环氧/聚氨酯涂层在4种环境中失效行为的EIS

用电化学交流阻抗法(EIS)研究了环氧富锌底漆/环氧云铁中间漆/丙烯酸聚氨酯面漆这一涂层体系在3.5%NaCl溶液、3.5%NaCl溶液+紫外辐射、湿热和盐雾这4种环境中的失效行为,探讨了特征频率下的相位角和涂层电阻值之间对应的关系。结果表明:中频区10Hz处涂层相位角随时间的变化曲线和涂层电阻值随时间的变化曲线有良好的相似性,据此可以对所研究的涂层体系失效程度进行快速评价;所试验的4种腐蚀环境对所研究的涂层体系的破坏作用由小到大依次为:3.5%NaCl溶液盐雾湿热3.5%NaCl溶液+紫外辐射。     

利用EIS高频区参数评价两种环氧涂层的性能

利用10 kHz下的相位角、10 kHz下的相对介电常数和对应于45°相位角的特征频率这3种EIS高频区的参数对两种环氧涂层体系在盐水浸泡+紫外照射的腐蚀条件下的失效过程进行了表征,并与涂层阻抗值进行了对比。测量结果表明,上述3种高频区参数的结果一致,都能够反映涂层性能的变化及相对优劣。当频率10 kHz处的相位角下降到40°,相对介电常数增大到40,或特征频率接近10 kHz时,所研究的两种环氧涂层体系的阻抗值都对应降低到10⁶ Ω•cm²左右,涂层保护性能接近失效。由于这几种EIS高频区参数能够很快测得,因此可以利用这些参数快速评价该涂层的保护性能与失效程度。     

电化学方法研究环氧防锈涂料实验室实验与实海环境实验的相关性

用电化学交流阻抗法(EIS)研究了环氧防锈涂料在实海浸泡实验和3.5%NaCl溶液浸泡实验、盐雾实验、湿热实验3种实验室加速实验中的失效行为,探讨了实海浸泡实验和3种实验室加速实验的|Z|_(0.01 Hz)对应关系。结果表明:4种腐蚀环境对所研究的涂层体系的破坏作用由小到大依次为:3.5%NaCl溶液实海浸泡湿热盐雾;相对实海浸泡实验,盐雾实验对环氧涂层腐蚀失效的加速因子约为2.3。     

改性石墨烯/聚苯胺/环氧树脂复合材料的制备及防腐性能的研究

采用原位聚合法制备改性石墨烯/聚苯胺(PGO/PANI)复合材料,再通过共混的方式将PGO/PANI和环氧树脂复合制备PGO/PANI/EP复合涂层。利用电化学阻抗测试探究了PGO/PANI/EP的防腐能力,并模拟在3.5%NaCl溶液加速浸泡后复合涂层的防腐能力的变化。结果表明,当PGO含量为7%时,复合材料的防腐性能最佳,在3.5%NaCl溶液中浸泡24 h后复合涂层的涂层电阻为5.99×10~5Ω·cm~2,仍具有较好的阻隔性能。     

利用分子量分布探讨粉末活性炭对膜生物反应器的影响

采用空间排阻液相色谱法监测了不同粉末活性炭（PAC）投加量下膜生物反应器混合液分子量分布情况,发现当PAC投加量从1 g·L^-1增加到2 g·L^-1时,混合液中分子量大于10×10³的物质会增加;分子量小于0.5×10³及介于3×10³～10×10³的物质含量相当;分子量介于0.5×10³～3×10³的物质显著减少。膜污染速率分别为2.74、3.10 kPa·m^-1,证实了混合液中分子量大于10×10³的有机物是引起膜污染的主要物质。     

