蛋氨酸衍生物缓蚀剂的合成与性能研究

以蛋氨酸为基础通过酰胺化反应合成一种新型的蛋氨酸衍生物缓蚀剂,应用极化曲线、电化学阻抗谱图研究蛋氨酸及其衍生物在3(wt)%Na Cl溶液中对N80碳钢的缓蚀作用,利用SEM观察添加缓蚀剂过后钢片表面的腐蚀形貌,并从分子结构上探讨了缓蚀剂在碳钢表面的作用机理。结果表明,蛋氨酸及其衍生物都属于阳极型缓蚀剂,且缓蚀率随着添加浓度增加而增加,添加250mg/L蛋氨酸衍生物在3(wt)%Na Cl溶液中对N80碳钢的缓蚀率达到86.94%。相同浓度条件下蛋氨酸衍生物的缓蚀率要高于蛋氨酸,其原因是蛋氨酸衍生物分子结构中增加了吸附位点和疏水长链。     

抑制Q235钢CO2腐蚀的气液双相咪唑啉衍生物缓蚀剂的缓蚀行为

采用失重法、交流阻抗(EIS)及傅里叶变换红外光谱(FT-IR)、原子力显微镜(AFM)、X射线光电子能谱(XPS)等表面分析测试方法首次研究了硫脲基咪唑啉衍生物(TAI)作为抑制CO₂腐蚀的气液双相缓蚀剂的缓蚀行为. 结果表明, 该硫脲基咪唑啉缓蚀剂能有效地抑制Q235 钢在气液双相中的CO₂腐蚀. AFM测试结果表明该缓蚀剂能显著地降低碳钢表面的腐蚀破坏, 并且由于碳钢表面形成的缓蚀剂吸附膜的疏水作用,可在AFM探头和碳钢表面之间检测到更大的粘附力, 而探针与试样表面之间的长程静电斥力在气相中增加,在液相中由于表面电荷的屏蔽效应而减小. XPS和FT-IR 光谱测试表明液相中和气相中在碳钢表面形成吸附膜的缓蚀剂成分分别是硫脲基咪唑啉衍生物和其酸水解产物——酰胺. 以上结果也进一步证实了咪唑啉衍生物在酸性溶液中的水解机理.     

咪唑啉衍生物在含CO_2的模拟深层气井水溶液中缓蚀机理(英文)

应用电化学弱极化法和原子力显微镜(AFM)研究了咪唑啉衍生物类缓蚀剂在模拟深层气井水溶液中对碳钢的二氧化碳腐蚀的抑制效果和缓蚀作用机理.结果表明,在不同的实验温度下,该缓蚀剂均具有较好的缓蚀性能,属于以抑制阳极为主的混合型缓蚀剂.该咪唑啉衍生物在碳钢表面上的吸附遵从Langm iur方程.计算了该腐蚀体系热力学参数(ΔH°、ΔG°和ΔS°)以及腐蚀反应的活化能(Ea)和指前因子(A),并解释了实验结果.     

硫脲及其衍生物对铜阴极电沉积影响的电化学研究

铜的电解精炼中硫脲是一种重要的有机添加剂,它对铜阴极电沉积质量的影响已早有报道［１,４］,但硫脲及其衍生物对铜阴极电沉积过程的影响尚未见报道．为此,我们采用线性电位扫描法、循环伏安法、ＸＲＤ测试技术,研究了在铜电解液中分别添加硫脲、丙烯基硫脲或苯基硫脲等,对阴极铜沉积过程及其电化学参数ｉ０,αｎ,Ｉｄ产生的影响,实验采用的电解温度及铜、酸含量均以电解铜实际生产的条件给定．１　实　验采用三电极体系,阴、阳极均由含铜９９．９８％的纯铜片制备,面积１×１ｃｍ２,参比电极为饱和硫酸亚汞电极．电解前用１～…     

铜表面烯丙基硫脲自组装膜的电化学行为

为阐明金属Cu在含稀丙基硫脲NaCl溶液中的腐蚀行为和规律,利用自组装技术在铜表面制备了烯丙基硫脲自组装膜,并在中性氯化钠体系中测试了该自组装膜的电化学行为和缓蚀效率.电化学测定表明,烯丙基硫脲自组装膜对阴极过程有明显的抑制,并且发现自组装膜的保护性质与腐蚀电位、烯丙基硫脲的浓度和溶液中Cl-浓度密切相关.烯丙基硫脲的...     

