利用AFM对单晶硅表面加工化学反应理论分析

以原子力显微镜为工具,在空气条件下对单晶硅片表面加工得到下凹的三维微结构。给出了AFM金刚石针尖在对单晶硅的微加工中的化学反应和加工模型。对加工条件下发生的化学反应及其原理进行了理论分析。用化学热力学定律、化学动力学原理和相关的热力学数据自由能、生成热、化学键能、活化能等分析加工过程中发生的反应是空气中O2与单晶硅Si反应生成二氧化硅的过程;金刚石针尖磨损发生的反应主要是空气中O2与金刚石针尖C反应生成CO2的过程。     

基于非平衡态热力学的传递唯象研究

从广义力与流的角度,探讨了传递现象的共同本质,即各种强度量势场梯度作用下的能流和流。运用非平衡态热力学的相关理论,推导了多势场影响下的传递唯象方程。根据非平衡态热力学分析不可逆过程的一般步骤,提出确定传递唯象方程力与流的两种方法,体现了热力学和传输学在传递研究中的学科交叉。对热电耦合现象的应用分析表明,基于非平衡态热力学的传递唯象方程,能够完整、深入地揭示不可逆效应之间的耦合关系。     

离子交换树脂吸附TP5的热力学和动力学研究

针对凝胶型阳离子交换树脂对TP5的吸附行为,研究了间歇反应中TP5水溶液的吸附热力学与动力学特性。热力学研究表明,TP5在所用树脂上的吸附平衡数据符合Langmu ir吸附等温方程。在283.15~303.15 K之间,TP5的质量浓度在10 g/L时,离子交换树脂对TP5的吸附过程可分两个阶段,第一阶段受液膜扩散控制,第二阶段主要吸附过程受颗粒扩散的控制。利用TP5在不同条件下的动态吸附性能实验,考察了pH值、温度、溶液初始浓度、搅拌转速等因素的影响。采用两相阻力模型描述了TP5在离子交换介质中的动态吸附性能,通过计算得到了TP5在吸附剂颗粒中的颗粒扩散系数,有助于进一步研究小肽在吸附过程中的传质现象。     

Sulfur-Tolerant NOx Storage Traps: An Infrared and Thermodynamic Study of the Reactions of Alkali and Alkaline-Earth Metal Sulfates

The sulfur tolerance of a barium-containing NO_x storage/reduction trap was investigated using infrared analysis. It was confirmed that barium carbonate could be replaced by barium sulfate by reaction with low concentrations of sulfur dioxide (50 ppm) in the presence of large concentrations of carbon dioxide (10%) at temperatures up to 700 °C. These sulfates could at least be partially removed by switching to hydrogen-rich conditions at elevated temperatures. Thermodynamic calculations were used to evaluate the effects of gas composition and temperature on the various reactions of barium sulfate and carbonate under oxidizing and reducing conditions. These calculations clearly showed that if, under a hydrogen-rich atmosphere, carbon dioxide is included as a reactant and barium carbonate as a product then barium sulfate can be removed by reaction with carbon dioxide at a much lower temperature than is possible by decomposition to barium oxide. It was also found that if hydrogen sulfide was included as a product of decomposition of barium sulfate instead of sulfur dioxide then the temperature of reaction could be significantly lowered. Similar calculations were conducted using a selection of other alkaline-earth and alkali metals. In this case calculations were simulated in a gas mixture containing carbon monoxide, hydrogen and carbon dioxide with partial pressures similar to those encountered in real exhausts during switches to rich conditions. The results indicated that there are metals such as lithium and strontium with less stable sulfates than barium, which may also possess sufficient NO_x storage capacity to give sulfur-tolerant NO_x traps.     

