:28786961

Building Vocabulary of English Learners with Reading Disabilities through Computer-Assisted Morphology Instruction

ERIC Educational Resources Information Center

Lo, Ya-yu; Anderson, Adrienne L.; Bunch-Crump, Kimberly

2017-01-01

Many educators in public schools in the United States experience challenges in meeting the unique needs of the growing population of English learners who must simultaneously attain academic skills while acquiring English language proficiency. Such unique needs intensify for English learners with reading disabilities. Morphological awareness is key…

Morphology and kinetics of crystals growth in amorphous films of Cr2O3, deposited by laser ablation

NASA Astrophysics Data System (ADS)

Bagmut, Aleksandr

2018-06-01

An electron microscopic investigation was performed on the structure and kinetics of the crystallization of amorphous Cr2O3 films, deposited by pulsed laser sputtering of chromium target in an oxygen atmosphere. The crystallization was initiated by the action of an electron beam on an amorphous film in the column of a transmission electron microscope. The kinetic curves were plotted on the basis of a frame-by-frame analysis of the video recorded during the crystallization of the film. It was found that the amorphous phase - crystal phase transition in Cr2O3 films occurs as a layer polymorphic crystallization and is characterized by the values of the dimensionless relative length unit δ0 ≈ 2000-3100. The action of the electron beam initiates the formation of crystals of two basic morphological forms: disk-shaped and sickle-shaped. Growth of a disk-shaped crystals is characterized by a constant rate v and the quadratic dependence of the fraction of the crystalline phase x on the time t. Sickle-shaped crystal at an initial stage, as it grows, becomes as ring-shaped and disk-shaped crystal. The growth of a sickle-shaped crystal is characterized by normal and tangential velocity components, which depend on the time as ∼√t and as ∼1/√t respectively The end point of the arc at the interface between the amorphous and crystalline phases as the crystal grows describes a curve, which is similar to the Fermat helix. For sickle-shaped, as well as for disk-shaped crystals, the degree of crystallinity x ∼ t2.

A scanning electron microscope study of olivine crystal surfaces

NASA Technical Reports Server (NTRS)

Olsen, E. J.; Grossman, L.

1974-01-01

SEM photographs were taken of euhedral olivine grains from the Murchison C2 chondrite and several terrestrial and lunar occurrences. In general, the crystal faces of the meteorite grains are rough and uneven, with irregular growth patterns. They are very similar to crystal faces on terrestrial olivine grains that formed by sublimation from a vapor phase. They are very different from the relatively smooth and featureless surfaces of magmatic olivine crystals that precipitated from igneous melts. Qualitatively, the surface morphology of the crystal supports the contention that many euhedral crystals of olivine in C2 meteorites condensed from a gas phase.

Preliminary investigations of protein crystal growth using the Space Shuttle

NASA Technical Reports Server (NTRS)

Delucas, L. J.; Suddath, F. L.; Snyder, R.; Naumann, R.; Broom, M. B.; Pusey, M.; Yost, V.; Herren, B .; Carter, D.

1986-01-01

Four preliminary Shuttle experiments are described which have been used to develop prototype hardware for a more advanced system that will evaluate effects of gravity on protein crystal growth. The first phase of these experiments has centered on the development of micromethods for protein crystal growth by vapor-diffusion techniques (using a space version of the hanging-drop method) and on dialysis using microdialysis cells. Results suggest that the elimination of density-driven sedimentation can effect crystal morphology. In the dialysis experiment, space-grown crystals of concanavalin B were three times longer and 1/3 the thickness of earth-grown crystals.

Flow induced/ refined solution crystallization of a semiconducting polymer

NASA Astrophysics Data System (ADS)

Nguyen, Ngoc A.

Organic photovoltaics, a new generation of solar cells, has gained scientific and economic interests due to the ability of solution-processing and potentially low-cost power production. Though, the low power conversion efficiency of organic/ plastic solar cells is one of the most pertinent challenges that has appealed to research communities from many different fields including materials science and engineering, electrical engineering, chemical engineering, physics and chemistry. This thesis focuses on investigating and controlling the morphology of a semi-conducting, semi-crystalline polymer formed under shear-flow. Molecular structures and processing techniques are critical factors that significantly affect the morphology formation in the plastic solar cells, thus influencing device performance. In this study, flow-induced solution crystallization of poly (3-hexylthiophene) (P3HT) in a poor solvent, 2-ethylnapthalene (2-EN) was utilized to make a paint-like, structural liquid. The polymer crystals observed in this structured paint are micrometers long, nanometers in cross section and have a structure similar to that formed under quiescent conditions. There is pi-pi stacking order along the fibril axis, while polymer chain folding occurs along the fibril width and the order of the side-chain stacking is along fibril height. It was revealed that shear-flow not only induces P3HT crystallization from solution, but also refines and perfects the P3HT crystals. Thus, a general strategy to refine the semiconducting polymer crystals from solution under shear-flow has been developed and employed by simply tuning the processing (shearing) conditions with respect to the dissolution temperature of P3HT in 2-EN. The experimental results demonstrated that shear removes defects and allows more perfect crystals to be formed. There is no glass transition temperature observed in the crystals formed using the flow-induced crystallization indicating a significantly different morphology formation in comparison to that of the pristine (as-received) P3HT. As a result, single P3HT crystals with high surface energy chain folds were analyzed and determined. Previous reported results of infinite melting enthalpy of extended chain P3HT crystals are much higher than the result discovered in this study. The findings in this study revealed that the infinite melting enthalpy of chain-folded P3HT crystals is considerably decreased due to the presence of this P3HT chain-folded surface energy. In this study, the kinetics and mechanism of P3HT crystallization under shear-flow was thoroughly investigated as well. A homogeneous nucleation of P3HT was observed that allows one dimensional fibril crystal growth. The micrometer long P3HT crystals are formed and limited by the contact time between the P3HT molecules. Furthermore, it was found that phenyl-C61-butyric acid methyl ester (PCBM) nanoparticles inhibit the crystallization of P3HT under shear. However, the shear-flow leads to nanophase agglomeration of PCBM and creates percolation of P3HT fibril crystal networks and the PCBM phase separated domains that apparently present better pathways for transporting electrons and holes. Interestingly, the structured liquid was simply applied onto substrates with a paintbrush resulting in similar device performance to those made with current techniques in which the morphology is commonly formed during application or post-processing steps. These detailed findings are given and discussed in the thesis.

The influence of impurities on phosphoric acid hemihydrate crystallization

NASA Astrophysics Data System (ADS)

Dang, Leping; Wei, Hongyuan; Zhu, Zheng; Wang, Jingkang

2007-09-01

The influence of four typical impurities on phosphoric acid hemihydrate (H 3PO 4·0.5H 2O) crystallization in terms of kinetics and morphology is studied quantitatively. A new method for estimating growth rate is developed by taking the slopes of linearlized lines of transient chord length distribution (CLD) of crystals during the process using an in-line device of Focused Beam Reflectance Monitoring (FBRM). The presence of cations can reduce the nucleation rate of phosphoric acid while anions have less effect. Impurities of Fe 3+, Al 3+, and F - (>50 ppm) can widen the metastable zone to some extent. Adding small amounts of H 2SO 4 (<150 ppm) can enlarge metastable zone, but such effect becomes less after adding more H 2SO 4. The presence of the SO 42- tends to encourage H 3PO 4·0.5H 2O crystal growth in a wide concentration range with the maximum growth rate at 5000 ppm. Addition of Fe 3+ and Al 3+ at low level can increase crystal growth rate until it reaches a maximum at 500, 50, and 100 ppm for F -, Al 3+, and Fe 3+, respectively. Impurities of cations appear to have significant effect on crystal morphology; anions, however, appear not to change crystal shapes much.

Quantifying solubility enhancement due to particle size reduction and crystal habit modification: case study of acetyl salicylic acid.

PubMed

Hammond, Robert B; Pencheva, Klimentina; Roberts, Kevin J; Auffret, Tony

2007-08-01

The poor solubility of potential drug molecules is a significant problem in the design of pharmaceutical formulations. It is well known, however, that the solubility of crystalline materials is enhanced when the particle size is reduced to submicron levels and this factor can be expected to enhance drug product bioavailability. Direct estimation of solubility enhancement, as calculated via the Gibbs-Thompson relationship, demands reasonably accurate values for the particle/solution interfacial tension and, in particular, its anisotropy with respect to the crystal product's habit and morphology. In this article, an improved, more molecule-centered, approach is presented towards the calculation of solubility enhancement factors in which molecular modeling techniques are applied, and the effects associated with both crystal habit modification and solvent choice are examined. A case study for facetted, acetyl salicylic acid (aspirin) crystals in equilibrium with saturated aqueous ethanol solution reveals that their solubility will be enhanced in the range (7-58%) for a crystal size of 0.02 microm, with significantly higher enhancement for crystal morphologies in which the hydrophobic crystal faces are more predominant than the hydrophilic faces and for solvents in which the solubility is smaller. (c) 2007 Wiley-Liss, Inc. and the American Pharmacists Association.

Evolution of Morphology and Crystallinity of Silica Minerals Under Hydrothermal Conditions

NASA Astrophysics Data System (ADS)

Isobe, H.

2011-12-01

Silica minerals are quite common mineral species in surface environment of the terrestrial planets. They are good indicator of terrestrial processes including hydrothermal alteration, diagenesis and soil formation. Hydrothermal quartz, metastable low temperature cristobalite and amorphous silica show characteristic morphology and crystallinity depending on their formation processes and kinetics under wide range of temperature, pressure, acidity and thermal history. In this study, silica minerals produced by acidic hydrothermal alteration related to volcanic activities and hydrothermal crystallization experiments from diatom sediment are examined with crystallographic analysis and morphologic observations. Low temperature form of cistobalite is a metastable phase and a common alteration product occured in highly acidic hydrothermal environment around fumaroles in geothermal / volcanic areas. XRD analysis revealed that the alteration degree of whole rock is represented by abundance of cristobalite. Detailed powder XRD analysis show that the primary diffraction peak of cristobalite composed with two or three phases with different d-spacing and FWHM by peak profile fitting analysis. Shorter d-spacing and narrower FWHM cristobalite crystallize from precursor materials with less-crystallized, longer d-spacing and wider FWHM cristobalite. Textures of hydrothermal cristobalite in altered rock shows remnant of porphylitic texture of the host rock, pyroxene-amphibole andesite. Diatom has amorphous silica shell and makes diatomite sediment. Diatomite found in less diagenetic Quarternary formation keeps amorphous silica diatom shells. Hydrothermal alteration experiments of amorphous silica diatomite sediment are carried out from 300 °C to 550 °C. Mineral composition of run products shows crystallization of cristobalite and quartz progress depending on temperature and run durations. Initial crystallization product, cristobalite grains occur as characteristic lepispheres and granules with various surface structures. At the very initial stage of cristobalite crystallization within 2 days run duration, cristobalite shows lepispheres a few micron meters in diameter with irregular, submicron scale ridges and grooves on the surface. With the run duration up to 7 days, lepispheres change to granules with smooth surface remaining a few micron meters in diameter. Crystallinity of cristobalite lepispheres and granules corresponds to opal-CT. Euhedral quartz crystals grow with dissolution of cristobalite grains. Growth rate of cristobalite and quartz is controlled by crystallization kinetics with induction period strongly depending on temperature. Induction period of cristobalite crystallization from amorphous silica may exceed several million years at temperature below 100 °C. Crystallinity, morphology and growth rate of silica minerals occurred in various terrestrial and planetary processes are controlled by temperature and acidity of hydrothermal fluid and nucleation and growth kinetics of silica minerals.

Structure and morphology of magnetite anaerobically-produced by a marine magnetotactic bacterium and a dissimilatory iron-reducing bacterium

USGS Publications Warehouse

Sparks, N.H.C.; Mann, S.; Bazylinski, D.A.; Lovley, D.R.; Jannasch, H.W.; Frankel, R.B.

1990-01-01

Intracellular crystals of magnetite synthesized by cells of the magnetotactic vibroid organism, MV-1, and extracellular crystals of magnetite produced by the non-magnetotactic dissimilatory iron-reducing bacterium strain GS-15, were examined using high-resolution transmission electron microscopy, electron diffraction and 57Fe Mo??ssbauer spectroscopy. The magnetotactic bacterium contained a single chain of approximately 10 crystals aligned along the long axis of the cell. The crystals were essentially pure stoichiometric magnetite. When viewed along the crystal long axis the particles had a hexagonal cross-section whereas side-on they appeared as rectangules or truncated rectangles of average dimension, 53 ?? 35 nm. These findings are explained in terms of a three-dimensional morphology comprising a hexagonal prism of {110} faces which are capped and truncated by {111} end faces. Electron diffraction and lattice imaging studies indicated that the particles were structurally well-defined single crystals. In contrast, magnetite particles produced by the strain, GS-15 were irregular in shape and had smaller mean dimensions (14 nm). Single crystals were imaged but these were not of high structural perfection. These results highlight the influence of intracellular control on the crystallochemical specificity of bacterial magnetites. The characterization of these crystals is important in aiding the identification of biogenic magnetic materials in paleomagnetism and in studies of sediment magnetization. ?? 1990.

Faceting, composition and crystal phase evolution in III-V antimonide nanowire heterostructures revealed by combining microscopy techniques.

PubMed

Xu, Tao; Dick, Kimberly A; Plissard, Sébastien; Nguyen, Thanh Hai; Makoudi, Younes; Berthe, Maxime; Nys, Jean-Philippe; Wallart, Xavier; Grandidier, Bruno; Caroff, Philippe

2012-03-09

III-V antimonide nanowires are among the most interesting semiconductors for transport physics, nanoelectronics and long-wavelength optoelectronic devices due to their optimal material properties. In order to investigate their complex crystal structure evolution, faceting and composition, we report a combined scanning electron microscopy (SEM), transmission electron microscopy (TEM), and scanning tunneling microscopy (STM) study of gold-nucleated ternary InAs/InAs(1-x)Sb(x) nanowire heterostructures grown by molecular beam epitaxy. SEM showed the general morphology and faceting, TEM revealed the internal crystal structure and ternary compositions, while STM was successfully applied to characterize the oxide-free nanowire sidewalls, in terms of nanofaceting morphology, atomic structure and surface composition. The complementary use of these techniques allows for correlation of the morphological and structural properties of the nanowires with the amount of Sb incorporated during growth. The addition of even a minute amount of Sb to InAs changes the crystal structure from perfect wurtzite to perfect zinc blende, via intermediate stacking fault and pseudo-periodic twinning regimes. Moreover, the addition of Sb during the axial growth of InAs/InAs(1-x)Sb(x) heterostructure nanowires causes a significant conformal lateral overgrowth on both segments, leading to the spontaneous formation of a core-shell structure, with an Sb-rich shell.

A unique all-optic switch based on an innovatively designed liquid crystal waveguide

NASA Astrophysics Data System (ADS)

Nam, Sung-Hyun; Su, Wei-Hung; Chavez, Jesus; Yin, Shizhuo

2003-10-01

A unique, all-optic switch based on an innovatively designed planar lightwave circuit (PLC) is presented in this paper. The switching function is achieved by using ultra large birefringence of nematic liquid crystals (NLC) filled at the trench of waveguides. The trench at the crossing forms a waveguide mirror or a matching medium when extraordinary and ordinary refractive indices of NLC are employed, respectively. The major advantages of our unique design are: (1) the limitation that refractive index of liquid crystal must be less than that of waveguide material itself is eliminated so that conventional NCL material such as E7 can be used; (2) it is a self aligned fabrication process that alleviates the tight tolerance of later tilt error; (3) the design is thermally stable. The successful fabrication of this unqiue switch could result in an enabling element for the next generation all-optic networks.

Investigation of crystalline morphology in poly (ether ether ketone) using dielectric relaxation spectroscopy

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

Kalika, D.S.; Krishnaswamy, R.K.

1993-12-31

The relaxation behavior of poly (ether ether ketone) [PEEK] has been investigated using dielectric relaxation spectroscopy; the glass-rubber ({alpha}) relaxation and a sub-glass ({beta}) relaxation were examined for the amorphous material and both cold-crystallized and melt-crystallized specimens. Analysis of the data using the Cole-Cole modification of the Debye equation allowed determination of the dielectric relaxation strength and relaxation broadening parameter for both transitions as a function of material crystallization history. The crystallized specimens displayed a positive offset in isochronal loss temperature for both the {alpha} and {beta} relaxations, with the {alpha} relaxation broadened significantly. The measured dipolar response was interpretedmore » using a three-phase morphological model encompassing a crystalline phase, a mobile amorphous phase, and a rigid amorphous phase. Determination of phase fractions based on dipolar mobilization across the glass-rubber relaxation revealed a finite rigid amorphous phase fraction for both the cold-crystallized specimens which was relatively insensitive to thermal history and degree of crystallinity (W{sub RAP}40.20).« less

Influence of triethanolamine on the hydration product of portlandite in cement paste and the mechanism

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

Yan-Rong, Zhang; School of Civil Engineering, Beijing Key Laboratory of Track Engineering, Beijing Jiaotong University, Beijing 100044; Xiang-Ming, Kong

The influences of triethanolamine (TEA) on the portlandite in hardened cement pastes (HCPs) were systematically investigated. Results show that the addition of TEA in cement pastes leads to a visible reduction of Ca(OH){sub 2} (CH) content and considerably alters the morphology of CH crystals from large and parallel-stacked lamellar shape to smaller and distorted actinomorphic one. For the first time, the CH micro-crystals and even non-crystalline CH in HCPs were observed in the presence of TEA. Due to integration of CH micro-crystals in C–S–H phase, remarkable higher Ca/Si ratio of C–S–H phase was found. The formation of TEA-Ca{sup 2+} complexmore » via the interaction between Ca{sup 2+} and the oxygen atoms in TEA molecule was evidenced by the results of NMR and UV. It is believed that TEA can be introduced into the crystallization process of portlandite and thus significantly alters the morphology of CH crystals and even the content of the crystalline CH phase.« less

Electromagnetic induction heating for single crystal graphene growth: morphology control by rapid heating and quenching

NASA Astrophysics Data System (ADS)

Wu, Chaoxing; Li, Fushan; Chen, Wei; Veeramalai, Chandrasekar Perumal; Ooi, Poh Choon; Guo, Tailiang

2015-03-01

The direct observation of single crystal graphene growth and its shape evolution is of fundamental importance to the understanding of graphene growth physicochemical mechanisms and the achievement of wafer-scale single crystalline graphene. Here we demonstrate the controlled formation of single crystal graphene with varying shapes, and directly observe the shape evolution of single crystal graphene by developing a localized-heating and rapid-quenching chemical vapor deposition (CVD) system based on electromagnetic induction heating. Importantly, rational control of circular, hexagonal, and dendritic single crystalline graphene domains can be readily obtained for the first time by changing the growth condition. Systematic studies suggest that the graphene nucleation only occurs during the initial stage, while the domain density is independent of the growth temperatures due to the surface-limiting effect. In addition, the direct observation of graphene domain shape evolution is employed for the identification of competing growth mechanisms including diffusion-limited, attachment-limited, and detachment-limited processes. Our study not only provides a novel method for morphology-controlled graphene synthesis, but also offers fundamental insights into the kinetics of single crystal graphene growth.

Synthesis of Hexagonal Boron Nitride Mono layer: Control of Nucleation and Crystal Morphology

DOE PAGES

Stehle, Yijing Y.; Meyer, III, Harry M.; Unocic, Raymond R.; ...

2015-11-10

Mono layer hexagonal boron nitride (hBN) attracts significant attention due to the potential to be used as a complementary two-dimensional dielectric in fabrication of functional 2D heterostructures. Here we investigate the growth stages of the hBN single crystals and show that hBN crystals change their shape from triangular to truncated triangular and further to hexagonal depending on copper substrate distance from the precursor. We suggest that the observed hBN crystal shape variation is affected by the ratio of boron to nitrogen active species concentrations on the copper surface inside the CVD reactor. Strong temperature dependence reveals the activation energies formore » the hBN nucleation process of similar to 5 eV and crystal growth of similar to 3.5 eV. We also show that the resulting h-BN film morphology is strongly affected by the heating method of borazane precursor and the buffer gas. Elucidation of these details facilitated synthesis of high quality large area monolayer hexagonal boron nitride by atmospheric pressure chemical vapor deposition on copper using borazane as a precursor.« less

Effect of Water Vapor, Temperature, and Rapid Annealing on Formamidinium Lead Triiodide Perovskite Crystallization

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

Aguiar, Jeffery A.; Wozny, Sarah; Alkurd, Nooraldeen R.

Perovskite-based solar cells are one of the emerging candidates for radically lower cost photovoltaics. Herein, we report on the synthesis and crystallization of organic-inorganic formamidinium lead triiodide perovskite films under controlled atmospheric and environmental conditions. Using in situ (scanning) transmission electron microscopy, we make observations of the crystallization process of these materials in nitrogen and oxygen gas with and without the presence of water vapor. Complementary planar samples were also fabricated in the presence of water vapor and characterized by in situ X-ray diffraction. Direct observations of the material structure and final morphology indicate that the exposure to water vapormore » results in a porous film that is metastable, regardless of the presence of argon, nitrogen, or oxygen. However, the optimal crystallization temperature of 175 degrees C is unperturbed across conditions. Rapid modulation about the annealing temperature of 175 degrees C in +/-25 degrees C steps (150-200 degrees C) promotes crystallization and significantly improves the film morphology by overcoming the presence of impregnated water trapped in the material. Following this processing protocol, we demonstrate substantial growth to micron-size grains via observation inside of an environmentally controlled transmission electron microscope. Adapting this insight from our in situ microscopy, we are able to provide an informed materials protocol to control the structure and morphology of these organic-inorganic semiconductors, which is readily applicable to benchtop device growth strategies.« less

Effect of Water Vapor, Temperature, and Rapid Annealing on Formamidinium Lead Triiodide Perovskite Crystallization

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

Aguiar, Jeffery A.; Wozny, Sarah; Alkurd, Nooraldeen R.

Perovskite-based solar cells are one of the emerging candidates for radically lower cost photovoltaics. Herein, we report on the synthesis and crystallization of organic-inorganic formamidinium lead triiodide perovskite films under controlled atmospheric and environmental conditions. Using in situ (scanning) transmission electron microscopy, we make observations of the crystallization process of these materials in nitrogen and oxygen gas with and without the presence of water vapor. Complementary planar samples were also fabricated in the presence of water vapor and characterized by in situ X-ray diffraction. Direct observations of the material structure and final morphology indicate that the exposure to water vapormore » results in a porous film that is metastable, regardless of the presence of argon, nitrogen, or oxygen. However, the optimal crystallization temperature of 175 °C is unperturbed across conditions. Rapid modulation about the annealing temperature of 175 °C in ±25 °C steps (150-200 °C) promotes crystallization and significantly improves the film morphology by overcoming the presence of impregnated water trapped in the material. Following this processing protocol, we demonstrate substantial growth to micron-size grains via observation inside of an environmentally controlled transmission electron microscope. Adapting this insight from our in situ microscopy, we are able to provide an informed materials protocol to control the structure and morphology of these organic-inorganic semiconductors, which is readily applicable to benchtop device growth strategies.« less

Salvage of failed protein targets by reductive alkylation.

PubMed

Tan, Kemin; Kim, Youngchang; Hatzos-Skintges, Catherine; Chang, Changsoo; Cuff, Marianne; Chhor, Gekleng; Osipiuk, Jerzy; Michalska, Karolina; Nocek, Boguslaw; An, Hao; Babnigg, Gyorgy; Bigelow, Lance; Joachimiak, Grazyna; Li, Hui; Mack, Jamey; Makowska-Grzyska, Magdalena; Maltseva, Natalia; Mulligan, Rory; Tesar, Christine; Zhou, Min; Joachimiak, Andrzej

2014-01-01

The growth of diffraction-quality single crystals is of primary importance in protein X-ray crystallography. Chemical modification of proteins can alter their surface properties and crystallization behavior. The Midwest Center for Structural Genomics (MCSG) has previously reported how reductive methylation of lysine residues in proteins can improve crystallization of unique proteins that initially failed to produce diffraction-quality crystals. Recently, this approach has been expanded to include ethylation and isopropylation in the MCSG protein crystallization pipeline. Applying standard methods, 180 unique proteins were alkylated and screened using standard crystallization procedures. Crystal structures of 12 new proteins were determined, including the first ethylated and the first isopropylated protein structures. In a few cases, the structures of native and methylated or ethylated states were obtained and the impact of reductive alkylation of lysine residues was assessed. Reductive methylation tends to be more efficient and produces the most alkylated protein structures. Structures of methylated proteins typically have higher resolution limits. A number of well-ordered alkylated lysine residues have been identified, which make both intermolecular and intramolecular contacts. The previous report is updated and complemented with the following new data; a description of a detailed alkylation protocol with results, structural features, and roles of alkylated lysine residues in protein crystals. These contribute to improved crystallization properties of some proteins.

