Formation,growth and ageing of clathrate hydrate crystals in a porous medium

An experimental study was performed to visually observe the driving force dependence of hydrate growth in a porous medium filled with either liquid water and dissolved CO₂ or liquid water and gaseous CO₂. The given system subcooling, ΔT _sub, i.e. the deficiency of the system temperature from the triple CO₂?hydrate?water equilibrium temperature under a given pressure, ranged from 1.7?K to 7.3?K. The fine dendrites initially formed at ΔT _sub?=?7.3?K changed quickly into particulate crystals. For ΔT _sub?=?1.7?K, faceted hydrate crystals grew and the subsequent morphological change was hardly identified for an eight-day observation period. These results indicate that the physical bonding between hydrate crystals and skeletal materials becomes stronger with decreasing driving force, suggesting that the fluid dynamic and mechanical properties of hydrate-bearing sediments vary depending on the hydrate crystal growth process.     

In situ observation and simulation of growth process of faceted RE123 crystals

To clarify the growth mechanism of faceted REBa₂Cu₃O_7−δ (RE123, RE = Sm, Y) crystals, the growth process of the crystals was observed in situ by using a high temperature microscope. The growth rate of each faceted interface of a crystal growing from the liquid + 211 phases under an undercooling was obtained from the relationship between the position of each interface and growth time. It was observed that some of the faceted interfaces of a growing crystal stopped growing after a period of time, while other interfaces continued to grow with a growth rate approximated by a function of the undercooling. The above stoppage of the growth was observed in situ for the first time, and this fact could give powerful support to the mechanism for a similar phenomenon in REBCO films which were fabricated by the trifluoroacetates metal organic deposition method: growing microstructures of RE123 crystals in the film were revealed by transmission electron microscopy (TEM) for quenched specimens. Some very thin a-axis grains were formed by a change in c-axis growth rate. Furthermore, we showed the above growth and stop phenomena of faceted interfaces of REBCO crystal grains using numerical simulations.     

Assembly of body-centered cubic crystals in hard spheres

We investigate the crystallization of monodisperse hard spheres confined by two square patterned substrates (possessing the basic character of the body-centered cubic (bcc) crystal structure) at varying substrate separations via molecular dynamics simulation. Through slowly increasing the density of the system, we find that crystallization under the influence of square patterned substrates can set in at lower densities compared with the homogeneous crystallization. As the substrate separation decreases, the density, where crystallization occurs (i.e., pressure drops), becomes small. Moreover, two distinct regimes are identified in the plane of bcc particle fraction and density for the separation range investigated. For large substrate separations, the bcc particle fraction displays a local maximum as the density is increased, and the resulting formed crystals have a polycrystalline structure. However, and more importantly, another situation emerges for small substrate separations: the capillary effects (stemming from the presence of two substrates) overwhelm the bulk driving forces (stemming from the spontaneous thermal fluctuations in the bulk) during the densification, eventually resulting in the formation of a defect-free bcc crystal (unstable with respect to the bulk hard-sphere crystals) by using two square patterned substrates.     

Morphology,Crystallization, and Melting of Single Crystals and Thin Films of Star‐branched Polyesters with Poly(ϵ‐caprolactone) Arms as Revealed by Atomic Force Microscopy

The morphology and thermal stability of different sectors in solution‐ and melt‐grown crystals of star‐branched polyesters with poly(?‐caprolactone) (PCL) arms, and of a reference linear PCL, have been studied by tapping‐mode atomic‐force microscopy (AFM). Real‐time monitoring of melt‐crystallization in thin films of star‐branched and linear PCL has been performed using hot‐stage AFM. A striated fold surface was observed in both solution‐ and melt‐grown crystals of both star‐branched and linear PCL. The presence of striations in the melt‐grown crystals proved that this structure was genuine and not due to the collapse of tent‐shaped crystals. The crystals of the star‐branched polymers had smoother fold surfaces, which can be explained by the presence of dendritic cores close to the fold surfaces. The single crystals of linear PCL grown from solution showed earlier melting in the {100} sectors than in the {110} sectors, whereas no such sectorial dependence of the melting was found in the solution‐grown crystals of the star‐branched polymers. The proximity of the dendritic cores to the fold surface yields at least one amorphous PCL repeating unit next to the dendritic core and more nonadjacent and less sharp chain folding than in linear PCL single crystals; this evidently erased the difference in thermal stability between the {110} and {100} sectors. Melt‐crystallization in thin polymer films at 53–55°C showed 4 times faster crystal growth along b than along a, and more irregular crystals with niches on the lateral faces in star‐branched PCL than in linear PCL. Crystal growth rate was strictly constant with time. Multilayer crystals with central screw dislocation (growing with or without reorientation of the b–axis) and twisting were observed in both classes of polymers.     

