Measurement and prediction of solubilities and diffusion coefficients of carbon dioxide in starch–water mixtures at elevated pressures

The solubility and diffusion coefficient of carbon dioxide in intermediate‐moisture starch–water mixtures were determined both experimentally and theoretically at elevated pressures up to 16 MPa at 50 °C. A high‐pressure decay sorption system was assembled to measure the equilibrium CO₂ mass uptake by the starch–water system. The experimentally measured solubilities accounted for the estimated swollen volume by Sanchez–Lacombe equation of state (S‐L EOS) were found to increase almost linearly with pressure, yielding 4.0 g CO₂/g starch–water system at 16 MPa. Moreover, CO₂ solubilities above 5 MPa displayed a solubility increase, which was not contributed by the water fraction in the starch–water mixture. The solubilities, however, showed no dependence on the degree of gelatinization (DG) of starch. The diffusion coefficient of CO₂ was found to increase with concentration of dissolved CO₂, which is pressure‐dependent, and decrease with increasing DG in the range of 50–100%. A free‐volume‐based diffusion model proposed by Areerat was employed to predict the CO₂ diffusivity in terms of pressure, temperature, and the concentration of dissolved CO₂. S‐L EOS was once more used to determine the specific free volume of the mixture system. The predicted diffusion coefficients showed to correlate well with the measured values for all starch–water mixtures. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 607–621, 2006     

Dependence of calculated electron effective attenuation lengths on transport mean free paths obtained from two atomic potentials

We report changes in electron effective attenuation lengths (EALs) resulting from use of transport mean free paths (TMFPs) obtained from the Dirac–Hartree–Fock (DHF) potential instead of the Thomas–Fermi–Dirac (TFD) potential in an algorithm used in the National Institute of Standards and Technology (NIST) Electron Effective‐Attenuation‐Length Database (SRD 82). TMFPs from the former potential are believed to be more reliable than those obtained from the latter potential. We investigated changes in the EALs for selected photoelectron and Auger‐electron lines in four elemental solids (Si, Cu, Ag, and W), for Si 2p photoelectrons of varying energy in SiO₂, and for photoelectrons excited by Al Kα X rays in four candidate gate‐dielectric materials (HfO₂, ZrO₂, HfSiO₄, and ZrSiO₄). For each material, we computed the change in the average EAL for a range of overlayer‐film thicknesses from zero to a maximum value corresponding to attenuation of the substrate signal to 10% of its original value. This EAL change was a maximum for electrons emitted normally from the surface and decreased monotonically with increasing emission angle. The maximum EAL change varied between ?4.4% and 2.6% for the three groups of materials. We found that the maximum EAL change correlated mainly with the TMFP change. We found that TMFP changes in other solids could generally lead to maximum EAL changes between ?2.6% and 1.9% for electron energies between 500 and 2000 eV. For lower energies, the maximum EAL changes could be larger for some solids. Our revised EALs for Si 2p photoelectrons in SiO₂ excited by Mg and Al Kα X rays agree within 0.5% with values reported by Seah and Spencer from a detailed analysis of SiO₂ film‐thickness measurements by XPS and other techniques. Copyright © 2006 John Wiley & Sons, Ltd.     

绕圆柱体自由表面磁流体流动和传热的研究

本文对在不同雷诺数下,绕圆柱体的磁流体自由表面流动及传热进行了模拟,分析了磁场对绕流圆柱尾迹和涡分离的影响,获得了两种雷诺数下的电磁力密度、流场和温度场分布。结果表明,磁场不仅影响了流动的形态,而且对湍流有抑制作用,降低了自由表面的更新机制,从而减少了传热能力;在相同的Hartmann数下,相比低雷诺数下的流动换热情况,高雷诺数下的湍流不能被完全抑制,自由表面与尾迹的相互作用也较强,因而自由表面换热也较强。     

Gamma radiation effects on an amine antioxidant added in an ethylene-propylene copolymer

The aim of this work was to compare the gamma radiation induced effects on samples of an ethylene-propylene copolymer antioxidant free with samples loaded with an antioxidant characterised by the presence of an -NH functional group. The employed techniques were Electron Spin Resonance spectroscopy (ESR) and High Performance Liquid Chromatography (HPLC). Stable radicals R---NO° due to the interaction of free radicals produced in the irradiated polymer with the antioxidant have been observed by ESR at room temperature. The time evolution of the ESR signals following the irradiation was examined at different doses. The amount of antioxidant not involved in the oxidation reactions has been determined using HPLC.     