Salvage of Failed Protein Targets by Reductive Alkylation

PubMed Central

Tan, Kemin; Kim, Youngchang; Hatzos-Skintges, Catherine; Chang, Changsoo; Cuff, Marianne; Chhor, Gekleng; Osipiuk, Jerzy; Michalska, Karolina; Nocek, Boguslaw; An, Hao; Babnigg, Gyorgy; Bigelow, Lance; Joachimiak, Grazyna; Li, Hui; Mack, Jamey; Makowska-Grzyska, Magdalena; Maltseva, Natalia; Mulligan, Rory; Tesar, Christine; Zhou, Min; Joachimiak, Andrzej

2014-01-01

The growth of diffraction-quality single crystals is of primary importance in protein X-ray crystallography. Chemical modification of proteins can alter their surface properties and crystallization behavior. The Midwest Center for Structural Genomics (MCSG) has previously reported how reductive methylation of lysine residues in proteins can improve crystallization of unique proteins that initially failed to produce diffraction-quality crystals. Recently, this approach has been expanded to include ethylation and isopropylation in the MCSG protein crystallization pipeline. Applying standard methods, 180 unique proteins were alkylated and screened using standard crystallization procedures. Crystal structures of 12 new proteins were determined, including the first ethylated and the first isopropylated protein structures. In a few cases, the structures of native and methylated or ethylated states were obtained and the impact of reductive alkylation of lysine residues was assessed. Reductive methylation tends to be more efficient and produces the most alkylated protein structures. Structures of methylated proteins typically have higher resolution limits. A number of well-ordered alkylated lysine residues have been identified, which make both intermolecular and intramolecular contacts. The previous report is updated and complemented with the following new data; a description of a detailed alkylation protocol with results, structural features, and roles of alkylated lysine residues in protein crystals. These contribute to improved crystallization properties of some proteins. PMID:24590719

A review on the synthesis, crystal growth, structure and physical properties of rare earth based quaternary intermetallic compounds

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

Mumbaraddi, Dundappa; Sarkar, Sumanta; Peter, Sebastian C., E-mail: sebastiancp@jncasr.ac.in

2016-04-15

This review highlights the synthesis and crystal growth of quaternary intermetallic compounds based on rare earth metals. In the first part of this review, we highlight briefly about intermetallics and their versatile properties in comparison to the constituent elements. In the next part, we have discussed about various synthesis techniques with more focus on the metal flux technique towards the well shaped crystal growth of novel compounds. In the subsequent parts, several disordered quaternary compounds have been reviewed and then outlined most known ordered quaternary compounds with their complex structure. A special attention has been given to the ordered compoundsmore » with structural description and relation to the parent binary and ternary compounds. The importance of electronic and structural feature is highlighted as the key roles in designing these materials for emerging applications. - Graphical abstract: Rare earth based quaternary intermetallic compounds crystallize in complex novel crystal structures. The diversity in the crystal structure may induce unique properties and can be considered them as future materials. - Highlights: • Crystal growth and crystal structure of quaternary rare earth based intermetallics. • Structural complexity of quaternary compounds in comparison to the parent compounds. • Novel quaternary compounds display unique crystal structure.« less

Growth of NBT-BT single crystals by flux method and their structural, morphological and electrical characterizations

NASA Astrophysics Data System (ADS)

Kanuru, Sreenadha Rao; Baskar, K.; Dhanasekaran, R.; Kumar, Binay

2016-05-01

In this paper, one of the important, eco-friendly polycrystalline material, (1-x)(Na0.5Bi0.5)TiO3 (NBT) - xBaTiO3 (BT) of different compositions (x=0.07, 0.06 and 0.05 wt%) around the morphotropic phase boundary (MPB) were synthesized by solid state reaction technique. And the single crystals with 13×7×7 mm3, 12×12×7 mm3 and 10×7×4 mm3 dimensions were grown by self flux method. The morphology, crystal structure and unit-cell parameters have been studied and the monoclinic phase has been identified for 0.07 wt% of BT. Higher BT concentration changes the crystal habit and the mechanism has been studied clearly. Raman spectroscopy at room-temperature confirms the presence of functional groups. The quality of the as grown single crystals was examined by high resolution x-ray diffraction analysis. The dielectric properties of the as grown crystals were investigated in the frequency range of 20 Hz-2 MHz from room temperature to 450 °C. The broad dielectric peak and frequency dispersion demonstrates the relaxor behavior of grown crystals. The dielectric constant (εr), transition temperature (Tm), and depolarization temperature (Td) of the grown crystals are found to be comparatively good. The diffusive factor (γ) from Curie-Weiss law confirms the as grown NBT-BT single crystals are relaxor in nature.

Crystallization of perovskite film using ambient moisture and water as co-solvent for efficient planar perovskite solar cell (Conference Presentation)

NASA Astrophysics Data System (ADS)

Dubey, Ashish; Reza, Khan M.; Gaml, Eman; Adhikari, Nirmal; Qiao, Qiquan

2016-09-01

Smooth, compact and defect free morphology of perovskite is highly desired for enhanced device performance. Several routes such as thermal annealing, use of solvent mixtures, growth under controlled humidity has been adopted to obtain crystalline, smooth and defect free perovskite film. Herein we showed direct use of water (H2O) as co-solvent in precursor solution and have optimized the water content required to obtain smooth and dense film. Varying concentration of water was used in precursor solution of CH3NH3I and PbI2 mixed in γ-butyrolactone (GBL) and dimethylsulfoxide (DMSO). Perovskite films were crystallized using toluene assisted solvent engineering method using GBL:DMSO:H2O as solvent mixture. The amount of water was varied from 1% to 25%, which resulted in change in film morphology and perovskite crystallinity. It was concluded that an appropriate amount of water is required to assist the crystallization process to obtain smooth pin-hole free morphology. The change in morphology led to improved fill factor in the device, with highest efficiency 14%, which was significantly higher than devices made from perovskite film without adding water. We also showed that addition of up to 25% by volume of water does not significantly change the device performance.

Single crystal growth and characterization of pure and sodium-modified copper tartrate

NASA Astrophysics Data System (ADS)

Quasim, I.; Firdous, A.; Want, B.; Khosa, S. K.; Kotru, P. N.

2008-12-01

Single crystal growth of pure and modified copper tartrate crystals bearing composition (Cu) x(Na) yC 4H 4O 6· nH 2O (where x=1, 0.77, 0.65; y=0, 0.23, 0.35) is achieved using gel technique. The optimum conditions required for the growth of these crystals are worked out. The morphological development of these crystals is studied using optical and scanning electron microscopy. The dominant habit faces of the grown copper tartrate crystals are (0 0 1) and (1 1 1). Calculation of the cell parameters using CRYSFIRE software suggests that the pure copper tartrate crystal belongs to orthorhombic system with space group P2 1/c whereas the modified copper tartrate falls under tetragonal system with the space group P4 2/nbc. The external morphological development is shown to remain unaffected in the modified copper tartrate. The stoichiometric composition of the crystals is established by EDAX analysis, CH analysis, FTIR spectroscopy and thermoanalytical techniques. Thermal analysis of the grown crystals suggests that pure copper tartrate is thermally stable up to 42.84 °C whereas the modified copper tartrate crystals are stable only up to 33.11 and 25.11 °C. Calculation of the percentage weight loss from the thermogram supplemented by EDAX/CH analysis and FTIR spectroscopy suggest that the chemical formula of pure copper tartrate crystal is CuC 4H 4O 6·3H 2O whereas the chemical formula for the modified copper tartrate crystals is (Cu) 0.77(Na) 0.23C 4H 4O 6·3H 2O and (Cu) 0.65(Na) 0.35 C 4H 4O 6·H 2O.

Assembly of P3HT/CdSe nanowire networks in an insulating polymer host.

PubMed

Heo, Kyuyoung; Miesch, Caroline; Na, Jun-Hee; Emrick, Todd; Hayward, Ryan C

2018-06-27

Nanoparticles may act as compatibilizing agents for blending of immiscible polymers, leading to changes in blend morphology through a variety of mechanisms including interfacial adsorption, aggregation, and nucleation of polymer crystals. Herein, we report an approach to define highly structured donor/acceptor networks based on poly(3-hexylthiophene) (P3HT) and CdSe quantum dots (QDs) by demixing from an insulating polystyrene (PS) matrix. The incorporation of QDs led to laterally phase-separated co-continuous structures with sub-micrometer dimensions, and promoted crystallization of P3HT, yielding highly interconnected P3HT/QD hybrid nanowires embedded in the polymer matrix. These nanohybrid materials formed by controlling phase separation, interfacial activity, and crystallization within ternary donor/acceptor/insulator blends, offer attractive morphologies for potential use in optoelectronics.

Microstructure-sensitive Crystal Viscoplasticity for Ni-base Superalloys Targeting Long-term Creep-Fatigue Interaction Modeling

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

Neu, Richard W.

The aim of this project is to develop a microstructure-sensitive crystal viscoplasticity (CVP) model for single-crystal Ni-base superalloys to model the behavior of the material and components in the hot gas path sections of industrial gas turbines (IGT). Microstructure degradation associated with aging critical to predicting long-term creep-fatigue interactions will be embedded into the model through the γ' precipitate morphology evolution by coupling the coarsening drivers and kinetics into the constitutive equations of the CVP model. Model parameters will be determined using new experimental protocols that involve systematically artificially aging the alloy under different stress conditions to determine the relationshipmore » between the size and morphology g' precipitates on the creep and thermomechanical fatigue response.« less

A new bottom-up synthesis of MnBi particles with high magnetic performance

NASA Astrophysics Data System (ADS)

Liu, Shoufa; Wang, Jinpeng; Dong, Feng

2018-01-01

Mn and Bi nanoparticles were synthesized by a wet chemistry reduction process. The as-synthesized Mn and Bi nanoparticles were mixed in hexane with the molar ratio of 1 to 1, and annealed at 250 °C in an inert gas environment. In four parallel experiments, the annealing time was controlled to be 2, 4, 6, and 8 h. The impacts of annealing time on product morphology, crystallization, and magnetic properties were investigated. The results showed that within 6 h annealing, an increased annealing time resulted in more sintering among the particles in the products, enhanced crystallization, and improved magnetic properties. When the annealing time exceeded 6 h, further annealing did not bring much difference in morphology, crystallization, and magnetic properties, indicating a thermally stable state of the product.

Microstructure-sensitive Crystal Viscoelasticity for Ni-base Superalloys Targeting Long-term Creep-Fatigue Interaction Modeling

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

Neu, Richard W

The aim of this project is to develop a microstructure-sensitive crystal viscoplasticity (CVP) model for single-crystal Ni-base superalloys to model the behavior of the material and components in the hot gas path sections of industrial gas turbines (IGT). Microstructure degradation associated with aging critical to predicting long-term creep-fatigue interactions will be embedded into the model through the γ' precipitate morphology evolution by coupling the coarsening drivers and kinetics into the constitutive equations of the CVP model. Model parameters will be determined using new experimental protocols that involve systematically artificially aging the alloy under different stress conditions to determine the relationshipmore » between the size and morphology g' precipitates on the creep and thermomechanical fatigue response.« less

Preparation and Single-Crystal X-Ray Structures of Four Related Mixed-Ligand 4-Methylpyridine Indium Halide Complexes

NASA Technical Reports Server (NTRS)

Hepp, Aloysius F.; Clark, Eric B.; Schupp, John D.; Williams, Jennifer N.; Duraj, Stan A.; Fanwick, Philip E.

2013-01-01

We describe the structures of four related indium complexes obtained during synthesis of solid-state materials precursors. Indium adducts of halides and 4-methylpyridine, InX3(pic)3 (X = Cl, Br; pic = 4-methylpyridine) consist of octahedral molecules with meridional (mer) geometry. Crystals of mer-InCl3(pic)3 (1) are triclinic, space group P1(bar) (No. 2), with a = 9.3240(3), b = 13.9580(6), c = 16.7268 (7) A, alpha = 84.323(2), beta = 80.938(2), gamma = 78.274(3)Z = 4, R = 0.035 for 8820 unique reflections. Crystals of mer-InBr3(pic)3 (2) are monoclinic, space group P21/n (No. 14), with a = 15.010(2), b = 19.938(2), c = 16.593(3), beta = 116.44(1)Z = 8, R = 0.053 for 4174 unique reflections. The synthesis and structures of related compounds with phenylsulfide (chloride) (3) and a dimeric complex with bridging hydroxide (bromide) (4) coordination is also described. Crystals of trans-In(SC6H5)Cl2(pic)3 (3) are monoclinic, space group P21/n (No. 14), with a = 9.5265(2), b = 17.8729(6), c = 13.8296(4), beta = 99.7640(15)Z = 4, R = 0.048 for 5511 unique reflections. Crystals of [In(mu-OH)Br2(pic)22 (4) are tetragonal, space group = I41cd (No. 110) with a = 19.8560(4), b = 19.8560(4), c = 25.9528(6), Z = 8, R = 0.039 for 5982 unique reflections.

Fast-responding bio-based shape memory thermoplastic polyurethanes

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

Petrovic, Zoran S.; Milic, Jelena; Zhang, Fan

Fast response shape-memory polyurethanes were prepared from bio-based polyols, diphenyl methane diisocyanate and butane diol. The bio-based polyester polyols were synthesized from 9-hydroxynonanoic acid, a product obtained by ozonolysis of fatty acids extracted from soy oil and castor oil. The morphology of polyurethanes was investigated by synchrotron ultra-small angle X-ray scattering, which revealed the inter-domain spacing between the hard and soft phases, the degree of phase separation, and the level of intermixing between the hard and soft phases. We also conducted thorough investigations of the thermal, mechanical, and dielectric properties of the polyurethanes, and found that high crystallization rate ofmore » the soft segment gives these polyurethanes unique properties suitable for shapememory applications, such as adjustable transition temperatures, high degree of elastic elongations, and good mechanical strength. In conclusion, these materials are also potentially biodegradable and biocompatible, therefore suitable for biomedical and environmental applications.« less

Application of atomic force microscopy to microbial surfaces: from reconstituted cell surface layers to living cells.

PubMed

Dufrêne, Y F

2001-02-01

The application of atomic force microscopy (AFM) to probe the ultrastructure and physical properties of microbial cell surfaces is reviewed. The unique capabilities of AFM can be summarized as follows: imaging surface topography with (sub)nanometer lateral resolution; examining biological specimens under physiological conditions; measuring local properties and interaction forces. AFM is being used increasingly for: (i) visualizing the surface ultrastructure of microbial cell surface layers, including bacterial S-layers, purple membranes, porin OmpF crystals and fungal rodlet layers; (ii) monitoring conformational changes of individual membrane proteins; (iii) examining the morphology of bacterial biofilms, (iv) revealing the nanoscale structure of living microbial cells, including fungi, yeasts and bacteria, (v) mapping interaction forces at microbial surfaces, such as van der Waals and electrostatic forces, solvation forces, and steric/bridging forces; and (vi) probing the local mechanical properties of cell surface layers and of single cells.

Fast-responding bio-based shape memory thermoplastic polyurethanes

DOE PAGES

Petrovic, Zoran S.; Milic, Jelena; Zhang, Fan; ...

2017-05-31

Fast response shape-memory polyurethanes were prepared from bio-based polyols, diphenyl methane diisocyanate and butane diol. The bio-based polyester polyols were synthesized from 9-hydroxynonanoic acid, a product obtained by ozonolysis of fatty acids extracted from soy oil and castor oil. The morphology of polyurethanes was investigated by synchrotron ultra-small angle X-ray scattering, which revealed the inter-domain spacing between the hard and soft phases, the degree of phase separation, and the level of intermixing between the hard and soft phases. We also conducted thorough investigations of the thermal, mechanical, and dielectric properties of the polyurethanes, and found that high crystallization rate ofmore » the soft segment gives these polyurethanes unique properties suitable for shapememory applications, such as adjustable transition temperatures, high degree of elastic elongations, and good mechanical strength. In conclusion, these materials are also potentially biodegradable and biocompatible, therefore suitable for biomedical and environmental applications.« less

Use of inorganic Fullerene-like WS2 to produce new high-performance polyphenylene sulfide nanocomposites: role of the nanoparticle concentration.

PubMed

Naffakh, Mohammed; Marco, Carlos; Gómez, Marián A; Gómez-Herrero, Julio; Jiménez, Ignacio

2009-07-30

The use of tungsten disulfide (WS2) nanoparticles offers the opportunity to produce novel and advanced polymer-based nanocomposite materials via melt blending. The developed materials, based on the high-performance engineering thermoplastic polyphenylene sulfide (PPS), display a unique nanostructure on variation of the nanoparticle concentration, as confirmed by time-resolved synchrotron X-ray diffraction. The cold-crystallization kinetics and morphology of PPS chains under confined conditions in the nanocomposite, as determined by differential scanning calorimetry (DSC) and atomic force microscopy (AFM), also manifest a dependence on the IF-WS2 concentration which are unexpected for polymer nanocomposites. The addition of IF-WS2 with concentrations greater than or equal to 0.5 wt % of IF-WS2 remarkably improves the mechanical performance of PPS with an increase in the storage modulus of 40-75%.

Hollow raspberry-like PdAg alloy nanospheres: High electrocatalytic activity for ethanol oxidation in alkaline media

NASA Astrophysics Data System (ADS)

Peng, Cheng; Hu, Yongli; Liu, Mingrui; Zheng, Yixiong

2015-03-01

Palladium-silver (PdAg) alloy nanospheres with unique structure were prepared using a one-pot procedure based on the galvanic replacement reaction. Their electrocatalytic activity for ethanol oxidation in alkaline media was evaluated. The morphology and crystal structure of the samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD). Electrochemical characterization techniques, including cyclic voltammetry (CV) and chronoamperometry (CA) measurements were used to analyze the electrochemical performance of the PdAg alloy nanospheres. The SEM and TEM images showed that the PdAg alloy nanospheres exhibit a hierarchical nanostructure with hollow interiors and porous walls. Compared to the commercial Pd/C catalyst, the as-prepared PdAg alloy nanospheres exhibit superior electrocatalytic activity and stability towards ethanol electro-oxidation in alkaline media, showing its potential as a new non-Pt electro-catalyst for direct alcohol fuel cells (DAFCs).

Fast-Responding Bio-Based Shape Memory Thermoplastic Polyurethanes.

PubMed

Petrović, Zoran S; Milić, Jelena; Zhang, Fan; Ilavsky, Jan

2017-07-14

Novel fast response shape-memory polyurethanes were prepared from bio-based polyols, diphenyl methane diisocyanate and butane diol for the first time. The bio-based polyester polyols were synthesized from 9-hydroxynonanoic acid, a product obtained by ozonolysis of fatty acids extracted from soy oil and castor oil. The morphology of polyurethanes was investigated by synchrotron ultra-small angle X-ray scattering, which revealed the inter-domain spacing between the hard and soft phases, the degree of phase separation, and the level of intermixing between the hard and soft phases. We also conducted thorough investigations of the thermal, mechanical, and dielectric properties of the polyurethanes, and found that high crystallization rate of the soft segment gives these polyurethanes unique properties suitable for shape-memory applications, such as adjustable transition temperatures, high degree of elastic elongations, and good mechanical strength. These materials are also potentially biodegradable and biocompatible, therefore suitable for biomedical and environmental applications.

Growth of urea crystals by physical vapor transport

NASA Technical Reports Server (NTRS)

Feigelson, R. S.; Route, R. K.; Kao, T.-M.

1985-01-01

This work demonstrates that high optical quality crystals of urea can be grown by the physical vapor transport method. The unique features of this method are compared with growth from methanol/water solutions. High growth rates, exceeding 2.5 mm/day, were achieved, and cm-size optical quality single crystals were obtained. Details of the growth technique and the physical properties of the crystals are presented.

Elemental distribution analysis of urinary crystals.

PubMed

Fazil Marickar, Y M; Lekshmi, P R; Varma, Luxmi; Koshy, Peter

2009-10-01

Various crystals are seen in human urine. Some of them, particularly calcium oxalate dihydrate, are seen normally. Pathological crystals indicate crystal formation initiating urinary stones. Unfortunately, many of the relevant crystals are not recognized in light microscopic analysis of the urinary deposit performed in most of the clinical laboratories. Many crystals are not clearly identifiable under the ordinary light microscopy. The objective of the present study was to perform scanning electron microscopic (SEM) assessment of various urinary deposits and confirm the identity by elemental distribution analysis (EDAX). 50 samples of urinary deposits were collected from urinary stone clinic. Deposits containing significant crystalluria (more than 10 per HPF) were collected under liquid paraffin in special containers and taken up for SEM studies. The deposited crystals were retrieved with appropriate Pasteur pipettes, and placed on micropore filter paper discs. The fluid was absorbed by thicker layers of filter paper underneath and discs were fixed to brass studs. They were then gold sputtered to 100 A and examined under SEM (Jeol JSM 35C microscope). When crystals were seen, their morphology was recorded by taking photographs at different angles. At appropriate magnification, EDAX probe was pointed to the crystals under study and the wave patterns analyzed. Components of the crystals were recognized by utilizing the data. All the samples analyzed contained significant number of crystals. All samples contained more than one type of crystal. The commonest crystals encountered included calcium oxalate monohydrate (whewellite 22%), calcium oxalate dihydrate (weddellite 32%), uric acid (10%), calcium phosphates, namely, apatite (4%), brushite (6%), struvite (6%) and octocalcium phosphate (2%). The morphological appearances of urinary crystals described were correlated with the wavelengths obtained through elemental distribution analysis. Various urinary crystals that are not reported under light microscopy could be recognized by SEM-EDAX combination. EDAX is a significant tool for recognizing unknown crystals not identified by ordinary light microscopy or SEM alone.

Phase-field-crystal investigation of the morphology of a steady-state dendrite tip on the atomic scale

NASA Astrophysics Data System (ADS)

Tang, Sai; Wang, Jincheng; Li, Junjie; Wang, Zhijun; Guo, Yaolin; Guo, Can; Zhou, Yaohe

2017-06-01

Through phase-field-crystal (PFC) simulations, we investigated, on the atomic scale, the crucial role played by interface energy anisotropy and growth driving force during the morphological evolution of a dendrite tip at low growth driving force. In the layer-by-layer growth manner, the interface energy anisotropy drives the forefront of the dendrite tip to evolve to be highly similar to the corner of the corresponding equilibrium crystal from the aspects of atom configuration and morphology, and thus affects greatly the formation and growth of a steady-state dendrite tip. Meanwhile, the driving force substantially influences the part behind the forefront of the dendrite tip, rather than the forefront itself. However, as the driving force increases enough to change the layer-by-layer growth to the multilayer growth, the morphology of the dendrite tip's forefront is completely altered. Parabolic fitting of the dendrite tip reveals that an increase in the influence of interface energy anisotropy makes dendrite tips deviate increasingly from a parabolic shape. By quantifying the deviations under various interface energy anisotropies and growth driving forces, it is suggested that a perfect parabola is an asymptotic limit for the shape of the dendrite tips. Furthermore, the atomic scale description of the dendrite tip obtained in the PFC simulation is compatible with the mesoscopic results obtained in the phase-field simulation in terms of the dendrite tip's morphology and the stability criterion constant.

Using Dynamic Mechanical Spectroscopy to Monitor the Crystallization of PP/MAPP Blends in the Presence of Wood

Treesearch

Michael P. Wolcott; Suzhou Yin; Timothy G. Rials

2000-01-01

Crystal morphology of thermoplastics is known to be strongly influenced by the presence of solid suhstrntes like fibers or fillers. For wood, this interphase development is govemed by the chemical composition of the thermoplastic and substrate. The crystallization of PP/MAPP blends WBS observed using polarized light microscopy and quantified using DSC and DM.4....

Protein crystal growth in low gravity

NASA Technical Reports Server (NTRS)

Feigelson, Robert S.

1992-01-01

A study is presented of the crystallization of isocitrate lyase (ICL) and the influence of the lack of thermal solutal convection in microgravity on the morphology of ICL crystals is discussed. The latest results of studies with thermonucleation are presented. These include the nucleation of a protein with retrograde solubility and an unknown solubility curve. A new design for a more microgravity compatible thermonuclear is presented.

Pyroxenes as recorders of lunar basalt petrogenesis - Chemical trends due to crystal-liquid interaction.

NASA Technical Reports Server (NTRS)

Bence, A. E.; Papike, J. J.

1972-01-01

Review of the crystallization histories suggested by the chemical, crystallographic, morphological, and paragenetic relationships observed in pyroxenes from basalts collected on the Apollo 11, 12, 14, 15, and Luna 16 missions. Although the final stages of lunar basalt crystallization appear to be rapid near-surface events, the initial stages are shown to vary considerably among the different basalt types.

