Organic corrosion inhibitors for zinc pigment

Abstract

A severe problem with waterborne paints containing zinc pigments is hydrogen corrosion of the zinc in the aqueous alkaline paint media. The subject of the present study is the examination of corrosion inhibition of the zinc pigment in aqueous alkaline media by different high and low molecular weight organic inhibitors compared with that given by potassium dichromate. Potassium dichromate inhibits this corrosion reaction moderately, but a 4·0 mmol addition in 100 mL of the corrodent (1·2 wt-%) is required. Heterocyclic compounds are very poor corrosion inhibitors and less effective than potassium dichromate. Certain polymers with low acid numbers and low molecular weights and one particular epoxy ester resin are more effective inhibitors than potassium dichromate. Thus, some non-toxic polymers or paint resins can be considered as possible substitutes for toxic potassium dichromate.     

Control of zinc corrosion in acidic media: Green fenugreek inhibitor

Fenugreek seeds extract was examined as a green corrosion inhibitor for Zn in 2.0 mol/L H₂SO₄ and 2.0 mol/L HCl solutions by mass loss and electrochemical measurements. Scanning electron microscope (SEM) images show that the surface damage is decreased in the presence of the inhibitor. X-rays photoelectron spectroscopy (XPS) analysis was performed to identify the corrosion product, ZnO, and to prove the inhibitor adsorption mechanism. The maximum inhibition efficiency values are 90.7% after 1 h and 66.6% after 0.5 h by 200 mL/L of fenugreek extract in H₂SO₄ and HCl solutions, respectively. Addition of I⁻ ion greatly improves the inhibition efficiency of fenugreek seeds extract for Zn corrosion in HCl due to the synergistic effect. Potentiodynamic polarization and EIS measurements prove the inhibition ability of fenugreek for Zn corrosion in HCl as indicated by the decreased corrosion current density and increased charge transfer resistance values in the presence of fenugreek.     

An in situ FT‐IR evaluation of candidate organic corrosion inhibitors for carbon steel in contact with alkaline aqueous solutions

The influence of some organic additives on the anodic behaviour of a carbon steel electrode in contact with alkaline aqueous solutions was studied by in situ Fourier transform infrared (FT‐IR) spectroscopy. FT‐IR spectroscopy allows to obtain information at the molecular level regarding the metal‐electrolyte interface. The following molecules have been considered: (i) benzyldimethylphenylammonium chloride (BDMPAC), (ii) glutamic acid, (iii) triethylenetetramine (TETA), (iv) sodium tartrate and (v) sodium benzoate. Potential‐dependent spectra have been recorded for the different investigated systems. Quantitative information about the formation kinetics of corrosion products was derived by numerical analysis of the peak area as a function of the applied potential for the different systems investigated.     

Synergistic inhibition effect of poly(ethylene glycol) and cetyltrimethylammonium bromide on corrosion of Zn and Zn—Ni alloys for alkaline batteries

The synergistic inhibition effect of poly(ethylene glycol)-400 (PEG-400) and cetyltrimethylammonium bromide (CTMAB) on the corrosion of Zn and Zn—Ni alloys in 8 mol/L KOH solution saturated with ZnO was observed by potentiodynamic anodic/cathodic polarization (PDP), and electrochemical impedance spectroscopy (EIS) measurements. The electrochemical studies confirmed that there was a synergism between PEG-400 and CTMAB on corrosion inhibition of Zn and its alloys. Corrosion inhibition efficiency of the mixed inhibitors, 250 mg/L CTMAB + 250 mg/L PEG-400, was found to be much higher than that of the single inhibitor, 500 mg/L PEG-400 or 500 mg/L CTMAB. Scanning electron microscopic (SEM) investigations before and after the corrosion inhibition process emphasize the synergistic effect of the mixed inhibitors. Accordingly, it was found that the addition of the investigated inhibitors to the alkaline solution enhanced the discharge and capacity of the alkaline battery anodes. The obtained electrochemical data exhibited a good correlation with the computational one.     

