Crystallization-driven migration of the low surface energy segment of a copolymer to the bulk

[(BA-C8)₁₈-(6FBA)]_n was synthesized by condensation polymerization of poly(bisphenol A-co-octane) containing 18 repeat units with bromine end groups, (Br-(BA-C8)₁₈-Br), and 4,4′-(hexafluoroisopropylidene)diphenol (6FBA). This copolymer was confirmed to be semicrystalline after a single melting temperature was detected by differential scanning calorimetry. The changes in the surface chemical composition were measured using time-of-flight secondary ion mass spectrometry and X-ray photoelectron spectroscopy, the changes in the surface energy were measured using contact angle measurements, and the changes in the surface morphology were detected using atomic force microscopy as the copolymer crystallized. A decrease in the surface fluorine concentration with time was detected because of the movement of the low surface energy units (6FBA) to the bulk during the development of the crystalline phase. This result shows that the decrease in the enthalpy as a result of crystallization overcomes the increase in the surface free energy due to the migration of the low surface energy units to the bulk and the decrease in entropy due to demixing.     

Chemical characterization of melt-textured YBCO produced by hybrid powder metallurgy

Monolithic YBCO samples were made by traditional top-seeded melt-texturing processes from cold-milled mixtures of Y123 (YBa₂Cu₃O_7−δ) and elemental Y. The bulk composition does not lie on the Y211 (Y₂BaCuO₅)–Y123 join so, formation of Y123 from liquid and Y211 is not an essentially isothermal process on cooling. The reaction liquid + Y211 = Y123 is a ternary reaction and occurs over several tens of degrees. The Y123 thus produced has a range in compositions – particularly in Cu:(Y + Ba) – which may reflect crystallization over the thermal interval. The liquid migrates to an invariant point at which CuO also crystallizes with complete loss of liquid. The presence of trains of CuO grains in the YBCO indicates the locations of the last liquids to be preserved in the sample. These trains are dominantly in an annulus 1–3 mm from the edge of the 20-mm diameter sample. Mapping the compositional variation in Y123 may allow mapping the path of crystallization of these monolithic YBCO samples.     

A comparative study of the hydrothermal crystallization of HfO2 using DSC/TG and XRD analysis

Hydrothermal crystallization of HfO₂ from aqueous suspensions of hydrous hafnia at different pH values and temperatures were monitored using differential scanning calorimetry/thermogravimetric (DSC/TG) analyses and powder X-ray diffraction (XRD). Both techniques showed that the hydrothermal crystallization proceeded much more slowly in a neutral pH medium than in an acidic or alkaline medium. However, the rate of this process appeared to be much slower according to XRD. The results of XRD analysis indicated the presence of a certain incubation time, whereas DSC/TG analysis indicated an almost immediate start of the crystallization process. The reasons for the obtained differences were discussed. The results of phase analysis of the products of hydrothermal treatment showed that, regardless of pH, hydrous hafnia crystallized into m-HfO₂. Stabilization of a metastable cubic or tetragonal HfO₂ occurred upon adding a sufficient amount of stabilizing Na⁺ ions. It was concluded that hydrothermal crystallization of HfO₂ proceeds via a dissolution/precipitation mechanism in the whole pH range.     

Effect of Solvent Composition on Crystallization Process of Ascorbic Acid

The crystal growth kinetics of ascorbic acid in water and in the solvent systems water/ethanol, water/methanol, and water/propanol is determined by means of seeded isothermal batch crystallization experiments. The measurements are correlated by a power low equation of the form (G = k_g σⁿ). The composition of the solvent system is found to have a significant influence on the kinetic parameters of growth of ascorbic acid. An increase in growth rate in the presence of alcoholic solvents (20 wt %) is measured compared to experiments with pure water. The thermodynamic effect of the solvent on the growth kinetics is approached by the UNIFAC method. The kinetic effect of solvent composition is explained using the two‐step model. Both thermodynamic and kinetic analyses give the same result: The addition of alcoholic solvents (20 wt % ethanol, methanol, and propanol) to the ascorbic acid/water system slightly reduces the diffusion rate and significantly accelerates the surface integration process.     

Osmotic Pressure of 3He-4He Solutions at 25.3 Bar and Low Temperatures

The osmotic pressures of dilute ³He-⁴He solutions were determined at 25.3 bar from measurements of crystallization curves at temperatures from 5 mK to 60 mK, when the ³He component of the solution obeying the Fermi-Dirac statistics was deep in the degenerate state. We determine the shift of the crystallization pressure of the solution of interest relative to pure ⁴He when both these substances are present in the cell in two separate volumes at the same temperature. We used our novel ultra-sensitive capacitive gauge for measurements of small pressure differences between the two substances. We used a quartz resonator for determination of solution’s concentration in situ. The difference between the crystallization pressure of the saturated solution and pure ⁴He, both extrapolated to zero temperature, is (339±2) mbar.      