Glancing angle deposition of Fe triangular nanoprisms consisting of vertically-layered nanoplates

NASA Astrophysics Data System (ADS)

Li, Jianghao; Li, Liangliang; Ma, Lingwei; Zhang, Zhengjun

2016-10-01

Fe triangular nanoprisms consisting of vertically-layered nanoplates were synthesized on Si substrate by glancing angle deposition (GLAD) with an electron beam evaporation system. It was found that Fe nanoplates with a crystallographic plane index of BCC (110) were stacked vertically to form triangular nanoprisms and the axial direction of the nanoprisms, BCC <001>, was normal to the substrate. The effects of experimental parameters of GLAD on the growth and morphology of Fe nanoprisms were systematically studied. The deposition rate played an important role in the morphology of Fe nanoprisms at the same length, the deposition angle just affected the areal density of nanoprisms, and the rotation speed of substrate had little influence within the parameter range we investigated. In addition, the crystal growth mechanism of Fe nanoprisms was explained with kinetically-controlled growth mechanism and zone model theory. The driving force of crystal growth was critical to the morphology and microstructure of Fe nanoprisms deposited by GLAD. Our work introduced an oriented crystal structure into the nanomaterials deposited by GLAD, which provided a new approach to manipulate the properties and functions of nanomaterials.

Improved performance of mesostructured perovskite solar cells via an anti-solvent method

NASA Astrophysics Data System (ADS)

Hao, Jiabin; Hao, Huiying; Cheng, Feiyu; Li, Jianfeng; Zhang, Haiyu; Dong, Jingjing; Xing, Jie; Liu, Hao; Wu, Jian

2018-06-01

One-step solution process is a facile and widely used procedure to prepare organic-inorganic perovskite materials. However, the poor surface morphology of the films attributed to the uncontrollable nucleation and crystal growth in the process is unfavorable to solar cells. In this study, an anti-solvent treatment during the one-step solution process, in which ethyl acetate (EA) was dropped on the sample during spinning the precursor solution containing CH3NH3Cl, was adopted to fabricate perovskite materials and solar cells. It was found that the morphology of the perovskite film was significantly improved due to the rapid nucleation and slow crystal growth process. The modified process enabled us to fabricate the mesoporous solar cell with power conversion efficiency of 14%, showing an improvement of 40% over the efficiency of 9.7% of the device prepared by conventional one-step method. The controlling effect of annealing time on the morphology, crystal structure and transport properties of perovskite layer as well as the performance of device fabricated by the anti-solvent method were investigated and the possible mechanism was discussed.

Visualization of Thin Liquid Crystal Bubbles in Microgravity

NASA Technical Reports Server (NTRS)

Park, C. S.; Clark, N. A.; Maclennan, J. E.; Glaser, M. A.; Tin, P.; Stannarius, R.; Hall, N.; Storck, J.; Sheehan, C.

2015-01-01

The Observation and Analysis of Smectic Islands in Space (OASIS) experiment exploits the unique characteristics of freely suspended liquid crystals in a microgravity environment to advance the understanding of fluid state physics.

A Quantile Regression Approach to Understanding the Relations Between Morphological Awareness, Vocabulary, and Reading Comprehension in Adult Basic Education Students

PubMed Central

Tighe, Elizabeth L.; Schatschneider, Christopher

2015-01-01

The purpose of this study was to investigate the joint and unique contributions of morphological awareness and vocabulary knowledge at five reading comprehension levels in Adult Basic Education (ABE) students. We introduce the statistical technique of multiple quantile regression, which enabled us to assess the predictive utility of morphological awareness and vocabulary knowledge at multiple points (quantiles) along the continuous distribution of reading comprehension. To demonstrate the efficacy of our multiple quantile regression analysis, we compared and contrasted our results with a traditional multiple regression analytic approach. Our results indicated that morphological awareness and vocabulary knowledge accounted for a large portion of the variance (82-95%) in reading comprehension skills across all quantiles. Morphological awareness exhibited the greatest unique predictive ability at lower levels of reading comprehension whereas vocabulary knowledge exhibited the greatest unique predictive ability at higher levels of reading comprehension. These results indicate the utility of using multiple quantile regression to assess trajectories of component skills across multiple levels of reading comprehension. The implications of our findings for ABE programs are discussed. PMID:25351773

Optical Constants of Crystallized TiO2 Coatings Prepared by Sol-Gel Process

PubMed Central

Wang, Xiaodong; Wu, Guangming; Zhou, Bin; Shen, Jun

2013-01-01

Titanium oxide coatings have been deposited by the sol-gel dip-coating method. Crystallization of titanium oxide coatings was then achieved through thermal annealing at temperatures above 400 °C. The structural properties and surface morphology of the crystallized coatings were studied by micro-Raman spectroscopy and atomic force microscopy, respectively. Characterization technique, based on least-square fitting to the measured reflectance and transmittance spectra, is used to determine the refractive indices of the crystallized TiO2 coatings. The stability of the synthesized sol was also investigated by dynamic light scattering particle size analyzer. The influence of the thermal annealing on the optical properties was then discussed. The increase in refractive index with high temperature thermal annealing process was observed, obtaining refractive index values from 1.98 to 2.57 at He-Ne laser wavelength of 633 nm. The Raman spectroscopy and atomic force microscopy studies indicate that the index variation is due to the changes in crystalline phase, density, and morphology during thermal annealing. PMID:28811410

Optical Constants of Crystallized TiO₂ Coatings Prepared by Sol-Gel Process.

PubMed

Wang, Xiaodong; Wu, Guangming; Zhou, Bin; Shen, Jun

2013-07-12

Titanium oxide coatings have been deposited by the sol-gel dip-coating method. Crystallization of titanium oxide coatings was then achieved through thermal annealing at temperatures above 400 °C. The structural properties and surface morphology of the crystallized coatings were studied by micro-Raman spectroscopy and atomic force microscopy, respectively. Characterization technique, based on least-square fitting to the measured reflectance and transmittance spectra, is used to determine the refractive indices of the crystallized TiO₂ coatings. The stability of the synthesized sol was also investigated by dynamic light scattering particle size analyzer. The influence of the thermal annealing on the optical properties was then discussed. The increase in refractive index with high temperature thermal annealing process was observed, obtaining refractive index values from 1.98 to 2.57 at He-Ne laser wavelength of 633 nm. The Raman spectroscopy and atomic force microscopy studies indicate that the index variation is due to the changes in crystalline phase, density, and morphology during thermal annealing.

Platelets to rings: Influence of sodium dodecyl sulfate on Zn-Al layered double hydroxide morphology

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

Yilmaz, Ceren; Unal, Ugur; Koc University, Chemistry Department, Rumelifeneri yolu, Sariyer 34450, Istanbul

2012-03-15

In the current study, influence of sodium dodecyl sulfate (SDS) on the crystallization of Zn-Al layered double hydroxide (LDH) was investigated. Depending on the SDS concentration coral-like and for the first time ring-like morphologies were obtained in a urea-hydrolysis method. It was revealed that the surfactant level in the starting solution plays an important role in the morphology. Concentration of surfactant equal to or above the anion exchange capacity of the LDH is influential in creating different morphologies. Another important parameter was the critical micelle concentration (CMC) of the surfactant. Surfactant concentrations well above CMC value resulted in ring-like structures.more » The crystallization mechanism was discussed. - Graphical abstract: Dependence of ZnAl LDH Morphology on SDS concentration. Highlights: Black-Right-Pointing-Pointer In-situ intercalation of SDS in ZnAl LDH was achieved via urea hydrolysis method. Black-Right-Pointing-Pointer Morphology of ZnAl LDH intercalated with SDS depended on the SDS concentration. Black-Right-Pointing-Pointer Ring like morphology for SDS intercalated ZnAl LDH was obtained for the first time. Black-Right-Pointing-Pointer Growth mechanism was discussed. Black-Right-Pointing-Pointer Template assisted growth of ZnAl LDH was proposed.« less

Spectroscopic studies of gel grown zinc doped calcium hydrogen phosphate dihydrate crystals

NASA Astrophysics Data System (ADS)

Suryawanshi, V. B.; Chaudhari, R. T.

2018-05-01

The influence of zinc doping on the gel grown calcium hydrogen phosphate dihydrate crystals was studied using the spectroscopic techniques, which included SEM, FTIR and EDAX. It was found that, zinc ions transform the morphology of brushite crystals from rectangular plate shaped crystals to branching microcrystal patterns. However in FT-IR spectroscopy, as compared to undoped brushite crystals few vibrations were shifted to higher value. The observed changes in the vibrations were due to the impact of zinc ions. EDAX techniques is use to determine the percentage composition of elements present in the doped crystals. It revealed that the sample was of a mixed composition.

In situ observation of ultrasonic cavitation-induced fragmentation of the primary crystals formed in Al alloys.

PubMed

Wang, Feng; Tzanakis, Iakovos; Eskin, Dmitry; Mi, Jiawei; Connolley, Thomas

2017-11-01

The cavitation-induced fragmentation of primary crystals formed in Al alloys were investigated for the first time by high-speed imaging using a novel experimental approach. Three representative primary crystal types, Al 3 Ti, Si and Al 3 V with different morphologies and mechanical properties were first extracted by deep etching of the corresponding Al alloys and then subjected to ultrasonic cavitation processing in distilled water. The dynamic interaction between the cavitation bubbles and primary crystals was imaged in situ and in real time. Based on the recorded image sequences, the fragmentation mechanisms of primary crystals were studied. It was found that there are three major mechanisms by which the primary crystals were fragmented by cavitation bubbles. The first one was a slow process via fatigue-type failure. A cyclic pressure exerted by stationary pulsating bubbles caused the propagation of a crack pre-existing in the primary crystal to a critical length which led to fragmentation. The second mechanism was a sudden process due to the collapse of bubbles in a passing cavitation cloud. The pressure produced upon the collapse of the cloud promoted rapid monotonic crack growth and fast fracture in the primary crystals. The third observed mechanism was normal bending fracture as a result of the high pressure arising from the collapse of a bubble cloud and the crack formation at the branch connection points of dendritic primary crystals. The fragmentation of dendrite branches due to the interaction between two freely moving dendritic primary crystals was also observed. A simplified fracture analysis of the observed phenomena was performed. The specific fragmentation mechanism for the primary crystals depended on their morphology and mechanical properties. Copyright © 2017 The Author(s). Published by Elsevier B.V. All rights reserved.

Rapid assessment of crystal orientation in semi-crystalline polymer films using rotational zone annealing and impact of orientation on mechanical properties

DOE PAGES

Ye, Changhuai; Wang, Chao; Wang, Jing; ...

2017-08-17

Crystal orientation in semi-crystalline polymers tends to enhance their performance, such as increased yield strength and modulus, along the orientation direction. Zone annealing (ZA) orients the crystal lamellae through a sharp temperature gradient that effectively directs the crystal growth, but the sweep rate (V ZA) of this gradient significantly impacts the extent of crystal orientation. Here in this work, we demonstrate rotational zone annealing (RZA) as an efficient method to elucidate the influence of V ZA on the crystal morphology of thin films in a single experiment using isotactic poly(1-butene), PB-1, as a model semi-crystalline polymer. These RZA results aremore » confirmed using standard, serial linear ZA to tune the structure from an almost unidirectional oriented morphology to weakly oriented spherulites. The overall crystallinity is only modestly changed in comparison to isothermal crystallization (maximum of 55% from ZA vs. 48% for isothermal crystallization). However, the average grain size increases and the spherulites become anisotropic from ZA. Due to these structural changes, the Young's modulus of the oriented films, both parallel and perpendicular to the spherulite orientation direction, is significantly increased by ZA. The modulus does become anisotropic after ZA due to the directionality in the crystal structure, with more than a threefold increase in the modulus parallel to the orientation direction for the highest oriented film in comparison to the modulus from isothermal crystallization. Lastly, RZA enables rapid identification of conditions to maximize orientation of crystals in thin polymer films, which could find utility in determining conditions to improve crystallinity and performance in organic electronics.« less

Rapid assessment of crystal orientation in semi-crystalline polymer films using rotational zone annealing and impact of orientation on mechanical properties

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

Ye, Changhuai; Wang, Chao; Wang, Jing

Crystal orientation in semi-crystalline polymers tends to enhance their performance, such as increased yield strength and modulus, along the orientation direction. Zone annealing (ZA) orients the crystal lamellae through a sharp temperature gradient that effectively directs the crystal growth, but the sweep rate (V ZA) of this gradient significantly impacts the extent of crystal orientation. Here in this work, we demonstrate rotational zone annealing (RZA) as an efficient method to elucidate the influence of V ZA on the crystal morphology of thin films in a single experiment using isotactic poly(1-butene), PB-1, as a model semi-crystalline polymer. These RZA results aremore » confirmed using standard, serial linear ZA to tune the structure from an almost unidirectional oriented morphology to weakly oriented spherulites. The overall crystallinity is only modestly changed in comparison to isothermal crystallization (maximum of 55% from ZA vs. 48% for isothermal crystallization). However, the average grain size increases and the spherulites become anisotropic from ZA. Due to these structural changes, the Young's modulus of the oriented films, both parallel and perpendicular to the spherulite orientation direction, is significantly increased by ZA. The modulus does become anisotropic after ZA due to the directionality in the crystal structure, with more than a threefold increase in the modulus parallel to the orientation direction for the highest oriented film in comparison to the modulus from isothermal crystallization. Lastly, RZA enables rapid identification of conditions to maximize orientation of crystals in thin polymer films, which could find utility in determining conditions to improve crystallinity and performance in organic electronics.« less

Nucleation and growth studies of crystalline carbon phases at nanoscale

NASA Astrophysics Data System (ADS)

Mani, Radhika C.

Understanding the nucleation and early stage growth of crystals from the vapor phase is important for realizing large-area single-crystal quality films, controlled synthesis of nanocrystals, and the possible discovery of new phases of materials. Carbon provides the most interesting system because all its known crystalline phases (diamond, graphite and carbon nanotubes) are technologically important materials. Hence, this dissertation is focused on studying the nucleation and growth of carbon phases synthesized from the vapor phase. Nucleation experiments were performed in a microwave plasma chemical vapor deposition (CVD) reactor, and the resulting carbon nanocrystals were analyzed primarily using electron nanodiffraction and Raman spectroscopy. These studies led to the discovery of two new crystalline phases of sp 3 carbon other than diamond: face-centered and body-centered cubic carbon. Nanodiffraction results revealed possible hydrogen substitution into diamond-cubic lattices, indicating that these new phases probably act as intermediates in diamond nucleation. Nucleation experiments also led to the discovery of two new morphologies for sp2 carbon: nanocrystals of graphite and tapered, hollow 1-D structures termed here as "carbon nanopipettes". A Kinetic Monte Carlo (KMC) algorithm was developed to simulate the growth of individual diamond crystals from the vapor phase, starting with small clusters of carbon atoms (or seeds). Specifically, KMC simulations were used to distinguish the kinetic rules that give rise to a star-shaped decahedral morphology compared to decahedral crystals. KMC simulations revealed that slow adsorption on the {111} step-propagation sites compared to kink sites leads to star-decahedral crystals, and higher adsorption leads to decahedral crystals. Since the surfaces of the nanocrystals of graphite and nanopipettes were expected to be composed primarily of edge-plane sites, the electrochemical behavior of both these materials were investigated with compounds requiring chemisorption, specifically biologically important species. Both these materials exhibited a stable and reversible voltammetric behavior for dopamine (a neurotransmitter) similar to that of graphite edge planes. Furthermore, a simple bottom-up concept utilizing the tapered morphology of the nanopipettes was developed to assemble a nanoarray sensor for fast cyclic voltammetry. In summary, the main outcomes of this dissertation include: the discovery of new crystalline carbon phases, understanding kinetic faceting of multiply twinned diamond crystals and tapered morphologies of carbon nanotubes, and development of new electrode materials based on sp2 carbon nanocrystals for sensing biologically important analytes.

Effect of temperature on the formation of creep substructure in sodium chloride single crystals

NASA Technical Reports Server (NTRS)

Raj, Sai V.; Pharr, George M.

1992-01-01

The effect of temperature on the substructure morphology and the cell and subgrain size was investigated experimentally in NaCl single crystals under creep in the temperature range 573-873 K. It is found that the effect of temperature on the cell and subgrain sizes is weak in comparison with the effect of stress. However, there was a qualitative change in the substructure morphology with temperature, with the cells and subgrains better defined at higher temperatures. The volume fraction of the cell boundaries decreased with increasing temperature, thereby indicating a refinement of the microstructure at higher temperatures.

Erratum: Evolution of precipitate morphology during heat treatment and its implications for the superconductivity in K x F e 1.6 + y S e 2 single crystals [Phys. Rev. B 86 , 144507 (2012)

DOE PAGES

Liu, Y.; Xing, Q.; Dennis, K. W.; ...

2015-08-14

In this article, we study the relationship between precipitate morphology and superconductivity in K xFe 1.6+ySe 2 single crystals grown by self-flux method. Scanning electron microscopy (SEM) measurements revealed that the superconducting phase forms a network in the samples quenched above iron vacancy order-disorder transition temperature T s, whereas it aggregates into micrometer-sized rectangular bars and aligns as disconnected chains in the furnace-cooled samples.

Synthesis and Properties of Iron Oxide Particles Prepared by Hidrothermal Method

NASA Astrophysics Data System (ADS)

Saragi, T.; Santika, A. S.; Permana, B.; Syakir, N.; Kartawidjaja, M.; Risdiana

2017-05-01

Iron oxide of hematite (α-Fe2O3) has been successfully synthesized by hydrothermal method. The starting materials were Fe(NO3)3.9H2O, 2-methoxyethanol, diethanolamine and n-hexane. The optical, morphology and crystal structure were measured by UV-VIS, TEM and XRD, respectively. From UV-VIS measurement, it was found that the band-gap of sample was 4.17 eV. The morphology of particle was plate-like form. The sample which sintered at 1100°C has high quality crystal with hexagonal structure of α-Fe2O3 phase.

Sea urchin spine calcite forms via a transient amorphous calcium carbonate phase.

PubMed

Politi, Yael; Arad, Talmon; Klein, Eugenia; Weiner, Steve; Addadi, Lia

2004-11-12

The skeletons of adult echinoderms comprise large single crystals of calcite with smooth convoluted fenestrated morphologies, raising many questions about how they form. By using water etching, infrared spectroscopy, electron diffraction, and environmental scanning electron microscopy, we show that sea urchin spine regeneration proceeds via the initial deposition of amorphous calcium carbonate. Because most echinoderms produce the same type of skeletal material, they probably all use this same mechanism. Deposition of transient amorphous phases as a strategy for producing single crystals with complex morphology may have interesting implications for the development of sophisticated materials.

Structural, morphological and Raman studies on hybridized PVDF/BaTiO3 nanocomposites

NASA Astrophysics Data System (ADS)

Rajamanickam, N.; Jayakumar, K.; Ramachandran, K.

2017-05-01

Hybridized nanocomposites of polyvinylidene fluoride (PVDF) and nano - barium titanate (BaTiO3) were prepared using the solution casting method for different concentrations of nano-BaTiO3 and were characterized by X-ray diffraction and scanning electron microscopy. The flower like structure for morphology was observed in SEM. Raman analysis showed that the modified BaTiO3 particles, due to higher specific surfaces, induce, predominantly, the crystallization of the electrically active β-phase of PVDF, while the initial micron size particles induce the formation of the most common but non-polar α-crystal form.

Ca2+ transport and signalling in enamel cells.

PubMed

Nurbaeva, Meerim K; Eckstein, Miriam; Feske, Stefan; Lacruz, Rodrigo S

2017-05-15

Dental enamel is one of the most remarkable examples of matrix-mediated biomineralization. Enamel crystals form de novo in a rich extracellular environment in a stage-dependent manner producing complex microstructural patterns that are visually stunning. This process is orchestrated by specialized epithelial cells known as ameloblasts which themselves undergo striking morphological changes, switching function from a secretory role to a cell primarily engaged in ionic transport. Ameloblasts are supported by a host of cell types which combined represent the enamel organ. Fully mineralized enamel is the hardest tissue found in vertebrates owing its properties partly to the unique mixture of ionic species represented and their highly organized assembly in the crystal lattice. Among the main elements found in enamel, Ca 2+ is the most abundant ion, yet how ameloblasts modulate Ca 2+ dynamics remains poorly known. This review describes previously proposed models for passive and active Ca 2+ transport, the intracellular Ca 2+ buffering systems expressed in ameloblasts and provides an up-dated view of current models concerning Ca 2+ influx and extrusion mechanisms, where most of the recent advances have been made. We also advance a new model for Ca 2+ transport by the enamel organ. © 2016 The Authors. The Journal of Physiology © 2016 The Physiological Society.

Crystal Phase and Architecture Engineering of Lotus-Thalamus-Shaped Pt-Ni Anisotropic Superstructures for Highly Efficient Electrochemical Hydrogen Evolution.

PubMed

Zhang, Zhicheng; Liu, Guigao; Cui, Xiaoya; Chen, Bo; Zhu, Yihan; Gong, Yue; Saleem, Faisal; Xi, Shibo; Du, Yonghua; Borgna, Armando; Lai, Zhuangchai; Zhang, Qinghua; Li, Bing; Zong, Yun; Han, Yu; Gu, Lin; Zhang, Hua

2018-06-07

The rational design and synthesis of anisotropic 3D nanostructures with specific composition, morphology, surface structure, and crystal phase is of significant importance for their diverse applications. Here, the synthesis of well-crystalline lotus-thalamus-shaped Pt-Ni anisotropic superstructures (ASs) via a facile one-pot solvothermal method is reported. The Pt-Ni ASs with Pt-rich surface are composed of one Ni-rich "core" with face-centered cubic (fcc) phase, Ni-rich "arms" with hexagonal close-packed phase protruding from the core, and facet-selectively grown Pt-rich "lotus seeds" with fcc phase on the end surfaces of the "arms." Impressively, these unique Pt-Ni ASs exhibit superior electrocatalytic activity and stability toward the hydrogen evolution reaction under alkaline conditions compared to commercial Pt/C and previously reported electrocatalysts. The obtained overpotential is as low as 27.7 mV at current density of 10 mA cm -2 , and the turnover frequency reaches 18.63 H 2 s -1 at the overpotential of 50 mV. This work provides a new strategy for the synthesis of highly anisotropic superstructures with a spatial heterogeneity to boost their promising application in catalytic reactions. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Pressure-induced amorphization in single-crystal Ta2O5 nanowires: a kinetic mechanism and improved electrical conductivity.

PubMed

Lü, Xujie; Hu, Qingyang; Yang, Wenge; Bai, Ligang; Sheng, Howard; Wang, Lin; Huang, Fuqiang; Wen, Jianguo; Miller, Dean J; Zhao, Yusheng

2013-09-18

Pressure-induced amorphization (PIA) in single-crystal Ta2O5 nanowires is observed at 19 GPa, and the obtained amorphous Ta2O5 nanowires show significant improvement in electrical conductivity. The phase transition process is unveiled by monitoring structural evolution with in situ synchrotron X-ray diffraction, pair distribution function, Raman spectroscopy, and transmission electron microscopy. The first principles calculations reveal the phonon modes softening during compression at particular bonds, and the analysis on the electron localization function also shows bond strength weakening at the same positions. On the basis of the experimental and theoretical results, a kinetic PIA mechanism is proposed and demonstrated systematically that amorphization is initiated by the disruption of connectivity between polyhedra (TaO6 octahedra or TaO7 bipyramids) at the particular weak-bonding positions along the a axis in the unit cell. The one-dimensional morphology is well-preserved for the pressure-induced amorphous Ta2O5, and the electrical conductivity is improved by an order of magnitude compared to traditional amorphous forms. Such pressure-induced amorphous nanomaterials with unique properties surpassing those in either crystalline or conventional amorphous phases hold great promise for numerous applications in the future.

Magnetite pollution nanoparticles in the human brain

NASA Astrophysics Data System (ADS)

Maher, Barbara A.; Ahmed, Imad A. M.; Karloukovski, Vassil; MacLaren, Donald A.; Foulds, Penelope G.; Allsop, David; Mann, David M. A.; Torres-Jardón, Ricardo; Calderon-Garciduenas, Lilian

2016-09-01

Biologically formed nanoparticles of the strongly magnetic mineral, magnetite, were first detected in the human brain over 20 y ago [Kirschvink JL, Kobayashi-Kirschvink A, Woodford BJ (1992) Proc Natl Acad Sci USA 89(16):7683-7687]. Magnetite can have potentially large impacts on the brain due to its unique combination of redox activity, surface charge, and strongly magnetic behavior. We used magnetic analyses and electron microscopy to identify the abundant presence in the brain of magnetite nanoparticles that are consistent with high-temperature formation, suggesting, therefore, an external, not internal, source. Comprising a separate nanoparticle population from the euhedral particles ascribed to endogenous sources, these brain magnetites are often found with other transition metal nanoparticles, and they display rounded crystal morphologies and fused surface textures, reflecting crystallization upon cooling from an initially heated, iron-bearing source material. Such high-temperature magnetite nanospheres are ubiquitous and abundant in airborne particulate matter pollution. They arise as combustion-derived, iron-rich particles, often associated with other transition metal particles, which condense and/or oxidize upon airborne release. Those magnetite pollutant particles which are <˜200 nm in diameter can enter the brain directly via the olfactory bulb. Their presence proves that externally sourced iron-bearing nanoparticles, rather than their soluble compounds, can be transported directly into the brain, where they may pose hazard to human health.