冷却速率对温敏聚N-异丙基丙烯酰胺胶体结晶过程的影响

冷却速率对结晶过程具有重要的影响. 本文采用温敏poly-N-isopropylacrylamide (PNIPAM) 胶体晶体体系实时观察了冷却速率对结晶晶粒尺寸的影响. 通过高倍透射明场观察和Bragg衍射观察研究连续冷却下的晶粒形核和生长实时演化过程, 发现随着冷却速率的增加, PNIPAM胶体晶体晶粒尺寸不断减少. 晶粒尺寸与冷却速率符合幂指数关系, 与金属体系具有相似的演化规律.     

沉降对带电胶体粒子结晶过程的影响

采用密度匹配法(重水与水按一定比例混合),以及反射光谱法,研究了重力沉降作用对直径为98 nm的带电胶体粒子结晶过程的影响. 结果表明,重力沉降在晶体生长的初期提高了晶体生长速率,而后期降低了晶体生长速率,这是由于在晶体生长初期,沉降作用可使更多的粒子结合到晶体结构中,而当晶体尺寸进一步增加,其沉降速率也相应地增大,晶相与液相间的摩擦阻力导致一部分颗粒从胶体晶体上脱落. 总的来说,重力沉降在初期加剧了晶体的生长,后期阻碍了晶体的生长. 另外,在微重力环境下形成的胶体晶体比在重力环境下形成的胶体晶体更加完整紧密.     

Concentration dependence of the mixed crystal modes of vibration

The concentration dependence of the reststrahl absorption in various mixed crystals exhibiting one, two and mixed mode behaviour is investigated using the coherent potential approximation (cpa). The phonon Green’s function, the impurity mode frequencies and the strength of absorption are calculated in the Einstein model from the generalizedcpa proposed by Tripathi and Behera which takes into account both mass and force constant changes. The introduction of a phenomenological concentration dependence of the force constant change parameter is shown to provide a satisfactory explanation of the concentration dependence of the experimental data for the twenty mixed crystal systems analysed. It is conjectured that the nearest neighbour force constant of an impurity atom substituted at a host site is very much different from that of a perfect crystal consisting of these impurity atoms and that both these play an important role in determining the one, two and mixed mode behaviour of the mixed crystals.     

Morphology and orientational disorder of C70 single crystals

C₇₀ single crystals, free from solvent contamination, were grown via vapor phase transport technique. The (0001) face of the C₇₀ crystal was imaged with Atomic Force Microscopy (AFM) under ambient atmosphere. Low-resolution images of a freshly prepared crystal revealed well-ordered faceted regions with multiple terraces extending over a region of several hundred square nanometers. The terraced structure in the images indicates that the crystals formed as a layer growth. In the high-resolution images, C₇₀ molecules were resolved in a hexagonal close packed (hcp) structure with an average center-to-center distance of 10.5±0.5 Å. After one month's exposure to the ambient atmosphere, the molecules rearranged into a mixed structure consisting of hcp and face centered cubic (fcc) regions.     

Polymer-mediated and ultrasound-assisted crystallization of ropivacaine: Crystal growth and morphology modulation

The objective of this research was to modify the crystal shape and size of poorly water-soluble drug ropivacaine, and to reveal the effects of polymeric additive and ultrasound on crystal nucleation and growth. Ropivacaine often grow as needle-like crystals extended along the a-axis and the shape was hardly controllable by altering solvent types and operating conditions for the crystallization process. We found that ropivacaine crystallized as block-like crystals when polyvinylpyrrolidone (PVP) was used. The control over crystal morphology by the additive was related to crystallization temperature, solute concentration, additive concentration, and molecular weight. SEM and AFM analyses were performed providing insights into crystal growth pattern and cavities on the surface induced by the polymeric additive. In ultrasound-assisted crystallization, the impacts of ultrasonic time, ultrasonic power, and additive concentration were investigated. The particles precipitated at extended ultrasonic time exhibited plate-like crystals with shorter aspect ratio. Combined use of polymeric additive and ultrasound led to rice-shaped crystals, which the average particle size was further decreased. The induction time measurement and single crystal growth experiments were carried out. The results suggested that PVP worked as strong nucleation and growth inhibitor. Molecular dynamics simulation was performed to explore the action mechanism of the polymer. The interaction energies between PVP and crystal faces were calculated, and mobility of the additive with different chain length in crystal-solution system was evaluated by mean square displacement. Based on the study, a possible mechanism for the morphological evolution of ropivacaine crystals assisted by PVP and ultrasound was proposed.     

