酸性体系中聚天冬氨酸对碳钢的缓蚀作用初探

用电化学方法研究了在酸性环境中聚天冬氨酸(PASP)对45#碳钢的缓蚀作用及影响因素。结果表明:PASP具有一定的缓蚀保护作用;缓蚀效率随添加PASP浓度增加而增大;当PASP含量达到10 g/L时,缓蚀效率的增加趋势相对稳定,添加PASP 50 g/L时缓蚀效率达到80%以上;碳钢在介质中的浸泡时间、环境温度和碳钢基材表面状态均可影响PASP的缓蚀效果。     

Polyaspartic acid as a green corrosion inhibitor for carbon steel

The inhibitor effect of the environmentally friendly corrosion inhibitor polyaspartic acid (PASP) on the corrosion of carbon steel in 0.5 M H₂SO₄ was investigated by weight loss, potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), and scanning electron microscopy (SEM). Polarization curve results clearly reveal the fact that PASP is a good anode‐type inhibitor. EIS results confirm its corrosion inhibition ability. The inhibition efficiency increases with increasing PASP concentration, and the maximum inhibition efficiency was 80.33% at 10 °C. SEM reveals that a protective film forms on the surface of the inhibited sample. The adsorption of this inhibitor is found to follow the Freundlich adsorption isotherm. A mechanism is proposed to explain the inhibitory action of the corrosion inhibitor.     

聚天冬氨酸及其复配物阻垢缓蚀性能的研究

研究配制了一种高效的绿色阻垢缓蚀剂,其组成为聚天冬氨酸(PASP)、聚丙烯酸(PAA)和2-磷酸丁烷-1,2,4-三羧酸(PBTCA).通过碳酸钙沉积法对PASP及其复配物的阻垢性能进行了实验,得到其最优配方为m(PASP)∶m(PAA)∶m(PBTCA)=6∶1∶1.用旋转挂片法对复配物最优配方的缓蚀性能进行了测试.在测试条件下,该复配物阻垢率能达到91.71％,对碳钢的缓蚀率可达到92.23％,是一种性能优良的阻垢缓蚀剂.     

ATA及其与PASP复配在3.5%NaCl溶液中对碳钢的缓蚀作用

为寻找新的缓蚀荆来解决碳钢的腐蚀问题,采用极化曲线和交流阻抗方法,研究了3-氨基-1,2,4-三氮唑(ATA)及其与聚天冬氨酸(PASP)复配在3.5%NaCl溶液中对碳钢的缓蚀作用,并对比观察了碳钢在未加和加入复配缓蚀荆的3.5%NaCl溶液中浸泡后的腐蚀形貌.结果表明:ATA在3.5%NaCl溶液中对碳钢具有缓蚀作用,属阳极型缓蚀剂,其添加量以25 mg/L为最好,此时的缓蚀效果最佳,缓蚀率可达93.51%;ATA和PASP复配在3.5%NaCl溶液中对碳钢具有缓蚀协同作用,且15 mg/L ATA和10 mg/L PASP复配时的缓蚀协同作用最好,缓蚀率高达99.89%.     

苯并三唑和咪唑分子内缓蚀协同作用的研究

通过Ｍａｎｎｉｃｈ反应把苯并三唑和咪唑分子用亚甲基链连接起来,合成１－「１’－咪唑）－甲基」苯并三唑化合物,采用静态挂片法,电化学极化曲线法和电化学阻抗法研究了它对３％ＮａＣｌ溶溶中铜的缓蚀作用,讨论了分内苯并三唑单元和唑唑单元的协同缓蚀作用。     

