Evolution and structure of drying material bridges of pharmaceutical excipients: studies on a microscope slide

An experimental procedure was developed to study directly the process by which liquid bridges between small particles in a granule form and solidify. The evolution of saturated solutions of such pharmaceutical excipients as lactose and mannitol in a liquid bridge was studied on a system situated on a microscope slide. Solidification and crystallization kinetics and phase composition during and immediately following bridge formation were observed directly. It was shown that bridges on the microscope slide and in the granule behave very much the same regardless of the different length and diffusion-scales of the two systems.We found that solid bridge formation takes place in several consecutive but distinct steps. In the case of lactose, considerable shrinkage of the initial liquid bridge takes place prior to the onset of crystallization. Further bridge solidification at ambient conditions occurs via simultaneous crystallization and vitrification within minutes. As a result, a “solid” bridge usually contains both a crystalline and a non-crystalline phase, the crystalline phase being predominately α-lactose monohydrate. Most of the non-crystalline phase eventually converts to crystalline β-lactose but the process may take many hours or even days. Results for this process are compared for samples obtained from different manufacturers of commercially available lactose. In the case of mannitol, different polymorphic forms crystallize as the drying/crystallization process progresses. A formed “solid” bridge usually contains several polymorphs of mannitol. The relevance of the behavior of the two model systems (pure lactose and pure mannitol) to a real granulation and tabletting process is discussed.     

Electrical and optical properties of semi-insulating polycrystalline silicon thin films: the role of microstructure and doping

We have investigated the relationship between microstructure and electrical conductivity in semi-insulating polycrystalline silicon (SIPOS) with oxygen concentrations in the 2–35 at.% range and the effect of doping with boron, phosphorus, arsenic and erbium by ion implantation. SIPOS thin films are mixtures of silicon and silicon oxide phases. The chemical and morphological evolution of these phases upon annealing is emphasized. Electrical conductivity measurements are interpreted in terms of a physical model containing few free parameters related to the material microstructure. A direct extension of this model explains also the conductivity increase in SIPOS doped with elements of the third or the fifth group. In the last part of the paper, data of electroluminescence at 1.54 μm in Er-implanted SIPOS due to intra-4f transitions of the Er³⁺ ion are shown and discussed.     

Distribution of properties from sampling inhomogeneous materials by line transects

A theory related to the statistics of the structure and properties of inhomogeneous materials has been proposed, dealing with the distribution of properties from sampling of inhomogeneous structures by line transects. It is demonstrated that the empirical cumulative distribution functions of the intercepts from the microstructural constituents and their variances are important fingerprints of the inhomogeneous structures.Simulated sampling of the images of the microstructure by line transects has been proposed as a powerful method for characterization the distribution of properties of inhomogeneous structures. One of the advantages of the method based on the expected values of the order statistics of the intercepts is that the probability bounds of the property are determined without prior knowledge of the functional relationship between the property and the intercepts from the structural constituents.The concept intercept variance has an important application in determining the minimum transect length that stabilizes the variation of the intercept at a low value. Additionally, the concept ‘intercept variance’ can be used for topological optimization of the microstructure regarding the risk of intercepting a large amount of the weaker constituent. Equations regarding the variance of the intercepted fraction characterizing transect lengths with a specified distribution have also been derived.     

Studies on the microstructure of the black-glazed bowl sherds excavated from the Jian kiln site of ancient China

The Jian kiln, located in present-day Jianyang county of Fujian province, mainly produced black-glazed tea bowls. Jian tea bowl was used as a utensil for tea tasting and was greatly appreciated by emperor Huizong of the Northern Song dynasty. The black glaze of Jian bowl was sometimes marked with streaks or spots, usually called “hare's fur” or “oil spot”, which are the crystalline markings of iron oxide precipitated during firing in the dragon kiln. In this study, black-glazed Jian bowl sherds excavated from the late Northern Song strata of Luhuaping and Daluhoumen Jian kiln sites were adopted as test samples. Based on the physico-chemical foundation for the formation of glaze microstructure, the correlation among composition, microstructure, and visual appearance has been investigated by means of energy-dispersive X-ray fluorescence, X-ray diffraction, and field emission electron microscopy. For the first time, the study provides realizing proofs for two kinds of microstructural forming mechanics.     

Synthesis and characterization of functional gradient copolymers of glycidyl methacrylate and butyl acrylate

Epoxy-functional spontaneous gradient copolymers of glycidyl methacrylate (G) and n-butyl acrylate (B) were synthesized via atom transfer radical polymerization (ATRP). The copolymerization reactions were carried out in toluene solution at 70 °C, using methyl 2-bromopropionate (MBrP) as initiator and copper chloride with N,N,N′,N′′,N′′-pentamethyldiethylenetriamine (PMDETA) as the catalyst system. The kinetic behaviour of the statistical copolymerizations was studied in a wide composition interval with molar fractions of G ranging from 0.10 to 0.75. The synthesized copolymers were characterized by size exclusion chromatography (SEC) and nuclear magnetic resonance (NMR) spectroscopy. ¹H NMR was employed to determine the copolymer composition, demonstrating the gradient character of the copolymers along the main chain in the whole monomer conversion interval. Apart from this, the sequence distribution and stereoregularity were analyzed. These microstructural experimental data agreed well with those calculated from Mayo-Lewis terminal model (MLTM) and a Bernoullian statistic with an isotacticity parameter of σ_G = 0.28 and a coisotacticity parameter of σ = 0.30.     

