镀锌层高耐蚀性三价铬钝化工艺研究

通过添加适当的氧化剂和螯合剂,对镀锌层三价铬钝化溶液进行改性,控制溶液的pH,钝化温度和时间,利用对比试验对镀锌层钝化工艺进行研究,通过50g/L的NaCl溶液浸泡试验,探讨三价铬钝化工艺参数对钝化膜耐腐蚀性的影响,通过观察腐蚀面积对钝化膜层的耐腐蚀性能进行初步分析.结果表明:采用改性后三价铬钝化液进行钝化,镀锌层的耐...     

Role of polyethylene glycol in electrodeposition of zinc–chromium alloys

The role of polyethylene glycol (PEG) as an additive in the electrodeposition of zinc–chromium alloys was investigated in sulfate baths containing trivalent chromium. PEG with high molecular weight enabled the codeposition of metallic chromium with zinc, while chromium(III) was present in the deposits obtained from the baths containing PEG with lower molecular weight as well as the PEG-free bath. The polarization curves for the alloy deposition revealed that PEG with high molecular weight polarized the deposition potential of zinc to the reduction potential of chromium to permit the codeposition of chromium with zinc.     

浅析三价铬彩钝膜中含六价铬的原因

从三价铬彩钝的配方、温度及镀锌工艺等方面,分析了三价铬彩色钝化膜中六价铬产生的原因。对如何避免三价铬彩色钝化膜中六价铬的产生,提出了一些建议。     

新型三价铬钝化技术

概述了镀锌三价铬钝化的发展历程。叙述了三价铬钝化的机理。介绍了一种新型三价铬钝化液的组成。该钝化液采用含有纳米微粒的封孔剂。通过NSS试验发现,当2种不同封孔剂配合使用时,膜层耐蚀性大大提高。对该三价铬钝化的使用方法与工艺特点,pH、温度及时间的控制,封闭剂的特点进行了简单介绍。提出应用于三价铬钝化前的碱性无氰镀锌及酸性镀锌的适用场合。使用该钝化工艺后,膜层耐蚀性达到甚至超过六价铬钝化工艺。     

Integrated use of liquid membranes and membrane contactors: Enhancing the efficiency of L-L reactive separations

Separation processes combining facilitated transport membranes and membrane contactors offer several advantages such as the ability of liquid membranes to promote the uphill transport of target species by the coupling between mass transfer and chemical reaction, together with the benefits of using membrane contactors: large interfacial area, non-dispersive contact and independent flow of the fluid phases that can play an important role in process intensification. In this work, computer simulation techniques using previously validated mathematical models which take into account mass transfer and chemical reaction are employed: (i) to design the integration of liquid contactors in an already existing electroplating process and (ii) to quantify the degree of intensification provided by liquid membrane separation processes through the definition of suitable intensification indexes such as productivity/size ratio and modularity. The methodology has been illustrated through two different real applications in the context of surface treatment industry which were extensively analyzed in previous works: (i) the regeneration of trivalent chromium passivation baths by the on-site continuous removal of zinc and iron trap ions derived from the electroplating process and, (ii) the treatment of spent pickling hydrochloric acid generated in the hot-dip galvanizing process, with the aim of recovering the valuable zinc.     

镀锌层三价铬黑色钝化工艺与性能研究

采用正交试验法对镀锌层三价铬黑色钝化工艺组分进行优化,研究了工艺参数对钝化膜外观和耐蚀性的影响。根据实验结果优选出镀锌层三价铬黑色钝化工艺,该工艺含有三价铬盐、硝酸盐、钴镍盐和磷酸根,采用有机羧酸作配位剂。此工艺能够获得外观均匀黑亮、附着力良好的膜层,中性盐雾试验出白锈时间大于120h。     

镀锌层的三价铬彩色钝化实践

碱性溶液所获得的镀锌镀层,采用三价铬溶液钝化。简述了三价铬钝化工艺条件及分析方法,并通过长期的生产实践,摸索出三价铬钝化中切实可行的工艺、维护管理方法及出现的钝化膜发雾、发黄、发花、不连续等故障产生的原因及排除措施。     