K~+, Na~+//Cl~-,SO_4~(2-),NO_3~--H_2O体系热力学研究

通过引入表达离子缔合或离子间的短程静电作用项,提高了局部组成模型关联单一电解质水溶液体系热力学性质的精度,并通过建立新的计算多元混合体系作用参数的方法,将其推广应用到多离子电解质溶液体系。在此基础上,预测了Na+//Cl-,SO2-3,H2O、K+//Cl-,SO2-4,NO-4,NO-3,H2O、K+,Na+//Cl-,SO2-4,H2O、K+,Na+//Cl-,NO-3,H2O3,H2O、K+,Na+//SO2-4,NO-3,H2O5个四元体系及K+,Na+//Cl-,SO2-4,NO-五元体系的溶解度,模型参数均通过上述体系所包含的二元、三元体系的溶解度数据获得,计算结果满意。     

Estimation of the critical properties of compounds using volume-based thermodynamics

The importance, yet scarcity of the critical constants of thermally unstable fluids warrants the development of reliable methods for the estimation of these essential thermodynamic properties. A thorough investigation undertaken in this study on 1,589 compounds belonging to 83 chemical classes, indicated that the ratio of critical temperature to critical pressure of both low and high molecular weight compounds could be well expressed in terms of their volumetric properties. In addition, two new methodologies are presented for estimating V_c, as well as an indirect approach for prediction of T_c from surface tension data, altogether allowing the calculation of Z_c. Moreover, comparative studies are made with five group contribution methods. It is also demonstrated that by employing the Peng-Robinson EOS, and without prior knowledge of the critical properties, it is possible to calculate various thermophysical properties including P^sat., T_b, , ∆H^vap. , C_p, and even the T_c and P_c themselves.     

Kinetics of esterification of cycloaliphatic epoxies with methacrylic acid

The esterification of cycloaliphatic epoxy resins CER I and CER II containing glycidyl and cyclohexane epoxy groups, respectively, as their reactive units was carried out using a 1 : 0.9 stoichiometric ratio of resin and methacrylic acid in the presence of triphenylphosphine. The reaction was performed at 80, 85, 90, 95, and 100°C and it followed second‐order kinetics. The specific rate constants, calculated by regression analysis, were found to obey an Arrhenius expression. Kinetic and thermodynamic parameters, activation energy, frequency factor, entropy, enthalpy, and free energy of the reaction, revealed that the reaction was spontaneous and irreversible and produced a highly ordered activated complex. The reactivity of CER II was found to be higher than that of CER I. The difference in the reactivity of the cycloaliphatic epoxies was explained by proposing a reaction mechanism. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3197–3204, 2002     

蛋白类防沾色剂与棉纤维作用机理探讨

探讨了自制蛋白类防沾色剂对棉纤维的吸附机理,包括动力学吸附性能和热力学吸附性能。结果表明,蛋白类防沾色助剂的最大吸收波长是190 nm,在此波长下蛋白类防沾色助剂的浓度与吸光度成线性关系;该防沾色剂在棉织物上的吸附过程为准二级动力学吸附;其最佳吸附温度为80℃;在棉织物上的吸附属于朗格缪尔(Langmuir)型,为化学定位吸附。     

基于热力学原理的混凝土热-力耦合本构模型

为了解决高温条件下混凝土材料力学性质描述的问题,基于热力学理论,将损伤理论与经典弹塑性理论结合,建立了一个考虑温度影响的混凝土热-力耦合本构模型,用于描述高温条件下混凝土材料的力学性质。基于热力学原理推导了考虑温度影响的弹性应变增量的表达式,并基于经典塑性理论,构造了一个考虑温度影响的硬化参数,推导出相应的塑性应变增量表达式,将上述2部分应变增量叠加得到混凝土热-力耦合本构模型的表达式。将模型预测结果与试验结果进行对比,符合良好,表明上述热-力耦合本构模型能够对高温条件下混凝土材料的力学性质进行较为准确的描述与预测。     

NH_4SCN解吸剂对负载Re的D296树脂的解吸影响

为了实现离子交换树脂中吸附离子的高效解离,研究了NH_4SCN解吸剂对负载Re的D296树脂的解吸影响,并探讨了其最优解吸工艺.通过静态实验探讨了解吸时间、解吸温度,以及解吸溶液的浓度和p H值对D296树脂的解吸影响,并测定了相应的解吸曲线.结果表明,NH_4SCN解吸剂对D296树脂的最佳解吸温度为323 K,最佳pH值为10,最佳解吸溶液浓度为100 g·L~(-1).在最佳解吸工艺条件下,反应20 min后,D296树脂中Re的解吸率可达98%以上,且解吸反应为吸热反应.当NH_4SCN解吸剂的流速为2 m L·min~(-1)时,淋洗效果较好.