绿色水处理剂聚天冬氨酸缓蚀协同效应的研究

聚天冬氨酸（PASP）是一种新型的绿色生物可降解缓蚀阻垢剂。该文用失重法研究了聚天冬氨酸对碳钢的缓蚀性能以及与HEDP、锌盐的缓蚀协同效应。研究表明。聚天冬氨酸、HEDP、锌盐在自来水中对碳钢具有良好的缓蚀协同效应。     

Enhanced corrosion inhibition behavior of carbon steel in aqueous solution by Phosphoserine-Zn2+ system

The corrosion inhibition effect of carbon steel in aqueous solution was using a synergistic mixture of an environmentally friendly inhibitor system phosphoserine (PS) and Zn²⁺ using gravimetric studies, potentiodynamic polarization, and electrochemical impedance studies. Potentiodynamic polarization studies showed that the inhibitor system is a mixed type inhibitor. Electrochemical impedance studies of the metal/solution interface indicated that the surface film is highly protective against the corrosion of carbon steel in the aqueous solution. X-ray photoelectron spectroscopic analysis of the protective film exhibited the presence of the elements viz., iron, phosphorus, nitrogen, oxygen, carbon, and zinc. The chemical shifts in the binding energies of these elements inferred that the surface film is composed of oxides/hydroxides of iron, Zn(OH)₂, and [Fe(II)/(III)-Zn(II)-PS] complex. Further, the surface examination techniques viz., FTIR, SEM, and AFM studies confirm the formation of an adsorbed protective film on the carbon steel surface. Based on the results obtained, a suitable mechanism of corrosion inhibition is presented.     

Investigation on the inhibition effect of aspartic acid and Zn2+ ions on carbon steel surface in aqueous solution

A protective film has been formed on the surface of carbon steel in aqueous environment using a synergistic mixture of an environment-friendly inhibitor, aspartic acid, and Zn²⁺. The synergistic effect of aspartic acid (AS) in controlling corrosion of carbon steel has been investigated by gravimetric studies in the presence of Zn²⁺. The formulation consisting of AS and Zn²⁺ has an excellent inhibition efficiency. The results of potentiodynamic polarization revealed that the formulations are of mixed-type inhibitor. Impedance studies of the metal/solution interface indicated that the surface film is highly protective against the corrosion of carbon steel in the aqueous environment. X-ray photoelectron spectroscopic analysis of the protective film showed the presence of the elements iron, nitrogen, oxygen, carbon, and zinc. The spectra of these elements in the surface film showed the presence of oxides/hydroxides of iron(III), Zn(OH)₂, and [Fe(III)/Fe(II)–Zn(II)-AS] complex. Further, surface characterization techniques such as Fourier transform infrared spectroscopy, scanning electron microscopy, and atomic force microscopy are used to ascertain the nature of the protective film formed on the carbon steel surface.     

聚天冬氨酸阻垢缓蚀剂的量子化学研究

用量子化学计算的方法,探讨了聚天冬氨酸（PASP）的分子结构和阻垢缓蚀性能的构效关系,计算结果显示,在阻垢性能方面,聚天冬氨酸分子氮原子和羧基团中氧原子呈负电性,这使得羧基上的氧原子易与晶面上的钙离子发生静电交互作用,且PASP分子中两个氮氧原子间距与方解石有关晶面上钙离子间距匹配,因而显著加强了阻垢剂分子与特定晶面之间的吸附力,从而起到了碳酸钙晶体的阻垢效能。在缓蚀性能方面,计算得到了PASP分子最高占据轨道能量、最低空轨道能量以及最低空轨道能量与最高占据轨道能量的差。计算表明结果与机理描述相符合。     