分子结构对咪唑啉缓蚀剂膜在Q235钢表面生长和衰减规律的影响

采用弱极化法、电化学阻抗谱等手段研究了烷基咪唑啉和硫脲基烷基咪唑啉缓蚀剂对Q235钢在饱和CO2盐溶液中的缓蚀行为变化, 探讨了吸附膜的形成与衰减规律. 结果表明, 烷基咪唑啉和硫脲基烷基咪唑啉缓蚀剂都是以控制阳极过程为主的混合界面型缓蚀剂. 在85 ℃下, 烷基咪唑啉成膜相对较慢, 吸附能力较弱, 容易发生脱附; 而硫脲基的引入, 使得硫脲基烷基咪唑啉缓蚀剂溶液存在自动修复能力, 增强了咪唑啉环的吸附性能, 提高了缓蚀剂的缓蚀性能; 硫脲基烷基咪唑啉水解开环后, 成膜性能下降, 膜寿命和缓蚀效率也大大降低. 最后采用量子化学计算对上述结论进行了验证和解释.     

模拟混凝土孔隙液中D-葡萄糖酸钠复合缓蚀剂对钢筋的阻锈作用

应用电化学技术, 结合扫描电子显微镜(SEM)观测, 研究D-葡萄糖酸钠、钼酸钠和硫脲三组分复合缓蚀剂对模拟混凝土孔隙液中钢筋腐蚀行为的影响及其阻锈作用. 结果表明: 在含3.5% (w) NaCl的模拟混凝土孔隙液中, 复合缓蚀剂具有协同效应, 对钢筋有良好的阻锈作用. 当D-葡萄糖酸钠、钼酸钠和硫脲浓度分别为750、250和500 mg·L^-1时, 对钢筋的缓蚀效率可达到94.5%. 应用软硬酸碱(HSAB)理论分析缓蚀机理, 可认为三组分复合缓蚀剂在钢筋表面共同形成保护膜而阻止钢筋的腐蚀.     

pH值对十二胺在碳钢表面的吸附行为及缓蚀机理的影响

采用电化学方法和扫描电镜技术, 研究了pH值对十二胺在碳钢表面的吸附以及对碳钢CO2腐蚀缓蚀机理的影响. 研究结果表明, 溶液的pH值对十二胺的吸附和缓蚀机理起决定性作用. 十二胺对碳钢的缓蚀作用随溶液pH值的增加而增强. pH值为4.9时, 十二胺主要抑制腐蚀的阴极过程. 缓蚀剂分子在金属表面上的吸附能比较低, 缓蚀剂容易发生脱附, 因此不能有效抑制腐蚀反应的进行. pH值为6.9时, 缓蚀剂的吸附能较高, 能够牢固地吸附在金属表面, 形成有效的扩散阻挡层, 同时抑制腐蚀的阴、阳极过程, 从而有效地抑制腐蚀反应的进行.     

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     

钙作为合金元素对铝在碱溶液中的缓蚀作用及其与酒石酸盐的协同效应

通过集气法、极化曲线和电化学阻抗谱研究了在铝中添加合金元素钙对其在碱 溶液中的缓蚀作用及其与酒石酸盐的协同效应。实验结果表明，铝电极的腐蚀速率 随钙含量的增加而减小。溶液中不含酒石酸盐时，钙对电极反应的阴极过程有显著 的抑制作用，对阳极过程作用不明显；而当溶液中含有酒石酸盐时，阴极过程和阳 极过程均被显著抑制。阻抗谱的解析结果还表明，钙离子或酒石酸钙络离子是通过 减小反应物在活性位上的反应速率而起缓蚀作用的，它们可能属于界面型缓蚀剂而 非成相型缓蚀剂。     

Calculation of the tau dependence of the vibration-internal rotation-overall rotation interactions in CH3OH from molecular structure and molecular dynamics

The Guan and Quade theory for vibration-large-amplitude internal-motion-rotation interactions has been applied to the internal rotation problem in CH(3)OH. Through the molecular dynamics, the cos 3tau and sin 3tau dependence of the torsional-rotational coefficients in the effective Hamiltonian have been calculated from molecular structure. The internal rotation coordinate tau(') for the vibrationally distorted molecule is shown to have the necessary threefold symmetry for all values of tau('). For the methyl deformation modes, the vibrational dependence of the internal rotation potential energy is shown to have a threefold symmetry. The S(t) and S(t)S(t) dependence of the inertia tensor and Coriolis coupling coefficients has been developed in terms of curvilinear internal coordinates. The T transformation separating rotation from vibrations in zeroth order is then applied, the kinetic-energy tensor inverted to momentum space, and finally the effective torsion-rotation coefficients are calculated by Van Vleck perturbation theory. When compared to the empirical results, the kinetic-energy contributions to the cos 3tau and sin 3tau dependence of the coefficients are as follows: 54% of P(a)(2) is accounted for, 28% of P(a)P(b), 16% of P(a)P(c), and 91% of the asymmetry. The calculation is inadequate to account for the P(b)(2),P(c)(2), and P(b)P(c) coefficients, ranging from factors of 20-70, even with the incorrect sign for some of the terms. Anharmonic force contributions from the vibrations have not been used in the calculation since these forces are not known at this time.     