The corrosion and electrochemical behavior of pure aluminum in additive-containing alkaline methanol–water mixed solutions

The corrosion and electrochemical behavior of aluminum in inhibited and uninhibited 4 M KOH–methanol–water mixed solutions with a methanol/water volume ratio of 3:2 were investigated by means of hydrogen collection, polarization curve, galvanostatic discharge, and electrochemical impedance spectroscopy (EIS). The results of hydrogen collection and electrochemical experiments showed that the addition of ZnO can obviously inhibit the corrosion of aluminum in the 4 M KOH–methanol–water solutions, and its inhibition effect can be enhanced in the hydroxytryptamine (HT)-containing KOH solution. The results of scanning electron microscopy (SEM) and energy dispersive analysis of X-ray (EDAX) revealed that ZnO produces the inhibition effect by the formation of a zinc-containing deposit layer on the surface of aluminum, and the cooperative effect of ZnO and HT may improve the deposit of zinc. The results of galvanostatic discharge indicated that aluminum can present good electrochemical activity in the 4 M KOH–methanol–water solution with 0.2 M ZnO and 1.0 mL/L HT.     

Inhibition behavior for copper corrosion by photoelectrochemical methods

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Growth and corrosion resistance of molybdate modified zinc phosphate conversion coatings on hot-dip galvanized steel

The modified zinc phosphate conversion coatings（ZPC） were formed on hot-dip galvanized（HDG） steel when 1.0 g/L sodium molybdate were added in a traditional zinc phosphate solution. The growth performance and corrosion resistance of the modified ZPC were investigated by SEM, open circuit potential（OCP）, mass gain, potentiodynamic polarization and electrochemical impedance spectroscopy（EIS） measurements and compared with those of the traditional ZPC. The results show that if sodium molybdate is added in a traditional zinc phosphate solution, the nucleation of zinc phosphate crystals is increased obviously; zinc phosphate crystals are changed from bulky acicular to fine flake and a more compact ZPC is obtained. Moreover, the mass gain and coverage of the modified ZPC are also boosted. The corrosion resistance of ZPC is increased with an increase in coverage, and thus the corrosion protection ability of the modified ZPC for HDG steel is more outstanding than that of the traditional ZPC.     

Interaction of inhibitors with corrosion scale formed on N80 steel in CO2‐saturated NaCl solution

The performance of the selected inhibitors, including thioglycolic acid (TGA), diethylenetriamine (DETA), and naphthene acid imidazolines (IM), on the bare surface of N80 steel and its scaled surface pre‐corroded in CO₂‐saturated 1%NaCl solution was investigated by weight‐loss method, electrochemical measurements using rotating cylinder electrode and surface analytical methods (SEM, XRD, and EPMA). The results indicate that there is a remarkable difference in inhibition efficiency of inhibitors on the N80 steel with and without pre‐corrosion scale. The synergistic effect between inhibitors and corrosion scale not only depends on the size of inhibitor molecules, but also depends on the interaction of the inhibitor with the corrosion scale. It shows that IM and DETA have a good positive synergistic effect with the corrosion scale formed on N80 steel, although DETA has no inhibition efficiency for bare N80 steel, which can easily enter into the apertures of the corrosion scale, and block the active sites on the metal surface and the diffusion routeways of the reactant so as to depress the corrosion of the substrate metal. While TGA shows excellent inhibition efficiency on bare N80 steel, but it has an antagonistic effect with the corrosion scale although it has a small molecular weight as well as DETA, because TGA can dissolve corrosion scale and break its integrality and protectiveness performance.     

Ethoxylated fatty alcohols as corrosion inhibitors for dissolution of zinc in hydrochloric acid

The effect of some ethoxylated fatty alcohols, with different numbers of ethylene oxide units, on the corrosion of zinc in 0.5 M HCl has been studied using weight loss and polarization measurements. The inhibition efficiency was found to increase with increasing concentration, number of ethylene oxide units per molecule and with decreasing the temperature. Inhibition was explained on the basis of adsorption of ethoxylated fatty alcohols molecules on the metal surface through their ethoxy groups. The degree of surface coverage varied linearly with logarithm of inhibitor concentration fitting Temkin isotherm. The thermodynamic parameters were calculated for the tested system from the data obtained at different temperatures.     

