Transparent Nano Crystalline Glass-Ceramics by Interface Controlled Crystallization

A prerequisite for the preparation of nano glass-ceramics is an increase in viscosity of the residual glassy matrix phase during the course of the crystallization process. This results in a deceleration of the crystal growth process due to increasing stresses, which finally may lead to a total freezing of the crystallization process. In principle, two routes for the preparation of nano glass-ceramics exist: in one of these routes, the first step is a phase separation in which a droplet phase is formed. Inside this droplet phase, the crystals are precipitated. In the other route, a preceding phase separation does not occur and the nucleation takes place in a homogeneous glassy phase. In both cases, the crystal growth velocity is high until the crystals reach a size of some nanometers or some ten nanometers, then the crystal growth velocity decreases strongly.     

Die Kristallisation von Mehrkomponentensystemen aus hochpolymeren Stoffen

The differences in the crystallization behaviour between a single component system and a multicomponent system are discussed. Examples for multicomponent systems are homopolymers with a broad distribution in molecular weight, mixtures of different homopolymers, swollen polymers, block copolymers, and statistical copolymers. A distribution in molecular weights manifests itself mainly in extended chain crystallization experiments in that way that a fractionation with respect to the chain length takes place. It causes also a broadening of the melting range. The presence of a second noncrystallizable homopolymer which is miscible with the crystallizable homopolymer leads to a reduction of the melting point and a change in the glass transition temperature. The crystallization remains spherulitic. The noncrystallizable component is expelled from the crystals. If the diffusion rate of this component is large, it is also expelled from the spherulites, otherwise it is incorporated into the spherulites. When the noncrystallizable component is expelled from the spherulites, the growth rate of the spherulites decreases during growth. The temperature range in which crystallization takes place is limited by the melting point of the crystallizable component and by the glass transition temperature of the two-component system. If the crystallizable component is not dissolved completely in the noncrystallizable component, this part which is not dissolved crystallizes much more rapidly than the part which is dissolved. Below the glass transition temperature only the part which is not dissolved crystallizes. This gives a possibility to determine the solubility above the melting point. By swelling, the glass transition temperature and therewith the crystallization temperatures are decreased. When, during swelling of an amorphous sample, the glass transition temperature is decreased below the temperature where swelling is performed one observes a front of spherulites penetrating into the sample simultaneously with the swelling agent. On the other hand, when the glass transition temperature remains above the swelling temperature, one can crystallize the sample after swelling is completed by raising the temperature. As in a pure polymer, one then observes the growth of spherulites from statistically distributed centers; the growth rate of the spherulites increases however with increasing time. Block copolymers of a crystallizable component and a non-crystallizable component sometimes are not able to crystallize. This is the case, if the chains of the noncrystallizable component have a cross section which is larger than that of the chains of the crystallizable component and if, in addition, the latter chains are not so long that they can fold several times in order to compensate the difference in the cross sections. When crystallization takes place, spherulites are formed only if the amount of the crystallizable component exceeds a well defined limit. Otherwise only a diffuse birefringence is developed. In this case a much larger supercooling is necessary to crystallize the sample than in the case of spherulitic crystallization. From long period measurements one can conclude how many times each noncrystallizable chain is folded. From the melting and swelling behaviour one learns whether the noncrystallizable chains form loops or tie molecules. With statistical copolymers consisting of crystallizable units and noncrystallizable units the melting point, the rate of crystallization, the degree of crystallization at the end of the process, and the melting point decrease with increasing amount of noncrystallizable units. The noncrystallizable units are incorporated partly also into the crystals.     

Investigation of UV aging influences on the crystallization of ethylene-vinyl acetate copolymer via successive self-nucleation and annealing treatment

Influences of UV aging on the crystallization of ethylene-vinyl acetate copolymer (EVA) were researched via successive self-nucleation and annealing (SSA) treatment. During the aging process, the polar vinyl acetate (VAc) units in the amorphous region were the most vulnerable structure. FTIR results demonstrated that, VAc units were initially attacked by the UV radiation, which further resulted in chain scission of molecules. Degradation expanded from the amorphous region to the crystal region gradually. Chain scission reaction freed crystallizable ethylene sequences from inter-/intra-molecular tanglement and confinement of neighboring VAc units. Although the crystallinity decreased after aging, newly freed crystallizable sequences preferentially arranged into more densely packed lamellae, leaving less residual fraction to arrange into loosely packed crystal region. WAXD patterns showed that the predominant orthorhombic crystal phase did not vary during aging. Simultaneously, re-arrangement in crystallization also resulted in the growth in lateral crystal size of EVA.     