Magnetite pollution nanoparticles in the human brain.

PubMed

Maher, Barbara A; Ahmed, Imad A M; Karloukovski, Vassil; MacLaren, Donald A; Foulds, Penelope G; Allsop, David; Mann, David M A; Torres-Jardón, Ricardo; Calderon-Garciduenas, Lilian

2016-09-27

Biologically formed nanoparticles of the strongly magnetic mineral, magnetite, were first detected in the human brain over 20 y ago [Kirschvink JL, Kobayashi-Kirschvink A, Woodford BJ (1992) Proc Natl Acad Sci USA 89(16):7683-7687]. Magnetite can have potentially large impacts on the brain due to its unique combination of redox activity, surface charge, and strongly magnetic behavior. We used magnetic analyses and electron microscopy to identify the abundant presence in the brain of magnetite nanoparticles that are consistent with high-temperature formation, suggesting, therefore, an external, not internal, source. Comprising a separate nanoparticle population from the euhedral particles ascribed to endogenous sources, these brain magnetites are often found with other transition metal nanoparticles, and they display rounded crystal morphologies and fused surface textures, reflecting crystallization upon cooling from an initially heated, iron-bearing source material. Such high-temperature magnetite nanospheres are ubiquitous and abundant in airborne particulate matter pollution. They arise as combustion-derived, iron-rich particles, often associated with other transition metal particles, which condense and/or oxidize upon airborne release. Those magnetite pollutant particles which are <∼200 nm in diameter can enter the brain directly via the olfactory bulb. Their presence proves that externally sourced iron-bearing nanoparticles, rather than their soluble compounds, can be transported directly into the brain, where they may pose hazard to human health.

Environment-oriented low-cost porous mullite ceramic membrane supports fabricated from coal gangue and bauxite.

PubMed

Lü, Qikai; Dong, Xinfa; Zhu, Zhiwen; Dong, Yingchao

2014-05-30

Porous mullite ceramic supports for filtration membrane were successfully fabricated via recycling of coal gangue and bauxite at sintering temperatures from 1100 to 1500°C with corn starch as pore-forming agent. The dynamic sintering behaviors, phase evolution, shrinkage, porosity and pore size, gas permeation flux, microstructure and mechanical property were systematically studied. A unique volume-expansion stage was observed at increased temperatures from 1276 to 1481°C caused by a mullitization-crystal-growth process. During this stage, open porosity increases and pore size distributions broaden, which result in a maximum of nitrogen gas flux at 1400°C. The X-ray diffraction results reveal that secondary mullitization took place from 1100°C and the major phase is mullite with a content of ∼84.7wt.% at 1400°C. SEM images show that the as-fabricated mullite supports have a porous microstructure composed of sintered glassy particles embedded with inter-locked mullite crystals, which grew gradually with increasing temperature from rod-like into blocky-like morphologies. To obtain mullite membrane supports with sufficient porosity and acceptable mechanical strength, the relationship between porosity and mechanical strength was investigated, which was fitted using a parabolic equation. Copyright © 2014 Elsevier B.V. All rights reserved.

Apparatus for detecting and recognizing analytes based on their crystallization patterns

DOEpatents

Morozov, Victor; Bailey, Charles L.; Vsevolodov, Nikolai N.; Elliott, Adam

2010-12-14

The invention contemplates apparatuses for recognition of proteins and other biological molecules by imaging morphology, size and distribution of crystalline and amorphous dry residues in droplets (further referred to as "crystallization patterns") containing predetermined amount of certain crystal-forming organic compounds (reporters) to which protein to be analyzed is added. Changes in the crystallization patterns of a number of amino-acids can be used as a "signature" of a protein added. Also, changes in the crystallization patterns, as well as the character of such changes, can be used as recognition elements in analysis of protein molecules.

Some Lower Valence Vanadium Fluorides: Their Crystal Distortions, Domain Structures, Modulated Structures, Ferrimagnetism, and Composition Dependence.

ERIC Educational Resources Information Center

Hong, Y. S.; And Others

1980-01-01

Describes some contemporary concepts unique to the structure of advanced solids, i.e., their crystal distortions, domain structures, modulated structures, ferrimagnetism, and composition dependence. (Author/CS)

Pin-Hole Free Perovskite Film for Solar Cells Application Prepared by Controlled Two-Step Spin-Coating Method

NASA Astrophysics Data System (ADS)

Bahtiar, A.; Rahmanita, S.; Inayatie, Y. D.

2017-05-01

Morphology of perovskite film is a key important for achieving high performance perovskite solar cells. Perovskite films are commonly prepared by two-step spin-coating method. However, pin-holes are frequently formed in perovskite films due to incomplete conversion of lead-iodide (PbI2) into perovskite CH3NH3PbI3. Pin-holes in perovskite film cause large hysteresis in current-voltage curve of solar cells due to large series resistance between perovskite layer-hole transport material. Moreover, crystal structure and grain size of perovskite crystal are also other important parameters for achieving high performance solar cells, which are significantly affected by preparation of perovskite film. We studied the effect of preparation of perovskite film using controlled spin-coating parameters on crystal structure and morphological properties of perovskite film. We used two-step spin-coating method for preparation of perovskite film with varied spinning speed, spinning time and temperature of spin-coating process to control growth of perovskite crystal aimed to produce high quality perovskite crystal with pin-hole free and large grain size. All experiment was performed in air with high humidity (larger than 80%). The best crystal structure, pin-hole free with large grain crystal size of perovskite film was obtained from film prepared at room temperature with spinning speed 1000 rpm for 20 seconds and annealed at 100°C for 300 seconds.

Containerless crystallization of silicon

NASA Astrophysics Data System (ADS)

Kuribayashi, K.; Aoyama, T.

2002-04-01

Crystallization from undercooled melt of silicon was carried out by means of electro-magnetic levitation method under controlled undercooling. The measured growth rate vs. undercooling was categorized into three regions, I, II and III, respectively, from the point of the interface morphology. Thin plate crystals whose interface consisted of both faceted (1 1 1) plane and wavy edge plane like saw-tooth were observed in the region I where the undercooling is less than 100 K. The growth rate of the wavy edge plane was well described by the dendrite growth model. The morphology of growing crystals was abruptly changed to faceted dendrite in the region II, though there was no abrupt change in the growth rate. Seeding at temperatures in the region I changes the drop to a mono-crystalline sphere, if the growth rate along the normal direction of the thin plate crystal is controlled by step-wise growth on the faceted plane. Actually, the sample of 5 mm in diameter seeded at undercooling of 26 K was a quasi-single crystal with large grain, except for a small area where twinning and cracking are observed. The result suggests that the single crystal could be grown, if a smaller sample, 1 or 2 mm in diameter, that is difficult to be levitated by electro-magnetic force were processed with other methods such as free fall in a drop tube.

Effect of alkali ions (Na+, K+, Cs+) on reaction mechanism of CZTS nano-particles synthesis

NASA Astrophysics Data System (ADS)

Kumar, Suresh; Altosaar, Mare; Grossberg, Maarja; Mikli, Valdek

2018-04-01

The control of morphology, elemental composition and phase composition of Cu2ZnSnS4 (CZTS) nano-crystals depends on the control of complex formation and surface stabilization of nano-particles in solution-based synthesis in oleylamine. At temperatures ≥280 °C, the control of nano-crystal's morphology and homogenous growth is difficult because of fast poly-nuclear growth occurring at higher temperatures. In the present work the effect of oleylamine complex formation with different alkali ions (Na+, K+ and Cs+) on nano-crystals growth at synthesis temperature of 280 °C was studied. It was found that nano-powders synthesized in the presence of Na+ and K+ ions showed the formation of crystals of different sizes - small nano-particles (18 nm-30 nm), large aggregated crystals (few nm to 1 μm) and large single crystals (1 μm - 4 μm). The presence of Cs+ ions in the nano-powder synthesis in oleylamine-metal precursor-CsOH solution promoted growth of nano-crystals of homogenous size. It is proposed that the formed oleylamine-Cs complexes a) enhance the formation and stabilization of oleylamine-metal (Cu, Zn and Sn) complexes before the injection of sulphur precursor into the oleylamine-metal precursor solution and b) after addition of sulphur stabilize the fast nucleated nano-particles and promote diffusion limited growth.

Exploration of crystal simulation potential by fluconazole isomorphism and its application in improvement of pharmaceutical properties

NASA Astrophysics Data System (ADS)

Thakur, Amitha; Kumar, Dinesh; Thipparaboina, Rajesh; Shastri, Nalini R.

2014-11-01

Control of crystal morphology during crystallization is a paramount challenge in pharmaceutical processing. Hence, there is need to introduce computational methods for morphology prediction to manage production cost of drugs and improve related pharmaceutical and biopharmaceutical properties. Layer docking approach with molecular dynamics opens a new avenue for crystal habit prediction in presence of solvent. In the present study, attempts were made to correlate predicted and experimental crystal habits of fluconazole considering solvent interactions using layer docking approach. Simulated results from layer docking approach with methanol as solvent gave two dominant facets (0 1 1) and (1 0 1) with a surface area 22.43% and 19.82% respectively, which were in agreement with the experimental results. Experimentally grown modified crystal habit of fluconazole in methanol showed enhanced dissolution rate (p<0.05) when compared to plain drug. This was attributed to the increased surface area on the specified facets caused by interactions with the solvent. Furthermore, Differential Scanning Calorimetry, Fourier Transform Infrared (FTIR) Spectroscopy and powder X-ray Diffraction of recrystallized samples confirmed only a habit change and absence of any polymorphs, hydrates or solvates. Flow and compressibility of fluconazole recrystallized in methanol was significantly improved when compared to plain drug. This study demonstrates a methodical approach using computational tools for prediction and modification of crystal habit, to enhance dissolution of poorly soluble drugs, for future pharmaceutical applications.

Comparative analysis of anti-polyglutamine Fab crystals grown on Earth and in microgravity.

PubMed

Owens, Gwen E; New, Danielle M; Olvera, Alejandra I; Manzella, Julia Ashlyn; Macon, Brittney L; Dunn, Joshua C; Cooper, David A; Rouleau, Robyn L; Connor, Daniel S; Bjorkman, Pamela J

2016-10-01

Huntington's disease is one of nine neurodegenerative diseases caused by a polyglutamine (polyQ)-repeat expansion. An anti-polyQ antigen-binding fragment, MW1 Fab, was crystallized both on Earth and on the International Space Station, a microgravity environment where convection is limited. Once the crystals returned to Earth, the number, size and morphology of all crystals were recorded, and X-ray data were collected from representative crystals. The results generally agreed with previous microgravity crystallization studies. On average, microgravity-grown crystals were 20% larger than control crystals grown on Earth, and microgravity-grown crystals had a slightly improved mosaicity (decreased by 0.03°) and diffraction resolution (decreased by 0.2 Å) compared with control crystals grown on Earth. However, the highest resolution and lowest mosaicity crystals were formed on Earth, and the highest-quality crystal overall was formed on Earth after return from microgravity.

Comparative analysis of anti-polyglutamine Fab crystals grown on Earth and in microgravity

PubMed Central

Owens, Gwen E.; New, Danielle M.; Olvera, Alejandra I.; Manzella, Julia Ashlyn; Macon, Brittney L.; Dunn, Joshua C.; Cooper, David A.; Rouleau, Robyn L.; Connor, Daniel S.; Bjorkman, Pamela J.

2016-01-01

Huntington’s disease is one of nine neurodegenerative diseases caused by a polyglutamine (polyQ)-repeat expansion. An anti-polyQ antigen-binding fragment, MW1 Fab, was crystallized both on Earth and on the International Space Station, a microgravity environment where convection is limited. Once the crystals returned to Earth, the number, size and morphology of all crystals were recorded, and X-ray data were collected from representative crystals. The results generally agreed with previous microgravity crystallization studies. On average, microgravity-grown crystals were 20% larger than control crystals grown on Earth, and microgravity-grown crystals had a slightly improved mosaicity (decreased by 0.03°) and diffraction resolution (decreased by 0.2 Å) compared with control crystals grown on Earth. However, the highest resolution and lowest mosaicity crystals were formed on Earth, and the highest-quality crystal overall was formed on Earth after return from microgravity. PMID:27710941

Crystallization behavior of polyamide-6 microcellular nanocomposites

Treesearch

Mingjun Yuan; Lih-Sheng Turng; Shaoqin Gong; Andreas Winardi

2004-09-01

The crystallization behaviors of polyamide-6 (PA-6) and its nanocomposites undergoing the microcellular injection molding process are studied using Transmission Electron Microscopy (TEM), X-ray Diffractometer (XRD), Polarized Optical Microscopy (POM), and Differential Scanning Calorimetry (DSC). The relationships among the morphology, the mechanical property of the...

A Successful Synthesis of the CoCrFeNiAl0.3 Single-Crystal, High-Entropy Alloy by Bridgman Solidification

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

Ma, S. G.; Zhang, S. F.; Gao, M. C.

2013-08-22

For the first time, a face-centered-cubic, single-crystal CoCrFeNiAl{sub 0.3} (designated as Al0.3), high-entropy alloy (HEA) was successfully synthesized by the Bridgman solidification (BS) method, at an extremely low withdrawal velocity through a constant temperature gradient, for which it underwent two BS steps. Specially, at the first BS step, the alloy sample underwent several morphological transitions accompanying the crystal growth from the melt. This microstructure evolves from as-cast dendrites, to equiaxed grains, and then to columnar crystals, and last to the single crystal. In particular, at the equiaxed-grain region, some visible annealing twins were observed, which indicates a low stacking faultmore » energy of the Al0.3 alloy. Although a body-centered- cubic CoCrFeNiAl (Al1) HEA was also prepared under the same conditions, only a single columnar-crystal structure with instinctively preferential crystallographic orientations was obtained by the same procedure. A similar morphological transition from dendrites to equiaxed grains occurred at the equiaxed-grain region in Al1 alloy, but the annealing twins were not observed probably because a higher Al addition leads to a higher stacking fault energy for this alloy.« less

Generation of mariner-based transposon insertion mutant library of Bacillus sphaericus 2297 and investigation of genes involved in sporulation and mosquito-larvicidal crystal protein synthesis.

PubMed

Wu, Yiming; Hu, Xiaomin; Ge, Yong; Zheng, Dasheng; Yuan, Zhiming

2012-05-01

Bacillus sphaericus has been used with great success in mosquito control programs worldwide. Under conditions of nutrient limitation, it undergoes sporulation via a series of well defined morphological stages. However, only a small number of genes involved in sporulation have been identified. To identify genes associated with sporulation, and to understand the relationship between sporulation and crystal protein synthesis, a random mariner-based transposon insertion mutant library of B. sphaericus strain 2297 was constructed and seven sporulation-defective mutants were selected. Sequencing of the DNA flanking of the transposon insertion identified several genes involved in sporulation. The morphologies of mutants were determined by electron microscopy and synthesis of crystal proteins was analyzed by SDS-PAGE and Western blot. Four mutants blocked at early stages of sporulation failed to produce crystal proteins and had lower larvicidal activity. However, the other three mutants were blocked at later stages and were able to form crystal proteins, and the larvicidal activity was similar to wild type. These results indicated that crystal protein synthesis in B. sphaericus is dependent on sporulation initiation. © 2012 Federation of European Microbiological Societies. Published by Blackwell Publishing Ltd. All rights reserved.

Optically addressed and submillisecond response phase only liquid crystal spatial light modulator

NASA Astrophysics Data System (ADS)

Zhao, Xiangjie; Duan, Jiazhu; Zhang, Dayong; Luo, Yongquan

2014-10-01

Liquid crystal based phase only spatial light modulator has attracted many research interests since last decades because of its superior advantage. Until now the liquid crystal spatial light modulator has been applied in many fields, but the response speed of nematic LC limited its further application. In this paper, an optically addressed phase only LC spatial light modulator was proposed based on polymer network liquid crystal. Morphology effect on the light scattering of PNLC was studied, which was mainly consisted of fiber and fiber bundles. The morphology nearly determined the light scattering and electro-optical property. Due to the high threshold voltage, to address the PNLC phase modulator was also concerned. Optical addressing method was proposed, in which BSO crystal was selected to replace one of the glass substrate. The response speed of PNLC was so fast that the reorientation of liquid crystal director will follow the change of effective voltage applied on LC layer, which was related with the voltage signal and especially with electron transport of photo-induced carriers due to diffusion and drift. The on state dynamic response of phase change was investigated. Based on this device, beam steering was also achieved by loading 488nm laser strip on the optical addressed phase only spatial light modulator.

Structural basis for unique hierarchical cylindrites induced by ultrahigh shear gradient in single natural fiber reinforced poly(lactic acid) green composites.

PubMed

Xu, Huan; Xie, Lan; Jiang, Xin; Hakkarainen, Minna; Chen, Jing-Bin; Zhong, Gan-Ji; Li, Zhong-Ming

2014-05-12

A local shear flow field was feasibly generated by pulling the ramie fiber in single fiber reinforced poly(lactic acid) (PLA) composites. This was featured by an ultrahigh shear gradient with a maximum shear rate up to 1500 s(-1), a level comparable to that frequently occurring during the practical polymer processing. To distinguish shear-induced self-nucleation and ramie fiber-induced heterogeneous nucleation, the shear history was classified by pulling the fiber for 5 s (pulled sample) and pulling out the fiber during 10 s (pulled-out sample), while the static fiber-induced crystallization was carried out as the counterpart. As a result of the ultrahigh shear gradient, the combination of primary shear-induced nucleation in the central region and secondary nucleation in the outer layer assembled the unique hierarchical superstructures. By comparing the architectural configurations of interphases formed in the static, pulled, and pulled-out samples, it was shown that the hierarchical cylindrites underwent the process of self-nucleation driven by the applied shear flow, very different from the formation of fiber-induced transcrystallinity (TC) triggered by the heterogeneous nucleating sites at the static fiber surface. The twisting of transcrystallized lamellae may take place due to the spatial hindrance induced by the incredibly dense nuclei under the intense shearing flow, as observed in the synchrotron X-ray diffraction patterns. The influence of chain characteristics on the crystalline morphology was further explored by adding a small amount of poly(ethylene glycol) (PEG) to enhance the molecular mobility of PLA. It was of interest to find that the existence of PEG not only facilitated the growth rates of TC and cylindrites but also improved the preferential orientation of PLA chains and thus expanded the ordered regions. We unearthed lamellar units that were composed of rich fibrillar extended chain crystals (diameter of 50-80 nm). These results are of importance to shed light on tailoring crystalline morphology for natural fibers reinforced green composite materials. Of immense practical significance, too, is the crystalline evolution that has been tracked in the simple model penetrated with an ultrahigh shear gradient, which researchers have so far been unable to replicate during the practical melt processing, such as extrusion and injection molding.

Nanostructured Ti-Ta thin films synthesized by combinatorial glancing angle sputter deposition

NASA Astrophysics Data System (ADS)

Motemani, Yahya; Khare, Chinmay; Savan, Alan; Hans, Michael; Paulsen, Alexander; Frenzel, Jan; Somsen, Christoph; Mücklich, Frank; Eggeler, Gunther; Ludwig, Alfred

2016-12-01

Ti-Ta alloys are attractive materials for applications in actuators as well as biomedical implants. When fabricated as thin films, these alloys can potentially be employed as microactuators, components for micro-implantable devices and coatings on surgical implants. In this study, Ti100-x Ta x (x = 21, 30) nanocolumnar thin films are fabricated by glancing angle deposition (GLAD) at room temperature using Ti73Ta27 and Ta sputter targets. Crystal structure, morphology and microstructure of the nanostructured thin films are systematically investigated by XRD, SEM and TEM, respectively. Nanocolumns of ˜150-160 nm in width are oriented perpendicular to the substrate for both Ti79Ta21 and Ti70Ta30 compositions. The disordered α″ martensite phase with orthorhombic structure is formed in room temperature as-deposited thin films. The columns are found to be elongated small single crystals which are aligned perpendicular to the (20\\bar{4}) and (204) planes of α″ martensite, indicating that the films’ growth orientation is mainly dominated by these crystallographic planes. Laser pre-patterned substrates are utilized to obtain periodic nanocolumnar arrays. The differences in seed pattern, and inter-seed distances lead to growth of multi-level porous nanostructures. Using a unique sputter deposition geometry consisting of Ti73Ta27 and Ta sputter sources, a nanocolumnar Ti-Ta materials library was fabricated on a static substrate by a co-deposition process (combinatorial-GLAD approach). In this library, a composition spread developed between Ti72.8Ta27.2 and Ti64.4Ta35.6, as confirmed by high-throughput EDX analysis. The morphology over the materials library varies from well-isolated nanocolumns to fan-like nanocolumnar structures. The influence of two sputter sources is investigated by studying the resulting column angle on the materials library. The presented nanostructuring methods including the use of the GLAD technique along with pre-patterning and a combinatorial materials library fabrication strategy offer a promising technological approach for investigating Ti-Ta thin films for a range of applications. The proposed approaches can be similarly implemented for other materials systems which can benefit from the formation of a nanocolumnar morphology.

Transformation from Nanofibers to Nanoribbons in Poly(3-hexylthiophene) Solution by Adding Alkylthiols.

PubMed

Pan, Shuang; Zhu, Mingjing; He, Luze; Zhang, Hongdong; Qiu, Feng; Lin, Zhiqun; Peng, Juan

2018-05-10

An intriguing morphological transition from poly(3-hexylthiophene) (P3HT) 1D nanofibers to 2D nanoribbons enabled by the addition of a series of alkylthiols is reported. First, P3HT 1D nanofibers are formed due to strong anisotropic π-π stacking between planar rigid backbones. Upon the addition of alkylthiols, P3HT nanofibers are transformed into nanoribbons associated with the crystallographic transition from edge-on orientation to flat-on orientation. The content of alkylthiols has a great influence on the P3HT morphology in the solution. The mechanism of such a morphological transformation is discussed based on the interaction between alkylthiols and P3HT chains. This work offers an effective strategy to tailor the crystal morphology and dimension of P3HT, which not only improves the understanding of P3HT crystallization but also may enable such discovery into conjugated polymer-based optoelectronic devices. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Near-liquidus growth of feldspar spherulites in trachytic melts: 3D morphologies and implications in crystallization mechanisms

NASA Astrophysics Data System (ADS)

Arzilli, Fabio; Mancini, Lucia; Voltolini, Marco; Cicconi, Maria Rita; Mohammadi, Sara; Giuli, Gabriele; Mainprice, David; Paris, Eleonora; Barou, Fabrice; Carroll, Michael R.

2015-02-01

The nucleation and growth processes of spherulitic alkali feldspar have been investigated in this study through X-ray microtomography and electron backscatter diffraction (EBSD) data. Here we present the first data on Shape Preferred Orientation (SPO) and Crystal Preferred Orientation (CPO) of alkali feldspar within spherulites. The analysis of synchrotron X-ray microtomography and EBSD datasets allowed us to study the morphometric characteristics of spherulites in trachytic melts in quantitative fashion, highlighting the three-dimensional shape, preferred orientation, branching of lamellae and crystal twinning, providing insights about the nucleation mechanism involved in the crystallization of the spherulites. The nucleation starts with a heterogeneous nucleus (pre-existing crystal or bubble) and subsequently it evolves forming "bow tie" morphologies, reaching radially spherulitic shapes in few hours. Since each lamella within spherulite is also twinned, these synthetic spherulites cannot be considered as single nuclei but crystal aggregates originated by heterogeneous nucleation. A twin boundary may have a lower energy than general crystal-crystal boundaries and many of the twinned grains show evidence of strong local bending which, combined with twin plane, creates local sites for heterogeneous nucleation. This study shows that the growth rates of the lamellae (10- 6-10- 7 cm/s) in spherulites are either similar or slightly higher than that for single crystals by up to one order of magnitude. Furthermore, the highest volumetric growth rates (10- 11-10- 12 cm3/s) show that the alkali feldspar within spherulites can grow fast reaching a volumetric size of ~ 10 μm3 in 1 s.