Static-lattice theory of crystalline HCN.: II. Elastic and piezoelectric properties

An effective dipole potential is used to calculate the elastic and piezoelectric coefficients for a static-lattice model of tetragonal HCN, using the generalized thermodynamic theory of internal strain. The model is unstable with respect to molecular rotation away from the tetragonal axis, owing to the use of a point effective dipole. An improved potential would represent the molecule as a set of polarizable point dipoles. Isotropic pressures makes HCN expand along the tetragonal axis as it contracts perpendicular to the axis, because of strong elastic cross-linking. The piezoelectric stress coefficient for shear strain is dominated by the contribution from molecular rotation. Both physical and thermodynamic coefficients are calculated; the differences between the coefficients, which arise from the permanent polarization in HCN, are especially marked in the strain coefficient.     

Simple expressions for diffusion coefficient determination of adsorption within spherical and cylindrical absorbents using direct simulation method

Various analytical expressions for solute adsorption kinetics within porous absorbents of defined geometry (planar sheet, cylinder, and sphere) are available in the literature. However, these expressions are limited for practical numerical evaluation because they are based on infinite series. An investigation of these expressions has been carried out and then accurate but simple expressions derived that enable rapid determination of effective diffusion coefficients for adsorption within geometrically categorical absorbents. These involve directly fitting calculated kinetic adsorption curves to experimental ones. A simple one point method is also proposed to estimate the effective diffusion coefficient for an adsorption process within these simple geometrical absorbents as an initial value for a best fit.     

锂离子在石墨负极材料中扩散系数的测定

锂离子电池是以各种碳材料为负极而起来的一 种新型电池,成功地解决了以 为负极瓣锂可充电电池的安全性问题,已经应用于锂离子电池的负极材料有石墨和石油焦炭,正在研究的负极材料有热解碳,石墨化碳纤维,硼炭或硼炭氮化合物以及锡基氧化物等[1],石墨的比容量要比石油焦炭的比容量高一倍左右,其理论比容量372mA.h.g^-1,但锂离子在石墨材料中的扩散系数比较低,限制了以其为负极材料的电池的大电流充放电能力,锂离子在电极材料中的扩散系数可以用多种电化学方法测量得到,主要有：电位间歇滴定方法（PITT）（Potentiostatic Intermittent Titratiobn Technique)^[2,3,4,6],恒电流间歇滴定法（GITT）（Galvanostatic Intermittent Titration Technology)^[6],电流脉冲松弛法（CPR）（Current Pulse Relaxation Method)^[3,6]和交流阻抗法（A－C Technology)^[4,5,6],GITT,CPR,A-C等方法测定锂离子扩散系数时,由于相变发生处dE/dy值不容易准确得到（相变时,dE/dy→0）,此时测得的扩散系数误差比较大,PITT方法测定锂离子扩展系统,不存在这个问题,能比较准确地测定整个嵌入组成范围内的锂离子扩散系数。     

某些单体-单体、单体-二聚体体系的活度系数

用气液色谱法测定了苯在二苯醚、联苄、二苄醚、二苯甲烷、二苯乙炔、二苯甲酮、联苯、二苯胺、α-甲基萘、α-氯萘、α-溴萘、氮萘、α-硝基萘、α-萘胺等十四种溶剂中的无限稀活度系数;用单体-二聚体的溶液模型对以上体系进行活度系数的计算,计算值与实验值接近。 用气液色谱法测定了甲苯、乙苯、邻二甲苯、对二甲苯、间二甲苯等五种溶质在环丁砜、二甲基环丁砜、N-甲基吡咯烷酮,5,N-二甲基吡咯烷酮等四种溶剂中的无限稀活度系数;用单体-单体的溶液模型计算溶剂的“溶解度参数”,计算得各溶剂的“溶解度参数”分别为一常数。     

Calculation of effective diffusion coefficient in a colloidal crystal by the finite-element method