Crystallization Kinetics of Lamellar Crystals Confined in Polymer Thin Films

We used dynamic Monte Carlo simulations to investigate the crystallization kinetics of flat-on lamellar polymer crystals in variable thickness films. We found that the growth rates linearly reduced with decreasing film thickness for the films thinner than a transition thickness d_t , while they were constant for the films thicker than d_t . Moreover, the mean stem lengths (crystal thickness) we calculated decreased with film thickness in a similar way to the growth rates, and the intramolecular crystallinities we calculated confirmed the film thickness dependence of the crytsal thickness. Besides, the crystal melting rates in thin films were calculated and increased with decreasing film thickness. We proposed a new interpretation on the film thickness dependence of the crystal growth rate in thin films, suggesting that it is dominated by the crystal thickness in terms of the driving force term (l–l _min) expressed by Sadler, rather than the chain mobility based on experiments. The crystal thickness can determine whether a crystal grows or melts in a thin film at a fixed temperature, indicating the reversibility between the crystal growth and melting.     

Electric field in two-dimensional complex plasma crystal:Simulated lattices

We focus on molecular dynamics simulated two-dimensional complex plasma crystals. We use rigid walls as a confinement force and produce square and rectangular crystals. We report various types of two-row crystals. The narrow and long crystals are likely to be used as wigglers; therefore, we simulate such crystals. Also, we analyze the electric fields of simulated crystals. A bit change in lattice parameters can change the internal structures of crystals and their electric fields notably. These parameters are the number of grains, grains charge, length, and width of the crystal. With the help of electric fields, we show the details of crystal structures.     

Enhancing nucleation and controlling crystal orientation by rubbing/scratching the surface of a thin polymer film

We used the tip of an atomic force microscope (AFM) in the contact mode to scratch/rub the surface of a glassy polymer thin film, i.e., isotactic polystyrene (i-PS) at room temperature. After subsequent isothermal crystallization, an extremely high nucleation density of edge-on crystals within the rubbed region or at the edge of the scratched area was observed. Furthermore, a transition from edge-on to flat-on lamellae occurred beyond a certain distance from the edge of the scratched region. Our results demonstrate that both, soft rubbing or hard scratching, allow to lower the nucleation barrier for polymer crystallization and to control the orientation of the resulting crystalline lamellae. The role of scratching/rubbing on chain deformation and its relation to nucleation and crystal orientation in polymer thin films is discussed.     

Dual-shunt branch circuit and harmonic suppressed device application

The morphological manipulation, structural characterization, and optical properties of different CdSe nanocrystals were reported. Several different CdSe nanostructures, including nanowires, tetrapod crystals, and nanoparticles were grown by varying the volume ratio of triethylenetetraamine (TETA) and water (WA) in their mixed solution. By manipulating the growth driving force (i.e., the degree of supersaturation) and kinetics of the process (i.e., growth rate), the morphology and crystal structure of CdSe nanocrystals can be tailored. Growth driving force changed their morphology from nanowires to tetrapod structures and from the latter structure to nanoparticles. Moreover, kinetics of the process altered their crystal structure from wurtzite to zinc blende. The optical property of CdSe nanocrystals was investigated using UV-vis spectroscopy. The absorption edge of CdSe nanostructures showed a blue shift. CdSe nanocrystals prepared under optimized conditions showed good microstructural and optical properties for solar cell application.     

Structure and crystallization of molecular complexes between poly(ethylene oxide) and hydroxybenzenes

The phase diagrams of the binary systems poly(ethylene oxide) (PEO)-resorcinol and poly(ethylene oxide)-p-nitrophenol show the presence of molecular complexes with well-defined stoichiometries. The crystal structure of these two molecular complexes has been determined from wide-angle x-ray diffraction patterns of stretched films and spherulites. The morphology of the two complexes crystallized from the melt is investigated by differential scanning calorimetry and small-angle x-ray scattering. The crystallization of the PEO-resorcinol complex from the melt gives integral-folded crystals with either extended chains (EC) or n-folded chains (n-FC). As observed for PEO oligomers, the fraction of EC crystals of the PEO-resorcinol complex increases with the crystallization temperature to give finally only EC crystals but in a larger range of crystallization temperatures than for pure PEO. On the other hand, the PEO-p-nitrophenol complex crystallizes over all the studied crystallization range as stable nonintegral-folded (NIF) crystals. Two proposals related to the crystal structure of these complexes and their mode of growth are invoked to explain these two greatly different morphologies at the lamellar level.     

Dislocation Generation in Dislocation-Free Germanium

A dislocation structure is studied in germanium single crystals grown in a regime of minimum temperature gradients at the crystallization front and low supercooling. The investigations show that the distortion of the flat crystallization front arising during crystal droplet detachment in the completion growth stage results in the dislocation generation in the lower parts of dislocation-free single crystals. The dislocations are generated at the phase boundary and propagate in the thermoplasticity zone. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 5, pp. 21–24, May, 2005.     

