盐酸介质中表面活性剂对碳钢缓蚀作用的研究

研究了几种表面活性剂在盐酸介质中的缓蚀作用以及与六次甲基胺复配时的协同缓蚀作用，探讨了碳钢在盐酸，六次甲基四胺和十二烷基硫酸钠混合溶液中的钝化机理。     

催化极谱测定铑

催化极谱测定铑,已有不少报道。高小霞等曾作专著论述。资料介绍,铑在1.5N盐酸—0.001M六次甲基四胺底液中有很好的灵敏度,但在此底液中铑产生的催化电流与其浓度之间不呈线性关系。为此,仍有进一步探讨的必要。本文在试验的基础上提出:采用0.1N盐酸—0.001M六次甲基四胺作为测定铑的新底液,铑的催化     

癸胺在金属铝上的缓蚀作用研究

采用电化学极化曲线、红外光谱等方法,对不同温度下癸胺对盐酸介质中铝的缓蚀性能进行了研究,计算了相关热力学函数,讨论了癸胺在铝表面的吸附模型.电化学极化测试表明,癸胺在铝表面吸附后,铝的腐蚀电流密度减小,极化电阻增大,缓蚀效率提高;红外光谱测试表明,癸胺通过竞争吸附形式在金属表面成膜.     

植物型缓蚀剂提取及灰色系统对其效果评价

研制了一种环保型酸洗缓蚀剂.采用索氏提取法从橙皮中提取酸洗缓蚀成分，用静态失重法确定酸洗缓蚀剂的最佳缓蚀条件:在研究范围内，腐蚀温度控制在35℃，腐蚀时间5小时20分钟，盐酸酸度为2%，缓蚀剂浓度为0.5%时，缓蚀效果最好;而与六亚甲基四胺复配使用后，缓蚀效果更佳，缓蚀效率达到96%.利用电化学极化曲线对其缓蚀机理进行探讨，发现其为阳极型缓蚀剂.通过考察温度对缓蚀效率的影响，得出缓蚀剂的加入使碳钢在盐酸中溶解反应的活化能升高的结论.通过Frumkin吸附等温式的拟合计算，得到缓蚀成分在碳钢上的吸附为单分子层吸附，且吸附分子间表现为斥力.运用灰色模型GM（1.1）对缓蚀效果进行评价和预测,也得到较理想的结果.     

一种曼尼希碱缓蚀剂的复配研究

目的利用常用复配剂对缓蚀剂进行复配,以获得更好的缓蚀效果。方法利用静态失重法测量缓蚀剂与KI、硫脲、花椒籽油、六次甲基四胺复配前后腐蚀速率的变化,通过电化学方法测量缓蚀剂复配前后交流阻抗谱和极化曲线的变化,借助等温吸附模型对缓蚀剂机理进行探讨。结果缓蚀剂单独使用且质量浓度为50 mg/L时,腐蚀速率为6.94 g/(m~2?h),随着复配剂KI、硫脲、花椒籽油、六次甲基四胺浓度的升高,金属的腐蚀速率逐渐下降,在复配剂质量浓度为100 mg/L时,腐蚀速率分别下降为4.22、3.69、5.97、3.28 g/(m~2?h)。极化曲线表明,缓蚀剂复配前后都为阴极抑制为主的混合型缓蚀剂。添加复配剂前后缓蚀剂在金属表面的吸附模型均未发生变化,都为Langmuir等温吸附,分别添加复配剂KI、硫脲、花椒籽油、六次甲基四胺后,缓蚀剂在金属表面吸附的ΔG~θ分别为–26.1、–25.3、–26.8、–27.4 k J/mol,说明缓蚀剂在金属表面物理吸附与化学吸附同时存在。结论 KI、硫脲、六次甲基四胺与缓蚀剂的协同作用良好。     