A computational investigation of the thermodynamics and structure in colloid and polymer mixtures

NASA Astrophysics Data System (ADS)

Mahynski, Nathan Alexander

In this dissertation I use computational tools to study the structure and thermodynamics of colloid-polymer mixtures. I show that fluid-fluid phase separation in mixtures of colloids and linear polymers cannot be universally reduced using polymer-based scaling principles since these assume the binodals exist in a single scaling regime, whereas accurate simulations clearly demonstrate otherwise. I show that rethinking these solutions in terms of multiple length scales is necessary to properly explain the thermodynamic stability and structure of these fluid phases, and produce phase diagrams in nearly quantitative agreement with experimental results. I then extend this work to encompass more geometrically complex "star" polymers revealing how the phase behavior for many of these binary mixtures may be mapped onto that of mixtures containing only linear polymers. I further consider the depletion-driven crystallization of athermal colloidal hard spheres induced by polymers. I demonstrate how the partitioning of a finite amount of polymer into the colloidal crystal phase implies that the polymer's architecture can be tailored to interact with the internal void structure of different crystal polymorphs uniquely, thus providing a direct route to thermodynamically stabilizing one arbitrarily chosen structure over another, e.g., the hexagonal close-packed crystal over the face-centered cubic. I then begin to generalize this result by considering the consequences of thermal interactions and complex polymer architectures. These principles lay the groundwork for intelligently engineering co-solute additives in crystallizing colloidal suspensions that can be used to thermodynamically isolate single crystal morphologies. Finally, I examine the competition between self-assembly and phase separation in polymer-grafted nanoparticle systems by comparing and contrasting the validity of two different models for grafted nanoparticles: "nanoparticle amphiphiles" versus "patchy particles." The latter suggests these systems have some utility in forming novel "equilibrium gel" phases, however, I find that considering grafted nanoparticles as amphiphiles provides a qualitatively accurate description of their thermodynamics revealing either first-order phase separation into two isotropic phases or continuous self-assembly. I find no signs of empty liquid formation, suggesting that these nanoparticles do not provide a route to such phases.

Unique Chiral Interpenetrating d-f Heterometallic MOFs as Luminescent Sensors.

PubMed

Wu, Zhi-Lei; Dong, Jie; Ni, Wei-Yan; Zhang, Bo-Wen; Cui, Jian-Zhong; Zhao, Bin

2015-06-01

One novel three-dimensional (3D) 3d-4f metal-organic framework (MOF), [TbZn(L)(CO3)2(H2O)]n (1) [HL = 4'-(4-carboxyphenyl)-2,2':6',2″-terpyridine], has been successfully synthesized and structurally characterized. Structural analysis shows that compound 1 features a unique chiral interpenetrating 3D framework for the first time. The resulting crystals of 1 are composed of enantiomers 1a (P41) and 1b (P43), as was clearly confirmed by the crystal structure and the corresponding circular dichroism (CD) analyses of eight randomly selected crystals. The investigations on CD spectra based on every single crystal clearly assigned the Cotton effect signals. The powder X-ray diffraction measurement of 1 after being immersed in common solvents reveals that 1 possess excellent solvent stability. Furthermore, luminescent studies imply that 1 displays highly selective luminescent sensing of aldehydes, such as formol, acetaldehyde, and propanal.

Tridimensional morphology and kinetics of etch pit on the {l_brace}0 0 0 1{r_brace} plane of sapphire crystal

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

Zhang Lunyong; Sun Jianfei, E-mail: jfsun_hit@263.net; Zuo Hongbo

2012-08-15

The tridimensional morphology and etching kinetics of the etch pit on the C-{l_brace}0 0 0 1{r_brace} plane of sapphire crystal ({alpha}-Al{sub 2}O{sub 3}) in molten KOH were studied experimentally. It was shown that the etch pit takes on tridimensional morphologies with triangular symmetry same as the symmetric property of the sapphire crystal. Pits like centric and eccentric triangular pyramid as well as hexagonal pyramid were observed, but the latter is less in density. In-depth analyses show the side walls of the etch pits belong to the {l_brace}1 1{sup Macron} 0 2{sup Macron }{r_brace} family, and the triangular pit contains edgesmore » full composed by Al{sup 3+} ions on the etching surface so it is more stable than the hexagonal pit since its edges on the etching surface contains Al{sup 2+} ions. The etch pits developed in a manner of kinematic wave by the step moving with constant speed, which is controlled by the chemical reaction with activation energy of 96.6 kJ/mol between Al{sub 2}O{sub 3} and KOH. - Graphical abstract: Schematic showing the atomic configuration of the predicted side walls of regular triangular pyramid shaped etch pit on the C-{l_brace}0 0 0 1{r_brace} plane of sapphire crystal. Highlights: Black-Right-Pointing-Pointer Observed the tridimensional morphology of etch pits. Black-Right-Pointing-Pointer Figured out the atomic configuration origin of the etch pits. Black-Right-Pointing-Pointer Quantitatively determined the etch rates of the etch pits.« less

Ikaite pseudomorphs in the Zaire deep-sea fan: An intermediate between calcite and porous calcite

NASA Astrophysics Data System (ADS)

Jansen, J. H. F.; Woensdregt, C. F.; Kooistra, M. J.; van der Gaast, S. J.

1987-03-01

Translucent brown aggregates of calcium-carbonate crystals have been found in cores from the Zaire deep-sea fan (west equatorial Africa). The aggregates are well preserved but very friable. Upon storage they become yellowish white and cloudy and release water. Chemical, mineralogical (XRD), petrographical, crystal-morphological, and stable-isotope data demonstrate that the crystals have passed through three phases: (1) an authigenic carbonate phase, probably calcium carbonate, which is represented by the external habit of the present crystals; (2) a translucent brown ikaite phase (CaCO3·6H2O), unstable at temperatures above 5 °C; and (3) a phase consisting of calcite microcrystals that are poorly cemented and form a porous mass within the crystal form of the morphologically unchanged first phase. The transformation from the first phase into ikaite was probably a kinetic replacement. The transformation from ikaite into the third phase occurred because of storage at room temperature. The presence of ikaite is indicative of a low-temperature, anaerobic, organic-carbon-rich marine environment. Ikaite is probably the precursor of a great number of porous calcite pseudomorphs, and possibly also of many marine authigenic microcrystalline carbonate nodules.

Morphological Control of Co3O4 and Its Photocatalytic Properties

EPA Science Inventory

Cobaltosic oxide (Co3O4), a p-type semiconductor, belongs to the normal spinel crystal structure based on a cubic close packing array of oxide ions. The size, surface, geometry, and crystal phase of catalysts are important parameters for controlling their chemical, optical, and ...

Characterization of calcium crystals in Abelia using x-ray diffraction and electron microscopes

USDA-ARS?s Scientific Manuscript database

Localization, chemical composition, and morphology of calcium crystals in leaves and stems of Abelia mosanensis and A. ×grandiflora were analyzed with a variable pressure scanning electron microscope (VP-SEM) equipped with an X-ray diffraction system, low temperature SEM (LT-SEM) and a transmission ...

The Influence of Surface Morphology and Diffraction Resolution of Canavalin Crystals

NASA Technical Reports Server (NTRS)

Plomp, M.; Thomas, B. R.; Day, J. S.; McPherson, A.; Chernov, A. A.; Malkin, A.

2003-01-01

Canavalin crystals grown from material purified and not purified by High Performance Liquid Chromatography were studied by atomic force microscopy and x-ray diffraction. After purification, resolution was improved from 2.55Angstroms to 2.22Angstroms and jagged isotropic spiral steps transformed into regular, well polygonized steps.

Fundamental Studies of Crystal Growth of Microporous Materials

NASA Technical Reports Server (NTRS)

Dutta, P.; George, M.; Ramachandran, N.; Schoeman, B.; Curreri, Peter A. (Technical Monitor)

2002-01-01

Microporous materials are framework structures with well-defined porosity, often of molecular dimensions. Zeolites contain aluminum and silicon atoms in their framework and are the most extensively studied amongst all microporous materials. Framework structures with P, Ga, Fe, Co, Zn, B, Ti and a host of other elements have also been made. Typical synthesis of microporous materials involve mixing the framework elements (or compounds, thereof) in a basic solution, followed by aging in some cases and then heating at elevated temperatures. This process is termed hydrothermal synthesis, and involves complex chemical and physical changes. Because of a limited understanding of this process, most synthesis advancements happen by a trial and error approach. There is considerable interest in understanding the synthesis process at a molecular level with the expectation that eventually new framework structures will be built by design. The basic issues in the microporous materials crystallization process include: (1) Nature of the molecular units responsible for the crystal nuclei formation; (2) Nature of the nuclei and nucleation process; (3) Growth process of the nuclei into crystal; (4) Morphological control and size of the resulting crystal; (5) Surface structure of the resulting crystals; (6) Transformation of frameworks into other frameworks or condensed structures. The NASA-funded research described in this report focuses to varying degrees on all of the above issues and has been described in several publications. Following is the presentation of the highlights of our current research program. The report is divided into five sections: (1) Fundamental aspects of the crystal growth process; (2) Morphological and Surface properties of crystals; (3) Crystal dissolution and transformations; (4) Modeling of Crystal Growth; (5) Relevant Microgravity Experiments.

Structural Color Patterns by Electrohydrodynamic Jet Printed Photonic Crystals.

PubMed

Ding, Haibo; Zhu, Cun; Tian, Lei; Liu, Cihui; Fu, Guangbin; Shang, Luoran; Gu, Zhongze

2017-04-05

In this work, we demonstrate the fabrication of photonic crystal patterns with controllable morphologies and structural colors utilizing electrohydrodynamic jet (E-jet) printing with colloidal crystal inks. The final shape of photonic crystal units is controlled by the applied voltage signal and wettability of the substrate. Optical properties of the structural color patterns are tuned by the self-assembly of the silica nanoparticle building blocks. Using this direct printing technique, it is feasible to print customized functional patterns composed of photonic crystal dots or photonic crystal lines according to relevant printing mode and predesigned tracks. This is the first report for E-jet printing with colloidal crystal inks. Our results exhibit promising applications in displays, biosensors, and other functional devices.

Protein crystal growth in low gravity

NASA Technical Reports Server (NTRS)

Feigelson, Robert S.

1990-01-01

The effect of low gravity on the growth of protein crystals and those parameters which will affect growth and crystal quality was studied. The proper design of the flight hardware and experimental protocols are highly dependent on understanding the factors which influence the nucleation and growth of crystals of biological macromolecules. Thus, those factors are investigated and the body of knowledge which has been built up for small molecule crystallization. These data also provide a basis of comparison for the results obtained from low-g experiments. The flows around growing crystals are detailed. The preliminary study of the growth of isocitrate lyase, the crystal morphologies found and the preliminary x ray results are discussed. The design of two apparatus for protein crystal growth by temperature control are presented along with preliminary results.

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.

Hydrothermal synthesis of zinc oxide nanoparticles using rice as soft biotemplate.

PubMed

Ramimoghadam, Donya; Bin Hussein, Mohd Zobir; Taufiq-Yap, Yun Hin

2013-01-01

Rice as a renewable, abundant bio-resource with unique characteristics can be used as a bio-template to synthesize various functional nanomaterials. Therefore, the effect of uncooked rice flour as bio-template on physico-chemical properties, especially the morphology of zinc oxide nanostructures was investigated in this study. The ZnO particles were synthesized through hydrothermal-biotemplate method using zinc acetate-sodium hydroxide and uncooked rice flour at various ratios as precursors at 120°C for 18 hours. The results indicate that rice as a bio-template can be used to modify the shape and size of zinc oxide particles. Different morphologies, namely flake-, flower-, rose-, star- and rod-like structures were obtained with particle size at micro- and nanometer range. Pore size and texture of the resulting zinc oxide particles were found to be template-dependent and the resulting specific surface area enhanced compared to the zinc oxide synthesized without rice under the same conditions. However, optical property particularly the band gap energy is generally quite similar. Pure zinc oxide crystals were successfully synthesized using rice flour as biotemplate at various ratios of zinc salt to rice. The size- and shape-controlled capability of rice to assemble the ZnO particles can be employed for further useful practical applications.

A Review of In Situ Observations of Crystallization and Growth in High Temperature Oxide Melts

NASA Astrophysics Data System (ADS)

Wang, Zhanjun; Sohn, Il

2018-05-01

This review summarizes the significant results of high-temperature confocal laser scanning microscopy (CLSM) and single hot thermocouple technology (SHTT) and its application in observing the crystallization and growth in high-temperature oxide melts from iron- and steel-making slags to continuous casting mold fluxes. Using in situ observations of CLSM and SHTT images of high-temperature molten oxides with time, temperature, and composition, the crystallization behavior, including crystal morphology, crystallization temperature, initial nucleation and growth rate, could be obtained. The broad range of applications using in situ observations during crystallization have provided a wealth of opportunities in pyrometallurgy and is provided in this review.

DENTAL ENAMEL FORMATION AND IMPLICATIONS FOR ORAL HEALTH AND DISEASE.

PubMed

Lacruz, Rodrigo S; Habelitz, Stefan; Wright, J Timothy; Paine, Michael L

2017-07-01

Dental enamel is the hardest and most mineralized tissue in extinct and extant vertebrate species and provides maximum durability that allows teeth to function as weapons and/or tools as well as for food processing. Enamel development and mineralization is an intricate process tightly regulated by cells of the enamel organ called ameloblasts. These heavily polarized cells form a monolayer around the developing enamel tissue and move as a single forming front in specified directions as they lay down a proteinaceous matrix that serves as a template for crystal growth. Ameloblasts maintain intercellular connections creating a semi-permeable barrier that at one end (basal/proximal) receives nutrients and ions from blood vessels, and at the opposite end (secretory/apical/distal) forms extracellular crystals within specified pH conditions. In this unique environment, ameloblasts orchestrate crystal growth via multiple cellular activities including modulating the transport of minerals and ions, pH regulation, proteolysis, and endocytosis. In many vertebrates, the bulk of the enamel tissue volume is first formed and subsequently mineralized by these same cells as they retransform their morphology and function. Cell death by apoptosis and regression are the fates of many ameloblasts following enamel maturation, and what cells remain of the enamel organ are shed during tooth eruption, or are incorporated into the tooth's epithelial attachment to the oral gingiva. In this review, we examine key aspects of dental enamel formation, from its developmental genesis to the ever-increasing wealth of data on the mechanisms mediating ionic transport, as well as the clinical outcomes resulting from abnormal ameloblast function. Copyright © 2017 the American Physiological Society.

Solid-state dewetting of single- and bilayer Au-W thin films: Unraveling the role of individual layer thickness, stacking sequence and oxidation on morphology evolution

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

Herz, A., E-mail: andreas.herz@tu-ilmenau.de, E-mail: dong.wang@tu-ilmenau.de; Franz, A.; Theska, F.

2016-03-15

Self-assembly of ultrathin Au, W, and Au-W bilayer thin films is investigated using a rapid thermal annealing technique in an inert ambient. The solid-state dewetting of Au films is briefly revisited in order to emphasize the role of initial film thickness. W films deposited onto SiO{sub 2} evolve into needle-like nanocrystals rather than forming particle-like agglomerates upon annealing at elevated temperatures. Transmission electron microscopy reveals that such nanocrystals actually consist of tungsten (VI) oxide (WO{sub 3}) which is related to an anisotropic oxide crystal growth out of the thin film. The evolution of W films is highly sensitive to themore » presence of any residual oxygen. Combination of both the dewetting of Au and the oxide crystal growth of WO{sub 3} is realized by using various bilayer film configurations of the immiscible Au and W. At low temperature, Au dewetting is initiated while oxide crystal growth is still suppressed. Depending on the stacking sequence of the Au-W bilayer thin film, W acts either as a substrate or as a passivation layer for the dewetting of Au. Being the ground layer, W changes the wettability of Au which clearly modifies its initial state for the dewetting. Being the top layer, W prevents Au from dewetting regardless of Au film thickness. Moreover, regular pattern formation of Au-WO{sub 3} nanoparticles is observed at high temperature demonstrating how bilayer thin film dewetting can create unique nanostructure arrangements.« less

Photonic crystal microprisms obtained by carving artificial opals

NASA Astrophysics Data System (ADS)

Fenollosa, R.; Ibisate, M.; Rubio, S.; López, C.; Meseguer, F.; Sánchez-Dehesa, J.

2003-01-01

A method for fabrication of photonic crystal prisms is demonstrated. The procedure is based on micromanipulation techniques, here applied to artificial opals. By means of a microgrinder an opal prism comprising a single crystal (several tens of microns in size) has been carved with three different faces: (111), (110), and (100). The faces were morphologically characterized by scanning electron microscopy and their optical reflectance spectra measured and compared with the theoretical band structure.

Method for growth of crystals by pressure reduction of supercritical or subcritical solution

NASA Technical Reports Server (NTRS)

Shlichta, P. J. (Inventor)

1985-01-01

Crystals of high morphological quality are grown by dissolution of a substance to be grown into the crystal in a suitable solvent under high pressure, and by subsequent slow, time-controlled reduction of the pressure of the resulting solution. During the reduction of the pressure interchange of heat between the solution and the environment is minimized by performing the pressure reduction either under isothermal or adiabatic conditions.

Investigating Dissolution and Precipitation Phenomena with a Smartphone Microscope

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

Lumetta, Gregg J.; Arcia, Edgar

A novel smartphone microscope can be used to observe the dissolution and crystallization of sodium chloride at a microscopic level. Observation of these seemingly simple phenomena through the microscope at 100× magnification can actually reveal some surprising behavior. These experiments offer the opportunity to discuss some basic concepts such as how the morphological features of the crystals dictates how the dissolution process proceeds, and how materials can be purified by re-crystallization techniques.

Imaging Implicit Morphological Processing: Evidence from Hebrew

ERIC Educational Resources Information Center

Bick, Atira S.; Frost, Ram; Goelman, Gadi

2010-01-01

Is morphology a discrete and independent element of lexical structure or does it simply reflect a fine-tuning of the system to the statistical correlation that exists among orthographic and semantic properties of words? Hebrew provides a unique opportunity to examine morphological processing in the brain because of its rich morphological system.…

A Quantile Regression Approach to Understanding the Relations Among Morphological Awareness, Vocabulary, and Reading Comprehension in Adult Basic Education Students.

PubMed

Tighe, Elizabeth L; Schatschneider, Christopher

2016-07-01

The purpose of this study was to investigate the joint and unique contributions of morphological awareness and vocabulary knowledge at five reading comprehension levels in adult basic education (ABE) students. We introduce the statistical technique of multiple quantile regression, which enabled us to assess the predictive utility of morphological awareness and vocabulary knowledge at multiple points (quantiles) along the continuous distribution of reading comprehension. To demonstrate the efficacy of our multiple quantile regression analysis, we compared and contrasted our results with a traditional multiple regression analytic approach. Our results indicated that morphological awareness and vocabulary knowledge accounted for a large portion of the variance (82%-95%) in reading comprehension skills across all quantiles. Morphological awareness exhibited the greatest unique predictive ability at lower levels of reading comprehension whereas vocabulary knowledge exhibited the greatest unique predictive ability at higher levels of reading comprehension. These results indicate the utility of using multiple quantile regression to assess trajectories of component skills across multiple levels of reading comprehension. The implications of our findings for ABE programs are discussed. © Hammill Institute on Disabilities 2014.

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.

Macromolecule Crystal Quality Improvement in Microgravity: The Role of Impurities

NASA Technical Reports Server (NTRS)

Judge, Russell A.; Snell, Edward H.; Pusey, Marc L.; Sportiello, Michael G.; Todd, Paul; Bellamy, Henry; Borgstahl, Gloria E.; Pokros, Matt; Cassanto, John M.

2000-01-01

While macromolecule impurities may affect crystal size and morphology the over-riding question is; "How do macromolecule impurities effect crystal X-ray quality and diffraction resolution?" In the case of chicken egg white lysozyme, crystals can be grown in the presence of a number of impurities without affecting diffraction resolution. One impurity however, the lysozyme dimer, does negatively impact the X-ray crystal properties. Crystal quality improvement as a result of better partitioning of this impurity during crystallization in microgravity has been reported'. In our recent experimental work dimer partitioning was found to be not significantly different between the two environments. Mosaicity analysis of pure crystals showed a reduced mosaicity and increased signal to noise for the microgravity grown crystals. Dimer incorporation however, did greatly reduce the resolution limit in both ground and microgravity grown crystals. These results indicate that impurity effects in microgravity are complex and may rely on the conditions or techniques employed.

Morphology-controlled synthesis of Co{sub 3}O{sub 4} by one step template-free hydrothermal method

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

Zhou, Keqing; Liu, Jiajia; Wen, Panyue

2015-07-15

Highlights: • Co{sub 3}O{sub 4} crystals had been synthesized by one step template-free hydrothermal method. • The H{sub 2}O{sub 2} plays a crucial role in morphological control of Co{sub 3}O{sub 4} nanostructures. • The morphology has significant effect on the optical property of Co{sub 3}O{sub 4}. - Abstract: We had developed a facile synthetic route of Co{sub 3}O{sub 4} crystals with different morphologies via one step template-free hydrothermal method. The phase and composition of the Co{sub 3}O{sub 4} were investigated by X-ray powder diffraction and Raman spectrum. The morphology and structure of the synthesized samples were characterized by scanning electronmore » microscopy and transmission electron microscopy. The H{sub 2}O{sub 2} played a crucial role in morphological control of Co{sub 3}O{sub 4} nanostructures. It only obtained Co-based precursor in the absence of H{sub 2}O{sub 2}. On the contrary, the Co{sub 3}O{sub 4} with different morphologies including nanoparticles, nano-discs and well-defined octahedral nanostructures were synthesized in the presence of H{sub 2}O{sub 2}. In addition, the optical property of the obtained Co{sub 3}O{sub 4} samples was investigated by UV–vis spectra.« less

The role of amorphous precursors in the crystallization of La and Nd carbonates

NASA Astrophysics Data System (ADS)

Vallina, Beatriz; Rodriguez-Blanco, Juan Diego; Brown, Andrew P.; Blanco, Jesus A.; Benning, Liane G.

2015-07-01

Crystalline La and Nd carbonates can be formed from poorly-ordered nanoparticulate precursors, termed amorphous lanthanum carbonate (ALC) and amorphous neodymium carbonate (ANC). When reacted in air or in aqueous solutions these precursors show highly variable lifetimes and crystallization pathways. We have characterized these precursors and the crystallization pathways and products with solid-state, spectroscopic and microscopic techniques to explain the differences in crystallization mechanisms between the La and Nd systems. ALC and ANC consist of highly hydrated, 10-20 nm spherical nanoparticles with a general formula of REE2(CO3)3.5H2O (REE = La, Nd). The stabilities differ by ~2 orders of magnitude, with ANC being far more stable than ALC. This difference is due to the Nd3+ ion having a far higher hydration energy compared to the La3+ ion. This, together with temperature and reaction times, leads to clear differences not only in the kinetics and mechanisms of crystallization of the amorphous precursor La- and Nd-carbonate phases but also in the resulting crystallite sizes and morphologies of the end products. All crystalline La and Nd carbonates developed spherulitic morphologies when crystallization occurred from hydrous phases in solution at temperatures above 60 °C (La system) and 95 °C (Nd system). We suggest that spherulitic growth occurs due to a rapid breakdown of the amorphous precursors and a concurrent rapid increase in supersaturation levels in the aqueous solution. The kinetic data show that the crystallization pathway for both La and Nd carbonate systems is dependent on the reaction temperature and the ionic potential of the REE3+ ion.Crystalline La and Nd carbonates can be formed from poorly-ordered nanoparticulate precursors, termed amorphous lanthanum carbonate (ALC) and amorphous neodymium carbonate (ANC). When reacted in air or in aqueous solutions these precursors show highly variable lifetimes and crystallization pathways. We have characterized these precursors and the crystallization pathways and products with solid-state, spectroscopic and microscopic techniques to explain the differences in crystallization mechanisms between the La and Nd systems. ALC and ANC consist of highly hydrated, 10-20 nm spherical nanoparticles with a general formula of REE2(CO3)3.5H2O (REE = La, Nd). The stabilities differ by ~2 orders of magnitude, with ANC being far more stable than ALC. This difference is due to the Nd3+ ion having a far higher hydration energy compared to the La3+ ion. This, together with temperature and reaction times, leads to clear differences not only in the kinetics and mechanisms of crystallization of the amorphous precursor La- and Nd-carbonate phases but also in the resulting crystallite sizes and morphologies of the end products. All crystalline La and Nd carbonates developed spherulitic morphologies when crystallization occurred from hydrous phases in solution at temperatures above 60 °C (La system) and 95 °C (Nd system). We suggest that spherulitic growth occurs due to a rapid breakdown of the amorphous precursors and a concurrent rapid increase in supersaturation levels in the aqueous solution. The kinetic data show that the crystallization pathway for both La and Nd carbonate systems is dependent on the reaction temperature and the ionic potential of the REE3+ ion. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr01497b

Inverse Mopho butterfly: a new approach to photonic crystal.

PubMed

Zhang, Ji-Zhong; Gu, Zhong-Ze; Chen, Hai-Hua; Fujishima, Akira; Sato, Osamu

2006-04-01

In this paper we showed a new approach for the fabrication of a photonic crystal with a three-dimensional structure. By replicating biomaterials such as the wing of Mopho butterfly with TiO2 nanoparticles using the nanoparticles infiltration method, we can derive photonic crystals with unique structures, which is difficult to fabricate by other approaches. New optical properties are anticipated.