聚天冬氨酸对硫酸介质中碳钢的缓蚀性能研究

采用常规的失重法对聚天冬氨酸(PASP)在硫酸介质中对碳钢的缓蚀性能进行了研究。研究了聚天冬氨酸的用量、温度、硫酸的浓度等因素对其缓蚀性能的影响。得出聚天冬氨酸用量为0.2%,温度为30℃,硫酸浓度小于15%时对碳钢都有较好的缓蚀性能。用线性扫描伏安法和电化学阻抗谱对聚天冬氨酸的缓蚀机理进行了电化学研究,发现随着PASP浓度增加,金属的自腐蚀电位有变大的趋势,表明聚天冬氨酸应属于阳极型缓蚀剂;同时阻抗谱在高频区出现了半圆容抗弧,加入聚天冬氨酸的体系半圆半径变大,进一步验证了聚天冬氨酸对碳钢的缓蚀性能。     

一种新型联吡啶双子季铵盐的合成及缓蚀性能

以4,4'-联吡啶和氯化苄为原料,经季铵化反应制备了化合物1,1?-二苄基-4,4?-联吡啶双子季铵盐(PBA),产率为76.3%,通过FTIR、~1HNMR对产物结构进行了表征;利用失重法、电化学技术、AFM考察了PBA对1 mol/L盐酸溶液中Q235钢的缓蚀作用和其在Q235钢表面的吸附行为。结果表明,PBA是一种同时抑制阴、阳极的混合型缓蚀剂,缓蚀率随PBA浓度的增加而增加,随温度的升高而略有降低。当PBA质量浓度为80 mg/L时,缓蚀率可达96.53%。PBA在Q235钢表面的吸附为放热反应,遵循Langmuir等温式,是以化学吸附为主的混合型吸附。PBA在钢表面形成了一层致密的保护膜,大大阻碍了钢腐蚀。使用量子化学法研究了PBA的缓蚀机理,结果表明,PBA的活性区域集中于苯环和杂环上,且PBA分子接受电子的能力大于提供电子的能力。     

多支化聚天冬氨酸衍生物的合成及其阻垢性能研究

先以顺酐和氨水等为原料合成聚天冬氨酸(PASP),再以PASP和赖氨酸为原料进行接枝反应得到改性聚天冬氨酸衍生物(Lys-PASP)。实验结果表明,与聚天冬氨酸相比,在聚天冬氨酸与赖氨酸质量比为10∶1,改性时间2 h,改性温度120℃条件下得到的改性产品Lys-PASP不仅对碳酸钙具有更好的阻垢性能,而且对碳钢表面也有更好的缓蚀效果,并对氧化铁也具有很好的分散效果;Lys-PASP的加入,不仅改变了碳酸钙的晶型,而且大大降低了碳酸钙晶体的完整程度和有序度,达到了阻止碳酸钙垢形成的目的,起到了阻垢缓蚀的效果。     

ATA与PASP复配对稀碱液中碳钢的缓蚀研究

研究了3-氨基-1,2,4-三氮唑(ATA)及其与聚天冬氨酸(PASP)复配对5%NaOH溶液中碳钢的缓蚀作用。结果表明,25mg/L ATA的缓蚀率可达80.78%,15 mg/LATA和10 mg/LPASP缓蚀协同后的缓蚀率高达91.28%。     

Synthesis,Characterization and Inhibition Performance of Vanillin‐Modified Chitosan Quaternary Ammonium Salts for Q235 Steel Corrosion in HCl Solution

In order to enhance the solubility of chitosan in water and its corrosion inhibition performance on Q235 steel in 1 M HCl solution, N‐vanillyl‐O‐2′‐hydroxypropyltrimethylammonium chloride chitosan (VHTC) was synthesized. The structure of VHTC was characterized by FT‐IR and ¹H‐NMR spectroscopy. The corrosion inhibition performance of VHTC on Q235 steel in 1 M HCl solution was studied by weight loss, polarization, electrochemical impedance spectroscopy (EIS) and stereo microscope analysis. Experimental results indicate that VHTC shows better inhibition efficiency compared to chitosan. When the concentration of VHTC increases to 200 mg L^?1, the inhibition efficiency reaches 90 %, which is almost equal to the conventional corrosion inhibitors (e.g., imidazoline). The polarization study demonstrates that VHTC is a mixed‐type inhibitor caused by a geometrical blanketing effect. The charge transfer resistance is proportional to the inhibitor concentration as revealed by the EIS results, indicating that the protective film on the Q235 steel surface is formed by adsorption of the inhibitor molecules. The inhibition efficiency of VHTC achieves the maximum value within 24 h when the concentration of VHTC is 200 mg L^?1. The morphology observation of the corroded steel surface indicates that the corrosion of Q235 steel in 1 M HCl solution is significantly inhibited after introducing VHTC into the acidic solution.     

