Thermodynamic and Kinetic Studies of Effective Adsorption of 2,4,6-trichlorophenol onto Calcine Mg/Al-CO_3 Layered Double Hydroxide

Adsorption of 2, 4, 6-trichlorophenol(TCP) onto the calcined Mg/Al-CO_3 layered double hydroxide(CLDH) was investigated. The prepared Mg/Al-CO_3 layered double hydroxide(LDH) and CLDH were characterized by powder X-ray diffraction(XRD) and thermo gravimetric analyzer-differential scanning calorimeters(TG-DSC). Moreover, 2,4,6-trichlorophenol(TCP) was removed effectively(94.7% of removal percentage in 9h) under the optimized experimental conditions. The adsorption kinetics data fitted the pseudosecond-order model well. The Freundlich, Langmuir, and Tempkin adsorption models were applied to the experimental equilibrium adsorption data at different temperatures of solution. The adsorption data fitted the Freundlieh adsorption isotherm with good values of the correlation coefficient. A mechanism of the adsorption process is proposed according to the intraparticle diffusion model, which indicates that the overall rate of adsorption can be described as three steps.     

Thermodynamic and kinetic studies of effective adsorption of 2,4,6-trichlorophenol onto calcine Mg/Al-CO<Subscript>3</Subscript> layered double hydroxide

Adsorption of 2, 4, 6-trichlorophenol (TCP) onto the calcined Mg/Al-CO₃ layered double hydroxide (CLDH) was investigated. The prepared Mg/Al-CO₃ layered double hydroxide (LDH) and CLDH were characterized by powder X-ray diffraction (XRD) and thermo gravimetric analyzer-differential scanning calorimeters (TG-DSC). Moreover, 2,4,6-trichlorophenol (TCP) was removed effectively (94.7% of removal percentage in 9 h) under the optimized experimental conditions. The adsorption kinetics data fitted the pseudo-second-order model well. The Freundlich, Langmuir, and Tempkin adsorption models were applied to the experimental equilibrium adsorption data at different temperatures of solution. The adsorption data fitted the Freundlieh adsorption isotherm with good values of the correlation coefficient. A mechanism of the adsorption process is proposed according to the intraparticle diffusion model, which indicates that the overall rate of adsorption can be described as three steps.     

十二烷基苯磺酸钠对磁性多壁碳纳米管吸附水中重金属离子的影响

通过水溶液中磁性多壁碳纳米管(MWCNTs)对Cd(II)、Zn(II)、Cu(II)三种重金属离子的吸附实验,探讨了十二烷基苯磺酸钠(SDBS)表面活性剂的添加量对吸附效率的促进与抑制效应,以及溶液pH值和碱金属离子强度对磁性MWCNTs吸附重金属离子的影响.实验结果表明:溶液的酸性或强碱性对磁性MWCNTs吸附重金属离子有较强的负面影响;而溶液呈中性偏碱性时(pH值在7~10)吸附效果较好,其最大值达90%以上;水中存在SDBS时,磁性MWCNTs吸附重金属离子的效果受溶液酸碱性的影响很小,但SDBS剂量较大时,吸附效果则会受影响;添加Na+、K+改变水溶液中的离子强度,吸附效果几乎不受影响.吸附动力学研究发现,准二级方程能够真实地拟合重金属离子在磁性MWCNTs上的吸附过程.     

用金的阳极溶解方法研究氯化钠在硫代硫酸盐浸金过程中的作用

用极谱法研究了金在不同浓度的S_2O_3~(2-)溶液及其中加氨、加Cl~-以及同时加氨和Cl~-的阳极溶解行为。结果表明,在前两种溶液中的行为与文献基本一致,在加Cl~-的溶液中的行为与加氨的类似,电流峰值较加氨时的高,同时加氨和Cl~-的溶液则可得到更高的电流峰值,但氨和Cl~-的浓度应相互配合。说明Cl~-与NH_3在金的阳极溶解中的作用类似,但作用更强,尤其是NH_3与Cl~-有适当的浓度比时。     

Passivation Mechanism of 316L Stainless Steel in Oxidizing Acid Solution

The compositions and the chemical valence states of elements of 316L stainless steel passive film formed in the oxidizing acid solution were studied by X-ray Photoelectron Spectroscopic (XPS) analysis. The electrochemical polarization curve was measured. The passivation process in the oxidizing acid solution was studied by AC impedance technology. The results indicated that the stable compounds layer was formed on the surface of the sample and the adsorption was the main step in the nitrite solution during passivation process. The catalysis passivation mechanism was put forward according to the experimental results. During passivation process, the water molecule was adsorbed on the surface of the sample at first in the oxidizing acid solution. The oxidizer in the solution played a role as catalyst. The oxide and hydroxide, which could be changed each other and finally formed stable passive film, were generated from adsorbing intermediate under the catalytic action. The mathematical models for predicting the steady polarization curve and the AC impedance spectra at certain conditions have been obtained. The passivation mechanism of 316L stainless steel in the oxidizing acid solution can be interpreted by the catalysis passivation mechanism.     

