Photochemical reaction of azobenzene in solvent-swollen Nafion membranes

The photochemical reactions of azobenzene (AB) incorporated into different solvent-swollen Nafion membranes were investigated. The location of azobenzene in water-swollen Nafion membranes was different from that in methanol-swollen Nafion membranes, which was responsible for the different photochemical reactions of AB. In methanol-swollen Nafion membranes only trans-cis isomerization took place, while in water-swollen Nafion membranes photochemical cyclization of AB occurred after rapid trons-cis isomerization. The relation between the relative quantum yields and the light intensity showed that the cyclization was a two-photo process. The numbers of AB molecules per cluster (nAB /cluster) in Nafion membranes with different AB concentrations and different water contents were calculated. Under the experimental condition two competitive photocyclization mechanisms were suggested by nAB /cluster in Nafion membranes, relative quantum yields of the cyclization, and the change of the ratio of benzidine to benz     

Image Contrast Inversion of a Solvent Cast SEBS Film

The image contrast inversion was investigated in detail when soft polymeric materials were imaged with tapping mode atomic force microscopy （TM-AFM）. Solvent cast film of polystyrene-block-poly（ethylene/butylene）block-polystyrene （SEBS） triblock copolymers was used as a model system in this study, which showed phase separation domains with a size of several tens of nanometers. AFM contrast reversal process, through positive image, to an intermediary and till negative image, could be clearly seen in height images of the soft block copolymer using different tapping force. The higher tapping force would lead to not only contrast inversion, but also the different size of the microdomains and different roughness of the images. Moreover, contrast inversion was explained on the basis of attractive and repulsive contributions to the tip-sample interaction and indentation of the soft domains.     

An Electrochemical Study on the Corrosion Inhibition of Stainless Steel by Polyaniline Film

Polyaniline(PANI)film was electrosynthesized on 304 stainless steel by cyclic voltammetry using aqueous oxalic acid as supporting electrolyte.The potential sweep rates were changed to achieve the PANI film with different thickness and structures.Protective properties of the PANI film for corrosion of stainless steel in 3% NaC1 aqueous solution were investigated by monitoring potentiodynamic polarization curves and electrochemical impedance spectroscopy(EIS).The results showed that the PANI film which was formed with lower sweep rate led to more positive shift of corrosion potential and greater charge transfer resistance,reflecting higher inhibition for corrosion of the stainless steel.     

Analysis of the suspension polymerization flows of polyvinyl chloride with the exergy analysis involving resource utilization and environmental influence

In order to comprehensively assess the resource utilization of a process system and its influence on the environment, the application range of the traditional exergy analysis was expanded in this paper to include the pollution degree of the discharged wastes to the environment. So technology indexes can be obtained to comprehensively assess the resource utilization and the environment impact of a process system. The harm coefficient and effect coefficient were introduced to concern the different harm to the environment of the different wastes and the pollution effect relative to resource waste by environment. The determination method of the harm coefficient and effect coefficient was discussed. Two suspension polymerization flows of polyvinyl chloride were calculated with this method. The results show that the method can comprehensively assess the resource utilization and the environment impact of the chemical process system by comparing and analyzing.     

Preparation and Characterization of Nano-Structured SiO2 Thin Films on Carbon Steel

Nano-structured SiO2 thin films were prepared on the surface of carbon steel for the first time by LPD. The compositions of the films were analyzed by XPS, and the surface morphology of the thin films were observed by AFM. The thin films were constituted by compact particles of SiO2, and there was no Fe in the films. In the process of film forming, the SiO2 colloid particles were deposited or absorbed directly onto the surface of carbon steel substrates that were activated by acid solution containing inhibitor, and corrosion of the substrates was avoided. The nano-structured SiO2 thin films that were prepared had excellent protective efficiency to the carbon.     

Influences of Electrolytes on the Soap-free Emulsion Copolymerization of St-MMA-AA

Monodisperse functional polymer microspheres with different particle size and with clean surface were prepared by batch soap-free emulsion polymerization of styrene, methyl methacrylate and acrylic acid in the presence of salts, and the influences of type and amount of electrolytes on polymerization process and particle morphology were investigated. Results showed that there was a critical concentration for different electrolyte to make polymerization process and the resultant emulsion stable, and the particle size increased with the increase of electrolyte concentration. The effect of metal ions was Ca^2＋〉〉K^＋〉Na^＋〉Li^＋, and the effect of haloids was Br〉Cl〉F. Keywords： Electrolyte, soap-free emulsion polymerization, polystyrene, latex particle morphology.     