2,3-二巯基丁二酸对铜的缓蚀性能研究

目的以马来酸为原料制备2,3-二巯基丁二酸(DMSA),研究DMSA对铜在0.5 mol/L NaOH溶液中的缓蚀作用。方法以马来酸为原料,通过加成、消去、加成再水解的方法制备2,3-二巯基丁二酸,利用红外光谱和质谱对其结构进行表征。通过静态腐蚀失重实验研究铜在添加不同含量DMSA的NaOH溶液中的腐蚀速度,采用极化曲线和交流阻抗谱技术研究铜在添加不同含量DMSA的NaOH溶液中电化学行为,并用电子扫描电镜观察铜表面腐蚀形貌。结果红外光谱和质谱结合证明,目标产物为DMSA。铜在DMSA质量浓度分别为0,2.5,5.0 g/L的NaOH溶液中的腐蚀速率分别为7.60,3.25,2.13μg/(cm2·h)。当NaOH溶液中DMSA的质量浓度为5.0 g/L时,缓蚀率可达到94.92%。结论 DMSA在铜表面的吸附能降低水分子的侵蚀,增大铜表面的腐蚀产物膜电阻和电荷转移电阻,属于阳极型缓蚀剂。     

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。     

硫酸介质中桂花果提取液对Q235钢的缓蚀作用

目的研究在0.5 mol/L硫酸溶液介质中,桂花果提取液(OFFE)对Q235钢的缓蚀作用及机理。方法通过失重法和极化曲线、电化学阻抗谱等电化学方法研究了桂花果提取液对Q235钢在0.5 mol/L硫酸溶液介质中的缓蚀性能,考察了25℃下桂花果提取液浓度对缓蚀效率的影响,并对缓蚀机理进行了探讨。结果以95%的乙醇为溶剂浸提制备的桂花果提取液在0.5 mol/L硫酸介质中对Q235钢具有良好的缓蚀性能,缓蚀效率随其质量浓度的增加而增大,当其浓度达到10 g/L时,其缓蚀效率可达91.48%。电化学测试结果表明,桂花果提取液为混合型缓蚀剂,主要通过抑制阴极析氢过程来减缓Q235钢的腐蚀,缓蚀机理为"几何覆盖效应",其有效缓蚀成分在Q235钢表面的吸附符合Langmuir等温式,吸附平衡常数为1.09 L/g。结论在0.5 mol/L的硫酸介质中,桂花果提取液对Q235钢具有明显的缓蚀作用,是一种有广泛应用前景的天然绿色缓蚀剂。     

Photoelectrochemical Study of the Corrosion and Inhibition on Copper

用光电化学方法研究了Cu在不同浓度NaCl的硼酸--硼砂溶液中的腐蚀以及缓蚀剂聚天冬氨酸(PASP)对Cu的缓蚀作用. Cu在硼酸--硼砂缓冲溶液中, 表面的Cu2O膜为p型半导体. 当Cu所在的溶液中存在少量NaCl (小于0.5 g/L)时, Cu表面Cu2O膜会受轻微Cl-掺杂但不会改变半导体性质; 当溶液中存在较多NaCl (0.5-15 g/L)时, Cu2O膜会受Cl-较严重的侵蚀, Cl-掺杂使Cu2O膜部分转成n型; 当溶液中存在大量NaCl (大于15 g/L)时, Cu$_{2}$O膜完全被Cl-掺杂而转型成n型. 缓蚀剂PASP的加入能够对Cu起到缓蚀作用：当NaCl浓度为2 g/L时, PASP与溶液中的Cl-在Cu表面竞争吸附, 明显抑制了Cl-对Cu2O膜的掺杂, Cu2O受到了保护仍为p型; 在NaCl浓度为30 g/L时, PASP与Cl-竞争吸附只能削弱Cl-对Cu2O膜的掺杂, Cu2O膜仍受Cl-掺杂而转成n型, 但n型性质变弱. 对Cu2O膜性质的Mott-Schottky测试结果与光电化学结果一致.     