A Method of Preparation of Ag/AgCl Chloride Selective Electrode

We put forward a method of rapid preparation of chloride selective electrode (Ag/AgCl electrode) by dipping silver wire into sodium hypochlorite solution. The electrodes were prepared through different immersion time. The properties of the electrodes, such as Nernst response, response time and long-term stability, were tested in simulated concrete pore solutions (SCPS). Moreover, the surface morphology of the electrodes was also detected after immersion in solutions over three months. The experimental results reveal that the Ag/AgCl electrode with the fabrication time of 20 minutes (E-20) which is recommended to work as the chloride ion selective electrode has the best performance. Compared to that fabricated by the electrolytic process (E-EP), E-20 can be manufactured in mass. The method has almost the same good performance of Nernst response as E-EP, and has a better response time which is less than 25 seconds. The method also shows a better good long-term stability in SCPS containing chloride ions over three months.     

Localized electrochemical impedance spectroscopy study on the corrosion behavior of Fe-Cr alloy in the solution with Cl− and SO4 2−

The corrosion behaviors of Fe-Cr alloy under three different pH values solutions with Cl- and SO42- were investigated by localized electrochemical impedance spectroscopy (LEIS) measurements and the corrosion products were analyzed by laser Raman spectrometry. The results show that the high corrosion resistance of Fe-Cr Alloy is attributed to a passive film which is formed more easily when the alloy contains a large quantity of Cr element. However, its corrosion resistance varies in the solutions with different pH values, especially in the initial corrosion. The average impedance values in neutral and alkaline solution are much higher than that in acidic solution because the passive film is more likely to dissolve in the acidic condition. Moreover, the destructive effect of Cl- and SO42+ ions on the passive film is also demonstrated in corrosion process through the change of the impedance value with the steeping time.     

分子筛吸附碳四烃中甲醇的实验研究

用小型固定床吸附实验装置测定了碳四烃中甲醇在ＮＪ－１Ａ型吸附剂上的透过曲线,利用数值方法对吸附平衡常数进行了估值。实验结果显示,３０℃时,在０％～５％的浓度范围内甲醇在ＮＪ－１Ａ分子筛上的吸附等温线可用Ｌａｎｇｍｕｉｒ方程近似,计算结果与实验数据符合良好。     

改性斜发沸石对OH~-吸附动力学的研究

以5种改性斜发沸石为原料,通过吸附不同碱溶液中的OH-,确定了最佳的碱溶液和改性沸石,并对OH-浓度和吸附动力学进行了研究.研究表明:钙改性沸石和镁改性沸石对Ca(OH)2溶液中OH-的单位吸附量最大;在25℃下,钙改性沸石的全吸附容量为22.21mg/g,镁改性沸石的全吸附容量为25.30mg/g;通过动边界模型理论可确定在25℃下钙改性沸石和镁改性沸石吸附OH-的动力学吸附过程主要由颗粒扩散控制.     

Anticorrosion performance of the coating/metal system by electrochemical impedance spectra

In order to investigate the anticorrosion performance of the organic coating/metal system, electrochemical impedance spectra (EIS) were measured in the 3.5wt% NaCl solution, the chemical component and the formation of corrosion products scale were analyzed by laser Raman microspectroscopy, and the pattern of the organic coating/metal system was observed by scanning electron microscopy (SEM). The characteristics and the delamination process of the organic coating/metal system were investigated systematically, and the emphases were on the transportation of the corrosive medium and the changes of the coating/metal interface. The results show that the impedance decreases at the initial immersion, then increases at the middle-immersion, and again decreases at last, which is related to the corrosion products scale. The concentration of Cl- in the coating, which destroys the corrosion products scale, increases with the immersion time.     

