PEN/PTT共混聚酯的熔融行为

利用差示扫描量热仪对不同配比的聚萘二甲酸乙二醇酯/聚对苯二甲酸丙二醇酯(PEN/PTT)共混体系的熔融行为进行了分析,发现在共混体系中两组分形成各自的晶体,PEN和PTT的熔点均随另一组分含量的增加而下降。根据Nishi-Wang方程,按300℃计算,由PEN/PTT共混体系中PEN熔点下降计算所得到的相互作用能密度为-0．214 2 J/cm~3,相互作用参数为-0．006 8,表明PEN/PTY共混体系在熔融态是热力学性质稳定的相容体系。     

(CO2 + 2‐propanol) mixture as a foaming agent for polystyrene: A simple thermodynamic model for the high pressure VLE‐phase diagrams taking into account the foam vitrification

The equation of state model developed by Lacombe and Sanchez (J Phys Chem 1976, 80, 2352) is used in the form proposed later by Sanchez and Stone (Polymer Blends, Vol. 1: Formulation, 2000; Chapter 2) to correlate experimental vapor‐liquid equilibrium (VLE) data for the three binaries and the ternary systems. Experimental data from the binary systems carbon dioxide‐isopropyl alcohol (CO₂‐IPrOH), isopropyl alcohol‐polystyrene (IPrOH‐PS), and carbon dioxide‐polystyrene (CO₂‐PS) are used to calculate VLE properties for the ternary system CO₂‐IPrOH‐PS. Two‐dimensional VLE‐phase diagrams were calculated and used to describe from a thermodynamic point of view the pressure, volume, and temperature values that characterize a thermoplastic foam evolution process, from the extruder to the foaming die. For different initial mixture CO₂ + IPrOH concentrations, pressure reduction produces liquid foaming until the vitrification curve arrests the final foam volume expansion. The dependence of the vitreous transition with the system CO₂ + IPrOH concentration while foaming is represented by the Chow (Macromolecules 1980, 13, 362) equation. The calculation procedure is proposed as a design tool to reduce the amount of experimental data usually needed as a requirement previous to the design stage. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2663–2671, 2007     

Non-isothermal reaction-diffusion systems with thermodynamically coupled heat and mass transfer

Non-isothermal reaction-diffusion (RD) systems control the behavior of many transport and rate processes in physical, chemical, and biological systems. A considerable work has been published on mathematically coupled nonlinear differential equations of RD systems by neglecting the possible thermodynamic couplings among heat and mass fluxes, and reaction velocities. Here, the thermodynamic coupling refers that a flux occurs without its primary thermodynamic driving force, which may be gradient of temperature, or chemical potential, or reaction affinity. This study presents the modeling equations of non-isothermal RD systems with coupled heat and mass fluxes excluding the coupling of chemical reactions using the linear non-equilibrium thermodynamic approach. For a slab catalyst pellet, it shows the dynamic behavior of composition and temperature profiles obtained from the numerical solutions of non-linear partial differential equations by Mathematica for two industrial reaction systems of synthesis of vinyl chloride and dissociation of N₂O.     

NiFe2O4及添加TiO2的尖晶石的烧结过程

以NiO和Fe2O3为主要原料,通过添加少量TiO2粉末来改善NiFe2O4试样的烧结性能。研究了NiFe2O4和TiO2-NiFe2O4 2种样品反应烧结过程中的热力学及动力学条件,同时利用球模型推导的扩散机制的烧结方程测算出2种材料的烧结活化能。结果表明：NiO和Fe2O3固相烧结过程是固相反应和致密化过程同时进行的。添加质量分数为1％TiO2粉末,当合成温度为1250℃时,TiO2-NiFe2O4样品就已达到致密,其烧结活化能由NiFe2O4样品时的245.36kJ/mol降低为142.71kJ/mol。     

Co-Mo-K催化剂上COS、HCN转化率的热力学分析

利用热力学基础数据和相关软件对Co-Mo-K催化剂上COS、HCN加氢和水解反应进行了热力学计算。在热力学上,COS、HCN加氢和水解反应在耐硫变换条件下均为自发过程。计算结果表明在Co-Mo-K耐硫变换条件下COS、HCN主要发生的是水解反应,该结果与工业经验数据基本一致,可以作为工业实际借鉴。     

Methods to determine solubility parameters of polymers using inverse gas chromatography

Experimental values of the Flory–Huggins parameter, χ, between polymers and solvents, are frequently used to determine the solubility parameters of the polymers. A method using nonlinear curve fitting of RTχ/V was compared to the linear regression method commonly used. It was found that the formulas for the solubility parameter were the same, but the linear method produced a slightly different entropy term. The nonlinear method gave a lower correlation coefficient and wider confidence intervals and was more effective at distinguishing systems than the linear model. The effect of the deviation of probes in the solubility parameter model is discussed. Using probes with low solubility parameters to measure the polymer solubility parameter gave wider confidence intervals. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2894–2902, 2004     

Thermodynamic Analysis of Chemical Vapor Deposition of BN + AIN Composite Coatings

Thermodynamic calculations were performed using a modified solgasmix-pv computer program in order to study the feasibility of codepositing boron nitride (BN) plus aluminum nitride (AIN) by chemical vapor deposition. Reactants considered were AICl₃, BCl₃ or B₂H₆, NH₃, and H₂. Deposition diagrams were generated for the BCl₃-AICl₃-NH₃ system over a range of processing conditions such as temperature, total system pressure, and reagent concentrations. Codeposition of BN + AIN was predicted by the calculations for temperatures in the range of 900 to 1700 K and pressures of 10.13 to 101.3 kPa. The predicted deposition efficiency at equilibrium was much higher for BN than for AlN at most reagent compositions. The AlN deposition efficiency increased with decreasing temperature and decreasing BCl₃ content, with increasing NH₃ content, or with the addition of H₂. Aluminum chlorides were found to be the dominant gaseous species.     

Reaction of YBa2Cu3O7-δ Powder with NOx Gas in an Aerosol Reactor

Thermodynamic calculations predict, and experiments verify, that YBa₂Cu₃O₇-₈ (123) powder is unstable in the presence of NO_x-containing aerosol reactor exhaust gases at temperatures below about 600°C. Powders collected above the stability temperature are single-phase 123, while powders collected at lower temperature contain Ba(NO₃)₂ formed by reaction of the powder with NO_x, after exit from the hot zone.     

非平衡态热力学理论与钢铁冶金过程

钢铁冶金过程具有典型的非平衡和非线形特征。本文分析讨论了基于非平衡态热力学、耗散结构和混沌理论来研究处理实际钢铁冶金过程。认为：为真实地定量描述实际冶金过程，应该加强、加速开展和进行冶金过程非平衡态热力学及其应用的研究。     

抗氧剂3114合成反应热力学和动力学的研究

研究了常温溶剂法合成抗氧剂3114反应热力学和动力学过程。控制温度在117±2℃,研究结果表明,反应是零级反应,反应速率常数k=1.91×10-3/min,反应的平衡常数K=138.4(mol/L)-6,反应活化能Ea=1366.2J/mol。