3%NaCl溶液中咪唑和苯并三唑对Cu缓蚀协同作用的研究

采用失重法考察了3%NaCl溶液中咪唑和苯并三唑对Cu 的缓蚀作用,结果表明100 mg/L的咪唑对Cu的缓蚀率仅为477%,100 mg/L的苯并三唑对Cu 的缓蚀效率为732%,当70 mg/L的咪唑和30 mg/L的苯并三唑复配使用后,其缓蚀效率提高 到943%,电化学极化曲线研究表明苯并三唑对Cu电极的阳极过程有抑制作用,咪唑对Cu电 极的阴极过程有抑制作用,咪唑和苯并三唑的复配使用显著增加了对Cu电极阴极和阳极电化 学过程的抑制作用.     

The synergistic effect of Na3PO4 and benzotriazole on the inhibition of copper corrosion in tetra‐n‐butylammonium bromide aerated aqueous solution

The effect of Na₃PO₄ and the mixture of benzotriazole (BTA) and Na₃PO₄ (SP) on the corrosion of copper in 17 wt% (0.534 mol/L) tetra‐n‐butylammonium bromide (TBAB) aerated aqueous solution has been investigated by means of weight‐loss test, potentiodynamic polarization test, electrochemical impedance spectroscopy (EIS), and scanning electron microscopy/energy dispersive X‐ray techniques. The experimental results showed that a dosage of Na₃PO₄ stimulated the copper corrosion, and the corrosion rate increased with increasing Na₃PO₄ concentration, whereas the mixture of BTA and Na₃PO₄ could protect copper in aqueous TBAB solution. The inhibition action of the mixture of BTA and Na₃PO₄ on the corrosion of copper is mainly due to the inhibition of the anodic process of corrosion. The inhibition efficiency of a mixture consisting of 2 g/L BTA and 1 g/L Na₃PO₄ was about 96%. The mixture of BTA and Na₃PO₄ inhibits the corrosion of copper better than BTA by itself, indicating that Na₃PO₄ has a synergistic role with BTA on the corrosion inhibition of copper in TBAB aqueous solution.     

A novel green depressant for flotation separation of scheelite from calcite

Polyaspartic acid (PASP) was used as a novel environmental-friendly depressant, and its inhibition effect on flotation performance of scheelite and calcite using sodium oleate (NaOL) as a collector was investigated by ways of flotation experiments, zeta potential measurement, contact angle measurement and infrared spectroscopic analysis (IR). The results show that PASP exhibits stronger inhibition capability and selectivity than acidified water glass, and the flotation separation of scheelite from calcite can be realized in the presence of 6 mg/L PASP and 20 mg/L NaOL at pH>6. In the presence of PASP, the zeta potential of calcite surface almost keeps unchanged after adding NaOL, and the contact angle decreases sharply. Therefore, it is indicated that PASP significantly decreases the adsorption of NaOL on calcite surface. By contrast, it has no distinct effect on the adsorption of NaOL on the scheelite surface, which is further confirmed by IR results.     

固定化溶菌酶的缓蚀机理及性能

采用物理吸附方法将溶菌酶固定在MCM-41介孔分子筛上,并与化学缓蚀剂[氨基三亚甲基膦酸(ATMP)与聚天冬氨酸(PASP)]复配用作循环冷却水缓蚀剂。利用电化学法分析复配缓蚀剂的缓蚀机理,并用失重法所测得的复配缓蚀剂缓蚀性能为指标优化复配条件。结果表明:复配缓蚀剂为混合型缓蚀剂,可以同时抑制腐蚀过程的阴极反应与阳极反应,最佳复配方案为固定化溶菌酶投加量0.7g/L、ATMP质量浓度10mg/L、PASP质量浓度20mg/L,缓蚀率可达88.55%,循环冷却水对碳钢腐蚀速率降至0.017 3mm/a,作用时间为11~13d。     

Oil palm empty fruit bunch extract and powder as an eco‐friendly corrosion inhibitor for mild steel: A comparison study