Evaluation of corrosion inhibitors for cooling water systems operating at high concentration cycles

The present work aimed at evaluating AISI 1020 carbon steel corrosion resistance of a 6:4:1:1 (MoO/HEDP/PO/Zn²⁺) inhibitor mixture present in a solution which simulates an industrial cooling water system operating at high concentration cycles (1050 ppm Cl⁻ and 450 ppm Ca²⁺). High concentration cycles are desirable, because system purge and treated water consumption are decreased. On the other hand, a high number of concentration cycles can increase the concentration of salts and dissolved impurities, causing corrosion, incrustations, and deposits inside the pipes, heat exchangers, and cooling towers. Thus, the chloride (Cl⁻) and calcium (Ca²⁺) ions aggressiveness was studied on the proposed inhibiting mixture, at the temperatures of 40 and 60 °C, through electrochemical techniques like open circuit potential measurements, anodic and cathodic polarization, and weight loss. The results showed that the inhibitor mixture conferred adequate protection to carbon steel in low concentrations, even in high aggressive media.     

The effects of polyethylene glycol (PEG) as an electrolyte additive on the corrosion behavior and electrochemical performances of pure aluminum in an alkaline zincate solution

The effects of zinc oxide and/or polyethylene glycol (PEG) as electrolyte additives on the corrosion and electrochemical performances of pure aluminum in 4.0 M KOH solutions were investigated by means of hydrogen collection, polarization curve, galvanostatic discharge, scanning electron microscopy (SEM), and energy dispersive analysis of X‐ray (EDAX). The addition of ZnO markedly inhibited the corrosion of aluminum in 4.0 M KOH solutions, resulting from the deposition of zinc with high hydrogen evolution overpotential in aluminum surfaces. The introduction of PEG in the alkaline zincate solution obviously improved the deposition of zinc by increase in the overpotential of zinc deposition, thus the corrosion rate of aluminum in the alkaline zincate solutions with PEG was further decreased. The enhancement effect of PEG on the inhibition of zinc oxide first increased and then decreased with increasing the content of PEG in the electrolyte. The electrolyte system with 0.2 M ZnO and 2.0 mM PEG presented the highest inhibition efficiency (98.8%) for the corrosion of aluminum. The results of galvanostatic discharge indicated that the aluminum anode shows excellent discharge performances in the 4.0 M KOH solution with 0.2 M ZnO and 2.0 mM PEG.     

热镀锌层上磷酸锌转化膜的生长与耐蚀性

热镀锌钢板在pH3.0、45℃的磷酸锌溶液中磷化2～600s,用扫描电镜、能谱仪和X射线衍射仪分析磷化膜的组织形貌和成分,并探讨膜层的生长行为。结果表明:磷酸锌晶体在锌晶粒内及晶界处均可成核,开始是以接近平行的片状生长,并逐渐向多方向生长成扇骨状的晶片。随着磷酸锌晶体的成核和生长,磷化膜的覆盖率增加,但晶体之间的孔隙难以完全消除;长大的磷酸锌晶片容易折断脱落,导致磷化后期膜层的质量增量减小;磷化膜主要由Zn3(PO4)2.4H2O组成。热镀锌钢板经磷化处理后,耐蚀性显著提高,磷化膜的耐蚀性随磷化时间和膜层覆盖率的增加而提高。     

