ADC12铝合金表面硅锆复合转化膜的研究

通过化学转化法在ADC12铝合金表面制备出新型硅锆复合转化膜。利用硫酸铜点滴实验与极化曲线测试对胺基双硅烷含量进行优化，利用场发射扫描电镜(FESEM)对转化膜的微观形貌进行分析，采用Fourier变换红外光谱分析仪(FT-IR)与X射线光电子谱(XPS)研究了转化膜的结构与成分并对成膜过程进行了分析，利用电化学测试、中性盐雾实验研究转化膜的耐蚀性能。结果表明：60%胺基双硅烷转化膜的耐蚀性能最优。胺基双硅烷的引入明显改善了转化膜的均匀性和致密性。胺基双硅烷大大提升了转化膜的耐蚀性能。相较于锆转化膜，硅锆复合转化膜的容抗弧半径增加了3倍以上；低频阻抗值增加了3倍以上；耐盐雾时间提升了20倍以上。     

5182铝合金表面锆化膜的制备及其性能研究

目的提高5182铝合金的耐蚀性能及与有机漆膜的结合力。方法采用氟锆酸试剂与5182铝合金反应制备锆化膜,探究锆化液pH值、浸泡时间对锆化膜耐蚀性能的影响,并优化制膜工艺。采用SEM、EDS能谱仪及超薄切片仪分析锆化膜的微观结构和成分,结合SKPFM分析合金中第二相颗粒的电位对锆化膜形成机理的影响,采用EIS对锆化膜的耐蚀性能进行评价分析,采用涂层附着力自动划痕仪评价锆化涂层对巴斯夫有机漆膜结合力的影响。结果制备锆化膜的最佳工艺为:pH=4.5,浸泡时间2.5 min。在5182铝合金表面制备了一层50～100 nm厚的锆化膜,且该锆化膜优先在阴极性的第二相颗粒上形成。EIS分析表明,在Na_2B_4O_7×10H_2O和NaOH水溶液中,锆化处理试样的低频阻抗值比未锆化处理试样高80?。划痕测试表明,锆化处理试样与未锆化处理试样相比,其临界载荷提高了75%。结论经过锆化最佳工艺处理后,5182铝合金的耐蚀性能提高,且锆化涂层作为中间层,能显著提高有机漆膜与合金基体的结合强度。     

冷轧钢表面磷化膜和硅烷膜的制备与性能

通过在冷轧钢表面进行磷化处理和硅烷化处理,应用极化曲线、硫酸铜点滴和盐水全浸泡测试其耐蚀性能,并对其与有机涂层间的结合力进行评价。结果表明,经硅烷化处理形成的硅烷膜耐蚀性能及与有机涂层间的结合力明显优于未处理的磷化膜。扫描电子显微镜(SEM)显示磷化膜的结构较为疏松,而γ-(甲基丙烯酰氧)丙基三甲氧基硅烷膜表面致密均匀。     

镁合金表面锆钛硅烷复合膜层的制备及耐蚀性研究

目的 在镁合金表面制备耐蚀环保锆钛硅烷复合膜层,并研究其腐蚀性能。方法 将锆盐、钛盐转化技术与绿色有机硅烷技术进行复合联用,通过先浸入含有锆盐、钛盐、单宁酸的无机溶液,再浸入5%（体积分数）的双-[γ-(三乙氧基硅)丙基]四硫化物有机硅烷溶液,在镁合金AZ31表面制备出了耐蚀环保锆钛硅烷复合膜层,通过扫描电子显微镜和能谱仪观察分析了复合膜层的微观形貌以及元素组成,利用极化曲线和交流阻抗谱电化学测试手段评价了膜层的耐腐蚀性能。结果 经过不同锆钛硅烷复合处理后,镁合金表面形成一层均匀、平整且有干枯河床状纳米尺度微裂纹的锆钛硅烷复合膜,膜层普遍表现出良好的耐蚀性能。与空白镁合金试样相比,复合膜层试样出现最小腐蚀电流密度,为1.51 μA/cm2,腐蚀速度约为空白样的1/50,交流阻抗值最大提高约20倍,腐蚀电位出现的最大正移接近100 mV。结论 锆钛硅烷复合膜层对腐蚀性介质有显著的物理阻隔作用,显著抑制了镁溶解,阻滞了镁合金表面的电化学反应过程,降低了镁合金的腐蚀速度。     