聚天冬氨酸复配物对碳钢、紫铜和不锈钢缓蚀性能研究

以聚天冬氨酸（PASP）、聚丙烯酸（PAA）、水解聚马来酸酐（HPMA）、苯并三氮唑（BTA）为原料,得到一种高效的复合型缓蚀剂配方ρ（PASP）∶ρ（PAA）∶ρ（HPMA）∶ρ（BTA）=2.4∶1.6∶2∶1。采用旋转挂片实验和电化学实验对该缓蚀剂的缓蚀性能进行了评价。结果表明,该缓蚀剂对碳钢、紫铜和不锈钢的缓蚀率分别为84.8%,96.4%,99.2%。动态模拟实验结果显示,该缓蚀剂满足循环冷却水运行要求。     

聚天冬氨酸和钨酸钠复配对模拟水中白铜(B10)的缓蚀作用

采用交流阻抗法和极化曲线法,研究了两种环境友好型水处理药剂聚天冬氨酸和钨酸钠的单一配方及其复配对模拟水中白铜(B10)的缓蚀效果。研究表明,聚天冬氨酸和钨酸钠各自的单一配方对于B10均具有一定的缓蚀效果,其中聚天冬氨酸质量分数为9×10-6时,对B10的缓蚀效果最佳,缓蚀率为65.0%;钨酸钠质量分数为20×10-6时,缓蚀效果最佳,缓蚀率为53.8%。缓蚀剂总质量分数为20×10-6,聚天冬氨酸与钨酸钠的质量比为1∶6时,对B10的缓蚀效果最佳,缓蚀率为89.0%,且具有缓蚀协同效应。     

4-氨基苯甲酸席夫碱自组装缓蚀膜对20#钢在饱和CO2油田水中的缓蚀性能

利用邻氧乙酸苯甲醛缩4-氨基苯甲酸钾盐席夫碱(K₂L1)缓蚀剂在20#碳钢表面制备了自组装单分子膜(SAMs),通过电化学方法研究了缓蚀剂的合成条件、自组装时间等因素对成膜的影响,结果表明,合成中KOH与邻氧乙酸苯甲醛按2:1摩尔比进行反应得到的K₂L1缓蚀剂在碳钢表面自组装3 h后,可以形成稳定、致密的缓蚀膜。缓蚀性能的研究表明,碳钢表面K₂L1-SAMS抑制了碳钢的阴极还原过程,改变了电极表面双电层结构,具有良好的缓蚀效果(最高缓蚀效率可达95%以上),交流阻抗和极化曲线得到的结论是一致的。同时研究表明K₂L1的吸附行为符合Langmuir吸附等温式,吸附机理是典型的化学吸附。量子化学计算结果表明,K₂L1分子具有多个吸附活性中心,这些活性原子的前线轨道能与碳钢表面铁原子的前线轨道相互作用,因而使得K₂L1分子在碳钢表面形成吸附膜,阻止了碳钢在饱和CO₂油田水介质中的溶解。X射线光电子能谱(XPS)分析表明,K₂L1通过配位键在碳钢表面形成了稳定的缓蚀膜。     

环境友好型海水缓蚀剂的研制及性能研究

环境友好型海水缓蚀剂由聚天冬氨酸(PASP)、硫酸锌、葡萄糖酸钠与2-羟基膦酰基乙酸(HPAA)复配制得,通过正交试验确定最佳复配质量比为4:5:8:0:5。利用失重法、电化学法和扫描电镜法研究了此四元海水缓蚀剂在海水中对A3碳钢的缓蚀性能。结果表明,当海水缓蚀剂的用量为90 mg/L时,缓蚀率达到97.26%,有效抑制了碳钢在海水中的腐蚀。该海水缓蚀剂具有优良的生物降解性能,28 d的生物降解率达到85.65%。     