Photoluminescence of vapor and solution grown ZnTe single crystals

NASA Astrophysics Data System (ADS)

Biao, Y.; Azoulay, M.; George, M. A.; Burger, A.; Collins, W. E.; Silberman, E.; Su, C.-H.; Volz, M. E.; Szofran, F. R.; Gillies, D. C.

1994-04-01

ZnTe single crystals grown by horizontal physical vapor transport (PVT) and by vertical traveling heater method (THM) from a Te solution were characterized by photoluminescence (PL) at 10.6 K and by atomic force microscopy (AFM). Copper was identified by PL as a major impurity existing in both crystals, forming a substitutional acceptor, Cu Zn. The THM ZnTe crystals were found to contain more Cu impurity than the PVT ZnTe crystals. The formation of Cu Zn-V Te complexes and the effects of annealing, oxygen contamination and intentional Cu doping were also studied. Finally, the surface morphology analyzed by AFM was correlated to the PL results.

Protein crystal growth aboard the U.S. Space Shuttle flights STS-31 and STS-32

NASA Technical Reports Server (NTRS)

Delucas, Lawrence J.; Smith, Craig D.; Carter, Daniel C.; Twigg, Pam; He, Xiao-Min; Snyder, Robert S.; Weber, Patricia C.; Schloss, J. V.; Einspahr, H. M.; Clancy, L. L.

1992-01-01

Results obtained from the Shuttle flight STS-32 flown in January 1990, and preliminary results from the most recent Shuttle flight, STS-31, flown in April 1990, are presented. Crystals grown in microgravity environment include Canavalin, isocitrate lyase, human serum albumin, and Anti-HPr Fab. It is concluded that about 20 percent of proteins flown exhibit better morphologies or better quality data than their earth-grown counterparts. About 40 percent do not yield crystals at all and the remaining 40 percent yield crystals that are either too small for X-ray analysis or produce data of poorer quality than the best earth-grown crystals.

Detection and recognition of analytes based on their crystallization patterns

DOEpatents

Morozov, Victor [Manassas, VA; Bailey, Charles L [Cross Junction, VA; Vsevolodov, Nikolai N [Kensington, MD; Elliott, Adam [Manassas, VA

2008-05-06

The invention contemplates a method for recognition of proteins and other biological molecules by imaging morphology, size and distribution of crystalline and amorphous dry residues in droplets (further referred to as "crystallization pattern") containing predetermined amount of certain crystal-forming organic compounds (reporters) to which protein to be analyzed is added. It has been shown that changes in the crystallization patterns of a number of amino-acids can be used as a "signature" of a protein added. It was also found that both the character of changer in the crystallization patter and the fact of such changes can be used as recognition elements in analysis of protein molecules.

Steering a crystallization process to reduce crystal polydispersity; case study of insulin crystallization

NASA Astrophysics Data System (ADS)

Nanev, Christo N.; Petrov, Kostadin P.

2017-12-01

The use of the classical nucleation-growth-separation principle (NGSP) was restricted hitherto to nucleation kinetics studies only. A novel application of the NGSP is proposed. To reduce crystal polydispersity internal seeding of equally-sized crystals is suggested, the advantage being avoidance of crystal grinding, sieving and any introduction of impurities. In the present study, size distributions of grown insulin crystals are interpreted retrospectively to select the proper nucleation stage parameters. The conclusion is that when steering a crystallization process aimed at reducing crystal polydispersity, the shortest possible nucleation stage duration has to be chosen because it renders the closest size distribution of the nucleated crystal seeds. Causes of inherent propensity to increasing crystal polydispersity during prolonged growth are also explored. Step sources of increased activity, present in some crystals while absent in others, are pointed as the major polydispersity cause. Insulin crystal morphology is also considered since it determines the dissolution rate of a crystalline medicine.

Effects of Saponification Rate on Electrooptical Properties and Morphology of Poly(vinyl alcohol)/Liquid Crystal Composite Films

NASA Astrophysics Data System (ADS)

Ono, Hiroshi; Kawatsuki, Nobuhiro

1995-03-01

The relationship between the saponification rate of poly(vinyl alcohol) (PVA), and the electrooptical properties and morphology of the PVA/liquid crystal (LC) composite films was investigated. Light transmission clazing and the LC droplet size were varied by changing the saponification rate or the blend ratio of two kinds of PVA with different saponification rates because the refractive index and surface tension could be controlled by the saponification rate of PVA. The threshold voltage decreased with increasing saponification rate though the extrapolation length was decreased. It was suggested that the electrooptical properties were strongly dependent on the droplet size.

Structural changes of anodic layer on titanium in sulfate solution as a function of anodization duration in constant current mode

NASA Astrophysics Data System (ADS)

Komiya, Shinji; Sakamoto, Kouta; Ohtsu, Naofumi

2014-03-01

The present study investigated the effect of anodization time, in constant current mode, on the anodic oxide layer formed on titanium (Ti). Anodization of the Ti substrate was　carried out in a 0.1 M (NH4)2SO4 aqueous solution with reaction times of various durations, after which the characteristics and photocatalytic activity were investigated in detail. The TiO2 layer fabricated in a short duration exhibited comparatively flat surface morphology and an anatase-type crystal structure. This layer acted as a photocatalyst only under ultraviolet light (UV) illumination. Upon prolonging the anodization, the layer structure changed drastically. The surface morphology became rough, and the crystal structure changed to rutile-type TiO2. Furthermore, the layer showed photocatalytic activity both under UV and visible light illumination. Further anodization increased the amount of methylene blue (MB) adsorbed on the surface, but did not cause additional change to the structure of the anodic layer. The surface morphology and crystal structure of the anodic layer were predominantly controlled by the anodization time; thus, the anodization time is an important parameter for controlling the characteristics of the anodic layer.

Reversible conversion of valence-tautomeric copper metal-organic frameworks dependent single-crystal-to-single-crystal oxidation/reduction: a redox-switchable catalyst for C-H bonds activation reaction.

PubMed

Huang, Chao; Wu, Jie; Song, Chuanjun; Ding, Ran; Qiao, Yan; Hou, Hongwei; Chang, Junbiao; Fan, Yaoting

2015-06-28

Upon single-crystal-to-single-crystal (SCSC) oxidation/reduction, reversible structural transformations take place between the anionic porous zeolite-like Cu(I) framework and a topologically equivalent neutral Cu(I)Cu(II) mixed-valent framework. The unique conversion behavior of the Cu(I) framework endowed it as a redox-switchable catalyst for the direct arylation of heterocycle C-H bonds.

Single crystal growth of 67%BiFeO 3 -33%BaTiO 3 solution by the floating zone method

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

Rong, Y.; Zheng, H.; Krogstad, M. J.

The growth conditions and the resultant grain morphologies and phase purities from floating-zone growth of 67%BiFeO3-33%BaTiO3 (BF-33BT) single crystals are reported. We find two formidable challenges for the growth. First, a low-melting point constituent leads to a pre-melt zone in the feed-rod that adversely affects growth stability. Second, constitutional super-cooling (CSC), which was found to lead to dendritic and columnar features in the grain morphology, necessitates slow traveling rates during growth. Both challenges were addressed by modifications to the floating-zone furnace that steepened the temperature gradient at the melt-solid interfaces. Slow growth was also required to counter the effects ofmore » CSC. Single crystals with typical dimensions of hundreds of microns have been obtained which possess high quality and are suitable for detailed structural studies.« less

Cu-based metal-organic framework thin films: A morphological and photovoltaic study

NASA Astrophysics Data System (ADS)

Khajavian, Ruhollah; Ghani, Kamal

2018-06-01

This work explores the layer-by-layer (LbL) fabrication of [Cu2(bdc)2(bpy)]n thin films by using pyridine and acetic acid as capping agents onto mesoporous titania surface. While in the presence of acetic acid highly-ordered crystals with nanoplate morphology are formed, modulation with pyridine gives rise to formation of leaf-like crystals. In addition, processing sequence also matters when modulator is added. According to our results, modulators should be added to metal solution rather than linker/pillar during LbL assembly. These films were subsequently shown to generate photocurrent in a sandwich-type Grätzel solar cell device in response to simulated 1 sun illumination. The results also demonstrated that the device consisted of well-aligned nanoplates exhibits higher power conversion efficiency than the similar cell with disordered leaf-like crystals after iodine loading.

Self-catalytic crystal growth, formation mechanism, and optical properties of indium tin oxide nanostructures

NASA Astrophysics Data System (ADS)

Liang, Yuan-Chang; Zhong, Hua

2013-08-01

In-Sn-O nanostructures with rectangular cross-sectional rod-like, sword-like, and bowling pin-like morphologies were successfully synthesized through self-catalytic growth. Mixed metallic In and Sn powders were used as source materials, and no catalyst layer was pre-coated on the substrates. The distance between the substrate and the source materials affected the size of the Sn-rich alloy particles during crystal growth in a quartz tube. This caused In-Sn-O nanostructures with various morphologies to form. An X-ray photoelectron spectroscope and a transmittance electron microscope with an energy-dispersive X-ray spectrometer were used to investigate the elemental binding states and compositions of the as-synthesized nanostructures. The Sn doping and oxygen vacancies in the In2O3 crystals corresponded to the blue-green and yellow-orange emission bands of the nanostructures, respectively.

Single crystal growth of 67%BiFeO3-33%BaTiO3 solution by the floating zone method

NASA Astrophysics Data System (ADS)

Rong, Y.; Zheng, H.; Krogstad, M. J.; Mitchell, J. F.; Phelan, D.

2018-01-01

The growth conditions and the resultant grain morphologies and phase purities from floating-zone growth of 67%BiFeO3-33%BaTiO3 (BF-33BT) single crystals are reported. We find two formidable challenges for the growth. First, a low-melting point constituent leads to a pre-melt zone in the feed-rod that adversely affects growth stability. Second, constitutional super-cooling (CSC), which was found to lead to dendritic and columnar features in the grain morphology, necessitates slow traveling rates during growth. Both challenges were addressed by modifications to the floating-zone furnace that steepened the temperature gradient at the melt-solid interfaces. Slow growth was also required to counter the effects of CSC. Single crystals with typical dimensions of hundreds of microns have been obtained which possess high quality and are suitable for detailed structural studies.

Assembly of potassium niobate nanosheets/silver oxide composite films with good SERS performance towards crystal violet detection

NASA Astrophysics Data System (ADS)

Zhu, Kun; Hong, Zhen; Kang, Shi-Zhao; Qin, Lixia; Li, Guodong; Li, Xiangqing

2018-04-01

The orderly potassium niobate nanosheets/silver oxide (Ag2O) composite films with uniform morphology were achieved by layer-by-layer self-assembly combined with ultraviolet light irradiation. The composition, structure and morphology of the potassium niobate nanosheets/Ag2O composite films were studied by XPS, XRD and SEM. Furthermore, the films were used as a SERS probe to detect crystal violet molecules. The results showed that the potassium niobate nanosheets/Ag2O composite films were an active substrate for fast and sensitive detection of crystal violet with low concentration. The limit of detection by the films can reach 1 × 10-6 mol L-1. Both electromagnetic enhancement and chemical enhancement contributed to the enhanced SERS in the (potassium niobate nanosheets/Ag2O)4 films. Moreover, it was found that the films were relatively stable under light irradiation or heat treatment in a certain range.

The effect of an electric field on the morphological stability of the crystal-melt interface of a binary alloy. III - Weakly nonlinear theory

NASA Technical Reports Server (NTRS)

Wheeler, A. A.; Mcfadden, G. B.; Coriell, S. R.; Hurle, D. T. J.

1990-01-01

The effect of a constant electric current on the crystal-melt interface morphology during directional solidification at constant velocity of a binary alloy is considered. A linear temperature field is assumed, and thermoelectric effects and Joule heating are neglected; electromigration and differing electrical conductivities of crystal and melt are taken into account. A two-dimensional weakly nonlinear analysis is carried out to third order in the interface amplitude, resulting in a cubic amplitude equation that describes whether the bifurcation from the planar state is supercritical or subcritical. For wavelengths corresponding to the most dangerous mode of linear theory, the demarcation between supercritical and subcritical behavior is calculated as a function of processing conditions and material parameters. The bifurcation behavior is a sensitive function of the magnitude and direction of the electric current and of the electrical conductivity ratio.

CRISTAPRESS: an optical cell for structure development in high-pressure crystallization.

PubMed

Boyer, S A E; Fournier, F E J; Gandin, Ch-A; Haudin, J-M

2014-01-01

An original optical high-pressure cell, named CRISTAPRESS, has been especially designed to investigate phase transitions of complex liquids, i.e., polymers, polymer blends, nano-composites, etc. The design of the cell is based on the optical properties of morphological entities through in situ light depolarizing microscopic observations. Pressure up to 200 MPa with a fine temperature control up to 300 °C can be applied. A striking advantage of this cell is the possibility to select the pressure transmitting medium that can be water, silicone oil, a fluid in the supercritical state, etc. The potential of the novel technique was demonstrated by carrying out time-resolved measurements during polymer crystallization induced by water pressure. These preliminary experimental investigations permit to discriminate the role of the barometric and thermal histories on the kinetics of polymer growth, as well as on the subsequent morphologies. It should lead to new reliable crystallization kinetics models.

Tautomerism and isomerism in some antitrichinellosis active benzimidazoles: Morphological study in polarized light, quantum chemical computations

NASA Astrophysics Data System (ADS)

Anichina, Kameliya; Mavrova, Anelia; Yancheva, Denitsa; Tsenov, Jordan; Dimitrov, Rasho

2017-12-01

The morphology of the crystal structure of some antitrichinellosis active benzimidazole derivatives including (1H-benzimidazol-2-ylthio)acetic acids, [1,3]thiazolo[3,2-a]benzimidazol-3(2H)-ones, 1H-benzimidazol-2-ylthioacetylpiperazines and starting 2-mercapto benzimidazoles, was studied by the use of Polarized Light Microscopy (PLM). Characterization of the crystal phase was complimented by Differential scanning calorimetry analysis (DSC) and spectroscopic data. DFT computations were performed in order to investigate the prototropic tautomerism and the geometry of the molecule of the synthesized compounds. One distinct type of crystal structure for each one of 5 or 6-methyl-(1H-benzimidazol-2-ylthio)acetic acid 6 was observed by PLM - dendritic and needle-shaped formations. Compound 14, containing a methyl substituent in the benzimidazole ring crystallized also into two phases; while for the unsubstituted compound 13 a separation of phases does not take place. The influence of the both solvents - chloroform and ethanol on the phase separation and the formation of the crystalline structure of compound 14 was investigated. The morphological study showed that the cyclization of 6 in the presence of acetic anhydride in pyridine medium led to a mixture of 6-methyl-[1,3]tiazolo[3,2-a]benzimidazol-3(2H)-one (10a) and 7-methyl-[1,3]thiazolo[3,2-a]-benzimidazole-3(2H)-one (10b), which crystallized in the form of fibrils and spherulites respectively. It was found that a difference in the crystal structures of substituted and unsubstituted benzimidazol-2-thiones, respectively benzimidazol-2-thiol derivatives exists, which may be due not only to the thiol-thione tautomerism but to the prototropic properties of the hydrogen atom in first position of the ring. The calculation results indicated that the thione form is more stable than the thiol tautomer by 51-55 kJ mol-1. But at the same time ΔG for the two thiol tautomers is below 0.5 kJ mol-1. In solid phase the 5(6)-substituted-1H-benzimidazol-2-thiols crystallized in two different crystal structures while the unsubstituted 1H-benzimidazol-2-thiol possess one type of crystal structure.

The assessment of pore connectivity in hierarchical zeolites using positron annihilation lifetime spectroscopy: instrumental and morphological aspects.

PubMed

Zubiaga, Asier; Warringham, Robbie; Boltz, Marilyne; Cooke, David; Crivelli, Paolo; Gidley, David; Pérez-Ramírez, Javier; Mitchell, Sharon

2016-04-07

Recent studies demonstrated the power of positron annihilation lifetime spectroscopy (PALS) to characterise the connectivity and corresponding effectiveness of hierarchical pore networks in zeolites. This was based on the fractional escape of ortho-positronium (Ps), formed within the micropore framework, to vacuum. To further develop this technique, here we assess the impact of the positron implantation energy and of the zeolite crystal size and the particle morphology. Conventional measurements using fast positrons and beam measurements applying moderated positrons both readily distinguish purely microporous ZSM-5 zeolites comprised of single crystals or crystal aggregates. Unlike beam measurements, however, conventional measurements fail to discriminate model hierarchical zeolites with open or constricted mesopore architectures. Several steps are taken to rationalise these observations. The dominant contribution of Ps diffusion to the PALS response is confirmed by capping the external surface of the zeolite crystals with tetraethylorthosilicate, which greatly enhances the sensitivity to the micropore network. A one-dimensional model is constructed to predict the out-diffusion of Ps from a zeolite crystal, which is validated experimentally by comparing coffin-shaped single crystals of varying size. Calculation of the trends expected on the application of fast or moderated positrons indicates that the distinctions in the initial distribution of Ps at the crystal level cannot explain the limited sensitivity of the former to the mesopore architecture. Instead, we propose that the greater penetration of fast positrons within the sample increases the probability of Ps re-entry from intercrystalline voids into mesopores connected with the external surface of zeolite crystals, thereby reducing their fractional escape.

Study of Te Inclusion and Related Point Defects in THM-Growth CdMnTe Crystal

NASA Astrophysics Data System (ADS)

Mao, Yifei; Zhang, Jijun; Min, Jiahua; Liang, Xiaoyan; Huang, Jian; Tang, Ke; Ling, Liwen; Li, Ming; Zhang, Ying; Wang, Linjun

2018-02-01

This study establishes a model for describing the interaction between Te inclusions, dislocations and point defects in CdMnTe crystals. The role of the complex environment surrounding the formation of Te inclusions was analyzed. Images of Te inclusions captured by scanning electron microscope and infrared microscope were used to observe the morphology of Te inclusions. The morphology of Te inclusions is discussed in light of crystallography, from the crystal growth temperature at 900°C to the melting temperature of Te inclusions using the traveling heater method. The dislocation nets around Te inclusions were calculated by counting lattice mismatches between the Te inclusions and the bulk CdMnTe at 470°C. The point defects of Te antisites were found to be gathered around Te inclusions, with dislocation climb during the cooling phase of crystal growth from 470°C to room temperature. The Te inclusions, dislocation nets and surrounding point defects are considered to be an entirety for evaluating the effect of Te inclusions on CdMnTe detector performance, and an effective mobility-lifetime product (μτ) was obtained.

Controlling morphology and crystallite size of Cu(In{sub 0.7}Ga{sub 0.3})Se{sub 2} nano-crystals synthesized using a heating-up method

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

Hsu, Wei-Hsiang; Hsiang, Hsing-I, E-mail: hsingi@mail.ncku.edu.tw; Chia, Chih-Ta

2013-12-15

CuIn{sub 0.7}Ga{sub 0.3}Se{sub 2}(CIGS) nano-crystals were successfully synthesized via a heating-up process. The non-coordinating solvent (1-octadecene) and selenium/cations ratio effects on the crystalline phase and crystallite size of CIGS nano-crystallites were investigated. It was observed that the CIGS nano-crystallite morphology changed from sheet into spherical shape as the amount of 1-octadecene addition was increased. CIGS nano-crystals were obtained in 9–20 nm sizes as the selenium/cations ratio increased. These results suggest that the monomer reactivity in the solution can be adjusted by changing the solvent type and selenium/cations ratio, hence affecting the crystallite size and distribution. - Graphical abstract: CuIn{sub 0.7}Ga{submore » 0.3}Se{sub 2}(CIGS) nano-crystals were successfully synthesized via a heating-up process in this study. The super-saturation in the solution can be adjusted by changing the OLA/ODE ratio and selenium/cation ratio.« less

Structural and optical properties of WTe2 single crystals synthesized by DVT technique

NASA Astrophysics Data System (ADS)

Dixit, Vijay; Vyas, Chirag; Pathak, V. M.; Soalanki, G. K.; Patel, K. D.

2018-05-01

Layered transition metal di-chalcogenide (LTMDCs) crystals have attracted much attention due to their potential in optoelectronic device applications recently due to realization of their monolayer based structures. In the present investigation we report growth of WTe2 single crystals by direct vapor transport (DVT) technique. These crystals are then characterized by energy dispersive analysis of x-rays (EDAX) to study stoichiometric composition after growth. The structural properties are studied by x-ray diffraction (XRD) and selected area electron diffraction (SAED) is used to confirm orthorhombic structure of grown WTe2 crystal. Surface morphological properties of the crystals are also studied by scanning electron microscope (SEM). The optical properties of the grown crystals are studied by UV-Visible spectroscopy which gives direct band gap of 1.44 eV for grown WTe2 single crystals.

Towards TiO2 nanotubes modified by WO3 species: influence of ex situ crystallization of precursor on the photocatalytic activities of WO3/TiO2 composites

NASA Astrophysics Data System (ADS)

Sun, Hui; Dong, Bohua; Su, Ge; Gao, Rongjie; Liu, Wei; Song, Liang; Cao, Lixin

2015-09-01

TiO2 nanotubes (TNT) crystallized at different temperatures were loaded with WO3 hydrate through the reaction between (NH4)6W7O24·6H2O and an aqueous solution of HCl. The photocatalytic activities of nanocomposites firstly increase and then decrease as a function of the crystallized temperature of the TNT precursor. The structural, morphologic and optical properties of WO3/TiO2 nanocomposites were also investigated in this study. The samples, initially anatase titania (573 K-773 K), presented phase transition to rutile titania at 873 K. With the crystallized temperature increasing, an evolution of samples morphology changing from nanotube-like structure to nanorod-like structure was observed. Meanwhile, the absorption edge of samples exhibited a red shift, and correspondingly their band gap decreased. Consistent with x-ray diffraction diffractograms, the existence of rutile titania as an impurity in the precursor TNT, crystallized at higher than 873 K, depressed photocatalytic activity evidently. As a result, the degradation rate of methyl orange (MO) increased with the samples crystallinity firstly, and then reduced due to the appearance of rutile titania. In our experimental conditions, the optimal photocatalytic activity was achieved for the sample crystalized at 773 K. Its degradation rate could reach 98.76% after 90 min UV light irradiation.

Hydrothermal temperature effect on crystal structures, optical properties and electrical conductivity of ZnO nanostructures

NASA Astrophysics Data System (ADS)

Dhafina, Wan Almaz; Salleh, Hasiah; Daud, Mohd Zalani; Ghazali, Mohd Sabri Mohd; Ghazali, Salmah Mohd

2017-09-01

ZnO is an wide direct band gap semiconductor and possess rich family of nanostructures which turned to be a key role in the nanotechnology field of applications. Hydrothermal method was proven to be simple, robust and low cost among the reported methods to synthesize ZnO nanostructures. In this work, the properties of ZnO nanostructures were altered by varying temperatures of hydrothermal process. The changes in term of morphological, crystal structures, optical properties and electrical conductivity were investigated. A drastic change of ZnO nanostructures morphology and decreases of 002 diffraction peak were observed as the hydrothermal temperature increased. The band gap of samples decreased as the size of ZnO nanostructure increased, whereas the electrical conductivity had no influence on the band gap value but more on the morphology of ZnO nanostructures instead.

Formation of ultrathin Ni germanides: solid-phase reaction, morphology and texture

NASA Astrophysics Data System (ADS)

van Stiphout, K.; Geenen, F. A.; De Schutter, B.; Santos, N. M.; Miranda, S. M. C.; Joly, V.; Detavernier, C.; Pereira, L. M. C.; Temst, K.; Vantomme, A.

2017-11-01

The solid-phase reaction of ultrathin (⩽10 nm) Ni films with different Ge substrates (single-crystalline (1 0 0), polycrystalline, and amorphous) was studied. As thickness goes down, thin film texture becomes a dominant factor in both the film’s phase formation and morphological evolution. As a consequence, certain metastable microstructures are epitaxially stabilized on crystalline substrates, such as the ɛ-Ni5Ge3 phase or a strained NiGe crystal structure on the single-crystalline substrates. Similarly, the destabilizing effect of axiotaxial texture on the film’s morphology becomes more pronounced as film thicknesses become smaller. These effects are contrasted by the evolution of germanide films on amorphous substrates, on which neither epitaxy nor axiotaxy can form, i.e. none of the (de)stabilizing effects of texture are observed. The crystallization of such amorphous substrates however, drives the film breakup.

Double layer effects on metal nucleation in deep eutectic solvents.

PubMed

Abbott, Andrew P; Barron, John C; Frisch, Gero; Gurman, Stephen; Ryder, Karl S; Fernando Silva, A

2011-06-07

The electrodeposition of zinc has been studied in two deep eutectic solvents. Unlike the metals studied to date in these liquids, zinc electrodeposition is not mass transport limited and the morphology of the deposit differs in the two liquids. This study shows that changing the concentration of solute affects the physical properties of the liquid to different extents although this is found to not effect the morphology of the metal deposited. EXAFS was used to show that the speciation of zinc was the same in both liquids. Double layer capacitance studies showed differences between the two liquids and these are proposed to be due to the adsorption of a species on the electrode which is thought to be chloride. The differences in zinc morphology is attributed to blocking of certain crystal faces leading to deposition of small platelet shaped crystals in the glycol based liquid.

