硫酸溶液中1,1’-硫代羰基二咪唑在碳钢上的吸附及缓蚀影响和碘离子的增强效应

The inhibition effect of 1,1’-thiocarbonyldiimidazole (TCDI) on the corrosion behaviors of mild steel (MS) in 0.5 mol·L -1 H2SO4 solution was studied with the help of potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), and linear polarization resistance (LPR) techniques. The effect of immersion time on the inhibition effect of TCDI was also investigated over 72 h. For the long-term tests, hydrogen evolution with immersion time (VH2-t) was measured in addition to the three techniques already mentioned. The thermodynamic parameters, such as adsorption equilibrium constant (Kads) and adsorption free energy (⊿Gads) values, were calculated and discussed. To clarify inhibition mechanism, the synergistic effect of iodide ion was also investigated. The potential of zero charge (PZC) of the MS was studied by electrochemical impedance spectroscopy method, and a mechanism of adsorption process was proposed. It was demonstrated that inhibition efficiency increased with the increase in TCDI concentration and synergistically increased in the presence of KI. The inhibition efficiency was discussed in terms of adsorption of inhibitor molecules on the metal surface and protective filmformation.     

硫酸溶液中1,1'-硫代羰基二咪唑在碳钢上的吸附及缓蚀影响和碘离子的增强应

The inhibition effect of 1,1'-thiocarbonyldiimidazole (TCDI) on the corrosion behaviors of mild steel impedance spectroscopy(EIS),and linear polarization resistance(LPR)techniques.The effect of immersion time on the inhibition effect of TCDI was also investigated over 72 h.For the long.term tests.hydrogen evolution with immersion time(VH2-t)was measured in addition to the three techniques already mentioned.The thermodynamic parameters.such as adsorption equilibrium constant(Kads) and adsorption free energy(△Gads)values,were calculated and discussed.To clarify inhibition mechanism,the synergistic effect of iodide ion was also investigated.The potential of zero charge (PZC)of the MS was studied by electrochemical impedance spectroscopy method.and a mechanism of adsorption process was proposed.It was demonstrated that inhibition efficiency increased with the increase in TCDI concentration and synergistically increased in the presence of KI.The inhibition efficiency was discussed in terms ofadsorption of inhibitormolecules on the metal surface and protective film formation.     

3.5% NaCl饱和Ca(OH)2溶液中醇胺缩聚物对碳钢腐蚀的抑制

利用动电位极化, 电化学阻抗谱(EIS)和表面形貌观察方法, 并结合量子化学计算, 在3.5% NaCl饱和Ca(OH)₂ 溶液中研究探讨了山梨醇与二乙烯三胺缩聚物(SDC)对碳钢腐蚀的抑制行为. 结果表明: SDC的加入可有效降低碳钢的腐蚀电流密度, 提高碳钢的点蚀电位, 表明阻绣剂对Cl^-诱导的局部腐蚀具有良好的抑制作用, 为混合型阻锈剂; 且在所研究浓度范围内, 随添加浓度增加, 缓蚀效率提高. 化合物对碳钢腐蚀的抑制主要源自阻锈剂分子在碳钢表面的静电吸附, 且吸附遵循Langmuir等温吸附规律.     

新型双子表面活性剂在H2S和CO2盐水溶液中对碳钢的缓蚀性能

合成了一系列含有羟基的双子表面活性剂:1,3-双(十二烷基二甲基氯化铵)-2-丙醇(12-3OH-12),1,3-双(十四烷基二甲基氯化铵)-2-丙醇(14-3OH-14),1,3-双(十六烷基二甲基氯化铵)-2-丙醇(16-3OH-16)和1,3-双(十八烷基二甲基氯化铵)-2-丙醇(18-3OH-18).采用静态失重法、极化曲线和交流阻抗技术研究了其在H2S/CO2腐蚀环境中对L360钢的缓蚀作用.结果表明,三种研究方法取得的结论是一致的,缓蚀效果为14-3OH-14>12-3OH-12>16-3OH-16>18-3OH-18.其中,12-3OH-12和14-3OH-14都表现出很好的缓蚀效果,在35mg·L-1的较低浓度下缓蚀率就达95%以上.极化曲线测试结果表明n-3OH-n(n=12,14,16,18)型双子表面活性剂是一种以阳极抑制为主的混合型缓蚀剂.除n=18外,其它三种双子表面活性剂n-3OH-n(n=12,14,16)在L360钢表面的吸附服从朗缪尔等温线,并且属于物理和化学混合吸附.提出了一个用来解释双子表面活性剂在H2S/CO2溶液中缓蚀机理的吸附模型.     