A comparison study in terms of inhibition performance between oil palm empty fruit bunch (OPEFB) extract and OPEFB powder against mild steel corrosion in 1 M hydrochloric acid was evaluated using weight loss technique and adsorption isotherms. OPEFB extract and powder were prepared at various concentrations of 0.2%, 0.4%, 0.6%, 0.8%, and 1.0% (v/v) and dosages of 0.2, 0.4, 0.6, 0.8, and 1.0 g, respectively. The results showed that OPEFB extract achieved higher inhibition efficiency (IE) at high concentration and short immersion time compared to OPEFB powder. Despite having lower IE, OPEFB powder seemed to have better behavior; 6.6% IE increment at longer immersion time, gradual release of active compounds and stronger adsorption capacity. Fourier transform infrared (FTIR) and energy‐dispersive X‐ray studies confirmed the presence of active compounds in OPEFB extract and powder that is responsible for inhibition. Thermodynamic study revealed that both OPEFB extract and powder obeyed Langmuir isotherm and worked through physical adsorption. Overall, OPEFB powder is concluded to have better performance as corrosion inhibitor compared with OPEFB extract.     

聚天冬氨酸及其衍生物的缓蚀性能和生物降解性能

在聚琥珀酰亚胺的基础上分别合成了含单羟基、双羟基、羧基、磺酸基四种基团的聚天冬氨酸(PASP)衍生物,采用静态失重法和电化学腐蚀法对其缓蚀性能进行了研究。试验结果表明,这几种聚天冬氨酸衍生物都是以抑制阳极为主的缓蚀剂,其中接枝双羟基的衍生物(DHPAP)的缓蚀效果最好,当加药量为100mg.L-1时缓蚀率达到92.8%,比聚天冬氨酸提高了50%以上。PASP、PASP-ASP(含羧基)在20天内的生物降解率在60%以上,具有优良的生物降解性,而PASP-SEA(含磺酸基)、HPAP(含单羟基)、DHPAP(含双羟基)属于可生物降解物质。     

聚环氧琥珀酸及其复配物的缓蚀性能研究

用旋转挂片法研究了聚环氧琥珀酸与锌盐复配对碳钢缓蚀作用的协同效应;同时研究了聚环氧琥珀酸与苯并三氮唑的复配对黄铜的缓蚀协同效应.实验结果表明:聚环氧琥珀酸与Zn2+质量比为6∶4时,协同增效作用最佳.以此比例在模拟水中,使用量为60 mg/L,缓蚀率达到97.57%.当聚环氧琥珀酸与苯并三氮唑复配时,在使用量聚环氧琥珀酸为20 mg/L,苯并三氮唑为1 mg/L时,缓蚀率达到82.14%,缓蚀协同效果也较好.     

氨基酸复配酸洗缓蚀剂的研究

目的氨基酸对环境无毒无害,生产成本低,可生物降解且水溶性较高,是一种极具发展潜力的新型绿色酸洗缓蚀剂。探究在盐酸介质中,氨基酸及复配缓蚀剂对Q235钢的缓蚀作用。方法采用失重法,利用电子分析天平精确称量浸入腐蚀介质前后金属试样的质量来确定金属的腐蚀速率。研究了L-半胱氨酸及其复配缓蚀剂在1 mol/L盐酸介质中对Q235钢的缓蚀性能,借助等温吸附模型对其缓蚀机理进行了探讨。结果单独使用L-半胱氨酸缓蚀效率较低。当质量浓度为800 mg/L时,L-半胱氨酸的缓蚀效率达到最大值,为65.57%。复配合成缓蚀剂能降低经济成本,并提高缓蚀效率。通过三元复配实验得出L-半光氨酸、KI和抗坏血酸的最佳复配比,当L-半胱氨酸、KI、抗坏血酸的质量浓度分别为20、30、250 mg/L时,其缓蚀效率可达96.37%,且成本较低,是较理想的复配缓蚀剂。复配缓蚀剂在Q235钢表面的吸附符合Langmuir吸附等温模型。结论在盐酸介质中,L-半胱氨酸三元复配缓蚀剂整体用量适中,价格合理,证明复配缓蚀剂是一种能够得到良好应用的绿色缓蚀剂。     