Pyrolysis Process of Plant Fibers北大核心CSCD

The natural plant fiber has a large molecular weight and complex structure and composition,and its thermal cracking products and the composition distribution are also more complex. The fast pyrolysiscomprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry（Py-GC×GC-TOF/MS）,thermogravimetry-Fourier transform infrared spectroscopy（TG-FT-IR）,and in situ Fourier transform infrared spectroscopy（in situ FT-IR）methods were used to study the thermal pyrolysis process of six different natural fibers. The distribution of thermal pyrolysis products of different fibers under different pyrolysis temperatures was investigated and the product form was fully discussed. The research results show that the products of fiber pyrolysis mainly include alcohols,aldehydes,ketones,acids,esters,hydrocarbons, dehydrated sugars and CO2,etc. The types of pyrolysis products of different natural plant fibers are obviously different,and the main product types obtained are all different. At the same time,the results of in situ infrared spectroscopy and mass spectrometry show that pyrolysis products are closely related to the pyrolysis temperature. The results of in situ infrared experiments show that when the pyrolysis temperature is lower than 100 °C,the adsorbed water on the surface of the fiber structure is desorbed,but the fiber structure does not change significantly. When the pyrolysis temperature range is 100~200 °C,the temperature has little effect toward the pyrolysis process. When the temperature exceeds 300 °C,the fiber pyrolysis reaction intensifies and the surface structure changes significantly,and the main products are aldehydes and ketones. © 2022, Science Press (China). All rights reserved.     

Modeling of Fischer-Tropsch Synthesis in a Slurry Reactor with Water Permeable Membrane

Fischer-Tropsch synthesis is an important chemical process for the production of liquid fuels and olefins. In recent years, the abundant availability of natural gas and the increasing demand of olefins, diesel, and waxes have led to a high interest to further develop this process. A mathematical model of a slurry membrane reactor used for syngas polymerization was developed to simulate and compare the maximum yields and operating conditions in the reactor with that in a conventional slurry reactor. The carbon polymerization was studied from a modeling point of view in a slurry reactor with a water permeable membrane and a conventional slurry reactor. Simulation results show that different parameters affect syngas conversion and carbon product distribution, such as the hydrogen to carbon monoxide ratio, and the membrane parameters such as membrane permeance.     

Growth Kinetics of Silicon Carbide Film Prepared by Heating Polystyrene/Si（111）

SiC films were prepared by heating polystyrene/Si（111） in normal pressure argon atmosphere at different temperatures. The films were investigated by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and Fourier transform infrared absorption measurements. The thicknesses of SiC films were calculated from FTIR spectra. The growth kinetics of the growth process of SiC films were investigated as well. The thicknesses of the SiC films grown for 1 h with increasing growth temperatures have different trends in the three temperature ranges： increasing slowly （1200-1250 ℃）, increasing quickly （1250- 12.70 ℃）, and decreasing （1270-1300 ℃）. The apparent activation energies of the growth process of SiC films in the three ranges were calculated to be 122.5,522.5, and -127.5 J/mol respectively. Mechanisms of the different growth processes were discussed. The relation between film thicknesses and growth temperatures indicated that the growth process was a 2D mechanism in the first range and 3D mechanism in the second range. In the third range, the thicknesses of SiC films were decreased by the volatility of Si and C atoms.     

In situ synthesis of DNA micro-arrays using typography technique

A novel typography technique was developed to in situ synthesize oligonucleotide arrays on glass slide,which has the celerity,high spatial resolution,lower cost,reliable operation,and high synthetic efficiency.The principle and process of the typography technique for fabricating gene-chips have been described in detail.A suit of poly(terafluoroethylene)devices for synthesizing oligonucleotide arrays were designed and prepared,and the fiber tubes with a number of nano-or micron-channels were em- ployed.The oligonucleotide arrays of 16 and 160 features with four different probes were synthesized using the typography technique.The four specific oligonucleotide probes including the matched and the mismatched by the fluorescent target sequence gave obviously different hybridization fluorescent signals.It was indicated that the gene-chip fabricated by the typography method could be used to rapidly screen single-nucleotide polymorphisms(SNP)and to detect mutations.     