双向非均质黏性阻尼土中管桩纵向振动特性

管桩施工会使土体产生扰动,从而引起桩周土体沿桩基径向的不均匀性,为同时考虑桩周土体此种径向非均质效应和纵向成层特性对管桩纵向振动动力阻抗的影响规律,提出基于土体黏性阻尼的多圈层平面应变模型,建立双向非均质土中管桩纵向振动简化分析模型,利用拉普拉斯变换和阻抗函数的传递性,推导得出管桩桩顶动力阻抗解析解答,计算结果表明,纵向软硬夹层对一定低频区间内动力阻抗曲线振幅水平影响显著,夹层越软（硬）,共振频率处对应的动力阻抗曲线振幅水平越高（低）.施工扰动引起桩周土径向非均匀性对管桩桩顶复刚度曲线影响显著,在对管桩进行纵向振动特性分析时宜采用双向非均质黏性阻尼土-管桩相互作用模型推导所得解析解答更为合理.     

水合二氧化钛吸附与除铁影响因素

为探究水合二氧化钛对亚铁离子的吸附平衡与吸附动力学,通过静态吸附实验,研究了吸附平衡时间、亚铁离子浓度、吸附硫酸质量浓度和温度对水合二氧化钛吸附亚铁离子的影响;通过真空抽滤洗涤实验考察了洗水硫酸质量浓度和温度对洗涤过程中铁去除率的影响.结果表明,水合二氧化钛吸附亚铁离子的平衡吸附时间为9h,亚铁离子初始浓度最佳为300mg/L,硫酸质量浓度的增加和温度的升高均不利于水合二氧化钛对亚铁离子的吸附;吸附动力学符合一级动力学Lagergren方程,吸附等温方程符合Freundlich方程;洗涤过程中洗水的温度升高和洗水的硫酸质量浓度提高均利于亚铁离子的去除.     

钢筋在混凝土模拟孔溶液中的腐蚀研究

钢筋锈蚀是影响混凝土结构耐久性的主要因素.研究了模拟孔溶液pH值、Cl-浓度、SO42-浓度以及空气等对钢筋锈蚀的影响.试验结果表明：随溶液pH值降低,钢筋锈蚀程度增加.随孔溶液中Cl-浓度增加,锈蚀钢筋增重率线性增加.依据钢筋增重率判断,Cl-导致钢筋锈蚀临界值为0.065%.氯盐溶液中SO42-存在使钢筋锈蚀速度变为原来的2~3倍.将腐蚀溶液中钢筋与空气隔绝将延缓钢筋锈蚀.     

嵌岩桩沉渣特性对桩顶动力响应的影响

基于虚土桩模型,运用Laplace积分变换和阻抗函数递推方法研究了纵向任意激振力作用下沉渣特性对成层土中嵌岩桩桩顶动力响应的影响.将桩端沉渣模拟为虚土桩,对桩侧土采用平面应变模型,并考虑其成层特性,结合初始条件和桩顶及沉渣底部的边界条件,求得在桩顶任意激振力作用下,考虑沉渣影响的桩顶频域响应解析解及时域响应半解析解.基于理论解,分析了沉渣特性对桩顶动力响应的影响,并将理论计算结果与工程桩低应变反射波法实测曲线进行了拟合对比,结果表明,基于虚土桩模型的理论解能较好地反演出沉渣特性对桩顶动力响应的影响.     

毛细作用下硫酸钠半浸泡水泥基材料抗氯离子渗透性研究

硫酸盐和氯盐复杂盐蚀环境中的服役结构会受到两者产生的耦合作用。研究毛细作用下硫酸钠半浸泡混凝土试样的抗氯离子渗透性能,设计不同水灰比、不同硫酸钠溶液浓度的砂浆毛细上升试验,测试硫酸钠半浸泡混凝土试样的扫描电镜（SEM）、X射线衍射（XRD）和氯离子电通量。结果表明：硫酸钠半浸泡混凝土抗氯离子渗透性能劣化,前期劣化严重,随着半浸泡时间的延长,抗氯离子渗透性能有所回升,但依然比未浸泡试样的差。结合微观测试结果可知,混凝土抗氯离子渗透性能劣化的主要原因是：前期,在毛细作用下硫酸钠溶液填充了混凝土孔隙,减弱了固化氯离子的结合能力,释放了较多自由氯离子,从而增大了氯离子的扩散量;后期,随着浸泡时间的延长和环境湿度的变化,孔隙中的硫酸钠溶液过饱和后,形成无水Na₂SO₄和Na₂SO₄·10H₂O结晶体的混合物,结晶混合物沉淀于孔壁,部分阻碍了氯离子的扩散,从而减缓了抗氯离子渗透性能的劣化。硫酸钠溶液浓度超过5%以后,随着硫酸钠溶液浓度的升高,毛细上升速度减缓,混凝土抗氯离子渗透性能相应提高。硫酸钠溶液半浸泡下,水泥基材料毛细上升快慢可作为衡量混凝土抗氯离子渗透性能好坏的指标。硫酸钠和氯化钠的复合溶液对硫酸钠毛细上升有延缓作用,会改善混凝土的抗氯离子渗透性能。     