不同镀锌层的三价铬钝化膜耐蚀性能比较

采用中性盐雾实验NSS、Tafel曲线研究了酸性氯化钾镀锌层、碱性锌酸盐镀锌层和碱性氰化物镀锌层采用三价铬溶液进行钝化处理所得钝化膜的耐腐蚀能力和电化学行为。盐雾实验结果表明:碱性氰化物镀锌层采用三价铬溶液进行钝化处理所得钝化膜的耐蚀性能最好,碱性锌酸盐镀锌层次之,酸性氯化钾镀锌层最差;5%NaCl及3%NaOH溶液中的Tafel曲线显示:碱性氰化物镀锌层采用三价铬溶液进行钝化处理所得钝化膜的腐蚀速率最小,碱性锌酸盐镀锌层次之,酸性氯化钾镀锌层最大。     

Recovery of chromium from tannery effluents using a redox–adsorption approach

Adsorption isotherms for sodium and trivalent chromium uptake from aqueous solutions onto Amberlite resin were prepared at 18°C. Adsorption of each cation followed the Langmuir model. The rate of uptake of each cation was found to be film diffusion controlled with sodium showing the most rapid uptake. In aqueous solutions containing both chromium and sodium as the only cationic species, it was found that with increasing initial concentration of sodium, the trivalent chromium uptake on the resin decreased substantially. To overcome this difficulty a four step redox–adsorption system has been developed for the removal of Cr³⁺ from tannery effluents. The first step comprises the oxidation of trivalent chromium to the hexavalent form using selected common oxidising agents. The liquid effluent is then passed through an Amberlite cation-exchange resin in step 2 where the sodium in the waste stream is completely removed. The anionic hexavalent form of chromium (Cr₂O) passes unaltered through the resin along with the waste stream. In the third stage the dichromate is reduced back to the trivalent cationic form which is subsequently removed from the waste stream by a second Amberlite ion-exchange bed in stage 4. Each step in this process is assessed in batch and flow mode using simulated and real tannery effluents.     

三价铬钝化膜为什么会产生六价铬

根据三价铬和六价铬的氧化还原性质,指出在碱性介质中三价铬可以被氧气氧化成六价铬,认为三价铬钝化膜中三价铬的存在形式(某种三价铬的碱式盐)是其在空气中放置时三价铬被氧化为六价铬的内在原因.提出了采用无铬钝化工艺,钝化后封闭及加强三价铬钝化工艺管理和钝化产品的存放管理等应对措施.     

镀锌钝化研究进展概述

镀锌钝化领域运用最多的六价铬钝化效果比较理想但是具有高污染和致癌等缺点。为寻找替代工艺,三价铬钝化以及无铬钝化应运而生。本文介绍了镀锌六价铬钝化、三价铬钝化以及无铬钝化基本原理及工艺,列举了一些国内外已经发布工艺配方,具有实用参考价值。     

镀锌层三价铬钝化研究进展

铬酸盐溶液常用作镀锌层钝化处理,但六价铬毒性大,近年来人们在研究以三价铬钝化溶液代替。综述了三价铬钝化的机理及钝化液的主要组成,介绍了一些典型的三价铬钝化配方,提出今后三价铬钝化研究应该是以封闭技术为重点,努力提高钝化膜的耐蚀性和附着力。     

镀锌层三价铬蓝白色钝化工艺的研究

由于六价铬的高毒性,镀锌层三价铬钝化工艺是一种替代六价铬钝化工艺的良好选择.其中三价铬蓝白钝化是一种优良的防护-装饰性膜层.详细阐述了影响蓝白色钝化膜性能的主要因素.经过不断的试验,研究出了一种组分简洁的镀锌层三价铬蓝白色钝化液,性能稳定,外观和耐蚀性优良.     

镀锌层三价铬钝化工艺

概述了镀锌层三价铬钝化膜形成机理及特性,及国内外三价铬钝化工艺应用情况,三价铬钝化液的使用寿命长,镀液成分较稳定,并可得到不同色泽的钝化膜,采用封闭剂处理显著提高了膜层耐蚀性;三价铬钝化能减少对环境的污染,是我国电镀清洁生产推荐的工艺,具有实用参考价值。     

Separation and Recovery of Silver(I) Ions from Base Metal Ions by Melamine‐formaldehyde‐thiourea (MFT) Chelating Resin

Abstract

Melamine‐formaldehyde‐thiourea (MFT) chelating resin were prepared using melamine (2,4,6‐triamino‐1,3,5‐triazine), formaldehyde, and thiourea and this resin has been used for separation and recovery of silver(I) ions from copper(II) and zinc(II) base metals and calcium(II) alkaline‐earth metal in aqueous solution. The MFT chelating resin was characterized by elemental analysis and FT‐IR spectra. The effect of pH, adsorption capacity, and equilibrium time by batch method and adsorption, elution, flow rate, column capacity, and recovery by column method were studied. The maximum uptake values of MFT resin were found as 60.05 mg Ag⁺/g by batch method and 11.08 mg Ag⁺/g, 0.052 mg Zn²⁺/g, 0.083 mg Cu²⁺/g and 0.020 mg Ca²⁺/g by column method. It was seen that MFT resin showed higher uptake behavior for silver(I) ions than base and earth metals due to chelation.     