Inhibition by tween-85 of the corrosion of cold rolled steel in 1.0?M hydrochloric acid solution

The inhibition effect of tween-85 on the corrosion of cold rolled steel (CRS) in 1.0 M hydrochloric acid (HCl) was studied by weight loss and potentiodynamic polarization methods. The results show that tween-85 is a good inhibitor in 1.0 M HCl and its maximum inhibition efficiency (IE) is 92% at very low concentration. Its adsorption obeys the Langmuir adsorption isotherm equation. The thermodynamic parameters of adsorption enthalpy (ΔH ⁰), adsorption free energy (ΔG ⁰) and adsorption entropy (ΔS ⁰) were calculated and discussed. Polarization curves show that tween-85 acts as a mixed-type inhibitor in hydrochloric acid. IE values obtained from weight loss and polarization are consistent. The adsorbed film on a CRS surface containing an optimum dose of tween-85 was investigated by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and atomic force microscope (AFM). An inhibitive mechanism is proposed from the viewpoint of adsorption theory.     

A Green Multifunctional Antiscaling Inhibitor for Crystallization Control of Ca‐Scale Crystals

Histidine‐polyaspartic acid (His‐PASP), an effective antiscaling inhibitor, was synthesized by polysuccinimide (PSI) and histidine. His‐PASP exhibited a promising antiscaling property by inhibiting the reaction crystallization of Ca‐scale crystals. The crystal form and surface morphology of Ca‐scale crystals were changed after the addition of His‐PASP. The hard scale was turned into soft dirt and can be easily washed away. The binding between His‐PASP and calcite was exothermic and the energy was higher than the traditional adsorption energy. His‐PASP possessed a favorable anticorrosion efficiency for carbon steel in cooling water. In the test of dispersing Fe₂O₃, the transmittance of the supernatant was reduced with increasing His‐PASP dosage.     

An experimental and theoretical investigation of adsorption characteristics of a Schiff base compound as corrosion inhibitor at mild steel/hydrochloric acid interface

This study investigates the effect of a Schiff base namely 2-[2-(2-(3-phenylallylidene)hydrazine carbonothioyl)hydrazinecarbonyl]benzoic acid (SB), on corrosion inhibition of mild steel in 1 M HCl. Electrochemical impedance measurement, potentiodynamic polarization and weight loss methods were applied to study adsorption of SB at metal/solution interface. Results revealed that SB is an excellent inhibitor for mild steel corrosion in 1 M HCl; showing a maximum efficiency 99.5% at concentration of 1.36 × 10⁻⁶ M. Fourier transform infrared spectroscopy (FTIR) observations of the mild steel surface confirmed the formation of protective film on the metal surface by studied compound. Polarization studies showed that SB is a mixed-type inhibitor. Adsorption process obeyed Langmuir’s model with a standard free energy of adsorption (∆G°_ads) of −46.7 kJ mol⁻¹. Energy gaps for interactions between mild steel surface and inhibitor were found to be close to each other showing that SB possess capacity to behave as both electron donor and acceptor.     

New Biodegradable Nonionic-Anionic Surfactants Based on Different Fatty Alcohols as Corrosion Inhibitors for Aluminum in Acidic Medium

Two series of eco-friendly nonionic anionic surfactants based on itaconic acid and 1, 6 hexane diol were synthesized. The chemical structures of the prepared surfactant were confirmed by FTIR and ¹H NMR spectroscopy. The prepared surfactants were evaluated to prevent the corrosion of aluminum in 1.0 M HCl solution by electrochemical and chemical methods. The data obtained showed that the prepared compounds have good inhibition efficiency (IE%) even at 10⁻⁵ M concentrations and act as mixed-type inhibitors, they do not affect the mechanism of the electrode processes, as well as the IE% increase by increasing the concentrations of the inhibitors, immersion time, and hydrophilic chain length. The high inhibition efficiency is due to the adsorption of the inhibitors molecules on the metal surface and the formation of a protective film. The surface activities of these compounds were also investigated and were correlated to their inhibition efficiencies and chemical structure. Through studying biodegradability of the synthesized surfactants we find that they are readily biodegradable in the environment and thus they are considered as eco-friendly corrosion inhibitors. Finally, the effect of the addition of these compounds on the aluminum surface was identified by atomic force microscopy (AFM) technique.     