钨酸钠及其复配缓蚀剂在模拟海水中对碳钢的缓蚀性能

目的考察在模拟海水中,钨酸钠及其与月桂酰肌氨酸钠复配物对Q235钢的缓蚀性能。方法进行挂片失重法实验,研究缓蚀剂添加量对缓蚀效率的影响;测定电化学极化曲线及阻抗谱,对比单一钨酸钠缓蚀剂与复配缓蚀剂的缓蚀效率以及相关拟合数据。结果钨酸钠单独使用时的缓蚀效果良好,缓蚀效率随着添加量的增加而增大,且在碳钢表面的吸附符合修正了的Langmuir吸附模型;与月桂酰肌氨酸钠复配后,缓蚀效率更高,阴极、阳极的塔菲尔斜率均减小,腐蚀电流密度也降低了很多。结论钨酸钠与月桂酰肌氨酸钠复配后比单独使用效果更好,二者有较好的协同缓蚀增效作用;复配缓蚀剂为混合型缓蚀剂。     

Spatial distribution and formation of corrosion products in relation to zinc release for zinc sheet and coated pre‐weathered zinc at an urban and a marine atmospheric condition

Zinc release data from 5 years of unsheltered exposures in a marine and an urban site is compiled for different zinc material types. The thin surface treatment on zinc materials is gradually detached after approximately 2 years at both sites, revealing the pre‐weathered zinc surface unprotected. This consequently increased the release rates of zinc from this surface, whereas the zinc runoff rate from the bare zinc sheet remained relatively stable. Raman studies on bare zinc sheet exposed for 5 years at the marine site revealed zinc oxide of varying crystalline nature and hydrozincite to appear localized and separated from each other.     

吐温-40 与植酸复配对碳钢的缓蚀作用

目的提高0.5 mol/L HCl中植酸对热轧碳钢(HRCS)的缓蚀性能。方法用失重法和电化学阻抗法测试植酸、吐温-40以及复配缓蚀剂的缓蚀效率,从热力学和动力学方面分析复配缓蚀剂的作用机制。结果失重法测试表明,植酸和吐温均对热轧碳钢有一定缓蚀作用。当293 K,植酸质量浓度为0.3g/L时,缓蚀效率达到69.1%,在质量浓度为0.8 g/L时缓蚀效率下降为9.6%;吐温-40的缓蚀效率随着质量浓度的增大而增大,0.8 g/L时达到73.4%。在0.5 mol/L盐酸中加入0.05 g/L吐温-40后,复配缓蚀剂的缓蚀效率随着质量浓度的增加而增大,且优于植酸和吐温-40单独使用,表现出协同效应。电化学测试得到了相同的结论,表明复配缓蚀剂在碳钢表面产生自发的Langmuir吸附,使碳钢腐蚀反应的活化能增大,是熵减少的放热过程。结论吐温-40和植酸在盐酸中对热轧碳钢的腐蚀有缓蚀协同作用。     

Comparative estimation of long-term predictions of corrosion losses for carbon steel and zinc using various models for the Russian territory

Based on the results of 1-year tests at 12 sites in the Far Eastern region of Russia, priority dose–response functions (DRFs) that provide the best match with experimental data on corrosion losses for carbon steel and zinc have been selected. Long-term (up to 50 years) predictions of corrosion losses of these metals in the continental territory of Russia have been given. A comparative estimation of the mass loss predictions by priority DRFs and the power–linear model has also been given.     

Electrochemical characteristics of phosphorus doped Si-C composite for anode active material of lithium secondary batteries

Phosphorus doped silicon-carbon composite particles were synthesized through a DC arc plasma torch. Silane(SiH₄) and methane(CH₄) were introduced into the reaction chamber as the precursor of silicon and carbon, respectively. Phosphine(PH₃) was used as a phosphorus dopant gas. Characterization of synthesized particles were carried out by scanning electron microscopy(SEM), X-ray diffractometry(XRD), X-ray photoelectron spectroscopy(XPS) and bulk resistivity measurement. Electrochemical properties were investigated by cyclic test and electrochemical voltage spectroscopy(EVS). In the experimental range, phosphorus doped silicon-carbon composite electrode exhibits enhanced cycle performance than intrinsic silicon and phosphorus doped silicon. It can be explained that incorporation of carbon into silicon acts as a buffer matrix and phosphorus doping plays an important role to enhance the conductivity of the electrode, which leads to the improvement of the cycle performance of the cell.