缓蚀剂对镁合金化学镀镍的影响

目的寻找有效抑制镁合金腐蚀的缓蚀剂,提高镀层质量。方法研究缓蚀剂的种类和用量对缓解镁合金腐蚀的影响,研究不同缓蚀剂对化学镀镍层的影响。采用全浸失重实验对缓蚀剂的性能进行评价,并通过扫描电子显微镜(SEM)、能谱仪(EDS)、X射线衍射仪(XRD)和电化学测试对不同缓蚀剂下所得镀镍层的性能进行表征。结果经过初步筛选,六次甲基四胺(Hexamethylenetetramine)、氟化胺(NH_4F)、氟化氢铵(NH_4HF_2)缓蚀剂的效果较明显。AZ9l D镁合金在腐蚀溶液中,随着添加六次甲基四胺浓度的增加,腐蚀速率先减小后增加。随着添加氟化铵、氟化氢铵浓度的增加,腐蚀速率逐渐减小。添加缓蚀剂的体系中较不加缓蚀剂的体系中测得的电化学曲线好。六次甲基四胺、氟化铵、氟化氢铵效果最好时,质量分数分别为1%、1.5%、2%。不同种类缓蚀剂均可以有效抑制镁合金的腐蚀,减小腐蚀电流。加入缓蚀剂的化学镀镍配方沉积和镀覆效果明显,镀层电化学性能也有很大的提升。结论六次甲基四胺(Hexamethylenetetramine)、氟化胺(NH_4F)、氟化氢铵(NH_4HF_2)缓蚀剂的使用可以有效抑制镁合金的腐蚀,提高化学镀镍层的质量。     

钢在浓盐酸中的腐蚀和某些缓蚀剂作用机理探讨

用经典的恒电势极化曲线方法研究了25℃下,浓度高达12N的盐酸对于45钢的腐蚀以及在8.7N(～28％)HCl中不同浓度六次甲基四胺(U)和2.4.6-三甲基吡啶(TMP)单独或复合加入时的缓蚀作用。发现盐酸浓度在8.7N以上时,阴极极化曲线趋于重合,使腐蚀作用的增加趋势逐渐减缓。在8.7NHCl中U是强烈的阴极缓蚀剂,它的缓蚀作用比TMP高出许多,当两者复合使用时,TMP中杂质较少时只超加和作用,但杂质较多时能产生强烈的协合作用。本文用在Fe/高浓盐酸界面上H~+Cl~-_“分子”达到饱和吸附,U又较强地吸附在H~+Cl~-表面这一观点,对上述现象进行了定性的解释。     

多孔氧化铈空心微球的合成、表征及其脱色性能

以聚苯乙烯微球为模板、六水硝酸亚铈为铈源、六亚甲基四胺为沉淀剂,制备不同壳厚的氧化铈空心微球;利用XRD、TEM、FESEM、XPS和氮气吸附一脱附等手段,对所制备样品的微观结构进行表征.将所制备的Ce02空心微球用于甲基橙模拟染料废水的脱色处理.结果表明:CeO2空心微球具有多孔结构,表面平均孔径约为10 nm,球径约为200～250 nm,壳厚约为10～30 nm,壳层是由粒径为5～10 nm的CeO2颗粒所组成;甲基橙溶液经CeO2空心微球处理60 min后,其脱色率可达95%以上,表现出良好的脱色性能.     

硫酸中环己基炔氧甲基胺氨基三甲撑膦酸盐作用于纯铁电极的腐蚀电化学特征

采用稳态极化曲线技术和交流阻抗测试技术研究了环己基二炔氧甲基胺氨基三甲撑膦酸盐在硫酸介质中的缓蚀作用机理.研究结果表明,环己基二炔氧甲基胺氨基三甲撑膦酸盐在硫酸介质中腐蚀电位负移,其缓蚀机理为混合抑制负催化效应,缓蚀剂分子可能参与了阴极反应过程.吸附等温式符合Frumkin等温式.该缓蚀剂存在浓度极值现象.     

化学除锈法在焊接生产上的应用

我厂以化学除锈法取代了机械除锈,对数千个废钢瓶进行了返修,经X射线探伤,其一次合格率达96.7％,比机械除锈法提高17.4％。化学除锈以盐酸、六次甲基四胺、纯碱、亚硝酸钠为原料。其流程为:酸洗(配方为:盐酸31％、六次甲基四胺1～3％,温度:常温,时间:3分,以除去氧化皮为准。)→冷水冲洗(以冷水冲刷除锈部位的黑色泥灰,时间为30秒)→中和(配方:纯碱15～30克/升、亚硝酸钠20～30克/升,温度:常温,时间:30秒)～热水干燥(水温:90℃以上,时间:30～60秒)。为避免未乾残液沾污焊接     

Synthesis and evaluation of hexamethylenetetramine quaternary ammonium salt as corrosion inhibitor

A novel corrosion inhibitor, hexamethylenetetramine quaternary ammonium salt, is synthesized using hexamethylenetetramine (HMTA) and bromohexane as main reactants. The inhibitive action of HQAS on QT800‐2 steel in hydrochloric acid medium is evaluated by weight‐loss method, electrochemical method, and quantum chemical calculation. The obtained results show that the efficiency of 0.5 wt% HQAS inhibitor in 30 wt.% HCl solution at 363 K is 92.95% and HQAS can form an excellent synergistic effect with some additives. Polarization curves reveal that HQAS behaves as a mixed‐type inhibitor with dominant anodic inhibition. Furthermore, the theoretical calculation verifies the relationship between the HQAS molecular structure and corrosion inhibition properties.     

