Change in the molecular weight distribution of poly(ethylene oxide) caused by the complexation with poly(acrylic acid)

The complexation between poly(ethylene oxide) (PEO) and poly(acrylic acid) (PAA) was made by using double the molar quantity of either polymer component at pH 2 where the resulting complex completely precipitates. After the removal of the precipitate, PEO or PAA remaining in the supernatant was subjected to gel permeation chromatography to investigate the change in the molecular weight distribution (MWD) caused by the complexation. No remarkable difference is observed in the MWD curves for PEO[1] (M_w=1.37 × 10⁴) before and after the complexation with PAA[1] (M_w=1.10 × 10³) and PAA[2] (M_w=4.16 × 10⁵). However, the MWD curves of PEO[2] (M_w=1.26 × 10⁵) and PAA[2] become shortened and shift to the low molecular weight side after the complexation with PAA[1] or [2] and PEO[2], respectively. This tendency is enhanced by increasing the complexation temperature. From these results, it is indicated that the complexation between PEO and PAA deals with an equilibrium reaction, and the equilibrium constant is dependent on the chain length of both polymer components and also on the complexation temperature.     

A/O法废水处理碱源的研究与实践

从理论到实践阐述了以具有价格优势的 Na OH替代 Na2 CO3做碱源 ,解决 A / O法运行成本高的问题。     

光化学反应中的磁场效应 Ⅱ.电子转移光敏化1,2-二苯乙烯的顺反异构化反应

前文报道了外加磁场对吸附在硅胶表面上的芳砜光解反应的影响,本文报道外加磁场影响光化学反应的另一个例子——电子转移光敏化1,2-二苯乙烯的异构化。 近年来电子转移光敏化反应引起了有机光化学家们的极大注意。一些异构化、重排、裂解、氧化反应都可以通过电子转移机理敏化。电子转移光敏化的机理可以用(1)描述。图中A和D分别代表电子的受体和给体。     

基于反应扩散方程的水平集结构拓扑优化方法与实现

为实现更加先进的拓扑优化算法,研究采用反应扩散方程的水平集结构拓扑优化方法,通过理论推导给出算法中的参数选择建议.该方法允许在拓扑优化过程中生成新的孔洞,初始结构无须包含孔洞,不需要重新初始化步骤,从而可提高算法的收敛性.针对传统拓扑优化中主要采用体积约束、以柔度最小为目标和体积保留率设定存在一定主观性的问题,探究不同体积保留率下的结构应力水平的变化规律,结果显示可以依据结构最大应力水平与体积保留率的变化规律确定最优体积保留率.     

2-（4-氯苯氨基）甲基苯酚降解的动力学研究

采用高效液相色谱技术,开展了Fenton试剂对2-（4-氯苯氨基）甲基苯酚（CMP）的氧化降解动力学的研究。考察了初始双氧水摩尔浓度、亚铁离子摩尔浓度和温度等因素对CMP降解速率的影响,结果表明,当双氧水摩尔浓度、亚铁离子摩尔浓度增大和温度升高时,CMP的氧化速率明显加快。在30~45℃的温度范围内,其氧化降解符合假一级反应动力学模型,反应的表观活化能Ea为102.90kJ/mol。     

基于表面反应和扩散迁移控制的灰岩单裂隙渗流—溶解模型及其数值模拟

针对碳酸盐类可溶岩地区水电站坝址流场、化学场以及固相介质属性等随时间发生改变,从而对工程安全运行造成不利影响等问题,研究了灰岩地区地下水运移过程中各物理场间的相互作用,分析了影响灰岩溶解速率的两个因素,即表面反应控制和扩散迁移控制。在此基础上,建立了单裂隙中的渗流—溶解耦合模型,并进行数值求解。模拟结果表明,在垂直裂隙延伸方向,其溶蚀锋面为非齐整平面,而是呈似“虫洞”状非均一变化,而沿裂隙延伸方向即自上游侧向下游方向溶蚀程度逐渐减轻;而通过裂隙的流量呈现随时间逐渐增大的趋势,但变幅不大;根据流量求得的等效水力隙宽,其增幅和增长速率均小于实际平均隙宽;同时,化学场中Ca2+浓度的分布与裂隙开度变化具有相似性,不同时刻下上游侧反应速率R均大于下游侧。就反应机制而言,在初期均受表面反应控制,而随反应进行,位于上游补给区部位转为受扩散迁移控制,但在下游位置仍受表面反应控制。     