Invading track of chloride ions in cemented-based materials

Invading track of chloride ions and chloride ion distribution rule in cement-based materials were investigated by partially soaking in 3.5% (mass fraction) NaCl solution and fully immerging in 3.5% and 5.0% (mass fraction) NaCl solution, respectively, and relevant invading mechanisms were discussed. Results indicate that under full immerging condition, the invading track of chloride ions in cement mortar is similar to beeline that is vertical to chloride ion invading direction, and chloride ion content decreases rapidly with the increase of chloride ion invading depth. Under partial soaking condition, the invading track of chloride ion in cement mortar is similar to the shape of concave parabola, and chloride ion content decreases slowly along the lengthway direction of cement mortar samples in the distance of 20-80 mm from the bottom. Lots of chloride ions accumulate in cement mortar surface layer under the effect of capillary rise and evaporation and then invade cement mortar by diffusion effect. Under partial soaking condition, cement mortar is distinguished by four areas, i.e., immerging area, wet area, crystallization area and dry area.     

养护湿度对混凝土内氯离子传输的影响

为得出早期养护湿度对混凝土内腐蚀介质传输的定量影响,以氯盐侵蚀为例,从水化度及孔隙率角度分析了混凝土养护湿度与氯离子扩散系数之间的相互关系,建立了不同养护湿度下氯离子扩散系数的计算模型.对制作的普通混凝土及掺纤维混凝土试件采用不同湿度进行养护,然后将试件在Na Cl溶液中分别浸泡60 d和180 d,测试得到的氯离子质量分数表明,早期养护湿度越大,混凝土的表观氯离子扩散系数越小.相对于正常浇水养护,饱水养护可降低氯离子扩散系数10%~20%,而不养护将使氯离子扩散系数增大14%~29%.纤维的加入能减弱不正常养护对混凝土耐久性的影响.最终利用试验数据回归得出了模型中不同材料所对应的参数,给出了不同湿度养护后混凝土的表观氯离子扩散系数计算公式.     

NaA沸石与阳离子型表面活性剂的相容性

采用分光光度测量和离子交换能力测定等方法,研究在不同溶液环境中阳离子型表面活性剂在沸石粒子表面的吸附量,并由此推断ＮａＡ沸石与阳离子型表面活性剂的相容性及影响条件。     

2A12铝合金电化学腐蚀行为研究

采取正交试验方法,利用极化曲线和电化学阻抗谱(EIS)等电化学方法研究了2A12铝合金在不同溶液浓度、pH值以及温度的NaCl溶液中的腐蚀行为。试验结果表明,溶液浓度、pH值以及温度对2A12铝合金在NaCl溶液中耐腐蚀行为的影响依次为：pH值、温度、溶液浓度。2A12铝合金的耐腐蚀性能随着NaCl溶液浓度的增加而变差;NaCl溶液温度越高,腐蚀电流密度Icorr越大,合金耐腐蚀性能下降;溶液中性条件下,合金耐腐蚀性能最强,碱性条件下耐腐蚀性能最差;酸性条件下腐蚀电流密度Icorr随pH值的降低而增大,合金耐腐蚀性能减弱。     

变信赖域序列凸规划RLV再入轨迹在线重构

针对可重复使用运载器（RLV）的再入轨迹重构问题,提出一种基于变信赖域序列凸规划的RLV再入轨迹快速求解方法. 首先,通过离散化及对非凸约束的线性化处理,将RLV的非凸轨迹优化问题转换为凸优化问题,然后通过序列凸规划方法对凸优化问题进行求解. 在序列凸规划求解过程的初始迭代中,采用预测校正算法对初值猜测轨迹进行设计,确定轨迹求解的终端时间;在后续迭代过程中,设计基于优化性能指标的信赖域更新策略,提升算法的收敛性能. 在轨迹快速求解方法的基础上,考虑RLV再入过程中可能发生的突发事件,如实际轨迹大幅度偏离参考轨迹或目标点变更,基于变化的初值约束及终端约束在线重构轨迹,并结合重构轨迹和LQR（Linear quadratic regulator）方法设计再入制导律实现对重构轨迹的有效跟踪. 最后,将此设计方法与Gauss伪谱法及传统序列凸规划算法进行仿真对比验证. 仿真结果表明:变信赖域序列凸规划方法相较于伪谱法和传统的序列凸规划方法在轨迹求解实时性及收敛性方面有较大的提升,具备应用于轨迹在线重构的能力,此外,所提出的轨迹在线重构方法具备良好的鲁棒性以及抗扰性.