Reaction of 3,3′,4,4′-tetramethyl-1,1′-diphosphaferrocene with [Re2(CO)8(CH3CN)2]: Novel coordination modes of the 1,1′-diphosphaferrocene ligand

Reaction of 3,3′,4,4′-tetramethyl-1,1′-diphosphaferrocene (1) with [Re₂(CO)₈(CH₃CN)₂] afforded two trimetallic complexes in which the heterometallocene is ligated across the Re-Re bond. The structure of the complex having 1 bridging the Re₂(CO)₈ moiety through two P atoms was determined by X-ray diffraction and compared with those of analogous complexes with organic bridging bis-phosphines. The second complex obtained in this reaction presumably contains 1 acting as a (P,Fe) bridging ligand.     

丙炴醇聚合膜对铁在酸性溶液中的缓蚀作用

The formation of polymer film of propargyl alcohol(PA) and its protective ability against corrosion in Fe/H_2SO_4 and Fe/H_2SO_4+H_2S systems have been investigated using impedance measurement. The composition and morphology of the corrosion surface of iron, on which PA polymerized at different bines, were obtained with the aid of SEM and AFM as well as EDX. The results showed that PA polymerized into compact polymer film in Fe/H_2SO_4 and Fe/ H_2SO_4 + H_2S systems, which made iron surface smooth and have a morphologies of regular square structure in microscopic level. In Fe/H_2SO_4 system, macroscopic continuous polymer film of PA was not formed leading to local corrosion on electrode surface. In Fe/H_2SO_4 +H_2S system, the adsorption of H_2S and HS - on electrode surface slowed down the formation of polymer film of PA. However, the iron sulfide, produced after a longer time, increased the continuity of the polymer film of PA and therefore, the polymer film could perform its long-te...更多rm inhibition action.     

酸性介质中羧甲基纤维素钠在低碳钢表面的吸附和缓蚀作用

The effect of sodiumcarboxymethyl cellulose (Na-CMC) on the corrosion behavior of mild steel in 1.0 mol·L-1 HCl solution has been investigated by using weight loss (WL) measurement, potentiodynamic polarization, linear polarization resistance (LPR), and electrochemical impedance spectroscopy (EIS) methods. These results showed that the inhibition efficiency of Na-CMC increased with increasing the inhibitor concentration. Potentiodynamic polarization studies revealed that the Na-CMC was a mixed type inhibitor in 1.0 mol·L-1 HCl. The adsorption of the inhibitor on mild steel surface has been found to obey the Langmuir isotherm. The effect of temperature on the corrosion behavior of mild steel in 1.0 mol·L -1 HCl with addition of 0.04% of Na-CMC has been studied in the temperature range of 298-328 K. The associated apparent activation energy (E*a) of corrosion reaction has been determined. Scanning electron microscopy (SEM) has been applied to investigate the surface morphology of mild steel in the absence and presence of the inhibitor molecules.     

Adsorption Behavior and Inhibition Corrosion Effect of Sodium Carboxymethyl Cellulose on Mild Steel in Acidic Medium

The effect of sodium carboxymethyl cellulose (Na-CMC) on the corrosion behavior of mild steel in 1.0 mol·L-1 HCl solution has been investigated by using weight loss (WL) measurement, potentiodynamic polarization, linear polarization resistance (LPR), and electrochemical impedance spectroscopy (EIS) methods. These results showed that the inhibition efficiency of Na-CMC increased with increasing the inhibitor concentration. Potentiodynamic polarization studies revealed that the Na-CMC was a mixed type inhibitor in 1.0 mol·L-1 HCl. The adsorption of the inhibitor on mild steel surface has been found to obey the Langmuir isotherm. The effect of temperature on the corrosion behavior of mild steel in 1.0 mol·L-1 HCl with addition of 0.04% of Na-CMC has been studied in the temperature range of 298-328 K. The associated apparent activation energy (E*a ) of corrosion reaction has been determined. Scanning electron microscopy (SEM) has been applied to investigate the surface morphology of mild steel in the absence and presence of the inhibitor molecules.     

