对叔丁基氯苄的合成工艺研究

以叔丁基苯、多聚甲醛和盐酸为原料,通过氯甲基化反应制备对叔丁基氯苄。研究了投料摩尔比、反应温度、反应时间以及催化剂对产物收率的影响,优惠工艺条件为:磷酸作催化剂,叔丁基苯∶甲醛∶氯化氢=1∶3∶3(mol/mol),反应温度80～85℃,反应时间15h。     

乙炔氢氯化反应铜基催化剂研究进展

开发乙炔氢氯化无汞催化剂对我国聚氯乙烯(PVC)工业具有重要意义,目前以金为代表的贵金属催化剂已经接近工业化应用,但其生产成本高限制了其市场推广,因此相对价廉的铜基催化剂受到广泛关注。主要从配体和载体改性等方面综述了科研人员对金属铜基催化剂在乙炔氢氯化反应中性能提升所做的工作,并且总结了含铜多金属催化剂在乙炔氢氯化反应中的研究进展,最后对铜催化剂工业发展前景进行了展望。     

Laboratory investigation of reinforcement corrosion initiation and chloride threshold content for self-compacting concrete

Time-to-corrosion (T_i) of reinforcement in concrete and chloride threshold content (C_th) are important service life determinants for reinforced concrete structures in chloride-laden environments. In this study, the two determinants of a series of self-compacting concretes (SCC) and regular concretes were experimentally investigated. A new sampling approach for C_th determination (milling powder from corrosion active site at the rebar/concrete interface) was adopted to accurately express chloride content resulting in corrosion occurrence. It is found that the T_i and C_th follow the 3-parameter Weibull distribution. The results indicate that the corrosion initiation of rebar in concrete slabs depends upon both cement alkalinity and superplasticizer. Rebar, embedded in high alkalinity cement SCC, exhibits better corrosion resistance as indicated by the longer T_i, higher C_th and larger Weibull modulus, m. A larger Weibull modulus indicates that anti-corrosion performance of rebar in slabs is more stable and less scattered. The effects of specific superplasticizer on rebar corrosion resistance are discussed from the viewpoint of air void amount and size distribution at the rebar/concrete interface.     

Electrochemical corrosion behavior of 300M ultra high strength steel in chloride containing environment

The electrochemical corrosion behavior of 300M ultra high strength steel in chloride containing environment was investigated by potentiodynamic polarization technique, electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM). The results show that uniform corrosion occurs on 300M steel during the electrochemical measurements because no anodic passivation phenomenon is observed on polarization curves within the measurement range. The tests also show that 300M steel is highly susceptible to chloride containing solution, which is characterized by corrosion current density increasing with the addition of chlorides, and corrosion potential shifting towards positive direction and corrosion resistance decreasing, positively suggesting that chloride ions speed up the corrosion rate of 300M steel. Meanwhile corrosion products on the 300M steel surface formed during the salt spray test are too loose and porous to effectively slow down the corrosion rate. Additionally, a schematic structure of uniform corrosion mechanism can explain that 300M steel has better property of stress corrosion cracking (SCC) resistance than stainless steels.     

Effects of chloride and sulfate on the rate of oxidation of ferrous ion by H2O2

The rates of oxidation of Fe(II) by H(2)O(2) in the presence of sodium perchlorate, sodium nitrate, sodium chloride and sodium sulfate salts (0-1M) have been compared in the study. Experiments were carried out in a batch reactor, in the dark, at pH <3, 25+/-0.5 degrees C and at controlled ionic strength (< or =1M). The experimental results showed that the rates of oxidation of Fe(II) in the presence of chloride, nitrate and perchlorate were identical. In the presence of sulfate, the rate of oxidation of Fe(II) was faster and depended on the pH and the concentration of sulfate. The pseudo second-order rate constants for the reaction of H(2)O(2) with Fe(2+), FeCl(+) and FeSO(4) were determined as 55+/-1, 55+/-1 and 78+/-3 M(-1) s(-1), respectively.     