低碳环保型碱性镀锌自动生产线工艺设计

阐述了某军工企业无氰镀锌工艺设计秉持的原则和依据.介绍了2699型碱性镀锌智能化生产线的工艺流程,其主要包括:化学除油,除锈,阳极电解除油,浸碱液,镀锌,硝酸出光,彩色钝化或三价铬厚膜钝化,热水洗,烘干,检验,装箱.给出了各工序的溶液组成及工艺条件.从槽液带出损失及废水处理方面,比较了该工艺与高氰镀锌工艺的运行成本.实...     

Preconcentration and determination of chromium in water with flame atomic absorption spectrometry by thiourea-formaldehyde as chelating resin

Thiourea-formaldehyde chelating resin is synthesized simply and rapidly from thiourea and formaldehyde by condensation polymerization and characterized by IR spectra and studied for the preconcentration and determination of trace Cr(III) ion from solution samples. The optimum pH value for sorption of the metal ion was 6.5. The sorption capacity of resin for Cr(III) was determined. The chelating resin can be reused for 20 cycles of sorption-desorption without any significant change in sorption capacity. A recovery of 96% was obtained for the metal ion with 0.5M HNO₃ as eluting agent. The equilibrium adsorption data of Cr(III) on modified resin were analyzed by Langmuir, Freundlich and Temkin models. Based on equilibrium adsorption data the Langmuir, Freundlich and Temkin constants were determined as 0.016, 0.040 and 0.074 at pH 6.5 and 20°C. The method was applied for chromium ion determination from river water sample.     

Synthesis and analytical application of a chelating resin based on a crosslinked styrene/maleic acid copolymer for the extraction of trace‐metal ions

A new chelating polymer sorbent was synthesized through the copolymerization of styrene and maleic anhydride in the presence of divinyl benzene as the crosslinking agent, followed by hydrolysis. This polymeric resin, bearing O donor groups, had the advantage of being stable in basic and saline media, unlike its linear analogue. This newly developed chelating matrix has a high resin capacity for metal ions such as Cr, Fe, Ni, Cu, and Pb. Various physicochemical parameters, such as the pH, volume, and flow rate, and the interference effect on metal uptake were studied. The sorption capacities of the crosslinked resin for Cr(III), Fe(III), Ni(II), Cu(II), and Pb(II) were 10.2, 14.3, 14.2, 15.4, and 8.8 mg/g, respectively. A high recovery of 98% was obtained for all the metal ions with 2N HCl as the eluting agent. The chelating resin was characterized by swelling studies, Fourier transform infrared, elemental analysis, X‐ray studies, and thermal analysis. The Langmuir and Freundlich adsorption isotherms were used to validate the metal‐uptake data. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1771–1779, 2004     

镀锌层三价铬蓝白钝化工艺的研究

三价铬蓝白钝化对环境污染小,但钝化液成分较复杂,钝化膜耐蚀性及外观不如六价铬钝化膜.为此,本文探讨了工艺参数对钝化层外观和耐蚀性的影响,并得到了组分简单的镀锌层三价铬蓝白钝化工艺.钝化膜耐蚀性能好,经84 h的中性盐雾试验不产生白锈.     

无钴硫酸体系三价铬黑色钝化工艺

以过渡金属硫化物M替代钴(镍)盐作发黑剂,在镀锌层表面得到黑色钝化膜。钝化液的配方与工艺为:Cr2(SO4)335g/L,有机羧酸X6g/L,柠檬酸32g/L,过渡金属硫化物M2g/L,FeSO410g/L,NaNO37g/L,NaH2PO415g/L,pH=2.0,室温,时间30s。钝化膜层乌黑均匀、附着力合格;经封闭后的三价铬黑色钝化膜,其耐蚀性等级高于市售含钴盐发黑剂的三价铬黑色钝化膜,且达到六价铬钝化的耐蚀等级;钝化膜中不含六价铬;钝化液性能稳定。