薄层缓蚀剂液膜对907A钢防蚀效果的电化学测量技术

本文研究饱和海水湿气环境中对 90 7A钢施加缓蚀剂的防蚀作用 ,利用恒电量技术等电化学方法对同材质的三电极大气腐蚀监测探头 (ACM )进行腐蚀测量 .结果表明 :利用电化学方法监测薄层缓蚀剂液膜的防蚀效果可以更清楚地获知缓蚀剂成膜的过程 ,并对薄层缓蚀剂液膜防蚀效果作出快速评价     

YKI-05缓蚀剂对不同浸没条件下907A钢的缓蚀性能研究

利用动电位极化方法 ,研究了有机膦酸醇酯类缓蚀剂 (YKI_0 5 )对 90 7A钢在天然海水中的缓蚀行为 .实验表明 :静态海水中 ,浓度为 30 0mg/L的YKI_0 5缓蚀剂能在 90 7A钢表面形成稳定的缓蚀膜层 ,是一负催化阴极型缓蚀剂 ,于实验周期内其对 90 7A钢的缓蚀效率可稳定在 90 %左右 ;在周期性间歇浸没情况下 ,此种缓蚀剂所形成的膜层很不稳定 ,随着间浸次数的增加 ,膜层破损程度愈甚 ,缓蚀效果减弱 ,缓蚀膜对 90 7A钢表面仅仅是个覆盖层 ,起到抑制了部分阴、阳极反应的作用 ,从而可将缓蚀机制归结为覆盖效应     

天然海水中绿色碳钢缓蚀剂的研究

根据分子设计和官能团剪裁方法,结合有机缓蚀剂分子在金属表面和氧化膜表面的配位理论,选择葡萄酸钙,葡萄糖酸锌,硫酸锌,蒜素,丙烯酸聚合物,椰子油基烷醇酰胺,APG,OCTA,多聚磷酸钠等多种缓蚀剂成分,利用极化曲线法和重量法研究了上述缓蚀剂复配后对海水中碳钢的缓蚀作用,并由正交实验对筛选出的葡萄酸钙,硫酸锌和OCTA研究确定其以及相互之间的最佳复配比和协同效应,然后通过分段实验法再研究其最佳配方的后效能性,从而得到一种可生物降解的无磷高效绿色缓蚀剂.     

阴极保护和缓蚀剂技术联合保护成膜的阻抗谱研究

本文应用电化学阻抗谱 (EIS)研究了 90 7A钢在海水中受到阴极保护的同时 ,添加多元醇磷酸酯类缓蚀剂 ,其表面膜层变化的情况和缓蚀机理 ,对膜层在海水中浸泡的破损过程也进行了分析 .结果表明缓蚀剂和阳极保护相互促进成膜 ,与成膜过程相对应的EIS变化清楚地显示膜层的变化 ,这种膜层是多层膜结构 ,有良好的持久性和耐蚀能力 .     

LD-2复合缓蚀剂对海水介质混凝土中钢筋阻锈作用研究

利用电化学检测技术和海水浸泡试验等方法 ,观测和研究了经筛选研制的LD_2复合缓蚀剂对海水介质中钢筋腐蚀电化学行为的影响 ,考察和评价了复合缓蚀剂对钢筋的阻锈作用 .结果表明 ,LD_2复合缓蚀剂主要起阳极型缓蚀剂作用 .在海水中加入 2 5 g·L- 1复合缓蚀剂后 ,钢筋的腐蚀电位提高约 0 .2 2 0V ,腐蚀电流降低至未加缓蚀剂的 1% ,缓蚀效率达 99% .钢筋混凝土试样在海水中浸泡 2年 ,表明混凝土中加入占水泥重量 1.0 %～ 2 .5 %LD_2复合缓蚀剂时 ,能有效阻止混凝土中钢筋的腐蚀     

Electrochemical interferometry of a carbon steel in 5–20 ppm KGR-134 inhibited seawater

In the present investigation, holographic interferometry was utilized for the first time to determine the rate change of the number of the fringe evolutions during the corrosion test of a carbon steel in blank seawater and with seawater with different concentrations of a corrosion inhibitor. In other words, the anodic dissolution behaviors (corrosion) of the carbon steel were determined simultaneously by holographic interferometry, an electromagnetic method, and by the electrochemical impedance spectroscopy (EIS), an electronic method. So, the abrupt rate change in the number of the fringe evolutions during corrosion test, EIS, of the carbon steel is called electrochemical interferometry. The corrosion process of the steel samples was carried out in blank seawater and seawater with different concentrations, 5–20 ppm, of KGR-134 corrosion inhibitor using the EIS method, at room temperature. The electrochemical interferograms of the carbon steel in different solutions represent a detail picture of the rate change of the anodic dissolution of the steel throughout the corrosion processes. Furthermore, the optical interferometry data of the carbon steel were compared to the data which were obtained from the EIS tests. Consequently, holographic interferometry is found to be very useful as an electrochemical interferometer for monitoring the anodic dissolution behaviors of metals in aqueous solutions, in which the number of the fringe evolutions of the steel samples can be determined in situ.     