Adsorption Behavior and Inhibition Corrosion Effect of Sodium Carboxymethyl Cellulose on Mild Steel in Acidic Medium

The effect of sodium carboxymethyl cellulose (Na-CMC) on the corrosion behavior of mild steel in 1.0 mol·L⁻¹ HCl solution has been investigated by using weight loss (WL) measurement, potentiodynamic polarization, linear polarization resistance (LPR), and electrochemical impedance spectroscopy (EIS) methods. These results showed that the inhibition efficiency of Na-CMC increased with increasing the inhibitor concentration. Potentiodynamic polarization studies revealed that the Na-CMC was a mixed type inhibitor in 1.0 mol·L⁻¹ HCl. The adsorption of the inhibitor on mild steel surface has been found to obey the Langmuir isotherm. The effect of temperature on the corrosion behavior of mild steel in 1.0 mol·L⁻¹ HCl with addition of 0.04% of Na-CMC has been studied in the temperature range of 298–328 K. The associated apparent activation energy (E^*_a) of corrosion reaction has been determined. Scanning electron microscopy (SEM) has been applied to investigate the surface morphology of mild steel in the absence and presence of the inhibitor molecules.     

硫酸介质中控制碳钢腐蚀的烷基取代Piperidin-4-one Oximes的立体效应

Three synthesized piperidin-4-one oximes,3-ethyl-2,6-diphenyl-piperidin-4-one oxime(A),1-methyl-3-isopropyl-2,6-diphenyl-piperidin-4-one oxime(B),and 3-isopropyl-2,6-diphenyl-piperidin-4-one oxime(C),were tested at different concentrations to determine their ability to inhibit corrosion of mild steel in 1 mol.L-1 H2SO4 and measured by a mass loss method(at various temperatures),polarization and impedance measurements,X-ray diffraction(XRD),scanning electron microscopy(SEM) with energy-dispersive X-ray spectroscopy(EDS),and a quantum chemical method.The synergistic influence of compounds A,B and C with iodides has also been evaluated.All three compounds show good inhibition efficiency in the following order:A>B>C.Compounds A,B and C were found to physically adsorb on the surface of mild steel while obeying the Temkin isotherm.Polarization measurements indicated that these compounds behave as a mixed mode inhibitor.XRD and SEM with EDS studies revealed the formation of a protective barrier on the mild steel surface by these oximes.The electron donating ability of the studied molecules was tested using semi empirical methods.The studies revealed that the oxime nitrogen,the piperidine moiety,and the phenyl ring assist largely in corrosion control.The studies also showed that the steric crowding by the alkyl group in the piperidine ring affects the inhibitor efficiency.Further,it is interesting to note that all of the studied compounds exhibit synergism with iodide ions.     

氯化硝基四氮唑蓝对钢在盐酸溶液中的缓蚀作用

采用失重法、动电位极化曲线、电化学阻抗谱(EIS)和扫描电子显微镜(SEM)研究了氯化硝基四氮唑蓝(NTBC)在1.0-5.0mo·lL-1HCl溶液中对冷轧钢(CRS)的缓蚀作用.结果表明:NTBC在1.0mo·lL-1HCl溶液中对冷轧钢具有良好的缓蚀作用,且在钢表面的吸附符合Langmuir吸附等温式.缓蚀率随缓蚀剂浓度的增加而增大,但随盐酸浓度和温度的增加而减小.求出了相应的吸附热力学(吸附自由能ΔG0,吸附焓ΔH0,吸附熵ΔS0)和腐蚀动力学参数(腐蚀速率常数k,动力学常数B),并根据这些参数讨论了缓蚀作用机理.动电位极化曲线表明:NTBC为混合抑制型缓蚀剂;EIS谱在高频区呈容抗弧,在低频区出现感抗弧,电荷转移电阻随缓蚀剂浓度的增加而增大.SEM再次表明NTBC对钢在盐酸介质中的腐蚀产生了明显的抑制作用.     

