Thermodynamic Interactions of Si and Ti in Liquid Cu

The activity coefficients of titanium in liquid Cu-Ti at 1623 and 1673 K were measured by equilibrating the liquids with Ti₃O₅ in a oxygen partial pressure controlled by C(s)/CO(g) equilibrium. Furthermore, the thermodynamic interaction parameter of silicon on titanium and the self-interaction parameter of titanium in liquid Cu-Ti-Si at 1773 K were determined by equilibrating the 58 mass% TiO₂-42 mass% CaF₂ slag with Cu-Si-Ti liquids. And the interaction parameters e_\textTi^\textTi e_{\text{Ti}}^{\text{Ti}} and e_\textTi^\textSi e_{\text{Ti}}^{\text{Si}} obtained using a multiple regression were as large as −69.32 and 15.44 respectively. Based on the above determined value of e_\textTi^\textTi e_{\text{Ti}}^{\text{Ti}} , the relationship between Henrian constant of titanium in liquid Cu-Ti melt, \upgamma_{\textTi(\texts)}⁰ \upgamma_{{{\text{Ti}}({\text{s}})}}^{0} , from 1473 to 1923 K was evaluated, and is expressed as:

High yield synthesis of diverse well‐defined end‐functionalized polymers by combination of anionic polymerization and “click” chemistry

Well‐defined poly(methyl methacrylate) (M_n = 3630 g mol^?1, PDI = 1.06) with a primary benzylic bromide prepared using anionic polymerization was successfully transformed into diverse end‐functionalities (ω‐carboxyl, ω‐hydroxy, ω‐methyl‐vinyl, ω‐trimethylsilane, and ω‐glycidyl‐ether) via “click” reaction. The bromine end‐terminated poly(methyl methacrylate) was first substituted by an azide function and sequentially was reacted with various functional alkynes (propiolic acid, propargyl alcohol, 2‐methyl‐1‐buten‐3‐yne, propargyl trimethylsilane, and propargyl glycidylether). In all the cases, ¹H‐NMR, ¹³C NMR, FT‐IR, and GPC measurements show qualitative and quantitative transformation of the chain‐end poly(methyl methacrylate) into the desired functionalities with high conversion (above 99%). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

The structure‐property relationship of novolac cured epoxy resin/clay nanocomposites

Intercalated or exfoliated novolac cured epoxy resin nanocomposites were prepared with two different kinds of layered silicates – montmorillonite (PK‐802) and nontronite (PK‐805). The bifunctional modifiers (PI/BEN or MI/BEN) are used to modify the clays for improvement of the properties of polymer where benzalkonium chloride (BEN) acts as a compatibilizing agent and 2‐phenylimidazole (PI) or 2‐methylimidazole (MI) as the accelerators. Both the compatibilizer and accelerator are simultaneously intercalated into the gallery space of pure clays to form the modified clay. The novolac cured epoxy nanocomposites are prepared with these modified clays by crosslinking polymerization reaction. The properties of novolac cured epoxy/clay nanocomposites were characterized by wide‐angle X‐ray diffraction (WAXD), thermo‐gravimetric analysis (TGA), dynamic mechanical analysis (DMA), and transmission electron microscopy (TEM) methods. According to the measurement, these novolac cured epoxy‐clay nanocomposites have been shown the significant improvement in the thermal, mechanical, and barrier properties that may be applied to make printed circuit board. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Preparation of a nanosilica‐modified negative‐type acrylate photoresist

A new type of negative photoresist, which incorporated nanosized silica into a photosensitive acrylic resin, was developed. First, free‐radical polymerization was employed to synthesize the acrylic resin, poly[methyl methacrylate/methacrylic acid/3‐(trimethoxysilyl) propyl methacrylate], and then a silica precursor, prepared by hydrolysis and condensation of tetraethoxysilane in a sol–gel process, was introduced into the as‐formed resin solution. After the addition of photosensitive monomers and photoinitiators, a negative‐type organic–inorganic photoresist was produced. The morphology of the UV‐cured photoresist, as observed by field emission scanning electron microscopy, indicated that the size of the silica domain in the material could be reduced from 300 to about 50 nm by appropriate dosage of 3‐(trimethoxysilyl) propyl methacrylate. Thermogravimetric analysis, dynamic mechanical analysis, differential scanning calorimetry, and thermal mechanical analysis were used to evaluate the thermal and dimensional stabilities of the cured photoresists. It was found that the thermal decomposition temperature and glass‐transition temperature increased, whereas the thermal expansion coefficients before and after the glass transition decreased, with increasing silica content. The incorporation of 3‐(trimethoxysilyl) propyl methacrylate also enhanced the thermal and dimensional stabilities; however, the level of enhancement was moderate for the thermal decomposition temperature and thermal expansion coefficient and low for the glass‐transition temperature. In addition, a photoresist coated on a copper substrate demonstrated high hardness (5H) and strong adhesion (100%) with a resolution of 30 μm. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Chitosan–Polyelectrolyte complexation for the preparation of gel beads and controlled release of anticancer drug. I. Effect of phosphorous polyelectrolyte complex and enzymatic hydrolysis of polymer