无机盐强化烷基多苷清洗石油污染土壤的机理

研究了无机盐对一种烷基多苷(APG)产品APG1214物理化学性质的影响, 以期解释无机助剂对APG1214清洗老化石油污染土壤的强化作用. 实验发现无机助剂能够显著降低APG1214的临界胶束浓度(CMC)和浊点, 提高其表面活性, 对除油过程有促进作用. 利用动态光散射(DLS)和透射电镜(TEM)研究了无机助剂对APG1214聚集体流体力学半径(Rh)和形态的影响, 发现低浓度无机助剂可减小APG1214聚集体尺寸, 而高浓度助剂则增加聚集体尺寸. 研究结果显示出APG1214与常见非离子表面活性剂不同的特性. 洗油后溶液中表面活性剂聚集体的Rh分布明显变窄, 但平均半径有所增加; TEM观察显示, 洗油后溶液中囊泡壁明显变厚, 证明增溶是APG1214去除石油污染物的一条途径. 本实验得到的结论为APG1214在石油污染土壤修复方面的应用提供了依据, 并为在其他领域更好地利用这类绿色表面活性剂提供了参考.     

DNA与非离子糖基表面活性剂相互作用的研究

用动态表面张力法、键合等温线、紫外光谱及荧光光谱等方法研究了不同链长烷基葡萄糖苷(APG)与DNA的相互作用．研究发现APG对DNA键合可分为两阶段,第一阶段：多苷依靠多羟基结构与DNA形成动力学稳定的复合物;第二阶段：随时间延长,单苷由于其较小的空间位阻而与DNA形成能量更低的热力学稳定复合物．由平衡渗析法得到的单苷与DNA相互作用键合等温线显示,APG与DNA键合为一非协同过程．证实了其非离子氢键吸附的本质,同时也支持了DNA对胶束及预胶束的缠绕模型．紫外光谱结果证明了在APG与DNA作用过程中疏水作用的重要性．以溴化乙锭为探针,荧光光谱法研究证明,随APG链长增加,DNA构象缩拢程度加大,但即使是C2APG也仅能使DNA构象部分缩拢,推测DNA仅是部分链段对APG胶束进行包裹,其它链段仍处于伸展状态．与阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)可使DNA构象强烈缩拢的事实相比,证明了静电作用在大分子与表面活性剂相互作用中的主导性．     

缓蚀剂对船用钢在潮湿大气中的防蚀研究

模拟 90 7A钢在海水的潮湿大气环境和表面覆有薄层缓蚀剂液膜状态下其腐蚀受抑制的情况 ,利用恒电量仪连接ACM控头 ,监测其腐蚀状态 ,结合电化学阻抗谱 (EIS)的测量 ,探讨 90 7A钢在薄层缓蚀剂液膜下的腐蚀受到抑制机理 .结果表明 :此时大气腐蚀反应已转变为阳极过程控制占优势 ,在浸润后期的EIS呈现出由腐蚀介质扩散和电化学放电混合控制特征 ,如果利用恒电量激励下的等效电路模型解析 ,则可以更清楚地获知薄层缓蚀剂液膜下金属表面膜层的信息     

渗铝钢在海水中的电化学行为研究

应用化学浸泡实验,电化学测试技术研究渗铝钢在海水中的电化学行为.试验表明,在海水中渗铝钢的腐蚀电位比20#钢的负,其阳极活性大于后者,在低电位下发生阳极溶解.20#钢和渗铝钢的腐蚀速率分别为5.80mg/dm2·d和3.36mg/dm2·d.渗铝钢在海水中具有优良的耐蚀性能是由于环境遮断和电偶保护的综合效果.其腐蚀产物含有氯离子,说明氯离子参与海水中的腐蚀过程,是导致腐蚀的主要原因.渗铝钢除了表层形成的Al、Fe化合物和致密、连续、具有高效防护作用Al的氧化物保护膜外,Al Fe合金层起到牺牲阳极的电化学保护作用.