EIS法研究3种配套涂层体系的腐蚀电化学行为

采用电化学阻抗谱(EIS)研究了由水性无机富锌底漆、环氧中间漆和氯化橡胶面漆3种涂料配套而成的3种不同涂层体系在3.5%NaCl溶液中的电化学腐蚀行为,考察了氯化橡胶面漆、水性无机富锌底漆／氯化橡胶面漆、水性无机富锌底漆／环氧中间漆／氯化橡胶面漆这3种涂层体系的阻抗谱在浸泡过程中的演化并据此比较了3种涂层体系的防护性能。结果表明,两涂层体系的防护性能比单涂层的还要差,三复合涂层体系的防护性能最好。根据涂层腐蚀电化学阻抗谱特征推测,中间漆在三复合涂层体系中起到了使底漆和面漆结合更加紧密的桥梁作用。     

动力系统利用液化天然气冷能的节能减排分析

针对动力系统CO₂减排能耗过高的问题,将液化天然气（LNG）的冷能集成用于空气分离制氧和CO₂近零排放动力循环的CO₂捕集,提出了一种利用LNG冷能的CO₂近零排放动力系统设计方案。研究结果表明：空分装置利用LNG冷能生产高压氧气、液氮和液氩等产品,生产能耗比传统空分装置降低57.6％,CO₂近零排放动力循环的火用效率可从52%提高至55.9％。同时,建立了CO₂近零排放动力系统利用LNG冷能的节能减排效益的数学模型,并对动力系统参数进行了分析。以一个进口量为3.0×10⁶ t·a^-1的接收站为例,CO₂近零排放动力系统利用接收站的LNG冷能每年可节省用电2.78×10⁸ kW·h,减少排放CO₂约3.87×10⁵ t·a^-1,经济效益可达到2.19亿元·a^-1。     

MnO2/NH4NaY 催化剂上的NO低温选择性催化还原（SCR）

研究了NO在新型MnO₂/NH₄NaY催化剂上的低温转化行为，并对MnO₂/NH₄NaY的再生及稳态操作进行了考察。结果表明，以MnO₂/NaY为母体，用硫酸铵溶液离子交换制备的新型MnO₂/NH₄⁺NaY分子筛催化剂具有良好的低温活性，120 ℃时，NO转化率近100％。但催化剂不能在高于150 ℃的反应温度下操作，防止NH₄⁺挥发解吸。离子交换过程中，NH₄⁺的交换度可达40%，在120 ℃、氧体积分数6%、空速3 000h^-1和水体积分数7%和无外加还原剂条件下，MnO₂/NH₄NaY可保证入口浓度为1 000×10^-6的NOx在连续7 h内达到完全转化。在高空速（12 000 h^-1）有稳定氨源下，于MnO₂/NH₄NaY上进行的SCR稳态实验充分证明，存在于MnO₂/NH₄NaY的NH₄⁺对催化反应明显有利。 它可使NH₃与NOx物质的量比从以往的1.2降至1，大大减少由于NH₃泄露而造成的二次污染。     

UV/Fe3+/H2O2体系降解活性艳橙X-GN废水的动力学研究

在自制的光催化反应器中，采用UV/Fe³⁺/H₂O₂体系光解活性艳橙X-GN模拟废水，考察了X- GN、Fe³⁺和H₂O₂初始浓度、初始pH值及温度对光解过程的影响。结果表明，在8 W低压汞灯(λ＝254 nm)照射下，UV/Fe³⁺/H₂O₂能够有效地降解结构稳定的X-GN，在pH=3.0、温度50 ℃、时间120 min、Fe³⁺和H₂O₂初始浓度分别为2.5×10^－5 mol·L^－1和1.5×10^－4 mol·L^－1时，含200 mg·L^－1X GN模拟废水的色度去除率和TOC去除率分别达到100%和90.15%。在此基础上得到了该催化氧化反应的一级动力学模型，求得X-GN氧化和TOC降解动力学模型的表观活化能分别为867 kJ·mol^－1和25.38 kJ·mol^－1。同时依据离子色谱 (IC)、GC/MS对X-GN降解中间产物和最终产物的进行了鉴定，证实有导致X-GN氧化和TOC降解不同步的中间产物存在。     