L-赖氨酸改性聚天冬氨酸的阻垢缓蚀性能与生物降解性

L-赖氨酸经过氨解反应合成一种改性聚天冬氨酸衍生物（Lys-PASP）,用FTIR红外谱图证明了Lys-PASP分子中同时含有羧基和酰胺基等基团。扫描电子显微镜（SEM）的分析结果可知：Lys-PASP的加入使溶液中CaCO₃和CaSO₄的钙垢晶体的生长过程和形态发生变化,使得钙垢疏松、细小,抑制了它们长成致密结构的钙垢,从而达到很好的阻垢效果;Lys-PASP的加入使钙垢晶型变化,减缓了试片表面点蚀的发生;另外通过化学和物理的吸附作用在试片表面形成一层吸附膜而达到较好的缓蚀效果。探讨了Lys-PASP接枝聚合物对CaCO₃和CaSO₄垢的阻垢能力与Lys-PASP的投加量、Ca²⁺的浓度和测试体系的温度之间的密切联系。当Lys-PASP的投加量为10 mg·L^-1时,对CaCO₃的阻垢率为98.7%,对CaSO₄阻垢率接近于100%,而在温度达到80℃、Ca²⁺分别达到500 mg·L^-1和7000 mg·L^-1的浓度时,Lys-PASP也表现出很好的阻垢效果。另外,用失重法研究了当Lys-PASP和PASP均为150 mg·L^-1时,Lys-PASP的缓蚀率比PASP高13%;用摇床实验法证明了Lys-PASP属于易生物降解的物质。     

Inhibition by <Emphasis Type="Italic">Jasminum nudiflorum</Emphasis> Lindl. leaves extract of the corrosion of cold rolled steel in hydrochloric acid solution

The inhibition effect of Jasminum nudiflorum Lindl. leaves extract (JNLLE) on the corrosion of cold rolled steel (CRS) in 1.0 M hydrochloric acid (HCl) was investigated by weight loss, potentiodynamic polarization, and electrochemical impedance spectroscopy (EIS) methods. The results show that JNLLE acts as a very good inhibitor, and the inhibition efficiency increases with the concentration of JNLLE. The adsorption of JNLLE obeys Langmuir adsorption isotherm. Values of inhibition efficiency obtained from weight loss, potentiodynamic polarization, and electrochemical impedance spectroscopy (EIS) are in good agreement. Polarization curves show that JNLLE behaves as a mixed-type inhibitor in hydrochloric acid. EIS shows that charge-transfer resistance increase and the capacitance of double layer decreases with the inhibitor concentration, confirming the adsorption process mechanism. The adsorbed film on CRS surface containing JNLLE inhibitor was also measured by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscope (SEM). A probable inhibitive mechanism is proposed from the viewpoint of adsorption theory.     

聚天冬氨酸的合成及其性能研究

以马来酸酐和氨水为原料合成聚天冬氨酸.用红外光谱和核磁共振对聚天冬氨酸进行了结构表征,用黏度法测定了聚天冬氨酸的黏均分子量,用静态阻垢法评价聚天冬氨酸的阻垢性能,用旋转挂片法测定聚天冬氨酸的缓蚀性能;比较聚天冬氨酸与水解聚马来酸酐( HPMA)、氨基三甲叉膦酸(ATMP)的阻垢缓蚀性能.结果表明,最适宜合成工艺条件为:n(马来酸酐)∶n(氨水)=1∶1.1,热聚温度160℃,缩聚时间60 min;当阻垢剂浓度大于6.4 mg/L时,PASP和ATMP的阻垢性能相当,均优于HPMA.