胡萝卜茎叶提取物对碳钢在0.5 mol/L H2SO4溶液中的缓蚀作用

目的研究胡萝卜茎叶提取物(DCSLE)在硫酸介质中对碳钢的腐蚀抑制作用及机理。方法通过超声辅助的手段,用水浸提获得DCSLE,利用红外光谱(FTIR)对其含有的主要官能团进行表征。在25~40℃下,采用失重法、电化学极化和阻抗法(EIS)评价DCSLE在0.5 mol/L H2SO4溶液中对碳钢的缓蚀性能,并讨论了其缓蚀机理。结果DCSLE对碳钢在0.5mol/LH2SO4溶液中的腐蚀具有良好的抑制效果,其缓蚀效率随浓度的增加而增加,随温度的增加而先增加后降低(40℃<25℃<30℃<35℃),35℃下,质量浓度为0.6g/L时,缓蚀效率为92.85%。电化学测试表明,DCSLE是混合型缓蚀剂,但主要是抑制阴极的反应。其缓蚀机理是:DCSLE以物理和化学混合吸附的方式吸附在碳钢表面,形成一层保护膜,从而阻止酸溶液的侵蚀,且吸附遵循Langmuir吸附等温模型。扫描电镜(SEM)观察到加入DCSLE后,碳钢的腐蚀得到了明显控制。结论DCSLE可以有效抑制碳钢在0.5mol/LH2SO4溶液介质中的腐蚀,是一种具有广泛应用前景的天然绿色缓蚀剂。     

Inhibition of copper corrosion in 1M nitric acid with benzoyl benzaldehyde hydrazone derivatives

The effect of substituted benzoyl benzaldehyde hydrazone derivatives on the inhibition of copper corrosion in IM nitric acid solution at 303 K was investigated by potentiodynamic and weight-loss measurements. A significant decrease in the corrosion rate of copper was observed in the presence of the investigated compounds. The corrosion rate was found to depend on the nature and the concentration of the inhibitors. The Tafel slope is approximately constant independent of the concentration of the inhibitor. The observed corrosion data indicate that the inhibition of copper corrosion is due to surface adsorption of inhibitor molecules which follow the Langmuir adsorption isotherm. The results of potentiodynamic measurements indicate that all investigated compounds act mainly cathodically.     

复配BTA与TTA钝化纯铜工艺研究

目的为了提高纯铜表面的耐腐蚀性。方法通过苯并三氮唑(BTA)与甲基苯并三氮唑(TTA)复配,对纯铜进行钝化,并分析钝化温度、时间及pH值对纯铜钝化效果的影响。分别运用电化学法、硝酸点滴实验、中性盐雾实验、SEM等手段对不同钝化液钝化膜的微观结构与耐蚀性能进行研究,并与铬酸盐钝化结果进行对比。结果将4 g/L BTA、4 g/L TTA复配,辅以氧化剂20 m L/L H_2O_2,对纯铜以pH值为4、钝化时间3 min、钝化温度40℃、自然风干老化1 d的钝化工艺处理后,可以生成明显的钝化膜。其表面致密,耐蚀性较好,在盐雾试验中腐蚀缓慢,其平均腐蚀速率为0.76 mg/d,自腐蚀电流密度仅为1.5660μA/cm2,缓蚀率达到81.9%,接近铬酸盐钝化的抗腐蚀效果。结论在适宜的钝化工艺下,经过BTA与TTA复配钝化后,可以在基体表面生成Cu/Cu_2O/Cu(I)BTA聚合物保护膜,同时TTA的非极性甲基形成的单分子层膜的疏水性更好,两者共同作用,形成较为致密的钝化膜覆盖在铜基体表面,明显提高纯铜表面耐蚀性。