橡胶改性尼龙6动力学

采用酰基己内酰胺封端的丁腈橡胶(CHTBN)或丁苯橡胶(CHTBS)与NaOH作为引发催化体系,反应温度在145～160℃之间,通过绝热法测定反应过程的温升曲线,计算得到了动力学参数。采用CHTBN/NaOH时反应级数为一级,活化能在72.91～73.16 kJ·mol-1之间,指前因子在3.22×10¹¹～3.38×10¹¹mol ^1-n·s^-1范围内;采用CHTBS/NaOH时反应级数在1.23～1.34之间,偏离了1级反应,活化能在85.55～86.88 kJ·mol-1之间,指前因子在4.52×10¹¹～5.09×10¹¹mol ^1-n·s^-1范围内。在前人工作的基础上建立了阴离子聚合绝热反应动力学模型并对反应过程进行了模拟,结果与实验温升曲线具有很好相关性,从而证明了模型的合理。     

Enhanced corrosion resistance of layered double hydroxides/steam coating composite coating prepared by the hydrothermal method on LA43M magnesium–lithium alloy substrates

An excellent anticorrosion Mg–Al layered double hydroxide (LDH) composite coating was successfully fabricated on LA43M magnesium alloy substrates via an in situ steam coating (SC) process and a subsequent hydrothermal treatment at different temperatures. The microstructure, composition and phase formation of the composite coatings were studied via X-ray diffractometer, energy disperse spectroscopy, and scanning electron microscope, respectively. The corrosion resistance of composite coatings was further investigated using electrochemical measurements and corrosion test. The results showed that LDH/SC composite coating has typical nanosheets microstructure, which effectively seal the defects of SC. As the hydrothermal temperature increases, the thickness and density of nanosheets increases, and the corrosion resistance was significantly improved. Especially, the Mg–Al LDH/SC composite coating prepared at 100°C was the most dense and thickness, and exhibited the optimal and long-term anticorrosion resistance in 3.5 wt.% NaCl soultion. It has the lowest I_corr (1.767 × 10⁻⁸ A/cm²), which decreased by three and two orders of magnitude compared with the bare substrate and SC. Furthermore, it can maintain good chemical stability after immersion in the corrosion medium for 192 h and its hydrogen evolution rate (0.00416 mL·cm⁻²·h⁻¹) and weight lost rate (0.00266 mg·cm⁻²·h⁻¹) were the lowest compared with other samples.     

Tribological and corrosion behaviors of fluorocarbon coating reinforced with sodium iron titanate platelets and whiskers

A series of sodium iron titanate (NFTO)–fluorocarbon composite coatings have been prepared with the liquid-phase blending method. The effects of two types of NFTO, NFTO platelets, and NFTO whiskers, on the tribological and corrosion behaviors of the composite coatings, are systematically studied. The results show that the addition of NFTO can significantly enhance the friction-reducing and wear resistance performances of the fluorocarbon coating. Under dry sliding, the minimum specific wear rate is 1.67 × 10⁻⁴ mm³/Nm for the platelet-filled composite coatings and 1.15 × 10⁻⁴ mm³/Nm for the whisker-filled composite coatings, respectively, showing a decrease of 83.5 and 88.6% than that of pure coating. Under a simulated seawater environment, the minimum specific wear rate is 5.44 × 10⁻⁵ mm³/Nm for the platelet-filled composite coatings and 0.84 × 10⁻⁵ mm³/Nm for the whisker-filled composite coatings, respectively, showing a decrease of 90.5 and 98.5% than that of pure coating. The morphologies of worn surfaces, wear debris, and transfer films are analyzed, and the corresponding wear resistance mechanisms are discussed. The electrochemical impedance spectroscopy certifies a remarkably improved corrosion resistance of the composite coatings which have been immersed in 3.5 wt % NaCl solution for 30 days. The composite coating reinforced with 7.5 wt % platelets shows the highest resistance of 256.3 × 10⁶ Ω·cm², approximately two orders of magnitude higher than that of pure coating. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48936.     