Diffusion mechanisms between La2SiO5 and SiO2 during formation of textured lanthanum silicate oxyapatite crystals

Lanthanum silicate oxyapatite (LSO) is a promising alternative electrolyte for solid oxide fuel cell (SOFC) applications. They exhibit anisotropic oxide-ionic conduction; therefore, a preferential crystal orientation along the c-axis is necessary to achieve optimal conductivity. This study is performed to understand the reaction mechanisms involved in the formation of an LSO layer at the interface of the La₂SiO₅/SiO₂ diffusion pair during reactive sintering at high temperatures. Different La₂SiO₅/SiO₂ bilayers were fabricated in sandwich-type structures using silica-type quartz or La₂SiO₅ supports obtained via electrophoresis and uniaxial pressing, respectively. These supports were pre-sintered and then coated with a suspension of the opposite component. The diffusion pairs were isothermally heated at 1500 °C at different holding times (10, 20, and 40 h) and at 1600 °C for 10 h. Their surfaces and cross-sections were investigated via X-ray diffraction, scanning electron microscopy (SEM) observations, energy-dispersive X-ray spectroscopy (EDS), and Raman spectroscopy.Experimental results show that two different driving forces were involved in the nucleation and growth of apatite crystals. The first is the chemical potential gradient in lanthanum between the components of the layers, and the second is the electric field created to preserve the electroneutrality of the system. The predominant diffusing species in this bilayer system were La^+III and O^-II, and their diffusion is enhanced by the formation of a glassy phase on the silica grains through the transformation of silica-type quartz into cristobalite. The formation of a La₂Si₂O₇ intermediate phase was detected, which is vital to the interdiffusion of species and the nucleation and growth of oriented apatite crystals. The porosity gradient observed in the cross-section after reactive diffusion suggests the possibility of achieving an SOFC half-cell device via this process.     

Piezoelectric glass-ceramics: Crystal chemistry,orientation mechanisms,and emerging applications

Piezoelectric materials have coupled mechanical and electrical energies and have long been used in devices for actuators, sensors, energy harvesters, frequency filters, and various additional applications. Piezoelectricity requires a non-centrosymmetric crystal structure and is therefore confined to materials that possess a periodic crystalline structure. Due to the non-crystalline nature of glass, piezoelectricity is fundamentally forbidden. However, one way to exploit piezoelectric properties in a glassy matrix is by developing glass-ceramics that possess controlled growth of a crystalline phase. Growth and orientation of piezoelectric crystals in a glassy matrix is a non-trivial process that has long been explored to combine the formability of glass with the thermal and mechanical resilience of glass-ceramics. While extensive work has been done in the field of functional glass-ceramics, the results are presented in isolated articles and a comprehensive review pertaining to symmetry breaking methods to exploit anisotropic properties in glass-ceramics has been absent from the literature. Here, we present a global review of the fundamental symmetry requirements for piezoelectricity, the development of polar, piezoelectric glass-ceramic compositions (specifically those with LiNbO₃ and fresnoite-based crystal phases), and various crystal growth and orientation mechanisms, including relevant kinetic and thermodynamic driving forces. Lastly, we discuss the challenges associated with implementing gradients to drive oriented crystal growth to develop non-centrosymmetry, and the need for future modeling work to produce adequate time-temperature-transformation (TTT) diagrams that take into account kinetic and thermodynamic driving forces for oriented crystal growth. Going beyond technical challenges, we conclude with an examination of current and potential applications for piezoelectric glass-ceramics that combine the formability of glass with the symmetry-dependent properties of ceramics.     

Secondary Grain Growth of Li2O-A12O3-SiO2-TiO2 Glass-Ceramics

The kinetics of secondary grain growth in a Ti0₂-nucleated β-spodumene solid-solution glass-ceramic was studied. The thermal stability of the grains was excellent. Grain growth followed the cube-root-of-time law. The activation energy of the grain boundary migration was 55 ± 10 kcal/mol. Grain growth inhibition due to Ti0₂ precipitates and the residual glassy phase was closely examined. The excellent thermal stability of the grains is due to grain growth inhibition by the residual glassy phase, not by rutile precipitates. It is suggested that the diffusion of A²⁺, and probably the simultaneous diffusion of Li⁺, through the residual glass is the rate-limiting process for the grain boundary migration.     