Particle design Part B: batch quasi-emulsion process and mechanism of grain formation of ketoprofen

This study deals with the spherical crystallization process by the quasi-emulsion mechanism, applied to a pharmaceutical. The objective is to produce spherical agglomerates made of a number of small crystals of the drug, having properties adequate for direct compression when manufacturing tablets. The aim of this work is to make the link between the process and these properties. The different steps occurring in the process are the formation of an emulsion whose droplets are made of the drug dissolved in a solvent, the creation of the supersaturation of the drug in the droplets by mass and heat transfer and the nucleation, growth and agglomeration of drug crystals inside the droplets. The process has been carried out in a batch laboratory scale device. The variation of the operating parameters on the one hand and of the relative proportions of the various components on the other have enabled us to determine the influence on the internal and external structures of the produced agglomerates which influence the ability to be compressed. The identification of the phenomena occurring has led to a proposed mechanism for the formation of the agglomerates.     

Separation of fatty acids by crystallization using two liquid phases

First, the phase diagrams for the water+ethanol+fatty acids system were described, and the separation method was considered. Second, the separation of lauric acid+myristic acid mixture in the ethanol aqueous solution including ethanol by liquid-liquid extraction and crystallization has been examined. The extraction of fatty acids from the organic phase to the aqueous solution has been done. Fatty acids in the aqueous solution were crystallized using the aqueous SLE surface. The solvent-free mole fraction of lauric acid in the aqueous solution was a little higher than that in the organic phase. Fine crystals made in the aqueous solution had better purity for lauric acid than the solvent-free mole fraction of lauric acid in the aqueous solution. The effects of the mole fraction of ethanol in the aqueous solution, the mole fraction of lauric acid in the organic solution, extraction temperature and crystallization temperature on the purity of the crystals were reported.     

Polarized optical microscopy study on the superstructures of oxyethylene/oxybutylene block copolymers

The superstructures of oxyethylene/oxybutylene block copolymers with different compositions and architectures (E_mB_n, B_nE_mB_n and E_mB_nE_m) were studied using polarized optical microscopy (POM). Several novel superstructures, such as fibril crystals and different frontiers of spherulites and crystallized regions, have been observed. It is found that the ability of forming spherulites is reduced with the decrease in the volume fraction of the crystallizable block. The unfavorable interaction between the blocks, which can be indicated by order-disorder transition temperature (T_ODT), also affects the formation of superstructure. The B_nE_mB_n triblock copolymers exhibit the strongest ability of organization into spherulites, whereas the E_mB_nE_m triblock copolymers show the weakest ability of organization into spherulites.     

Characterization of the dual crystal population in an isothermally crystallized homogeneous ethylene-1-octene copolymer

The melting of a homogeneous ethylene-1-octene copolymer after isothermal crystallization is discussed based on DSC and time-resolved SALS, SAXS and WAXD data. Two melting peaks appear in DSC suggesting the presence of two crystal fractions. All crystals grow in a lamellar habit and there is no evidence for fringed micellar or isolated block-like crystals. The high melting fraction crystallizes while segregating comonomer-rich parts into separate regions where in a later stage the low melting fraction crystallizes. The data support the view of lamellae that grow via the secondary nucleation of crystalline blocks from a preexisting layer-like mesomorphic phase with preservation of the mesomorphic layer thickness. The stability of these blocks increases due to sintering, forming lamellae that melt slightly above the crystallization temperature. The high melting fraction is generated from those lamellae that are able to reduce the crystalline-amorphous interfacial tension.     

PET/ZnO纳米复合材料的制备及结晶性能

通过纳米ZnO存在下的对苯二甲酸／乙二醇(TPA／EG)酯化和缩聚反应制备聚对苯二甲酸乙二醇酯(PET)／ZnO纳米复合材料，研究了纳米ZnO用量及其分散方式对PET粘均摩尔质量、纳米ZnO在复合物中的分散及聚乙二醇(PEG)结晶性能的影响。发现纳米ZnO及分散改性剂(PEG)的加入，对合成PET的粘均摩尔质量均有一定影响；纳米ZnO在EG中直接分散再缩聚形成的复合物中，纳米ZnO团聚严重、分散性差，PET的结晶度和结晶速率降低；在纳米ZnO分散过程中加入PEG可以降低纳米ZnO在复合物中的团聚，提高分散性，PET的结晶度和结晶速率提高。