Effects of Ultrasonic Parameters on the Crystallization Behavior of Virgin Coconut Oil.

PubMed

Wu, Linhe; Cao, Jun; Bai, Xinpeng; Chen, Haiming; Zhang, Yuxiang; Wu, Qian

2016-12-01

Crystallization behavior of virgin coconut oil (VCO) in the absence and presence of ultrasonic treatment under a temperature gradient field was investigated. The effects of ultrasonic parameters on the crystallization behavior of VCO were studied by differential scanning calorimetry, ultraviolet/visible spectrophotometry and polarized light microscopy. The thermal effect of the ultrasonic treatment was also increased at higher power levels. Therefore, the optimal power level was determined at approximately 36 W. Induction time reduced evidently and the crystallization rate was accelerated under ultrasonic treatment at crystallization temperature (T c ) above 15°C. However, no significant difference in induction time was noted at 13°C. The result of morphological studies showed that the growth mechanism of crystals was significantly changed. Meanwhile, smaller and uniform crystals were produced by the ultrasonic treatment. This study shows a novel technique to accelerate the crystallization rate and alter the growth mechanism of VCO crystals.

Sponge-like nanoporous single crystals of gold

PubMed Central

Khristosov, Maria Koifman; Bloch, Leonid; Burghammer, Manfred; Kauffmann, Yaron; Katsman, Alex; Pokroy, Boaz

2015-01-01

Single crystals in nature often demonstrate fascinating intricate porous morphologies rather than classical faceted surfaces. We attempt to grow such crystals, drawing inspiration from biogenic porous single crystals. Here we show that nanoporous single crystals of gold can be grown with no need for any elaborate fabrication steps. These crystals are found to grow following solidification of a eutectic composition melt that forms as a result of the dewetting of nanometric thin films. We also present a kinetic model that shows how this nano-porous single-crystalline structure can be obtained, and which allows the potential size of the porous single crystal to be predicted. Retaining their single-crystalline nature is due to the fact that the full crystallization process is faster than the average period between two subsequent nucleation events. Our findings clearly demonstrate that it is possible to form single-crystalline nano porous metal crystals in a controlled manner. PMID:26554856

Results of the TTF-TCNQ and the calcium carbonate crystallization on the Long Duration Exposure Facility

NASA Technical Reports Server (NTRS)

Nielsen, Kjeld Flemming; Lind, M. David

1992-01-01

Experiment A0139A on the Long Duration Exposure Facility (LDEF) carried four large containers into orbit five years with crystal growth solutions for lead sulfide, calcium carbonate, and TTF-TCNQ. Although temperature data was lost, the experimental program had been working since the valves in all containers had been opened. All four experiments produced crystals of varying quality. The calcium carbonate crystals had the best appearance. The TTF-TCNQ crystals were packed together near the valve openings of the container. When taken apart, the single crystals showed some unusual morphological properties. X ray investigations as well as conductivity measurements on long duration space grown TTF-TCNQ crystals will be presented. Comparisons will be made with our previous space solution growth experiments. The TTF-TCNQ crystals are no longer of the highest interest, so this activity has been terminated in favor of calcium carbonate and calcium phosphate crystallizations.

VO{sub 2} (A): Reinvestigation of crystal structure, phase transition and crystal growth mechanisms

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

Rao Popuri, Srinivasa; University of Bordeaux, ICMCB, UPR 9048, F-33608 Pessac; National Institute for Research and Development in Electrochemistry and Condensed Matter, Timisoara, Plautius Andronescu Str. No. 1, 300224 Timisoara

2014-05-01

Well crystallized VO{sub 2} (A) microrods were grown via a single step hydrothermal reaction in the presence of V{sub 2}O{sub 5} and oxalic acid. With the advantage of high crystalline samples, we propose P4/ncc as an appropriate space group at room temperature. From morphological studies, we found that the oriented attachment and layer by layer growth mechanisms are responsible for the formation of VO{sub 2} (A) micro rods. The structural and electronic transitions in VO{sub 2} (A) are strongly first order in nature, and a marked difference between the structural transition temperatures and electronic transitions temperature was evidenced. The reversiblemore » intra- (LTP-A to HTP-A) and irreversible inter- (HTP-A to VO{sub 2} (M1)) structural phase transformations were studied by in-situ powder X-ray diffraction. Attempts to increase the size of the VO{sub 2} (A) microrods are presented and the possible formation steps for the flower-like morphologies of VO{sub 2} (M1) are described. - Graphical abstract: Using a single step and template free hydrothermal synthesis, well crystallized VO{sub 2} (A) microrods were prepared and the P4/ncc space group was assigned to the room temperature crystal structure. Reversible and irreversible phase transitions among different VO{sub 2} polymorphs were identified and their progressive nature was highlighted. Attempts to increase the microrods size, involving layer by layer formation mechanisms, are presented. - Highlights: • Highly crystallized VO{sub 2} (A) microrods were grown via a single step hydrothermal process. • The P4/ncc space group was determined for VO{sub 2} (A) at room temperature. • The electronic structure and progressive nature of the structural phase transition were investigated. • A weak coupling between structural and electronic phase transitions was identified. • Different crystallite morphologies were discussed in relation with growth mechanisms.« less

Influence of lignin on morphology, structure and thermal behavior of polylactic acid-based biocomposites

NASA Astrophysics Data System (ADS)

Canetti, Maurizio; Cacciamani, Adriana; Bertini, Fabio

2016-05-01

Polylactic acid (PLA) is a thermoplastic biodegradable polymer that can be made from annually renewable resources. Lignin is a natural amorphous polyphenolic macromolecule inexpensive and easily available. In the present study PLA and acetylated lignin biocomposites were prepared by casting from chloroform solution. PLA can crystallize from the melt in the α and α' forms, depending on the adopted crystallization conditions. The presence of the lignin in the biocomposites can interfere with the crystal formation process. Isothermal crystallizations were performed at different temperatures, the presence of lignin causes an increase of the time of crystallization, while the overall crystallization rate and the spherulite radial growth rate decrease with enhancing the lignin content in the biocomposites.

Experiment 3: Zeolite Crystal Growth in Microgravity- The USML-2 Mission

NASA Technical Reports Server (NTRS)

Bac, Nurcan; Warzywoda, Juliusz; Sacco, Albert, Jr.

1998-01-01

The extensive use of zeolites and their impact on the world's economy leads to many efforts to characterize their structure, and to improve the knowledge base for nucleation and growth of these crystals. The Zeolite Crystal Growth (ZCG) experiment on USML-2 aims to enhance the understanding of nucleation and growth of zeolite crystals while attempting to provide a means of controlling the defect concentration in microgravity. Zeolites A, X, Beta, and Silicalite were grown during the 16-day USML-2 mission. The solutions where the nucleation event was controlled yielded larger and more uniform crystals of better morphology and purity than their terrestrial/control counterparts. Space-grown Beta crystals were free of line defects while terrestrial/controls had substantial defects.

Changing Morphology of BaO/AI₂O₃ during NO₂ Uptake and Release

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

Szanyi, Janos; Kwak, Ja Hun; Hanson, Jonathan

2005-04-21

The changes in the morphology of Ba-oxide-based NOx storage/reduction catalysts were investigated using time resolved x-ray diffraction, transmission electron microscopy and energy dispersed spectroscopy. Large Ba(NO₃)₂ crystallites form on the alumina support when the catalyst is prepared by the incipient wetness method using an aqueous Ba(NO₃)₂ solution. Heating the sample to 873K in a He flow results in the decomposition of the Ba(NO₃)₂ phase and the formation of both a monolayer BaO film strongly interacting with the alumina support, and nano crystalline BaO particles. Upon NO₂ exposure of these BaO phases at room temperature, small (nano-sized) Ba(NO₃)₂ crystals and amore » monolayer of surface nitrate form. Heating this sample in NO₂ results in the coalescence of the nano crystalline Ba(NO₃)₂ particles into large crystals. The average crystal size in the re-formed Ba(NO₃)₂ layer is significantly smaller than that measured after the catalyst preparation. Evidence is also presented for the existence of a monolayer Ba(NO₃)₂ phase after thermal treatment in NO₂, in addition to these large crystals. These results clearly demonstrate the dynamic nature of the Ba-containing phases that are active in the NOx storage/reduction process. The proposed morphology cycle may contribute to the understanding of the changes observed in the performances of these catalysts during actual operating conditions.« less

Physical phenomena related to crystal growth in the space environment

NASA Technical Reports Server (NTRS)

Chu, T. L.

1973-01-01

The mechanism of crystal growth which may be affected by the space environment was studied. Conclusions as to the relative technical and scientific advantages of crystal growth in space over earth bound growth, without regard to economic advantage, were deduced. It was concluded that the crucibleless technique will most directly demonstrate the unique effects of the greatly reduced gravity in the space environment. Several experiments, including crucibleless crystal growth using solar energy and determination of diffusion coefficients of common dopants in liquid silicon were recommended.

Inorganic and Protein Crystal Assembly in Solutions

NASA Technical Reports Server (NTRS)

Chernov, A. A.

2005-01-01

The basic kinetic and thermodynamic concepts of crystal growth will be revisited in view of recent AFM and interferometric findings. These concepts are as follows: 1) The Kossel crystal model that allows only one kink type on the crystal surface. The modern theory is developed overwhelmingly for the Kessel model; 2) Presumption that intensive step fluctuations maintain kink density sufficiently high to allow applicability of Gibbs-Thomson law; 3) Common experience that unlimited step bunching (morphological instability) during layer growth from solutions and supercooled melts always takes place if the step flow direction coincides with that of the fluid.

Synthesis, electronic structure, molecular packing/morphology evolution, and carrier mobilities of pure oligo-/poly(alkylthiophenes).

PubMed

Zhang, Lei; Colella, Nicholas S; Liu, Feng; Trahan, Stephan; Baral, Jayanta K; Winter, H Henning; Mannsfeld, Stefan C B; Briseno, Alejandro L

2013-01-16

Monodispersed conjugated oligothiophenes are receiving attention in fundamental and applied science due to their interesting optical, optoelectronic, and charge transport properties. These "low molecular weight" polymers serve as model structures for the corresponding polymer analogues, which are inherently polydispersed. Here we report the synthesis, electronic structure, molecular packing/morphology, and charge transport properties of monodispersed oligothiophenes with up to six didodecylquaterthiophene (DDQT) building block repeat units (i.e., 24 thiophene units). At the point where the effective conjugation length is reached, the electronic structure showed convergence behavior to the corresponding polymer, poly(3,3"-didodecyl-quaterthiophene) (PQT-12). X-ray crystal structure analysis of the dimer (DDQT-2) showed that terminal thiophenes exhibit syn-conformations, similar to the terminal syn-conformations observed in the trimer (DDQT-3). The dimer also exhibits a rare bending of the terminal alkyl side chains in order to prevent steric hindrance with neighboring hydrogens attached to core thiophenes. Grazing incidence X-ray scattering measurements revealed a morphology evolution from small molecule-like packing to polymer-like packing in thin films, with a morphology transition occurring near the effective conjugation length. Charge transport measurements showed a mobility increase with decreasing chain length. We correlated the molecular packing and morphology to charge transport and determined that carrier mobilities are most sensitive to crystallinity and crystal grain misorientation. This indicates that molecular weight is not a decisive factor for improved carrier mobility in the low molecular weight region, but rather the degree in crystallinity and in-plane crystal orientation. These results represent a fundamental advancement in understanding the relationship between conjugation length and carrier mobilities in oligothiophene semiconductors.

Controlling Chirality of Entropic Crystals

NASA Astrophysics Data System (ADS)

Damasceno, Pablo F.; Karas, Andrew S.; Schultz, Benjamin A.; Engel, Michael; Glotzer, Sharon C.

2015-10-01

Colloidal crystal structures with complexity and diversity rivaling atomic and molecular crystals have been predicted and obtained for hard particles by entropy maximization. However, thus far homochiral colloidal crystals, which are candidates for photonic metamaterials, are absent. Using Monte Carlo simulations we show that chiral polyhedra exhibiting weak directional entropic forces self-assemble either an achiral crystal or a chiral crystal with limited control over the crystal handedness. Building blocks with stronger faceting exhibit higher selectivity and assemble a chiral crystal with handedness uniquely determined by the particle chirality. Tuning the strength of directional entropic forces by means of particle rounding or the use of depletants allows for reconfiguration between achiral and homochiral crystals. We rationalize our findings by quantifying the chirality strength of each particle, both from particle geometry and potential of mean force and torque diagrams.

Skin morphology at the site of postoperative cicatrix formed after the use of different surgical cutting instruments.

PubMed

Somova, L M; Plekhova, N G; Puzdaev, V I

2008-12-01

Experimental morphological study of the postoperative cicatrix forming after the use of scalpel made from a crystal material was carried out. The skin healed much sooner and the resultant cicatrix was more fine in comparison with the wound inflicted by a common metal scalpel.

Crystal growth, spectral, structural and optical studies of π-conjugated stilbazolium crystal: 4-bromobenzaldehyde-4'-N'-methylstilbazolium tosylate.

PubMed

Krishna Kumar, M; Sudhahar, S; Bhagavannarayana, G; Mohan Kumar, R

2014-05-05

Nonlinear optical (NLO) organic compound, 4-bromobenzaldehyde-4'-N'-methylstilbazolium tosylate was synthesized by reflux method. The formation of molecular complex was confirmed from (1)H NMR, FT-IR and FT-Raman spectral analyses. The single crystals were grown by slow evaporation solution growth method and the crystal structure and atomic packing of grown crystal was identified. The morphology and growth axis of grown crystal were determined. The crystal perfection was analyzed using high resolution X-ray diffraction study on (001) plane. Thermal stability, decomposition stages and melting point of the grown crystal were analyzed. The optical absorption coefficient (α) and energy band gap (E(g)) of the crystal were determined using UV-visible absorption studies. Second harmonic generation efficiency of the grown crystal was examined by Kurtz powder method with different particle size using 1064 nm laser. Laser induced damage threshold study was carried out for the grown crystal using Nd:YAG laser. Copyright © 2014 Elsevier B.V. All rights reserved.

Crystallization of human estrogenic 17β-hydroxysteroid dehydrogenase under microgravity

NASA Astrophysics Data System (ADS)

Zhu, Dao-Wei; Zhou, Ming; Mao, Ying; Labrie, Fernand; Lin, Sheng-Xiang

1995-11-01

Human 17β-hydroxysteroid dehydrogenase has been crystallized on the ground in the complex form with NADP + and a complete data set of the crystal was primarily collected at 2.9 Å [D.-W. Zhu, X. Lee, R. Breton, D. Ghosh, W. Pangborn, W.L. Duax and S.-X. Lin, J. Mol. Biol. 234 (1993) 242]. To eliminate multiseeding, formation of multicrystals and to obtain higher quality crystals, we carried out the crystallization aboard the Russian MIR space station and crystals were recovered in January, 1994. Crystals of the enzyme were formed in 9 of the total 12 sitting drops in the space mission, in the presence of NADP + or estradiol. This is a first attempt of crystallization of a membrane-associated protein under microgravity in the presence of a detergent. The space experiments showed better results in nucleation number, crystal size and morphology than the ground ones, obtaining crystals diffracting to resolutions between 2.5-2.7 Å. The too early ground mixing has limited a more important improvement of the crystallization.

Bimetallic Platinum-Rhodium Alloy Nanodendrites as Highly Active Electrocatalyst for the Ethanol Oxidation Reaction.

PubMed

Bai, Juan; Xiao, Xue; Xue, Yuan-Yuan; Jiang, Jia-Xing; Zeng, Jing-Hui; Li, Xi-Fei; Chen, Yu

2018-06-13

Rationally designing and manipulating composition and morphology of precious metal-based bimetallic nanostructures can markedly enhance their electrocatalytic performance, including selectivity, activity, and durability. We herein report the synthesis of bimetallic PtRh alloy nanodendrites (ANDs) with tunable composition by a facile complex-reduction synthetic method under hydrothermal conditions. The structural/morphologic features, formation mechanism, and electrocatalytic performance of PtRh ANDs are investigated thoroughly by various physical characterization and electrochemical methods. The preformed Rh crystal nuclei effectively catalyze the reduction of Pt 2+ precursor, resulting in PtRh alloy generation due to the catalytic growth and atoms interdiffusion process. The Pt atoms deposition distinctly interferes in Rh atoms deposition on Rh crystal nuclei, resulting in dendritic morphology of PtRh ANDs. For the ethanol oxidation reaction (EOR), PtRh ANDs display the chemical composition and solution pH co-dependent electrocatalytic activity. Because of the alloy effect and particular morphologic feature, Pt 1 Rh 1 ANDs with optimized composition exhibit better reactivity and stability for the EOR than commercial Pt nanocrystals electrocatalyst.

Controlled morphology and size of curcumin using ultrasound in supercritical CO2 antisolvent.

PubMed

Jia, Jingfu; Wang, Wucong; Gao, Yahui; Zhao, Yaping

2015-11-01

Controllable morphology and size of crystal materials prepared by using a supercritical antisolvent (SAS) technique is still challenge. In this study, ultrasound was introduced into the SAS process to produce the particles of curcumin, a model compound. The effects of ultrasound power on the particle morphology and size were investigated in the range of 0 and 240 W at three different pressures. The observation of jet flow indicated ultrasound could accelerate the mixing speed between the liquid solution and the CO2, and thus reduced the gaseous region and the local saturation gradient. Mixed polymorphic and uniform particles of the curcumin were produced at a low and high mixing speed, respectively, confirmed by scanning electron microscopy. The needle- or rod-like particle, irregular lumpy particle and nano spherical particle were generated with the increase of the ultrasound power, attributed to the changes of the degree of supersaturation. Therefore, the ultrasound can be potentially applied to adjust the morphology and size of the crystal materials in supercritical CO2 antisolvent. Copyright © 2015 Elsevier B.V. All rights reserved.

Morphological Decomposition in Reading Hebrew Homographs

ERIC Educational Resources Information Center

Miller, Paul; Liran-Hazan, Batel; Vaknin, Vered

2016-01-01

The present work investigates whether and how morphological decomposition processes bias the reading of Hebrew heterophonic homographs, i.e., unique orthographic patterns that are associated with two separate phonological, semantic entities depicted by means of two morphological structures (linear and nonlinear). In order to reveal the nature of…

Free energy perturbation method for measuring elastic constants of liquid crystals

NASA Astrophysics Data System (ADS)

Joshi, Abhijeet

There is considerable interest in designing liquid crystals capable of yielding specific morphological responses in confined environments, including capillaries and droplets. The morphology of a liquid crystal is largely dictated by the elastic constants, which are difficult to measure and are only available for a handful of substances. In this work, a first-principles based method is proposed to calculate the Frank elastic constants of nematic liquid crystals directly from atomistic models. These include the standard splay, twist and bend deformations, and the often-ignored but important saddle-splay constant. The proposed method is validated using a well-studied Gay-Berne(3,5,2,1) model; we examine the effects of temperature and system size on the elastic constants in the nematic and smectic phases. We find that our measurements of splay, twist, and bend elastic constants are consistent with previous estimates for the nematic phase. We further outline the implementation of our approach for the saddle-splay elastic constant, and find it to have a value at the limits of the Ericksen inequalities. We then proceed to report results for the elastic constants commonly known liquid crystals namely 4-pentyl-4'-cynobiphenyl (5CB) using atomistic model, and show that the values predicted by our approach are consistent with a subset of the available but limited experimental literature.

Fabrication of ZnO photonic crystals by nanosphere lithography using inductively coupled-plasma reactive ion etching with CH{sub 4}/H{sub 2}/Ar plasma on the ZnO/GaN heterojunction light emitting diodes

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

Chen, Shr-Jia; Chang, Chun-Ming; Kao, Jiann-Shiun

2010-07-15

This article reports fabrication of n-ZnO photonic crystal/p-GaN light emitting diode (LED) by nanosphere lithography to further booster the light efficiency. In this article, the fabrication of ZnO photonic crystals is carried out by nanosphere lithography using inductively coupled plasma reactive ion etching with CH{sub 4}/H{sub 2}/Ar plasma on the n-ZnO/p-GaN heterojunction LEDs. The CH{sub 4}/H{sub 2}/Ar mixed gas gives high etching rate of n-ZnO film, which yields a better surface morphology and results less plasma-induced damages of the n-ZnO film. Optimal ZnO lattice parameters of 200 nm and air fill factor from 0.35 to 0.65 were obtained from fittingmore » the spectrum of n-ZnO/p-GaN LED using a MATLAB code. In this article, we will show our recent result that a ZnO photonic crystal cylinder has been fabricated using polystyrene nanosphere mask with lattice parameter of 200 nm and radius of hole around 70 nm. Surface morphology of ZnO photonic crystal was examined by scanning electron microscope.« less

Defect-mediated phonon dynamics in TaS2 and WSe2

PubMed Central

Cremons, Daniel R.; Plemmons, Dayne A.; Flannigan, David J.

2017-01-01

We report correlative crystallographic and morphological studies of defect-dependent phonon dynamics in single flakes of 1T-TaS2 and 2H-WSe2 using selected-area diffraction and bright-field imaging in an ultrafast electron microscope. In both materials, we observe in-plane speed-of-sound acoustic-phonon wave trains, the dynamics of which (i.e., emergence, propagation, and interference) are strongly dependent upon discrete interfacial features (e.g., vacuum/crystal and crystal/crystal interfaces). In TaS2, we observe cross-propagating in-plane acoustic-phonon wave trains of differing frequencies that undergo coherent interference approximately 200 ps after initial emergence from distinct interfacial regions. With ultrafast bright-field imaging, the properties of the interfering wave trains are observed to correspond to the beat frequency of the individual oscillations, while intensity oscillations of Bragg spots generated from selected areas within the region of interest match well with the real-space dynamics. In WSe2, distinct acoustic-phonon dynamics are observed emanating and propagating away from structurally dissimilar morphological discontinuities (vacuum/crystal interface and crystal terrace), and results of ultrafast selected-area diffraction reveal thickness-dependent phonon frequencies. The overall observed dynamics are well-described using finite element analysis and time-dependent linear-elastic continuum mechanics. PMID:28503630

The Protein Crystallization Facility STS-95

NASA Technical Reports Server (NTRS)

2004-01-01

The Protein Crystallization Facility will be used to grow crystals of human insulin. Insulin is the primary treatment for diabetes, the fourth leading cause of death by disease. Research on STS-95 is aimed at producing crystals of even higher quality, which when combined with new analysis techniques will permit a better understanding of the interaction between insulin and its receptor. This has the potential to aid in the development of a new commercially available insulin product with unique time release properties that could reduce fluctuations in a patient's blood sugar level. The Protein Crystallization Facility supports large-scale commercial investigations.

Cloning, expression, and crystallization of Cpn60 proteins from Thermococcus litoralis.

PubMed

Osipiuk, J; Sriram, M; Mai, X; Adams, M W; Joachimiak, A

2000-01-01

Two genes of the extreme thermophilic archaeon Thermococcus litoralis homologous to those that code for Cpn60 chaperonins were cloned and expressed in Escherichia coli. Each of the Cpn60 subunits as well as the entire Cpn60 complex crystallize in a variety of morphological forms. The best crystals diffract to 3.6 A resolution at room temperature and belong to the space group 1422 with unit cell parameters a = b = 193.5 A, c = 204.2 A.

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.

Construction of hydrophobic wood surfaces by room temperature deposition of rutile (TiO2) nanostructures

Treesearch

Rongbo Zheng; Mandla A. Tshabalala; Qingyu Li; Hongyan Wang

2015-01-01

A convenient room temperature approach was developed for growing rutile TiO2 hierarchical structures on the wood surface by direct hydrolysis and crystallization of TiCl3 in saturated NaCl aqueous solution.The morphology and the crystal structure of TiO2 coated on the wood surface were characterized...

Formation of curved micrometer-sized single crystals.

PubMed

Koifman Khristosov, Maria; Kabalah-Amitai, Lee; Burghammer, Manfred; Katsman, Alex; Pokroy, Boaz

2014-05-27

Crystals in nature often demonstrate curved morphologies rather than classical faceted surfaces. Inspired by biogenic curved single crystals, we demonstrate that gold single crystals exhibiting curved surfaces can be grown with no need of any fabrication steps. These single crystals grow from the confined volume of a droplet of a eutectic composition melt that forms via the dewetting of nanometric thin films. We can control their curvature by controlling the environment in which the process is carried out, including several parameters, such as the contact angle and the curvature of the drops, by changing the surface tension of the liquid drop during crystal growth. Here we present an energetic model that explains this phenomenon and predicts why and under what conditions crystals will be forced to grow with the curvature of the microdroplet even though the energetic state of a curved single crystal is very high.