Kinetic Processes Involved in the Sintering and Crystallization of Glass Powders

Viscometry, crystal growth kinetics, and glass powder sintering were used to determine the activation energies of viscous flow, crystal growth, and sintering behavior of a standard NBS 710 glass and two crystallizable glass powders in the calciaaluminosilicate system. In a system which sintered successfully to zero porosity, the activation energy for sintering was comparable to the activation energy of viscous flow. When the apparent activation energy for the sintering process was lower than that of viscous flow, sintering was found to proceed at a slower rate because the precipitated crystalline phase retarded viscous flow and the shrinkage of the pores. Initial crystallization appeared to occur on the surfaces of coalesced particles. A chemical treatment was partially successful in suppressing the onset of surface nucleation of the precursor powder.     

Cold crystallization behavior of glassy poly(lactic acid) prepared by rapid compression

The cold crystallization behavior of glassy poly(lactic acid) was studied by comparison among samples obtained through three different treatments, which are naturally cooling (NC), liquid nitrogen quenching (NQ), and rapidly compressing (RC). The crystallization kinetics and structural changes of these glassy samples were analyzed by using in situ Fourier transform infrared (FTIR) and in situ wide angle X‐ray diffraction measurements. The results reveal that, the cold crystallization behavior is very similar between NC and NQ samples, but RC sample exhibits higher crystallization rate and lower crystallization temperature than them. FTIR investigation showed that, during the heating process for all the glassy samples, conformational adjustment in the amorphous phase occurs first, and followed by formation of the disordered crystals and then the disordered crystals further perfecting, while for RC sample the onset temperature of each step is much lower. Furthermore, for RC sample, the crystal grain number is larger and its initial α ′ form crystal induced by the heating is higher ordered than that of the others, and this unique crystallization behavior might be caused by the local ordered domains formed during the RC process. POLYM. ENG. SCI., 55:359–366, 2015. © 2014 Society of Plastics Engineers     

Crystallization of high purity ammonium meta-tungstate for production of ultrapure tungsten metal

The growth mechanism of Ammonium Meta-Tungstate (AMT) crystal was interpreted as two-step model. Growth rates of AMT crystals were measured in a fluidized bed crystallizer. The effects of temperature, supersaturation and crystal size on the crystal growth were investigated. The contribution of the diffusion step increased with the increase of temperature, crystal size and supersaturation. The nucleation kinetics from measurements on the width of the metastable region of Ammonium Meta-Tungstate (AMT) was also evaluated. The crystal size distribution from a programmed cooling crystallization system was predicted by the numerical simulation of a mathematical model using the kinetics of nucleation and crystal growth. It was also observed that the shape of AMT crystals was changed during the growth period. This paper was presented at The 5th International Symposium on Separation Technology-Korea and Japan held at Seoul between August 19 and 21, 1999.     

Rhodium (1) catalyst supported on polyethylene hollow fibers: Preparation and hydrogenation studies

In recent years polymers have been utilized as binding sites for transition metal catalysts (e.g. crosslinked polystyrene beads). However, general problems exist with the above system. The rate of reaction depends on the presence of solvents that adequately swell the polystyrene bead in order to allow access to the catalyst sites. Differences in polarity and reactant size can inhibit diffusion into the bead. Recently a new system has been developed where the catalyst is bound to polyethylene single crystal surfaces, this has solved the above problems. However, polyethylene single crystals are small and plate-like causing a new problem, when trying to filter the separate product the crystals cause clogging of the filtering system and limit the reactions to batch process. This paper describes the use of fine microporous polyethylene hollow fibers as the supporting polymer. This gives the advantages of the single crystal support, plus allows for the use of a fixed-bed flow reaction system.     

Self-induced field model for crystal twisting in spherulites

The observed twisting of crystals about the growth direction in spherulites is modeled as a response to fields generated during the crystal growth process. These fields can be compositional or mechanical. In either case, the high local field value in the melt near the interface acts to reduce the growth velocity. Twisting of the crystal about the growth direction places all portions of the growth surface in contact with melt of lower field value than would be the case for untwisted growth, thereby increasing the growth velocity. The effect of a compositional field is analyzed here, using an extension of the moving point source to compute the composition in the melt ahead of a twisting crystal. The retarding effect of the elastic twisting of the crystal is included in the analysis. Simulations using parameters for a crystallizable/uncrystallizable polyethylene blend are carried out for a crystal with thin, rectangular cross-section. The results are quantitatively and qualitatively consistent with observation. Comments on simplifications within and implications of the model are given.     

