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.     

CuO/ZnO甲醇合成催化剂的正电子湮没谱学研究

发展了用正电子湮没寿命参数测定用共沉淀方法制备的金属氧化物系固溶度的新方法。测量了一系列用共沉淀方法制备的不同CuO at％含量的CuO/ZnO甲醇合成催化剂粉末(压制成片)还原前后的正电子寿命谱。分析该种催化剂的固溶特性及其与正电子寿命参数的关系,得出还原后样品的固溶度为12CuOat％.支持了CuO/ZnO甲醇合成催化剂以Cu~+离子为活性中心的观点。     

Effect of Organic Additives on Electrochemical Surface Precipitation and Polymorphism of CaCO3

The inhibition effect of three organic additives on the precipitation and polymorphism of CaCO₃ deposited on gold surfaces was investigated using electrochemical and microscopic techniques. Additives, two polyacrylic acid (PAA) polymers with different molecular weights (Mw 2100, Mw 30,000), and 1,2,4,5‐benzenetetracarboxylic acid (BTCA), were either added to the solution before or during deposition. In the presence of 100 ppm of one of the three additives in solution, almost no scale was observed on the surface for at least 24 hours. In the presence of lower concentrations of PAA Mw 2100, only distorted calcite crystals were obtained while with PAA Mw 30,000 the polymorph was spherical vaterite. A mixture of calcite and vaterite was observed with the BTCA additive. Addition of the polymers inhibits further nucleation and growth even if added after partial deposition of CaCO₃ while BTCA has no effect once nucleation has started. The results indicate that the inhibit ion effect of the PAA polymers is due to adsorption on the electrode surface while the effect of BTCA is related to chelation of calcium ions in solution.     

含钇奥氏体基堆焊焊条堆焊层研究

针对高温、磨损、热疲劳工况下服役零件的失效，研制了一种含稀土元素钇的奥氏体基沉淀强化型堆焊焊条，并对堆焊层组织与性能进行了较系统的研究。     

Microstructural Effects of Ion Implantation on Molybdenum

The effects of ion implantation and subsequent annealing on the microstructure of molybdenum have been investigated by transmission electron microscopy. The ions investigated were carbon, nitrogen, and tellurium. The ion-induced damage was found to give rise to grain boundary migration phenomena both during implantation and during subsequent annealing. Precipitation or ordering was found to occur for each ion on annealing.     

Modelling diffusion-controlled kinetics in equilibrium and driven alloys

Summary We introduce a very simple model for thermally activated atomic migration on a lattice, and several techniques to handle it. For thermodynamical systems, the model can be used for simulating decomposition paths taking into account relevant metallurgical features. Close to equilibrium, the simplest mean-field approximation of the model can be linearized with respect to the departure from equilibrium; one then gets a microscopic interpretation of classical phenomenological coefficients, such as mobility, interfacial transfer coefficient, rate constants for the coupled relaxation of concentration and order fields. Further away from the equilibrium, the nonlinearities can be taken into account in a consistent way. For driven alloys, i.e. alloys submitted to external forcing, forced atomic migration is added to the model and new features emerge: the model is supported by several experimental results some of which confirmed its predictions a posteriori.     

Efficient solution of population balance equations with discontinuities by finite elements

Two refinements of Galerkin's method on finite elements were evaluated for the solution of population balance equations for precipitation systems. The traditional drawbacks of this approach have been the time required for computation of the two-dimensional integrals arising from the aggregation integrals and the difficulty in handling discontinuities that often arise in simulations of seeded reactors. The careful arrangement of invariant integrals for separable aggregation models allows for a thousandfold reduction in the computational costs. Discontinuities that may be present due to the hyperbolic nature of the system may be specifically tracked by the method of characteristics. These discontinuities will arise only from the initial distribution or nucleation and are readily identified. A combination of these techniques can be used that is intermediate in computational cost while still allowing discontinuous number densities. In a case study of calcium carbonate precipitation, it is found that the accuracy improvement gained by tracking the slope discontinuity may not be significant and that the computation speed may be sufficient for dynamic online optimization.     

Intra-seasonal NDVI change projections in semi-arid Africa

Early warning systems (EWS) tend to focus on the identification of slow onset disasters such famine and epidemic disease. Since hazardous environmental conditions often precede disastrous outcomes by many months, effective monitoring via satellite and in situ observations can successfully guide mitigation activities. Accurate short term forecasts of NDVI could increase lead times, making early warning earlier. This paper presents a simple empirical model for making 1 to 4 month NDVI projections. These statistical projections are based on parameterized satellite rainfall estimates (RFE) and relative humidity demand (RHD). A quasi-global, 1 month ahead, 1° study demonstrates reasonable accuracies in many semi-arid regions. In Africa, a 0.1° cross-validated skill assessment quantifies the technique's applicability at 1 to 4 month forecast intervals. These results suggest that useful projections can be made over many semi-arid, food insecure regions of Africa, with plausible extensions to drought prone areas of Asia, Australia and South America.     

Comparative Coreflood Studies for Precipitation and Adsorption Squeeze with PPCA as the Scales Inhibitor

Comparative adsorption and precipitation squeezes carried out on field core materials demonstrate that significant lifetime enhancement is achievable for precipitation squeeze with respect to more conventional adsorption squeeze. Coreflood tests have been carried out under reservoir conditions (135°C) employing a poly-phosphinocarboxylate (PPCA) as the scales inhibitor. Field treatment simulations, carried out starting from coreflood data and considering the characteristics of a North Sea formation taken as the reference, confirmed the higher performance, in term of squeeze lifetime, of the precipitation squeeze with respect to adsorption. The results pointed out the importance of choosing the appropriate formulation once the operative conditions are known, in order to promote the inhibitor precipitation into the formation. Some implications of these results for the optimization of the precipitation squeeze technology for field applications, with particular emphasis to formation damage, are also discussed.     

Avrami exponent and isothermal crystallization of Zr/Ti-based bulk metallic glasses

The isothermal crystallization kinetics of Zr/Ti-based bulk metallic glasses (BMGs) have been investigated by using Avrami exponent. It is a constant nucleation rate and a constant number of quenched-in nuclei that cause the linear John–Mehl–Avrami (JMA) modes in Avrami exponents of Zr₆₂Al₈Ni₁₃Cu₁₇ and Zr₆₅Al₈Ni₁₀Cu₁₇ BMGs, respectively. However, sub-T_g pre-annealing of Zr₆₂Al₈Ni₁₃Cu₁₇, and multiple-step phase transition in Ti₄₃Cu₄₃Zr₇Ni₇ and Ti₄₅Zr₅Cu₄₀Ni_7.5Sn_2.5 make their Avrami exponents deviate from the linear JMA mode. The difference in Avrami exponents maybe provides useful information for performing the microstructure control of BMG composites upon isothermal annealing.