Enzymic hydrolyzed chitosan was employed to prepare chitosan–tripolyphosphate and chitosan–polyphosphoric acid gel beads using a polyelectrolyte complexation method for the sustained‐release of anticancer agent, 6‐mercaptopurine (6‐MP). pH responsive swelling ability, drug‐release characteristics, and morphology of the chitosan gel bead depends on polyelectrolyte complexation mechanism and molecular weight of the enzymic hydrolyzed chitosan. The complexation mechanism of chitosan beads gelled in pentasodium tripolyphosphate or polyphosphoric acid solution was ionotropic crosslinking or interpolymer complex, respectively. The drug‐release patterns of all chitosan gel beads in pH 6.8 seemed to be diffusional based, which might be in accordance with the Higuchi model, whereas release profiles of the chitosan–tripolyphosphate gel beads in pH 1.2 medium seemed to be non‐Fickian diffusion controlled due to the swelling or matrix erosion of the beads. The rate of 6‐MP releasing from chitosan–tripolyphosphate or chitosan–polyphosphoric acid gel matrix were significantly increased with the decreased molecular weight of enzymic hydrolyzed chitosan. However, the dissolution rates of 6‐MP entraped in chitosan–tripolyphosphate and chitosan–polyphosphoric acid gel matrix were significantly slower than the dissolution rate of the original drug. These results indicate that the chitosan–polyphosphoric acid gel bead is a better polymer carrier for the sustained release of anticancer drugs in simulated intestinal and gastric juice medium than the chitosan–tripolyphosphate gel beads. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1868–1879, 1999     

Performance characteristic of isothermal chemical engines

Chemical engines process mass flow to convert the differences in chemical potentials into work. An isothermal endoreversible chemical engine, in which the sole irreversibility is finite-rate mass transfer, is modeled in this paper. The power versus efficiency relationships of the chemical engine, using the analogous method of finite-time thermodynamics for a heat engine, are derived. The performance comparison between a heat engine and a chemical heat engine is presented.     

Effect of the heat transfer law on the finite-time, exergoeconomic performance of heat engines

The efficiency bounds at maximum profit are obtained from finite-time exergoeconomic analysis for three common heat transfer laws: Newton's law (n = 1), a linear pheomenological law in irreversible thermodynamics (n = 1), and the radiative heat law (n = 4). The relation between optimal profit and efficiency of an endoreversible Carnot engine is derived on the basis of the general heat-transfer law q∝Δ(Tⁿ).     

Finite-time power limit for solar-radiant Ericsson engines in space applications

The power output and thermal efficiency of a finite-time optimized solar-radiant Ericsson heat engine is studied. The thermodynamic model adopted is a regenerative gas Ericsson cycle coupled to a heat source and heat sink by radiant heat transfer. Both the heat source and heat sink have infinite heat capacity rates. Mathematical expressions for optimum power and the efficiency at optimum power are obtained for the cycle based on higher and lower temperature bounds. The results of this theoretical work provide a base line criteria for use in the performance evaluation and design of such engines as well as for use in performance comparisons with existing extra-terrestrial solar power plants.     

Performance optimization of an irreversible four-heat-reservoir absorption refrigerator

On the basis of an endoreversible absorption refrigeration cycle model with linear phenomenological heat transfer law of Q∝Δ(T⁻¹), an irreversible four-heat-reservoir cycle model is built by taking account of the heat resistance, heat leak and irreversibilities due to the internal dissipation of the working fluid. The fundamental optimal relation between the coefficient of performance (COP) and the cooling load, the maximum COP and the corresponding cooling load, as well as the maximum cooling load and the corresponding COP of the cycle coupled to constant-temperature heat reservoirs are derived by using finite-time thermodynamics. The optimal distribution relation of the heat-transfer surface areas is also obtained. Moreover, the effects of the cycle parameters on the COP and the cooling load of the cycle are studied by detailed numerical examples. The results obtained herein are of importance to the optimal design and performance improvement of real absorption refrigerators.