Creation of Periodical Antiparallel Domain Structure in Lithium Niobate Crystals During Growth Process

The advantages of producing a periodically poled lithium niobate (PPLN) structure during crystal growth process are the possibility of obtaining thicker and wider structures that leads to greater useful surfaces in addition to the elimination of the subsequent poling process. We report in this paper a new technology of creating bulk periodically poled LiNbO 3 single crystals with antiparallel ferroelectric domains, by direct electric field poling during growth processes. Growth system configuration, crystal composition and geometry selection are explored to allow successful control of the direction of spontaneous polarization using external electric field. PPLN crystal samples with periodicity 20-100μm were grown using this electric field modulated growth technique.     

Real time observation of crystallization in polyethylene oxide with video rate atomic force microscopy

Video rate atomic force microscopy (VideoAFM), with a frame rate of 14 frames/s and a tip velocity of up to 15 cms⁻¹, is used to image polyethylene oxide films during crystal growth. The capabilities of VideoAFM when applied to semicrystalline polymer surfaces are explored. Image quality comparable to that found with conventional contact AFM is achieved but with a nearly 1000 times improvement in time resolution. By applying the technique to the real-time observation of crystal growth, different modes of rapid crystallization are followed in real time. Observation of the spherulite growth front allows measurement of growth rates at the lamellar scale, from which a factor of two difference in the rate of radial growth to the rate of tangential growth is observed, confirming that the elongated nature of spherulite lamellae is due to geometric constraints rather than an inherent fibrillar character. Measurements on screw dislocation growth, when large amounts of crystallizable material is trapped at the surface show that the terrace height does not influence the rate of crystal growth, confirming that under these conditions processes at the lamellar growth front control the rate of growth. When only a thin film of molten material is left on the surface of the already crystallized film dendritic growth is observed, implying a diffusion controlled process under these far from equilibrium conditions.     

A mechanistic growth model for inorganic crystals: Growth mechanism

Inorganic crystals grown from solution find wide application. A mechanistic growth model based on the spiral growth mechanism that operates at low supersaturation on inorganic crystal surfaces is presented. The long‐range electrostatic interactions on inorganic crystal surfaces are captured by methods developed in our previous article (Dandekar and Doherty, AIChE J., in press). The interactions of kink site growth units with the solvent molecules partially determine the growth kinetics. Relevant experimental parameters are systematically accounted for in the expression for the kink incorporation rate along step edges on the crystal surfaces. The growth model accurately predicts the asymmetric growth spirals on the surface of calcite crystals. The effect of supersaturation and ionic activity ratio on the step velocities of the acute and obtuse spiral edges is also correctly captured. This model can be used to predict the shapes of solution grown inorganic crystals and to engineer the growth process to design inorganic solids with functionally desirable shapes. © 2014 American Institute of Chemical Engineers AIChE J, 60: 3720–3731, 2014     

Preparation and mechanical properties of machinable alumina/mica composites

Using a mica-crystallizing glass powder in which a large amount of mica crystal was precipitated and a larger amount of MgF₂ component was contained as the raw materials of mica, machinable alumina/mica composites were obtained at 1400 °C. In the firing process, magnesia component in the mica crystals reacted with alumina to form spinel at 1150–1200 °C. The reaction made the mica crystals melt. However, the mica crystals were precipitated again during the cooling. Because a larger amount of MgF₂ component was contained in the mica-crystallizing glass powder, the nucleation of the mica crystals was caused during the cooling by the residual magnesium and fluorine in the liquid phase and succeedingly the mica crystals were precipitated. The precipitated mica crystals grew to anisotropicaly larger size than alumina grains, which lowered the bending strength and Vickers hardness and little heightened the fracture toughness.     

Structure of Alumina Grain Boundaries Prepared with and without a Thin Amorphous Intergranular Film

The presence of a thin amorphous intergranular film along grain boundaries in alumina is expected to affect the properties of the interface and hence those of the material. In the present study, two types of grain boundaries have been formed in hot-pressed alumina bicrystals. In one case, the surfaces of the sintered crystals were kept as clean as possible, while in the other a thin layer of SiO₂ was intentionally deposited onto the surface of one crystal. The distribution of SiO₂ along the resulting grain boundary was then monitored by transmission electron microscopy and compared with the morphological features of the interface. In the special cases chosen here, the glass receded into large pores which grew into the alumina itself. However, the presence of the glassy phase during the early stages of sintering clearly did influence the characteristics of the resulting grain boundaries.     