一种新型酮醛胺酸化缓蚀剂的合成及性能研究

介绍了一种新型酸化缓蚀剂的合成方法、缓蚀性能,并分析了其缓蚀机理。利用酮醛胺的缩合反应,筛选最佳反应条件,合成一种曼尼希碱,在15%盐酸（90℃）中的缓蚀率达到99.74%,超过了酸化缓蚀剂评价标准SY/T54JD5-1996规定的一级水平 在90℃土酸（7.5%HCl＋1.5%HF）中的缓蚀率达到99.44%,也达到了酸化缓蚀剂评价标准规定的一级水平,与碘化物、炔醇及六次甲基四胺复配后所得缓蚀剂性能超过了该标准的一级水平。     

Galvanic series of different stainless steels and copper- and aluminium-based materials in acid solutions

Galvanic series of AISI 304, 316, 316L, and 316Ti austenitic stainless steels, AISI 410 and 420 martensitic stainless steels, 63Cu37Zn brass, Cu, Al, and AlMg1 were established for 10% (wt.) hydrochloric, phosphoric, sulphamic, sulphuric, nitric, citric, acetic, and methanesulphonic (MSA) acids used as cleaners in order to predict galvanic corrosion when coupling these materials. It was found that each acid has a distinctive order of metallic materials in a galvanic series. The largest corrosion potential difference in all acids exists between Al-based materials and stainless steels, as well as Cu-based materials indicating the use of Al-based materials as sacrificial electrodes.     

微量铟对稀土铝黄铜腐蚀性能的影响

采用失重法、X射线衍射法、电化学测试、扫描电镜等手段对比分析研究了铈铝黄铜和添加微量铟的新型铝黄铜的耐蚀性能。结果表明,铈铝黄铜的平均腐蚀速率为7.3×10-3 mm/a,新型铝黄铜的腐蚀速率为6.7×10-3mm/a。添加铟后能大幅度提高极化电阻,从而减小了腐蚀电流密度,耐腐蚀性能进一步得到提高;铟的加入改善了膜的结构,含In铈铝黄铜在NaCl(3.5%)溶液中腐蚀后表面形成了一层致密、完整的腐蚀产物膜,一定程度地抑制了脱锌;铟能减少锌的析氢反应,从而进一步抑制了黄铜的脱锌腐蚀。因此微量铟的加入可以改善稀土铝黄铜的腐蚀性能。     

Inhibitoren der Korrosion 31 (1). Beitrag zur Inhibierung der Korrosion von Zink und Messing

Inhibitors of corrosion 31 (1). Contribution to the inhibition of the corrosion of zinc and brass The following compounds approved as inhibitors of the corrosion of copper are investigated as inhibitors of the corrosion of zinc and brass: 2-aminopyrimidine (A), 5-aminotetrazole monohydrate (B), benzotriazole (C), Kupferron (D), 2-mercaptopyrimidine (E), 2-mercaptothiazoline (F), 2-methyl-4-amino-5-cyanopyrimidine (G), tetrazine-B (H) and 2-amino-3,4,1-dithiazoline-1,5, thione (I). In the presence of the compounds A, B, C, E and G zinc plates are totally corroded in 15 days using standard conditions. With the compounds D, F and H the protective values are 29%, 14% and 39%. A more differentiated information is obtained with acid consumption-time-curves at constant pH using zinc powder. Only the compound C slows down the corrosion. The other compounds enhance the corrosion. In corrosion studies with mixtures of copper and zinc powders the compounds B–I inhibit the corrosion of copper. The acceleration of the corrosion in the presence of compound A was investigated. The corrosion of brass (plate, grain, powder) proceeds with primary removal of zinc. The compounds A, E, F and H are good inhibitors. The inhibition values for brass 64/36 are better than for brass 90/10. The composition of the protecting layers produced on the surface of brass in the presence of the organic inhibitors is determined by X-ray fluorescence measurements. With the inhibitors A, B, E, F and G the content of copper is over 90%, but 80% in the presence of the inhibitors C and H, which delay also the corrosion of zinc. The conception of primary loss of zinc and the subsequent production of a copper-rich copper-inhibitor-protection-layer is confirmed by determining the composition of the precipitations and of the solutions produced during the corrosion of brass.     