Derivatives of 1,1′-bis(diphenylphosphino)ferrocene (dppf): Electrochemistry, complexation and the X-ray structures of 1,1′-bis(diphenylphosphino)osmocene (dppo) and [PdCl2(dppo)]

The oxidative electrochemistry of 1,1′-bis(diphenylphosphino)osmocene (dppo) and 1,1′-bis(diphenylarsino)ferrocene (dpaf) was studied in dichloromethane with tetrabutylammonium hexafluorophosphate as the supporting electrolyte. The [MCl₂(P^∩P)] (M = Pd or Pt; P^∩P = dppo or 1,1′-bis(diphenylphosphinoindenyl)iron) complexes were prepared, studied electrochemically and the X-ray structures of dppo and [PdCl₂(dppo)] were determined.     

嘧啶衍生物对钢在盐酸溶液中的缓蚀作用

采用失重法、动电位极化曲线、电化学阻抗谱(EIS)、量子化学计算研究了两种嘧啶衍生物(2-羟基嘧啶(HP)和2-巯基嘧啶(MP))在1.0-5.0 mol·L^-1 HCl溶液中对冷轧钢(CRS)的缓蚀作用. 结果表明: HP和MP在1.0 mol·L^-1 HCl溶液中对冷轧钢具有良好的缓蚀作用, 且在钢表面的吸附符合Langmuir吸附等温式. 缓蚀率随缓蚀剂浓度的增加而增大, 但随盐酸浓度的增加而减小.求出了相应的吸附热力学参数(吸附平衡常数(K),吸附自由能(ΔG⁰))和腐蚀动力学参数(表观活化能(E_a)、指前因子(A)、腐蚀速率常数(k)、动力学常数(B)), 并根据这些参数讨论了缓蚀作用机理. 动电位极化曲线表明, MP和HP均为混合抑制型缓蚀剂; EIS谱呈单一容抗弧,电荷转移电阻随缓蚀剂浓度的增加而增大. 两种嘧啶化合物的缓蚀率排序为MP>HP. 量子化学计算结果表明,MP比HP更具吸附活性,缓蚀性能的理论计算和实验结果相一致.     

Corrosion Inhibition of Imidazoline Derivates with Benzene Rings on Mild Steel in CO2-Saturated Brine Solution

Corrosion inhibition of three imidazoline derivates with different numbers of benzene rings, namely 2-phenyl-1-ethylamino imidazoline(CI-1), 2-phenyl-1-ethylamino-1-methylbenzyl quaternary imidazoline(CI-12) and 2-phenyl-1-benzoyl ethylamino imidazoline(CI-13), on mild steel in CO₂-saturated brine solution was evaluated by mass-loss method and potentiodynamic polarization method. The results show that the three imidazoline derivates can inhibit CO₂ corrosion effectively with CI-12 ranking the highest. They mainly restrain the anodic dissolution and act as anodic-type inhibitors. The adsorptions of these derivates on the mild steel surface follow the Langmuir adsorption isothermal equation and belong to chemical adsorption.     

合金元素Nd对Pb-Ag阳极在H2SO4溶液中电化学行为的影响

采用循环伏安、线性扫描、电化学阻抗和环境扫描电镜对比研究了Pb-Ag和Pb-Ag-Nd阳极的阳极膜和析氧反应. 结果表明,合金元素Nd促进了Pb/PbO_n/PbSO₄ (1≤n<2)膜层的生长. 在高极化电位区间(高于1.20V (vs Hg/Hg₂SO₄/饱和K₂SO₄溶液)),Nd有利于低价铅的化合物(PbO_n,PbSO₄)向α-PbO₂和β-PbO₂转变. 此外,环境扫描电镜形貌和线性扫描分析证明Pb-Ag-Nd表面生成的阳极膜较Pb-Ag的阳极膜更厚且更致密. 因此,Pb-Ag-Nd阳极表面的阳极膜可以给合金基底提供更好的保护. 另一方面,电化学阻抗测试揭示了两种阳极的析氧反应均受中间产物的形成和吸附控制. Nd可以降低阳极膜/电解液界面处中间产物的吸附阻抗且增加中间产物的覆盖率,从而提高析氧反应活性. 综上所述,合金元素Nd可提高Pb-Ag阳极的耐腐蚀性,降低阳极电位进而起到节能降耗的作用.     