Substrate crystal recovery for homoepitaxial diamond synthesis

Homoepitaxial chemical vapor deposition (CVD) of diamond requires high quality substrate crystals. This paper describes the process of diamond substrate crystal recovery so that the original substrate can be reused for multiple synthesis processes. A three-stage treatment is applied after homoepitaxial CVD growth. First the original substrate is separated by laser cutting, then the cut surface is mechanically polished, and finally polycrystalline material at the edges of the recovered seed plate is laser trimmed. This recovery process yields reusable diamond substrates that do not differ appreciably from their original state in terms of stresses and impurity concentrations. While the recovery process was demonstrated using HPHT seed substrates the process can also be applied to the as-grown CVD diamond plates. Infrared absorption spectral analysis, surface profilometry, birefringence imaging and Raman spectroscopy are performed after each processing step to monitor crystal quality. The nitrogen concentration in the substrate crystal remains constant throughout CVD and recovery processes. When using HPHT type Ib substrates the detected nitrogen concentration is 110–180 ppm. The nitrogen is mainly incorporated in form of C center defects and no transformation to other forms of defect centers occurs during the CVD process. Birefringence imaging showed a low level of internal stress within the HPHT crystals. No change is observed during CVD growth and recovery processes. It is shown that the polycrystalline rim removal is essential for repeatable CVD deposition on the same seed substrate. Substrate crystal recovery allows growth of up to 20 crystals from one original seed.     

Molecular Dynamics Computer Simulations of the Interface Structure of Calcium–Alumino–Silicate Intergranular Films between Combined Basal and Prism Planes of α-Al2O3

The interface structures of calcium–alumino–silicate (CAS) glassy intergranular films (IGFs) formed between the combined basal and prism orientations of α-Al₂O₃ crystals were studied using molecular dynamics simulations. Preferential adsorption of specific ions from the IGFs to the contacting surfaces of the alumina crystals was observed. This segregation of specific ions to the interface enables formation of localized, ordered structures between the IGF and the crystal. However, the segregation behavior of the ions is anisotropic, depending on the orientation of the α-Al₂O₃ crystals. The results show that the enrichment of Ca atoms at the basal interface inhibits growth in the 〈0001〉 direction. However, at the (11 2 0) prism plane, Ca ions have little effect on the epitaxial adsorption of Al and O ions from the IGF onto the (11 2 0) surface. Increasing alumina concentration in the glassy IGF enhances adsorption of Al ions onto the prism surface, with little effect on the basal surface, indicating the tendency of growth in the 〈11 2 0〉 direction on the prism plane, but limited growth on the basal plane. These results are consistent with the experimental data regarding anisotropic grain growth in alumina sintered in the presence of CAS IGFs.     

吸附相反应结晶过程的模型与数值模拟

针对吸附相反应技术制备CuO/SiO2的过程,构建了体系中反应物的扩散传递、反应、成核、生长等过程的模型,通过深入剖析过程的机理,对复杂的微分方程组进行解耦。在MATLAB平台上数值求解模型,得到了本体相、吸附相中各组分的浓度随时间的变化以及CuO粒子的生长过程,为深入了解过程的内在规律提供了依据。结果表明:吸附层中Cu(OH)2的浓度迅速上升然后趋于定值,而本体相中的Cu(OH)2浓度一直维持在很低的水平;结晶过程的成核时间短,且最后获得了粒径窄分布的小粒径粒子。     

Features of the phase transformations in titanium-containing zinc aluminosilicate glasses doped with cobalt oxide

We demonstrated the efficiency of the Raman spectroscopy method in the study of the process of the formation of the amorphous zinc aluminotitanate (ZAT) phase during the phase decomposition of the titanium-containing zinc aluminosilicate glasses doped with cobalt oxide. The quantitative dependences of the variation of the intensity of the Raman bands characteristic for amorphous and crystalline phases on the temperature of the thermal treatment and the cobalt oxide concentration have been obtained. The speed of phase decomposition with the separation of the nanosize crystals of zinc aluminate spinel (gahnite) and ZAT phase increases at low-temperature thermal treatments with increasing cobalt oxide concentration. The addition of cobalt oxide increases the amount of the amorphous ZAT phase separated during phase decomposition and increases its thermal stability during high-temperature treatments. It has been shown that the Co²⁺ ions enter the zinc aluminate spinel (gahnite) crystals precipitated during phase decomposition. It has been supposed that the composition of the residual glass is close to that of the quartz glass and it contains a very small amount of titanium-oxygen tetrahedra.