负氢离子释放剂对2-甲基-2-丁烯氢转移反应的影响

负氢离子转移反应是氢转移反应的基元反应,促进负氢离子转移反应可以强化选择性氢转移反应。在反应温度510 ℃、剂/油质量比5、质量空速12 h^-1、N₂气氛条件下,分别考察了四氢萘和十氢萘作为负氢离子释放剂对2-甲基-2-丁烯氢转移反应的影响。结果表明：四氢萘和十氢萘均能有效地促进2-甲基-2-丁烯发生选择性氢转移反应,产物中C₅烯烃产率由52.95%最低分别降至37.83%和17.03%,异戊烷产率由17.80%最高分别增加至42.98%和54.58%,焦炭产率由5.28%最低分别降至3.11%和2.85%;且十氢萘比四氢萘具有更好的供氢能力,相同含量的十氢萘对于产物中烯烃产率的降低幅度、异构烷烃产率和选择性的增加幅度的影响均比四氢萘更大,对焦炭产率的抑制作用更强。在含烯烃汽油中分别加入质量分数10%四氢萘和十氢萘后,烯烃产率由11.20%分别降低至5.48%和4.01%;同时能够很好地抑制焦炭的生成,尤其加入十氢萘后焦炭产率由5.30%降到2.82%。     

四氢萘催化裂化研究进展

加氢处理油中含有一定量的环烷基单环芳烃,研究四氢萘催化裂化有利于加强对更多环数环烷基单环芳烃催化裂化的认识。综述了四氢萘催化裂化过程的反应机理,认为四氢萘主要遵循单分子裂化机理;从反应活化能、扩散、吸附等动力学角度对四氢萘裂解行为进行了解释;催化剂适宜的孔径和BrØnsted酸强度有利于四氢萘开环;随着反应温度升高、剂/油质量比增大、质量空速减小,四氢萘反应活性增强,同时氢转移反应愈发明显。适宜的催化剂孔径和Brnsted酸强度、反应温度、剂/油质量比以及质量空速有利于四氢萘裂化生成低碳烯烃。     

REACTIVE DIFFUSION BETWEEN Si AND NbC AT 1300℃

ＲＥＡＣＴＩＶＥＤＩＦＦＵＳＩＯＮＢＥＴＷＥＥＮＳｉＡＮＤＮｂＣＡＴ１３００℃Ｃ．Ｒ．Ｋａｏ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉｃａｌＥｎｇｉｎｅｅｒｉｎｇＮａｔｉｏｎａｌＣｅｎｔｒａｌＵｎｉｖｅｒｓｉｔｙＣｈｕｎｇＬｉ，Ｔａｉｗａｎ）Ｊ．Ｗｏｏｄｆ...     

Initial stages of the high-temperature corrosion of commercial Fe-Cr-Ni alloys in a carburizing atmosphere of low oxygen partial pressure

The early stages of corrosion of AISI 314, HK 40, and Alloy 800H have been studied in a strongly carburizing (a_C=0.8), weakly oxidizing atmosphere at 1098 K. Samples with electropolished and cold-worked surfaces were exposed for up to 400 min. at temperature, in a conventional corrosion rig or in a reaction vessel which was installed within an X-ray photoelectron spectrometer. The latter facility allowed the effects of the specimen heating rate and the rat of gas flow to be investigated. Examination of the corrosion products was accomplished with the aid of XPS, SEM, TEM, and conventional metallography. Initially, surface layers comprised of -Cr₂O₃, (Mn, Cr)₃O₄, and SiO₂ formed, with layer structure, microstructure, and composition being functions of alloy composition and surface condition. Only on the cold-worked surfaces did a well-developed duplex oxide, consisting of an outer, Cr-rich oxide layer and an inner, SiO₂ layer, form. In good agreement with the predicted value of 1.9 wt.%, between 1.4 and 2 wt.% Si in the alloy was required to form a complete SiO₂ layer. After an incubation period, -Cr₂O₃ became unstable and transformed to M₇C₃; the carbides then grew by diffusion of metal from the alloy substrate. The presence of manganese, as (Mn, Cr)₃O₄, in the surface oxide influenced the mode of carbide growth, whereas the rate of carbide growth was severely suppressed by a continuous SiO₂ layer which acted as a diffusion barrier both to metal and to carbon. It is argued that the SiO₂ layer is most effective in reducing carburization when it is free from or contains very few structural defects.