The work is devoted to the calculation of effective diffusion coefficient of ions from the bulk solution to the electrode through a mask and the calculation of the distribution of the limiting current density over the electrode surface. A colloidal crystal, which is formed by orderly arranged monodispersed spherical particles, serves as a mask. It is shown that the diffusion of electroactive ions in the pores between spherical particles can be simulated by unit cells with rhombic, rectangular, or triangular cross-section. In the latter case, the cell side surface has no periodical boundaries. This simplifies significantly the numerical solution of the Laplace??s equation by the finite-element method. The effective diffusion coefficient in the bulk colloidal crystal is calculated at various values of its porosity. The calculated results agree well with the literature data. It is found that, for close-packed spherical particles, the relative effective diffusion coefficient in the bulk colloidal crystal is 0.16. The thicknesses of transient zones adjacent to the electrode surface and outer boundary of colloidal crystal and the effective diffusion coefficients for these zones are determined. The dependence of effective diffusion coefficient on the number of spherical particle layers in the colloidal crystal is obtained. The distribution of the limiting current density over the electrode surface is analyzed at various numbers of particle layers.     

Interference of elements upon extraction by oxygen-containing extractants: Calculating the distribution coefficients

The extraction of tellurium (IV), tin (IV), and indium (III) by aliphatic alcohols and ketones from hydrochloric acid solutions was studied both upon the individual separation of elements and upon their simultaneous extraction. Electroconductivities of the extracts were measured and, using these data, the dissociation constants of the extracted metal-halogen acids in organic solvents were calculated by Fuoss-Krauss method. A method for calculating the distribution coefficients of elements upon their simultaneous extraction by hydrate-solvate and mixed solvate and hydrate-solvate mechanisms is proposed. It is shown that the calculated distribution coefficients are in good agreement with the experimental data.     

The Effective Permittivity of Reacting Mixture Solutions for Multiphysics Calculations

Huang and Yang (PIER Lett. 5: 99?C107, 2008) proposed a method based on experimental results to calculate the effective permittivity of liquid reacting mixture solutions. The method cannot be directly applied to multiphysics calculations for microwave heating on chemical reactions, because the derived formula of effective permittivity is a function of the reaction time. In this paper, we improve the method to obtain the effective permittivity as a function of the reactants?? concentrations and temperature by numerical fitting. Thus, the formula can be directly used for multiphysics calculation. Three measured effective permittivity curves for the iodination of acetone reaction under constant temperature were used to calculate the corresponding coefficients of the method at both 915?C2,450?MHz. The results calculated by the coefficients are in satisfactory agreement and approach the measured results.     

Thermodynamic perturbation theory of simple liquids. A hierarchy of equations for expansion coefficients

The properties of an expansion of the statistical sum of a simple liquid with respect to the potential in thermodynamic perturbation theory are analyzed. The coefficients of this expansion are determined by the unperturbed potential, depend on temperature and density, and can be calculated by means of mathematical modeling. It is shown here that the derivatives of these coefficients with respect to temperature and density are expressed through the higher expansion coefficient (these relations are usually called a hierarchy of equations). These coefficients determine the expansion of the Helmholtz free energy and RDF with respect to the perturbation potential. The thermodynamic characteristics of the system (entropy, internal energy, pressure) are expressed through both the differential relations for the Helmholtz free energy and the integral expressions containing RDF. It is found that the hierarchy of equations obtained in this work makes these different methods equivalent. This is important for the application of thermodynamic perturbation theory because it becomes unnecessary to model any other equilibrium properties of the system apart from the expansion coefficients.     

The influence of potential softness on the transport coefficients of simple fluids

This study explores the effects of interaction softness on the transport properties of simple fluids. The transport coefficients of soft-sphere fluids in which the particles interact via the potential, phi(r)=epsilon(rsigma)(-n), with n in the range from 6 to 1152, have been calculated by molecular-dynamics computer simulation. The self-diffusion coefficient D shear viscosity eta(s), bulk viscosity eta(b), and thermal conductivity lambda were computed over a wide packing fraction range. It was found that the Batschinski-Hildebrand expressions, in which D, eta(s) (-1), eta(b) (-1), and lambda(-1) are assumed to have a linear dependence on the molar volume, represent the data quite well for all n, although least well for the thermal conductivity. The density for which, on extrapolation, each of these quantities is zero, increases with the softness of the interaction (or approximately n(-1)), suggesting that the effective hard-sphere diameter decreases with increasing softness in the small n limit. This treatment leads to simple empirical formulas for the effect of density and n on the effective hard-sphere diameter and packing fraction (in an intermediate range) and the four transport coefficients of these fluids.