Micromechanical approach to damage mechanics of composite materials with fabric tensors

The purpose of this study is to apply continuum damage mechanics – introduced through the concept of fabric tensors – to composite materials within the framework of the theory of elasticity. A directional data model of damage mechanics for composite materials will be developed using fabric tensors. The introduction of fabric tensors into the analysis of damage of composite materials will allow for an enhanced and better understood physical meaning of damage. The micromechanical approach will be used here to relate the damage effect through fabric tensors to the behavior of composite materials. In this approach, damage mechanics is introduced separately to the constituents of the composite material through different constituents’ damage effect tensors. The damaged properties of the composite system as a whole can then be obtained by proper homogenization of the damaged properties of the constituents.

The derivation of a generalized formulation of damage evolution will be shown here in a mathematically consistent manner that is based on sound thermodynamic principles. Numerical examples will be presented to show applicability. In addition, damage evolution for the one-dimensional tension case is also illustrated.     

Highly ordered microstructures of poly(styrene-b-isoprene) block copolymers induced by solution meniscus

Microstructures of hundreds of micron thick poly(styrene-block-isoprene) copolymer films solution-cast in a cylindrical tube with the solvent evaporation controlled were investigated by transmission electron microscope (TEM), small angle X-ray scattering (SAXS) and optical microscope (OM). In a block copolymer with cylindrical polyisoprene microdomains, the orientation of the cylinders was varied along radial direction of the cylindrical tube. Highly aligned hexagonal arrays of in-plane polyisoprene cylinders were formed with their cylindrical axis parallel to the circumference of the tube in the regimes close to the wall edge. In contrast randomly ordered microdomains were observed at the center of the tube. We have also found that the orientation depends on the solvent evaporation rate and an intermediate rate (∼2.3 nL/s) provides the best orientation. In the case of a block copolymer with a bicontinuous double gyroid structure, we obtained a globally ordered microstructure where [111] crystallographic direction was parallel to the circumference of the tube. For both block copolymers, the area of highly ordered arrays of nanoscopic domains is over 1 mm². Development of the orientation was explained by coupling two orthogonal fields: (1) The flow of a solution induced by strong capillary force at a meniscus between the cylindrical tube wall and the block copolymer solution and (2) the solvent evaporation.     

Effect of type of processing on the microstructural features and mechanical properties of Al-Cu/SiC metal matrix composites

In this study, an aluminum based metallic matrix (Al-2wt.% Cu) was reinforced with SiC particulates using a conventional casting technique and a new disintegrated melt deposition technique. Microstructural characterization studies conducted on the samples taken from disintegrated melt deposition technique revealed a more uniform distribution of SiC particulates and good interfacial integrity between SiC particulates and metallic matrix when compared to the conventionally cast composite samples. Results of ambient temperature mechanical tests demonstrate an increase in 0.2% YS and ultimate tensile strength of samples taken from disintegrated melt deposition technique when compared with the unreinforced and conventionally cast composite samples. The results of microstructural characterization and mechanical testing were finally rationalized in terms of the nature of processing technique employed to reinforce Al-2wt.% Cu metallic matrix with SiC particulates.     

溅射——气体——聚集共沉积法制备金属／金属（介质）复合团簇镶嵌薄膜

提出了溅射－气体－聚集共沉积制备金属／金属（介质）复合团簇镶嵌薄膜的新方法，并利用该方法成功地在方华膜衬底上制备了系列Ｆｅ／Ａｇ及ＣａＦ２复合团簇镶嵌薄膜样品。透射电镜分析结果表明，样品中Ｆｅ（Ｃｕ）团簇都较好地镶嵌于Ａｇ（ＣａＦ２）基质中，其结构为两种材料的多晶共存形态。进一步分析发现，与块材相比，Ｆｅ／Ａｇ样品中Ｆｅ团簇晶格常数呈现出不同程度的收缩，而Ｃｕ／ＣａＦ２样品中Ｃｕ团簇晶格常数则呈现出不同程度的膨胀。运用附加压力的模型对该现象进行了解释。     

Structure and dynamics of dipolar fluids under strong shear

Molecular dynamical simulation has been carried out to investigate the structure and dynamics of a dipolar fluid under strong shear. Dipolar fluid consists of polarizable particles, which have an induced dipole moment in the applied field direction. Shear stress is perpendicular to the field direction. When shear stress is small, the flow has a flowing-chain structure. If shear stress increases to pass a critical value, flowing-chain structure changes to flowing layer structure. Each layer is parallel to the flow direction and shear direction. Within one layer, particles form strings in the flow direction.