The stress driven instability in elastic crystals: Mathematical models and physical manifestations

Summary Equilibrium equations and stability conditions for the simple deformable elastic body are derived by means of considering a minimum of the static energy principle. The energy is supposed to be sum of the volume (elastic) and the surface terms. The ability to change relative positions of different material particles is taken into account, and appropriate natural definitions of the first and second variations of the energy are introduced and calculated explicitly. Considering the case of negligible magnitude of the surface tension, we establish that an equilibrium state of a nonhydrostatically stressed simple elastic body (of any physically reasonable elastic energy potential and of any symmetry) possessing any small smooth part of free surface is always unstable with respect to relative transfer of the material particles along the surface. Surface tension suppresses the mentioned instability with respect to sufficiently short disturbances of the boundary surface and thus can probably provide local smoothness of the equilibrium shape of the crystal. We derive explicit formulas for critical wavelength for the simplest models of the internal and surface energies and for the simplest equilibrium configurations. We also formulate the simplest problem of mathematical physics, revealing peculiarities and difficulties of the problem of equilibrium shape of elastic crystals, and discuss possible manifestations of the above-mentioned instability in the problems of crystal growth, materials science, fracture, physical chemistry, and low-temperature physics.     

电位滴定法测定模拟高放废液中的游离酸

本文研究了用电位滴定法测定模拟高放废液中游离酸的方法。用草酸钾做络合剂以消除Ｆｅ＾３＋、Ａｌ＾３＋、Ｎｄ＾３＋等多种水解离子的影响，用标准碱直接进行电位滴定，即可快速准确地测定模拟高放废液中游离酸的含量。方法的相对标准偏差为１．８％，标准加入回收率为１００－１０１％，能为放射性废物固化试验提供可靠的分析数据。     

氮杂冠醚与碱金属离子配位反应的研究

滴定量效法是研究反应热化学和热力学的重要手段之一．用这种方法对冠醚与金属离子的配位反应热力学性质进行研究一直受到很大关注【且S习．但是对氨杂冠林，尤其是一系列结构相似的氨杂冠醚体系进行系统的热力学性质研究的报导不多．前文K则曾报导了用自组装的消定量热计对银（I）－a吹体系和铜（11）·N，N’一问位取代革基乙二胺体系的配位反应热化学研究结果·本文报导从（对位取代革基）k杂15冠5卜RPW15CS，R＝CIZH；CHa；CHso）与碘化钠和碘化钾在25T、无水乙过溶液中进行配位反应的消定量效研究结果．讨论了配体上取代基的电…     

Calorimetric approach to tetronic/water interactions

Tetronic^®comprises X-shaped copolymers formed by four poly(propylene oxide) (PPO) andpoly(ethylene oxide) (PEO) block chains bonded to an ethylene diamine centralgroup. Micellization behaviour of three representative Tetronics (T304, T904and T1307) was characterized to gain an insight into the interactions betweenthe copolymer unimers and the state of water in their solutions. The enthalpyof demicellization, recorded at 37°C in an isoperibol microcalorimeter,indicated that the process was in all cases exothermic and the enthalpy rankedin the order T1307≥T904>>T304. Micellization is entropy-driven owing tohydrophobic interactions between the PPO chains.DSC analysisshowed that the crystallization and melting peaks of the free water remainingin T304 and T904 solutions were progressively shifted toward lower temperaturesas the surfactant proportion increased, owing to a colligative effect. Boundwater corresponded to 3 water molecules per EO repeating unit. In the caseof T1307, which has longer PEO chains, a splitting of the melting peak wasobserved, one peak appearing around 0°C due to free water and anotherat –15°C due to interfacial water. As T1307 proportion raised, theenthalpy of the former decreased, whilst the enthalpy of the latter increased.In 40% T1307 solutions, interfacial water overcame the proportion of freewater; there being 1 interfacial and 3 bound water molecules per EO repeatingunit. Gaussian deconvolution of FTIR spectra also enabled to characterizethe evolution of free water as a function of Tetronic proportion. The dependenceof micellization and water interaction behaviour on Tetronics structure shouldbe taken into account to use these copolymers as drug solubilizers and micellarcarriers.     

用稳定自由基聚合及光引发聚合制备嵌段共聚物

介绍了稳定自由基聚合的反应原理、引发剂设计，以及用稳定自由基聚合制备嵌段共聚物的几种方法：连续加料法、双官能团引发剂法和一步法。对于光引发聚合的原理及硫自由基的稳定性对聚合反应的影响也进行了讨论。     

接触角法研究医用聚醚聚氨酯材料表面自由能与界面自由能

<正> 表面性质在医用材料与生物体的相互作用中起着至关重要的作用,如血液相容性材料的表面对血细胞具有吸附、变形、凝血、溶血等作用。表面能和界面能是医用材料的重要研究内容之一,材料的表面能及其极性与非极性分量在影响或控制材料与生物体的相互作用之面一直是医用材料的重要课题。Raier曾提出当材料的临界表面张力在20-30erg/cm~2时,血液相容性好,也有人认为,血液与材料的界面自由能趋于零时,才能