硅烷膏体浸渍剂在保护混凝土中的实际应用

渗透型有机硅成功用于保护混凝土在国外已有数十年的历史。用于保护钢筋混凝土，它可防止水分及氯离子的渗透，从而对于防止混凝土的腐蚀与破坏起到关键的作用。这种浸渍剂一般都由硅烷或硅氧烷组成。通常情况下，由于这些低粘度的液体非常容易挥发。尤其在桥梁底面及立面施工时，有效成分大量流失。为了避免出现这种情况，德国瓦克化学有限公司成功开发了一种新型的硅烷乳膏状产品。这种材料施工简单，只需一步完成，具有很高的遮盖率，由于不流淌，活性组分不会损失。与混凝土表面接触时间长，保证了在高等级混凝土中的渗透深度，而且在其表面不会残留任何痕迹。     

持续荷载下混凝土的氯离子扩散性能研究

基于实际海洋环境暴露条件,研究了力学荷载作用下混凝土中的氯离子扩散性能.以Fick第二定律理论为基础,用误差函数对混凝土中随深度变化的氯离子含量分布进行了曲线拟合,从而得到氯离子表现扩散系数,并以此表征氯离子在混凝土中的传输性.分析了氯离子的扩散系数与原材料、配合比、暴露环境以及力学荷载间的关系.结果表明,力学荷载对海洋环境下混凝土中的氯离子传输性能有显著影响,在利用氯离子扩散模型预测暴露海洋环境下混凝土结构的使用寿命时,需要考虑荷载因素的影响.     

Cl~-浓度对316L不锈钢点蚀行为的影响

运用电化学动电位扫描、电化学交流阻抗技术、金相显微以及电子扫描显微技术,对常温常压下,不同浓度的Cl-对316 L不锈钢的CO2腐蚀作用进行了一系列实验。经过实验结果发现,316 L不锈钢呈现出整体腐蚀速率不高而局部腐蚀严重的态势,当氯离子的浓度升高时,316 L的腐蚀表现出整体腐蚀速率有很小的上升,而点蚀电位随着氯离子浓度的上升而降低,导致严重的点蚀。说明氯离子浓度的升高使点蚀电位严重下降,在该环境下316 L不锈钢的腐蚀主要为点蚀特征。     

Influence of long-term chloride diffusion in concrete and the resulting corrosion of reinforcement on the serviceability of RC beams

This paper presents the chloride penetration and the effect of chloride ingress on the serviceability of reinforced concrete (RC) beams. A series of experimental studies were carried out on beams with various corroded ages up to 28 years. The chloride content in different locations were tested during various periods. Different states influencing the serviceability of the corroded beams were investigated, including the maximum width of the corrosion-induced cracks of the concrete cover, the mid-span deflection of the beams under the service load and their load-bearing capacity. Based on the results available from this programme, the service life of corroded beams was predicted by the corrosion process of the reinforcement. The results showed that the chloride corrosion could significantly deteriorate the serviceability of the beams. The current criteria concerning the chloride content at the level of the reinforcement of the concrete beams and the maximum width of the corrosion-induced cracks appear to be very conservative.     

Fenton degradation of 4-chlorophenol contaminated water promoted by solar irradiation

The degradation of 4-chlorophenol (4-CP) contaminated water by Fenton process with or without solar irradiation assistance were investigated. It was found that the COD degradation and mineralization efficiency of 4-CP were more than 90% when a 30 min treatment of solar photo-Fenton oxidation process was applied and under an optimum [H₂O₂]₀/[Fe²⁺]₀ ratio of 40, the COD degradation and mineralization efficiency increased 65% as compared to Fenton oxidation. Meanwhile, the AOS values increased from −0.33 to 2.13 in solar photo-Fenton process while no significant improvement for AOS values was found in Fenton process, implying a higher degree of oxidation for 4-CP in solar photo-Fenton process. In addition, increasing the intensity of solar irradiation seemed to be beneficial for treatment of 4-CP contaminated water. Formation of chloride ion as a result of mineralization of organically bounded chlorine was identified during the treatment of 4-CP solution. Near-stoichiometric accumulation of chlorine was observed during the degradation of 4-CP in both Fenton and solar photo-Fenton processes. However, accumulation rate of chloride ions were much faster in solar photo-Fenton process. The degradation of 4-CP was found to obey a pseudo-first-order reaction kinetics. As compared to Fenton process, the presence of solar light in photo-Fenton process increases the reaction rate by a factor of 6.5 and 15.8 for COD and TOC degradation, respectively. In other words, during the treatment of 4-CP contaminated water, solar photo-Fenton process possesses notably higher mineralization efficiency in a relatively short radiation time as compared to Fenton process, and could enhance the degradation treatment of refractory organic wastewater such as 4-CP in a cost-effective approach.