钢铁表面纯锆盐转化膜技术研究现状与进展

锆盐转化膜技术是一种十分重要的环境友好型钢铁表面处理技术,有望完全取代磷酸盐和铬酸盐转化技术。锆盐转化膜的耐蚀性与磷酸盐和铬酸盐转化膜接近,对有机涂层和钢铁基体有着优异的附着力。从纯锆盐转化基本原理、锆盐体系选择、制备方法、转化工艺参数控制、膜层形貌与结构、膜层耐蚀行为、膜层与后续涂层的附着力等方面,对国内外钢铁表面纯锆盐转化膜技术的研究进展和成果进行了综述。纯锆盐转化技术采用的转化液以氟锆酸及其盐为主,制备方法主要是浸渍法。为了获得质量稳定的纯锆盐转化膜,需要控制工艺参数:Zr~(4+)体积分数3%~5%,pH值3.5~4.5,转化时间90 s左右,温度20~35℃。锆盐转化膜一般为100~350 nm厚的双层结构,由纳米颗粒、小结节和聚集体构成,这种结构发挥的锚固作用会显著增加基体与后续涂层的结合强度。但是,锆盐转化成膜机理不够成熟,工艺欠稳定,在实际工业生产应用中仍面临挑战。所以,成膜机制和工艺稳定性的深入探究是未来锆盐转化膜的重点研究方向。     

乙烯基三乙氧基硅烷(VS)水解关键工艺

采用硅烷偶联剂对金属进行预处理是一种新型、环保的表面处理工艺,可以显著提高涂层的结合力及金属耐蚀性能,有望替代传统的磷化和钝化处理,而水解过程是决定金属表面硅烷化预处理好坏的关键。采用反射吸收红外光谱法研究了温度、pH、醇水比及硅烷体积分数等关键因素对乙烯基三乙氧基硅烷水解的影响,确定了水解液中获得最多硅醇单体时的水解工艺参数;在一定温度范围内,硅烷溶液水解程度随着水解温度的升高而增大;通过比较si-O-Fe与si-O-si峰强的变化,确定Si-O-Fe与si-O-si在金属表面存在竞争协同作用。     

铝合金表面锆盐转化膜的成分与电化学性能研究

在室温条件下向锆盐作为主盐的溶液中加入添加剂,在铝合金表面制备了黄色的锆盐转化膜。利用扫描电子显微镜(SEM)和X射线光电子能谱(XPS)等分析了转化膜的表面形貌与成分;通过电化学工作站测试了转化膜的极化曲线、阻抗谱图,研究了转化膜的耐蚀性能;依据国标对转化膜的附着力进行了测试。结果表明,铝合金表面的锆盐转化膜由粒度比较均匀的球形小颗粒构成,表面均匀,转化膜的主要组成元素为Al、F、Zr、O、C等;其极化电阻较空白铝合金有较大幅度的提升,自腐蚀电流密度降低,铝合金的耐腐蚀性得到显著的提升,并且转化膜提高了漆膜与铝合金的附着力。     

钢铁表面硅锰钼系化学转化膜的研究

目的通过研究硅锰钼系转化膜的新工艺,获得性能优良的膜层。方法采用单因素实验确定工艺条件,通过电化学方法研究成膜过程,采用盐雾实验检验膜层的耐蚀性能,采用划格法测试附着力,采用测厚仪测量膜厚,使用扫描电镜观察试样的表面形貌。结果筛选出最佳工艺条件为:磷酸二氢锰2.0 g/L,钼酸钠4 g/L,单宁酸0.4 g/L,氟化钠1.6 g/L,氟硅酸3 m L/L,p H=5,成膜时间8 min。所得转化膜均匀,呈非晶态,平均厚度为2.0μm,与基体的附着力达到0级。结论硅锰钼系转化膜的制备工艺中无促进剂亚硝酸钠,所得转化膜的厚度、耐腐蚀性及附着力能满足生产需要。     