Manipulating crystallization with molecular additives.

PubMed

Shtukenberg, Alexander G; Lee, Stephanie S; Kahr, Bart; Ward, Michael D

2014-01-01

Given the importance of organic crystals in a wide range of industrial applications, the chemistry, biology, materials science, and chemical engineering communities have focused considerable attention on developing methods to control crystal structure, size, shape, and orientation. Tailored additives have been used to control crystallization to great effect, presumably by selectively binding to particular crystallographic surfaces and sites. However, substantial knowledge gaps still exist in the fundamental mechanisms that govern the formation and growth of organic crystals in both the absence and presence of additives. In this review, we highlight research discoveries that reveal the role of additives, either introduced by design or present adventitiously, on various stages of formation and growth of organic crystals, including nucleation, dislocation spiral growth mechanisms, growth inhibition, and nonclassical crystal morphologies. The insights from these investigations and others of their kind are likely to guide the development of innovative methods to manipulate crystallization for a wide range of materials and applications.

Evaluating the Effectiveness of a Morphological Awareness Intervention: A Pilot Study

ERIC Educational Resources Information Center

Brimo, Danielle

2016-01-01

Researchers have established that morphological awareness is an important skill because it contributes unique variance to word-level reading and reading comprehension; however, few studies include students with reading disorders. The purpose of this pilot study was to investigate whether training morphological awareness would improve morphological…

In-Situ Atomic Force Microscope Imaging of Calcite Etch Pit Morphology Changes in Undersaturated and 1-Hydroxyethylidene-1,1-diphosphonic Acid Poisoned Solutions

PubMed Central

Britt, David W.

2012-01-01

Morphology changes in etch pits formed on the (1014) cleavage plane of calcite were induced by varying the ratio of [Ca2+] to [CO32−] in the bulk solution as well as through the addition of the crystal poison 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP). Three distinct morphologies were noted: symmetric rhombic, asymmetric rhombic, and triangular with a rough curved hypotenuse. The latter represents a transient morphology which is only observed during the actual dissolution process, while the former morphologies persist after dissolution is halted. PMID:25125794

Nucleation and Crystal Growth in the Formation of Hierarchical Three-Dimensional Nanoarchitecture

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

Wang, Xudong

This project is to obtain fundamental understandings of the operation of the Ostwald-Lussac (OL) Law and the oriented attachment (OA) mechanism in nucleation and growth of TiO2 nanorods (NR) via surface-reaction-limited pulsed chemical vapor deposition (SPCVD) process. Three-dimensional (3D) NW networks are a unique type of mesoporous architecture that offers extraordinary surface area density and superior transport properties of electrons, photons, and phonons. It is exceptionally promising for advancing the design and application of functional materials for photovoltaic devices, catalysts beds, hydrogen storage systems, sensors, and battery electrodes. Our group has developed the SPCVD technique by mimicking the mechanism ofmore » atomic layer deposition (ALD), which effectively decoupled the crystal growth from precursor concentration while retaining anisotropic 1D growth. For the first time, this technique realized a 3D NW architecture with ultrahigh density and achieved ~4-5 times enhancement on photo-conversion efficiency. Through the support of our current DOE award, we revealed the governing role of the OL Law in the nucleation stage of SPCVD. The formation of NR morphology in SPCVD was identified following the OA mechanism. We also discovered a unique vapor-phase Kirkendall effect in the evolution of tubular or core-shell NR structures. These understandings opened many new opportunities in designing 3D NW architectures with improved properties or new functionalities. Specifically, our accomplishments from this project include five aspects: (1) Observation of the Ostwald-Lussac Law in high-temperature ALD. (2) Observation of vapor-solid Kirkendall effect in ZnO-to-TiO2 nanostructure conversion. (3) Development of highly-efficient capillary photoelectrochemical (PEC) solar-fuel generation. (4) Development of efficient and stable electrochemical protections for black silicon PEC electrodes. (5) Development of doped polymers with tunable electrical properties. This project brings a new level of transformative knowledge on nucleation and crystal growth in the SPCVD NR growth processes. Specifically, quantification of the activation energy landscape guided by the OL law will allow us to establish a critical knowledge base of nucleation kinetics for SPCVD synthesis of NR branches on different material surfaces. Studying the OA kinetics will establish a transformative knowledge base to support this new crystal growth mechanism that can be applied to many functional material systems. This research will pave the road toward a capable and versatile synthesis technology for creating 3D hierarchical mesoscale structures.« less

Crystal Growth of ZnSe and Related Ternary Compound Semiconductors by Vapor Transport

NASA Technical Reports Server (NTRS)

Su, Ching-Hua; Brebrick, Robert F.; Volz, Martin P.; Burger, Arnold; Dudley, Michael; Matyi, Richard J.; Ramachandran, Narayanan; Sha, Yi-Gao; Volz, Martin P.; Shih, Hung-Dah

2001-01-01

Crystal growth by vapor transport has several distinct advantages over melt growth techniques. Among various potential benefits from material processing in reduced gravity the followings two are considered to be related to crystal growth by vapor transport: (1) elimination of the crystal weight and its influence on the defect formation and (2) reduction of natural buoyancy-driven convective flows arising from thermally and/ or solutally induced density gradient in fluids. The previous results on vapor crystal growth of semiconductors showed the improvements in surface morphology, crystalline quality, electrical properties and dopant distribution of the crystals grown in reduced gravity as compared to the crystals grown on Earth. But the mechanisms, which are responsible for the improvements and cause the gravitational effects on the complicated and coupled processes of vapor mass transport and growth kinetics, are not well understood.

Growth of sodium chlorate crystals in the presence of potassium sulphate

NASA Astrophysics Data System (ADS)

Kim, E. L.; Tsyganova, A. A.; Vorontsov, D. A.; Ovsetsina, T. I.; Katkova, M. R.; Lykov, V. A.; Portnov, V. N.

2015-09-01

In this work, we investigated the morphology and growth rates of NaClO3 crystals in solutions with K2SO4 additives. NaClO3 crystals were grown using the temperature gradient technique under concentration convection. We found that the crystal habitus changed from cubic to tetrahedral, and the growth of the cubic {100}, tetrahedral {111} and rhomb-dodecahedral {110} faces decelerated with an increase in the concentration of SO42- ions. The {110} face was the most and the {100} face was the least inhibited by sulphate ions. The mechanism of SO42- ions action is their adsorption on the crystal surface, which impedes attachment of the crystal's building units. We conclude that different atomic structure and charge state of various crystal faces determine their sensitivity to the action of the SO42- ions.

Zircon crystal morphology and internal structures as a tool for constraining magma sources: Examples from northern Portugal Variscan biotite-rich granite plutons

NASA Astrophysics Data System (ADS)

Brites Martins, Helena C.; Simões, Pedro P.; Abreu, Joana

2014-09-01

In northern Portugal, large volumes of granitoids were emplaced during the last stage (D3) of the Variscan orogeny and display a wide range of petrological signatures. We studied the morphologies and internal structures of zircons from syn-, late- and post-D3 granitoids. The sin-D3 granitoids include the Ucanha-Vilar, Lamego, Felgueiras, Sameiro, and Refoios do Lima plutons, the late- and post-D3 granitoids are represented by the Vieira do Minho and the Vila Pouca de Aguiar plutons, respectively. Typological investigations after Pupin (1980) along with scanning electron microprobe imaging reveal that the external morphology of zircon changes consistently with a decrease in the crystallization temperature. Zircon populations from the Refoios do Lima and the Vieira do Minho granites show gradual changes in the internal morphologies and their typologic evolution trends are consistent with their mainly crustal origin. The Sameiro, Felgueiras, Lamego and Ucanha-Vilar granites have more complex internal and external morphology and typological evolution trends that cross the domain of the calc-alkaline to the aluminous granites compatible with a mixing process. Finally, the morphological types of the Vila Pouca de Aguiar granites are found both in calc-alkaline and sub-alkaline granites and their typological evolutionary trends follow the calc-alkaline/sub-alkaline trend, suggesting crustal sources with some mantle contribution.

Unveiling a Drift Resistant Cryptotope within Marburgvirus Nucleoprotein Recognized by Llama Single-Domain Antibodies

PubMed Central

Garza, John Anthony; Taylor, Alexander Bryan; Sherwood, Laura Jo; Hart, Peter John; Hayhurst, Andrew

2017-01-01

Marburg virus (MARV) is a highly lethal hemorrhagic fever virus that is increasingly re-emerging in Africa, has been imported to both Europe and the US, and is also a Tier 1 bioterror threat. As a negative sense RNA virus, MARV has error prone replication which can yield progeny capable of evading countermeasures. To evaluate this vulnerability, we sought to determine the epitopes of 4 llama single-domain antibodies (sdAbs or VHH) specific for nucleoprotein (NP), each capable of forming MARV monoclonal affinity reagent sandwich assays. Here, we show that all sdAb bound the C-terminal region of NP, which was produced recombinantly to derive X-ray crystal structures of the three best performing antibody-antigen complexes. The common epitope is a trio of alpha helices that form a novel asymmetric basin-like depression that accommodates each sdAb paratope via substantial complementarity-determining region (CDR) restructuring. Shared core contacts were complemented by unique accessory contacts on the sides and overlooks of the basin yielding very different approach routes for each sdAb to bind the antigen. The C-terminal region of MARV NP was unable to be crystallized alone and required engagement with sdAb to form crystals suggesting the antibodies acted as crystallization chaperones. While gross structural homology is apparent between the two most conserved helices of MARV and Ebolavirus, the positions and morphologies of the resulting basins were markedly different. Naturally occurring amino acid variations occurring in bat and human Marburgvirus strains all mapped to surfaces distant from the predicted sdAb contacts suggesting a vital role for the NP interface in virus replication. As an essential internal structural component potentially interfacing with a partner protein it is likely the C-terminal epitope remains hidden or “cryptic” until virion disruption occurs. Conservation of this epitope over 50 years of Marburgvirus evolution should make these sdAb useful foundations for diagnostics and therapeutics resistant to drift. PMID:29038656

Effect of surfactant concentration on nifedipine crystal habit and its related pharmaceutical properties

NASA Astrophysics Data System (ADS)

Kumar, Dinesh; Thipparaboina, Rajesh; Modi, Sameer R.; Bansal, Arvind K.; Shastri, Nalini R.

2015-07-01

Crystallization in the presence of Polysorbate-80 (T-80), a non-ionic surfactant was explored for crystal habit modification of nifedipine polymorph I (Nif). A concentration dependent reduction in aspect ratio was observed with T-80. Generation of any new solvates/polymorphs was ruled out by Fourier Transform Infrared spectroscopy, differential scanning calorimetry, powder X-ray diffraction, and thermogravimetric analysis, while the absence of T-80 on the surface or bulk of the recrystallized samples was established by liquid chromatography mass spectroscopy. The dissolution rate order of the re-crystallized Nif habits was in the order of; Nif-D (Nif with 0.6%v/v T-80)>Nif-C (Nif with 0.4% v/v T-80)>Nif-B (Nif with 0.2% v/v T-80)>Nif-A (plain Nif). Wetting ability and surface free energy determination from contact angle measurements were used to explain the order of dissolution rate. The consequences of varying concentration of T-80 on Nif crystal habit was supported by means of molecular dynamics (MD) which was executed using COMPASS force field while modified attachment energy was computed to acquire the absolute morphology. The mechanism for alteration in the morphology was suggested based on the computed crystal surface chemistry. Nif-D crystal habit was nearly iso-diametric with majority of facets occupied by polar dominant surfaces {0 1 1} and {0 0 2} which ultimately resulted in higher dissolution rate. In Nif-B and Nif-C the dissolution rate was dependent on the proportion of polar and non-polar facet area. The methodology used in this study could be an influential tool for selection of concentration of habit-modifying additives in other crystallization studies.

Insights from the Shell Proteome: Biomineralization to Adaptation

PubMed Central

Arivalagan, Jaison; Yarra, Tejaswi; Marie, Benjamin; Sleight, Victoria A.; Duvernois-Berthet, Evelyne; Clark, Melody S.; Marie, Arul; Berland, Sophie

2017-01-01

Bivalves have evolved a range of complex shell forming mechanisms that are reflected by their incredible diversity in shell mineralogy and microstructures. A suite of proteins exported to the shell matrix space plays a significant role in controlling these features, in addition to underpinning some of the physical properties of the shell itself. Although, there is a general consensus that a minimum basic protein tool kit is required for shell construction, to date, this remains undefined. In this study, the shell matrix proteins (SMPs) of four highly divergent bivalves (The Pacific oyster, Crassostrea gigas; the blue mussel, Mytilus edulis; the clam, Mya truncata, and the king scallop, Pecten maximus) were analyzed in an identical fashion using proteomics pipeline. This enabled us to identify the critical elements of a “basic tool kit” for calcification processes, which were conserved across the taxa irrespective of the shell morphology and arrangement of the crystal surfaces. In addition, protein domains controlling the crystal layers specific to aragonite and calcite were also identified. Intriguingly, a significant number of the identified SMPs contained domains related to immune functions. These were often are unique to each species implying their involvement not only in immunity, but also environmental adaptation. This suggests that the SMPs are selectively exported in a complex mix to endow the shell with both mechanical protection and biochemical defense. PMID:27744410

Magnetite pollution nanoparticles in the human brain

PubMed Central

Maher, Barbara A.; Karloukovski, Vassil; MacLaren, Donald A.; Foulds, Penelope G.; Allsop, David; Mann, David M. A.; Torres-Jardón, Ricardo; Calderon-Garciduenas, Lilian

2016-01-01

Biologically formed nanoparticles of the strongly magnetic mineral, magnetite, were first detected in the human brain over 20 y ago [Kirschvink JL, Kobayashi-Kirschvink A, Woodford BJ (1992) Proc Natl Acad Sci USA 89(16):7683–7687]. Magnetite can have potentially large impacts on the brain due to its unique combination of redox activity, surface charge, and strongly magnetic behavior. We used magnetic analyses and electron microscopy to identify the abundant presence in the brain of magnetite nanoparticles that are consistent with high-temperature formation, suggesting, therefore, an external, not internal, source. Comprising a separate nanoparticle population from the euhedral particles ascribed to endogenous sources, these brain magnetites are often found with other transition metal nanoparticles, and they display rounded crystal morphologies and fused surface textures, reflecting crystallization upon cooling from an initially heated, iron-bearing source material. Such high-temperature magnetite nanospheres are ubiquitous and abundant in airborne particulate matter pollution. They arise as combustion-derived, iron-rich particles, often associated with other transition metal particles, which condense and/or oxidize upon airborne release. Those magnetite pollutant particles which are <∼200 nm in diameter can enter the brain directly via the olfactory bulb. Their presence proves that externally sourced iron-bearing nanoparticles, rather than their soluble compounds, can be transported directly into the brain, where they may pose hazard to human health. PMID:27601646

Response of Halimeda to ocean acidification: Field and laboratory evidence

USGS Publications Warehouse

Robbins, L.L.; Knorr, P.O.; Hallock, P.

2009-01-01

Rising atmospheric pCO2 levels are changing ocean chemistry more dramatically now than in the last 20 million years. In fact, pHvalues of the open ocean have decreased by 0.1 since the 1800s and are predicted to decrease 0.1-0.4 globally in the next 90 years. Ocean acidification will affect fundamental geochemical and biological processes including calcification and carbonate sediment production. The west Florida shelf is a natural laboratory to examine the effects of ocean acidification on aragonite production by calcareous green algae. Scanning electron microscopy (SEM) of crystal morphology of calcifying organisms reveals ultrastructural details of calcification that occurred at different saturation states. Comparison of archived and recent specimens of calcareous green alga Halimeda spp. from the west Florida shelf, demonstrates crystal changes in shape and abundance over a 40+ year time span. Halimeda crystal data from apical sections indicate that increases in crystal concentration and decreases in crystal width occurred over the last 40+ years. Laboratory experiments using living specimens of Halimeda grown in environments with known pH values were used to constrain historical observations. Percentages of organic and inorganic carbon per sample weight of pooled species did not significantly change. However, individual species showed decreased inorganic carbon and increased organic carbon in more recent samples, although the sample sizes were limited. These results indicate that the effect of increased pCO 2 and decreased pH on calcification is reflected in the crystal morphology of this organism. More data are needed to confirm the observed changes in mass of crystal and organic carbon. ?? Author(s) 2009.

"Daisy-like" crystals: A rare and unknown type of urinary crystal.

PubMed

Fogazzi, G B; Anderlini, R; Canovi, S; Covarelli, C; Gras, J; Kučera, J; Proietti, A; Rogic, D; Teboul, R; Ferraris Fusarini, C; de Liso, F; Garigali, G; Daudon, M

2017-08-01

Crystals are well known structures of urinary sediment, most of which are identified by the combined knowledge of crystal morphology, birefringence features at polarized light, and urine pH. In this paper, we report on a cohort of subjects whose urine contained a very rare type of crystal, which we first described in 2004 and which, based on its peculiar morphology, we define as "daisy-like crystal" (DLcr). Reports on DLcr were spontaneously sent to our laboratory over a 10.5-year period by different laboratory professionals and by one veterinary clinician who, in their everyday work, had come across DLcr. After the examination of DLcr images submitted, a number of other information were requested and partly obtained. DLcr were found in 9 human beings in 7 different laboratories, located in 4 countries (Italy, Belgium, Croatia, France). DLcr were found mostly in female (8/9), at all ages (3.5 to 93years), mostly in alkaline urine (pH6.0 to 7.5), at variable specific gravity values (1.010 to 1.030), either as isolated particles (2/8) or in association with other crystals (5/8) and/or leucocytes or bacteria (3/8). In addition, DLcr were found in the urine of a 1-year-old dog, examined in a veterinary clinic of Czech Republic. In 3 cases, DLcr were identified by manual microscopy, while in 7 cases by automated urine sediment analyzers. This paper confirms the possible presence in the urine of DLcr. However, further cases are needed to clarify their frequency, clinical meaning, and composition. Copyright © 2017. Published by Elsevier B.V.

Crystallization of Polymers in Confined Environments: Structural Development of Semi-crystalline Polymer-Layered Silicate Nanocomposites

NASA Astrophysics Data System (ADS)

Vaia, Richard A.; Lincoln, Derek M.; Wang, Zhi-Gang; Hsiao, Benjamin S.; Krishnamoorti, Ramanan

2000-03-01

Over the last decade, the utility of ultrafine dispersions of inorganic nanoparticles to enhance polymer performance and function as precursors to form self-passivating / self-healing inorganic coatings on the polymer surface has been established. Before developing the fundamental structure-property relationships though, a detailed understanding of processing / morphology relationships is necessary. As with other multiphase systems exhibiting nano (1-100 nm) and meso (100-500 nm) order (such as biopolymers, block-copolymers, colloidal suspensions, liquid crystals), physical properties ranging from toughness to optical clarity are determined by morphology on various length scales which in turn arise from processing history. This is anticipated to be especially important for blends containing two or more constituents with fundamental structural features on the nanoscale, such as crystal lamellae and aluminosilicate sheets. Small-angle x-ray scattering experiments with synchrotron radiation reveal the presence of ultra-long range (20-60 nm) mesoscopic ordering of the layered silicate in molten polyamide 6-layered silicate nanocomposites. This superstructure of these semi-rigid inorganic sheets provides a confined environment to examine the crystallization of polyamide 6 with traditional bulk characterization techniques. In addition to a change lamellae organization and lamellae size, the presence of the aluminosilicate layers and extent of interfacial interactions (end-tethered v. physiadsorbed chains) substantially alters the nucleation rate, growth kinetics and Brill transition of the crystal phase as revealed by isothermal crystallization experiments monitored in-situ with synchrotron radiation. These exfoliated nanocomposites provide new opportunities to investigate confined polymer crystallization as well as provide insight into the origin of various property enhancements in these systems.

Comparison study of PE epitaxy on carbon nanotubes and graphene oxide and PE/graphene oxide as amphiphilic molecular structure for solvent separation

NASA Astrophysics Data System (ADS)

He, Linghao; Zheng, Xiaoli; Xu, Qun; Chen, Zhimin; Fu, Jianwei

2012-03-01

Carbon nanotubes (CNTs) and graphene nanosheets, as one-dimensional and two-dimensional carbon-based nanomaterials respectively, have different abilities to induce the polymer crystallization. In this study, hybrid materials, polyethylene (PE) decorating on CNTs and graphene oxide (GO), were prepared by a facile and efficient method using supercritical carbon dioxide (SC CO2) as anti-solvent. And the morphology and crystallization behavior of PE on CNTs and GO were investigated by transmission electron microscopy, Fourier transform infrared spectroscopy, Raman spectra, wide angle X-ray diffraction, and differential scanning calorimetry. Although both CNTs and GO could act as nucleating agents to induce PE epitaxial growth, CNTs were decorated by PE lamellar crystals forming nanohybrid "shish-kebab" (NHSK) structure, whereas GO sheets were only decorated with petal-like PE crystals. The varying morphologies of the nanohybrids depend on the PE epitaxy and the interactions between polymer chains and substrates. High surface curvature and the perfect ordered crystal structure of CNTs make PE crystals periodically grow on CNTs. While PE crystals grow and form multiple orientation-lamellae on GO due to the lattice matching and complex interactions between PE chains and GO. In addition, our experimental results show an interesting and evident stratification phenomenon for the PE/GO hybrid material, implying that GO decorated by PE have a screening function for the solvents. We anticipate that this work can widen the area of functionalization of carbon-based nanomaterials with a controlled means by an environmentally benign method, which are important for the functional design in nanodevice applications.

On the role of the central nervous system in regulating the mineralisation of inner-ear otoliths of fish.

PubMed

Anken, Ralf H

2006-12-01

Stato- or otoliths are calcified structures in the organ of balance and equilibrium of vertebrates, the inner ear, where they enhance its sensitivity to gravity. The compact otoliths of fish are composed of the calcium carbonate polymorph aragonite and a small fraction of organic molecules. The latter form a protein skeleton which determines the morphology of an otolith as well as its crystal lattice structure. This short review addresses findings according to which the brain obviously plays a prominent role in regulating the mineralisation of fish otoliths and depends on the gravity vector. Overall, otolith mineralisation has thus been identified to be a unique, neuronally guided biomineralisation process. The following is a hypothetical model for regulation of calcification by efferent vestibular neurons: (1) release of calcium at tight junctions in the macular epithelia, (2) macular carbonic anhydrase activity (which in turn is responsible for carbonate deposition), (3) chemical composition of matrix proteins. The rationale and evidence that support this model are discussed.

Simple fabrication process for 2D ZnO nanowalls and their potential application as a methane sensor.

PubMed

Chen, Tse-Pu; Chang, Sheng-Po; Hung, Fei-Yi; Chang, Shoou-Jinn; Hu, Zhan-Shuo; Chen, Kuan-Jen

2013-03-20

Two-dimensional (2D) ZnO nanowalls were prepared on a glass substrate by a low-temperature thermal evaporation method, in which the fabrication process did not use a metal catalyst or the pre-deposition of a ZnO seed layer on the substrate. The nanowalls were characterized for their surface morphology, and the structural and optical properties were investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM), and photoluminescence (PL). The fabricated ZnO nanowalls have many advantages, such as low growth temperature and good crystal quality, while being fast, low cost, and easy to fabricate. Methane sensor measurements of the ZnO nanowalls show a high sensitivity to methane gas, and rapid response and recovery times. These unique characteristics are attributed to the high surface-to-volume ratio of the ZnO nanowalls. Thus, the ZnO nanowall methane sensor is a potential gas sensor candidate owing to its good performance.

Optimizing structure in nanodiamonds using in-situ strain-sensitive Bragg coherent diffraction imaging.

NASA Astrophysics Data System (ADS)

Hruszkewycz, Stephan; Cha, Wonsuk; Ulvestad, Andrew; Fuoss, Paul; Heremans, F. Joseph; Harder, Ross; Andrich, Paolo; Anderson, Christopher; Awschalom, David

The nitrogen-vacancy center in diamond has attracted considerable attention for nanoscale sensing due to unique optical and spin properties. Many of these applications require diamond nanoparticles which contain large amounts of residual strain due to the detonation or milling process used in their fabrication. Here, we present experimental, in-situ observations of changes in morphology and internal strain state of commercial nanodiamonds during high-temperature annealing using Bragg coherent diffraction imaging to reconstruct a strain-sensitive 3D image of individual sub-micron-sized crystals. We find minimal structural changes to the nanodiamonds at temperatures less than 650 C, and that at higher temperatures up to 750 C, the diamond-structured volume fraction of nanocrystals tend to shrink. The degree of internal lattice distortions within nanodiamond particles also decreases during the anneal. Our findings potentially enable the design of efficient processing of commercial nanodiamonds into viable materials suitable for device design. We acknowledge support from U.S. DOE, Office of Science, BES, MSE.