Electrochemical corrosion behavior of composite coatings of sealed MAO film on magnesium alloy AZ91D

Protective composite coatings were prepared on magnesium alloy AZ91D by micro-arc oxidation (MAO) treatment plus a top coating with sealing agent using multi-immersion technique under low-pressure conditions. The corrosion resistance of AZ91D alloy with composite coatings was superior evidently to that with merely MAO film. SEM observations revealed that the sealing agent was integrated with MAO film by physically interlocking; therewith covered uniformly the surface as well as penetrated into pores and micro-cracks of MAO film. The anti-corrosion properties in 3.5% NaCl solution of the composite coatings were evaluated by using electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization measurements. Based on the results of chronopotentiometric (E ∼ t) and EIS measurements for long time immersion in 3.5% NaCl solution, appropriate equivalent circuits for the composite coatings system were proposed. It follows that due to the blocking effect of the sealing agent in pores and cracks in MAO film, the composite coatings can suppress the corrosion process by holding back the transfer or diffusion of electrolyte and corrosion products between the composite coatings and solution during immersion.     

Study on electrochemical behavior of Nano‐ZnO modified alkyd‐based waterborne coatings

A nano‐composite coating was formed using nano‐ZnO as pigment in different concentrations, to a specially developed alkyd‐based waterborne coating. The nano‐ZnO modified composite coatings were applied on mild steel substrate by dipping. The dispersion of nano‐ZnO particles in coating system was investigated by scanning electron microscopic and atomic force microscopic techniques. The effect of the addition of these nano‐pigments on the electrochemical behavior of the coating was investigated in 3.5% NaCl solution, using electrochemical impedance spectroscopy. Coating modified with higher concentration of nano‐ZnO particles showed comparatively better performance as was evident from the pore resistance (R_po) and coating capacitance (C_c) values after 30 days of exposure. In general, the study showed an improvement in the corrosion resistance of the nano‐particle modified coatings as compared with the neat coating, confirming the positive effect of nano‐particle addition in coatings. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

中性体系中MoO42-对碳钢垢下局部腐蚀的抑制作用

设计了一种能够模拟垢下局部腐蚀自催化过程的闭塞电池,采用极化曲线和电化学阻抗方法研究了MoO₄^2-对N80钢在近中性NaCl溶液中闭塞区内化学及电化学状态变化的影响。结果表明,MoO₄^2-能有效地减缓闭塞区内pH值降低及Cl^-浓集、减弱酸化自催化效应、抑制垢下局部腐蚀。MoO₄^2-的作用机制在于使水合氧化铁腐蚀膜由阴离子选择性变为阳离子选择性,H⁺可以从膜下扩散出去,而Cl^-难以扩散到膜下富集,抑制了腐蚀反应的阴极过程;同时MoO₄^2-迁入闭塞区后增大了电极表面膜层阻抗,抑制了腐蚀反应的阳极过程。     

Designing of corrosion resistant epoxy coatings embedded with polypyrrole/SiO2 composite

Polypyrrole/SiO₂ composite was synthesized by chemical oxidative polymerization of pyrrole using FeCl₃. The synthesized polymer composite was loaded in epoxy resin to develop coatings for mild steel substrates using powder coating technique. SEM and TEM images reveal homogenous dispersion of SiO₂ particles in polypyrrole matrix. TGA analysis confirms good thermal stability of the polymer composite. Tafel polarization and electrochemical impedance spectroscopy (EIS) results exhibit remarkably high corrosion protection efficiency of epoxy coatings with polymer composite in 3.5% NaCl solution. Corrosion studies of coatings with an artificial defect reveal the passivation of defect by the polymer composite present in the epoxy coatings. Salt spray test results revealed superior corrosion resistance offered by the polymer composite.     