The adsorption, CMC determination and corrosion inhibition of some N-alkyl quaternary ammonium salts on carbon steel surface in 2 M H2SO4

Electrochemical measurements were performed to investigate the effectiveness of cationic surfactants of the N-alkyl quaternary ammonium salt type, i.e. myristyltrimethylammonium chloride (MTACl), cetyldimethylbenzylammonium chloride (CDBACl), and trioctylmethylammonium chloride (TOMACl), as corrosion inhibitors for type X4Cr13 ferritic stainless steel in 2 M H₂SO₄ solution. Potentiodynamic polarization measurements showed that these surfactants hinder both anodic and cathodic processes, i.e. act as mixed-type inhibitors. It was found that the adsorption of the N-alkyl ammonium ion in 2 M H₂SO₄ solution follows the Langmuir adsorption isotherm. Plots of log [θ/(1 − θ)] versus log c_inh yielded straight lines with a slope, which changed drastically at the critical micelle concentration (CMC) of the surfactants studied. Accordingly, the CMC could be accurately determined from these measurements. The calculated values of the free energy of adsorption ΔG_ads are, in cases when the charge on the metal surface is negative with respect to the PZC, relatively high what is characteristically for the chemisorption. On the other hand, for positive metal surfaces it is assumed that SO₄²⁻ anions are adsorbed first, so the cationic species would be limited by the surface concentration of anions. Accordingly ΔG_ads values were lower in this case and the adsorption is due to merely electrostatic attraction, which is characteristically of physisorption.     

Synthesis and electrochemistry of late transition metal complexes containing 1,1′-bis(dicyclohexylphosphino)ferrocene (dcpf). The X-ray structure of [PdCl2(dcpf)] and Buchwald-Hartwig catalysis using [PdCl2(bisphosphinometallocene)] precursors

The electrochemistry of 1,1′-bis(dicyclohexylylphosphino)ferrocene (dcpf) was examined in methylene chloride with tetrabutylammonium hexafluorophosphate or tetrabutylammonium tetrakis(pentafluorophenyl)borate as the supporting electrolyte. The oxidation of dcpf is complicated by a follow-up reaction. Seven new complexes containing dcpf and one new compound containing 1,1′-bis(di-tert-butylphosphino)ferrocene (dtbpf) were prepared and characterized. The new complexes were analyzed by cyclic voltammetry and the oxidation of these complexes occurred at a more positive potential than the free ligand. In addition, the X-ray structure of [PdCl₂(dcpf)] was determined and compared to other palladium complexes containing bisphosphinometallocene ligands. Five different palladium complexes containing bisphosphinometallocene ligands were examined as catalyst precursors in Buchwald-Hartwig catalysis.     

A simple route for the synthesis of 3,3,3′,3′-tetramethyl-2,3,3′,4′-tetrahydro-1H,1′H-[4,9′-bixanthene]-1,1′(2′H,9′H)-dione and its derivatives catalyzed by Mn and other transition metal cations

A simple and efficient unusual coupling reaction of 9-(2-hydroxy-4,4-dimethyl-6-oxocyclohex-1-en-1-yl)-3,3-dimethyl-2,3,4,9-tetrahydro-1H-xanthen-1-one and its derivatives was accomplished in the presence of Mn²⁺, Cu²⁺, Cd²⁺, Hg²⁺, Fe³, or La³⁺. The structure elucidation was accomplished by IR, ¹H NMR, ¹³C NMR, X-ray crystallography, UV-Visible and elemental analysis. A reaction mechanism is proposed.     

CO_2体系中咪唑啉季铵盐与十二烷基磺酸钠之间的缓蚀协同效应

采用失重法、电化学阻抗谱(EIS)、极化曲线、X射线光电子能谱仪(XPS)及扫描电子显微镜(SEM)研究了CO2饱和的3.5%NaCl腐蚀介质中,咪唑啉季铵盐(IAS)与十二烷基磺酸钠(SDSH)对Q235钢的缓蚀协同效应.结果表明,IAS与低浓度SDSH在腐蚀介质中具有较好的缓蚀协同效应,且当二者以1:1(50 mg·L-1:50 mg·L-1)的浓度比例复配时,协同效应最明显,缓蚀率为88.5%;而IAS与高浓度SDSH间会产生拮抗效应.本文通过建立合理的吸附模型,阐述了协同效应及拮抗效应的机理.SDSH与IAS在Q235钢表面的吸附过程均为放热的自发过程,前者符合Frumkin吸附模型,后者符合Temkin吸附模型.单独使用较高浓度的SDSH对Q235钢也有较好的缓蚀作用,缓蚀率接近90%.