A phase-field model for simulating various spherulite morphologies of semi-crystalline polymers

A modified phase-field model is proposed for simulating the isothermal crystallization of polymer melts. The model consists of a second-order phase-field equation and a heat conduction equation. It obtains its model parameters from the real material parameters and is easy to use with tolerable computational cost. Due to the use of a new free energy functional form, the model can reproduce various single crystal morphologies of polymer melts under quiescent conditions, including dendritic, lamellar branching, ring-banded, breakup of ring-banded, faceted hexagonal, and spherulitic structures. Simulation results of isotactic polystyrene crystals demonstrate that the present phase-field model has the ability to give qualitative predictions of polymer crystallization under isothermal and quiescent conditions.     

Ultrasound-assisted solution crystallization of fotagliptin benzoate: Process intensification and crystal product optimization

The ultrasound-assisted crystallization process has promising potentials for improving process efficiency and modifying crystalline product properties. In this work, the crystallization process of fotagliptin benzoate methanol solvate (FBMS) was investigated to improve powder properties and downstream desolvation/drying performance. The direct cooling/antisolvent crystallization process was conducted and then optimized with the assistance of ultrasonic irradiation and seeding strategy. Direct cooling/antisolvent crystallization and seeding crystallization processes resulted in needle-like crystals which are undesirable for downstream processing. In contrast, the ultrasound-assisted crystallization process produced rod-like crystals and reduced the crystal size to facilitate the desolvation of FBMS. The metastable zone width (MSZW), induction time, crystal size, morphology, and process yield were studied comprehensively. The results showed that both the seeding and ultrasound-assisted crystallization process (without seeds) can improve the process yield and the ultrasound could effectively reduce the crystal size, narrow the MSZW, and shorten the induction time. Through comparing the drying dynamics of the FBMS, the small rod-shaped crystals with a mean size of 9.6 μm produced by ultrasonic irradiation can be completely desolvated within 20 h, while the desolvation time of long needle crystals with an average size of about 157 μm obtained by direct cooling/antisolvent crystallization and seeding crystallization processes is more than 80 h. Thus the crystal size and morphology were found to be the key factors affecting the desolvation kinetics and the smaller size produced by using ultrasound can benefit the intensification of the drying process. Overall, the ultrasound-assisted crystallization showed a full improvement including crystal properties and process efficiency during the preparation of fotagliptin benzoate desolvated crystals.     

用时域有限差分法研究二维光子晶体传输特性

将时域有限差分方法用于光子晶体传输特性理论研究，分别计算了二维方型光子晶体TM模和TE模的透射率频率分布；根据光子晶体的标度不变性特征，在微波频段制作了光子晶体，并设计了实验装置；实验结果与计算结果一致表明：对于一定的入射方向，某些频率的光不能在光子晶体中传播。     

Size-Frustrated Thickening Growth of Extended-Chain Crystals in a Poly (Ethylene Terephthalate)/Bisphenol A Polycarbonate Blend Under High Pressure

High-pressure crystallized blend samples of poly (ethylene terephthalate)/bisphenol A polycarbonate (PET/BAPC) were investigated with scanning electron microscopy (SEM), confocal laser micro-Raman spectroscopy, and a standard general area detector diffraction system (GADDS) X-ray micro-diffraction system. The results showed that long time annealing at high pressure could result in extended-chain polymer single crystals with thicker lamellae. However, the large size of such crystals was also found to frustrate their thickening growth along the c-axis thickness, as demonstrated by the observation of a novel wrinkled crystal. The winkled crystals with different morphologies were thought to be formed as the compromise between the kinetic pathway and the thermodynamic driving force during the size-frustrated thickening growth of the large polymer crystals. Further observations revealed that environmental confinement was the main factor responsible for the creation of the wrinkled structures in polymer extended-chain crystals. The present study may promote understanding of the fundamental nature of the crystal thickening in these binary polyester blends.     

Research of band gap properties based on two-dimensional photonic crystal with mixed shapes of rods

Two new structures of photonic crystals were designed. The band gap properties of photonic crystals with square and circular dielectric rods mixed arrangement are researched. The band gap properties of mixed shapes rods photonic crystal are calculated and compared with the crystals with square rods or round rods by using plane wave expansion method. Simulation results show that for the square lattice, mixed shapes of rods make the higher-order bands of TM modes moving toward the low frequency range. The gap bands’ widths and locations are between the parameters of square and round rods photonic crystal. In triangle lattice, a significant band gap is presented in photonic crystal with mixed shapes of rods in TE mode, while it is almost not presented in square and round rods crystals. The phenomenon of bands moving toward the low frequency range is also found in the triangle lattice mixed shapes rods photonic crystal. The reasons of the results in the vision were analyzed.