滑动弧等离子体处理酸性橙Ⅱ废水

采用气液两相滑动弧等离子体降解酸性橙Ⅱ,研究了酸性橙Ⅱ的降解动力学及降解机理。结果表明：当电压为10 kV,载气为O₂,气体流速为0.4 m³·h^-1,废水流量为20 ml·min^-1,电极间最窄处距离为3.5 mm,溶液浓度在300 mg·L^-1以下时,滑动弧等离子体对酸性橙Ⅱ的降解符合一级动力学规律。检测了纯水放电时H₂O₂、O₃生成量以及OH·的相对量。运用紫外光谱（UV-Vis）、离子色谱（IC）、色谱-质谱联用（GC-MS）等方法,测定出酸性橙Ⅱ的主要降解产物有乙酸、乙二酸、丙二酸、苯酚、3-羟基苯乙酮、萘、苯磺酸、邻苯二甲酸（酐）、β-萘酚等,并依此推测酸性橙Ⅱ的降解机理,即羟基自由基攻击酸性橙Ⅱ分子上与萘环相连的C—N键,导致C—N键的断裂,进而染料脱色矿化。     

丙酮酸分批发酵的供氧控制模式

以一株光滑球拟酵母的多重维生素营养缺陷型为研究菌株,考察了分批发酵中不同体积传氧系数(KL_a)对其产丙酮酸性能的影响.高KL_a(450 h^-1)下,丙酮酸产率较高(0.797 g·g^-1),但葡萄糖消耗速度较慢(1.14 g·L^-1·h^-1);低KL_a(200 h^-1)下,葡萄糖消耗速度快(1.97 g·L^-1·h^-1),然而丙酮酸产率(0.483 g·g^-1)却明显下降.根据发酵过程主要参数和碳流分配的变化特性提出了发酵前16h控制KL_a为450h^-1、16h后控制KL_a为200 h^-1的分阶段供氧控制模式,结果实现了高产量(69.4 g·L^-1)、高产率(0.636 g·g^-1)和高葡萄糖消耗速度(1.95g·L^-1·h^-1)的相对统一,丙酮酸生产强度(1.24g·L^-1·h^-1)比控制KL_a恒定为450、300和200h^-1的过程分别提高了36％、23％和31％.实验数据表明,供氧良好状态下细胞产丙酮酸性能出现的差异可能是由维生素处于亚适量水平时酵解产生的NADH去路不同,导致细胞处于不同的能量水平而引起的.     

螺旋升流式反应器系统较长泥龄时运行效果及其流态释因

结合螺旋升流式反应器（SUFR）的特性,通过对比试验分析SUFR系统在较长泥龄时（主要在32 d左右）营养物去除的工艺特点。试验结果表明,SUFR系统（θ_c=32 d）出水COD和TN分别小于40 mg·L^-1﹑10 mg·L^-1,SUFR系统（θ_c=32 d）除磷率随着泥龄的延长有一定的下降,但出水TP一直稳定在1 mg·L^-1内, SUFR系统（θ_c=32 d）的SOUR值为10～18 mg·g^-1·h^-1。流态模拟结果表明,SUFR系统中单元反应器的推流流态容积利用率为63%。这说明SUFR系统反应器以活塞流为主要特征的流态特性有助于减轻较长泥龄对污水处理的负影响。该系统具有更宽的泥龄适宜范围。     

Corrosion resistance of Pb–Sn composite coatings reinforced by carbon nanotubes

Carbon nanotubes/Pb–Sn composite coatings were prepared by electrodeposition technology. The polarization curves and electrochemical impedance of the Pb–Sn coatings and carbon nanotube/Pb–Sn composite coatings were studied in 3.0 wt% HCl, 10 wt% NaOH, and 3.5 wt% NaCl electrolyte solutions, respectively. The results show that the corrosion potential of carbon nanotubes/Pb–Sn composite coatings were improved in the three kinds of corrosive medium, especially in 3.5 wt% NaCl electrolyte solution, where it increased significantly from −0.592 V (vs SCE) to −0.535 V (vs SCE). In addition, composite coatings have higher electrochemical impedance. Carbon nanotubes can improve the corrosion resistance of lead–tin electroplated coatings.