Amino acids as corrosion inhibitors in hydrochloric acid solutions

Inhibition of the corrosion of iron in hydrochloric acid solutions by amino acids was studied. Twenty-two different common amino acids and four related compounds were used. Potentiodynamic polarization curves were obtained for iron wire in deaerated 1 M hydrochloric acid solution. Intersection of the linear Tafel lines at the corrosion potential gave values of the corrosion current. At 10 mM concentration of the inhibitors, the best results were obtained with 3,5-diiodotyrosine, with an inhibition efficiency of 87%. The best common amino acid was tryptophan with an inhibition efficiency of 80%. Hydroxyproline, cystine, and cysteine acted as corrosion accelerators. Definite trends were observed which were related to the molecular structure. In general, amino acids with longer hydrocarbon chains showed greater inhibition. Additional amino groups or groups which increased electron density on the alpha amino group also increased the inhibition efficiency.     

SO2-4 ,PO3 4- 对曼尼希碱酸化缓蚀剂缓蚀性能的影响

目的：研究废酸液中介质离子对曼尼希碱酸化缓蚀剂缓蚀性能的影响,以解决碳钢在酸液中的腐蚀问题。方法采用静态失重法、极化曲线、扫描电镜及能谱分析法,研究SO2-4,PO3-4对曼尼希碱型酸化缓蚀剂缓蚀性能的影响,并探究其作用机理。结果在10%(质量分数)盐酸、0.1%(质量分数)曼尼希碱的缓蚀介质中,随SO2-4质量分数的增大,腐蚀电流密度由2.81μA/cm2增加至7.32μA/cm2,腐蚀速率显著增大,缓蚀效果变弱;随PO3-4质量分数的增加,腐蚀电流密度由2.81μA/cm2减小至2.41μA/cm2,腐蚀速率减小,缓蚀效果变强。结论 SO2-4会通过钢铁表面已经形成的吸附膜上的细孔和缺陷渗入膜内,使膜发生开裂,从而侵蚀和破坏已经形成的吸附膜,抑制缓蚀剂的缓蚀效果;PO3-4与腐蚀产物Fe3+络合并在钢材表面形成一层致密的保护层,使缓蚀剂形成的吸附膜更加致密,阻止腐蚀性介质与金属表面接触,同时增加对离子或溶解氧的扩散阻力,提高缓蚀剂的缓蚀效果。     

Corrosion of cold-deformed brass in acid sulphate solution

The corrosion behaviour and the dezincification process of cold-deformed CuZn-42 brass were tested in an acid sulphate solution at pH-value 2 with additional chloride and copper(II) ions by use of the linear polarization method.The measured corrosion potential and densities of corrosion currents were observed as characteristics of the dezincification process and the corrosion resistance of tested samples of cold-deformed CuZn-42 brass. The results obtained have shown that pH-value 2 of the tested solutions and increased concentrations of copper(II) ions result in increased values of densities of corrosion currents of the tested brass samples, as a result of selective zinc dissolution and the individual dissolution of zinc and copper including the process of anodic oxidation. The tested concentrations of chloride ions in certain conditions have an inhibiting effect, whereas in the other conditions they act as distinctive activators of brass corrosion. The lowest values of corrosion currents are present in the brass samples with the highest deformation degree at 80%. The process of dezincification and anode dissolution of cold deformed brass samples were developed in the whole range of tested potentials.     

环保型无磷缓蚀阻垢剂的制备

以低分子量聚丙烯酸钠(PAAS)为基础,将聚丙烯酸钠、钼酸钠、D-葡萄糖酸钠、苯并三氮唑、六次甲基四胺等物质按一定比例复配成无磷缓蚀阻垢剂配方,采用碳酸钙沉积法评价其阻垢性能,用旋转挂片法和电化学法评价其缓蚀性能。优选出的最佳缓蚀剂配方为:聚丙烯酸钠15mg/L、D-葡萄糖酸钠14mg/L、苯并三氮唑13mg/L、钼酸钠18mg/L、六次甲基四胺14mg/L,其阻垢率为92.63%,缓蚀率为92.78%。该配方具有无磷、无毒、高效、环保等特点,具有重要的经济和利用价值。