AZ31B镁合金钒/硅烷复合转化膜的制备与表征

目的 改善钒酸盐转化膜表面形貌,提高单一钒酸盐转化膜的耐蚀性能。方法 使用偏钒酸盐和硅烷通过两步法在镁合金表面制备钒/硅烷复合转化膜,比较不同硅烷制备的复合膜的耐蚀性能,从而确定使用硅烷的种类,采用扫描电子显微镜(SEM)、X射线能谱(EDS)、X射线光电子能谱(XPS)和傅里叶红外光谱(FT-IR)观察转化膜的微观形貌并分析转化膜的组成和结构,通过交流阻抗测试(EIS)、Tafel极化曲线测试和全浸腐蚀实验评价转化膜的耐蚀性能,并采用划格实验和接触角测试评价转化膜的结合力和疏水性。结果 确定使用BTEPST(双-[3-(三乙氧基硅)丙基]-四硫化物)作为成膜组分,使用偏钒酸钠和BTESPT在镁合金表面成功制备钒/BTESPT复合膜,复合膜表面均匀平整,致密无裂纹,与基体结合力好,具有疏水性,该复合膜的组成元素为Mg、V、C、O、Si和S,且元素分布较均匀,膜层是包含Si—O—S、Si—O—Mg、Si—O—V等共价键的交联结构。交流阻抗测试结果显示,钒/BTESPT复合转化膜的膜层电阻为1.17×10⁵?·cm²,电荷转移电阻为1.076×1...     

镁合金锡酸盐化学转化表面处理工艺研究

研究了AZ91D镁合金的锡酸盐化学转化表面处理工艺,利用中性盐雾试验和极化曲线法测试了转化膜的耐蚀性,使用划格法测试了转化膜对有机涂层的附着力,采用扫描电镜、能谱仪、射线衍射仪分析了转化膜的微观形貌、成分和结构并讨论了成膜机理.结果表明,最佳工艺条件下的锡酸盐转化膜为致密的MgSnO3·3H2O晶粒所构成,盐雾腐蚀评级达到了8级,自腐蚀电位降低了40 mV,对铁红漆的附着力达到了3B级.     

三乙醇胺及三乙醇胺/尿素复配物对氧化锆转化膜性能的影响

目的为了提高钢铁表面氧化锆转化膜的耐蚀性。方法以Q235钢片为研究对象,在基础成膜液中分别添加不同质量浓度的三乙醇胺及三乙醇胺与尿素复配物,制备氧化锆转化膜。通过Tafel极化曲线和交流阻抗探讨氧化锆转化膜在5%NaCl腐蚀液中的电化学行为,利用扫描电镜观察氧化锆转化膜的表面形貌,在氧化锆转化膜上涂不同底漆,采用划圈法测试漆膜的附着力。结果在氧化锆基础成膜液中添加100 mg/L三乙醇胺所制得的氧化锆转化膜在5%NaCl腐蚀液中的自腐蚀电流密度为1.66×10-5 A/dm~2,钝化区域最宽,阻抗最大,耐蚀性最好。用尿素代替50%三乙醇胺,其所制得的氧化锆转化膜在5%NaCl腐蚀液中的自腐蚀电位和自腐蚀电流密度变化不大,钝化区域略有加宽,但阻抗弧明显加大。在氧化锆基础成膜液中添加三乙醇胺及三乙醇胺与尿素复配物制得的氧化锆转化膜,分别经过2%硅醇封闭液和5%硅烷封闭液封闭处理后,与低表面处理环氧底漆和改性环氧底漆漆膜附着力为1级。结论在基础成膜液中添加三乙醇胺和三乙醇胺与尿素复配物后可提高Q235钢耐蚀性,氧化锆转化膜分别经过2%硅醇封闭液和5%硅烷封闭液封闭处理后,均与低表面处理环氧底漆和改性环氧底漆保持良好的附着力。     

不锈钢根管锉镀覆TiN、ZrN膜的沉积工艺与性能研究

目的通过在不锈钢根管锉表面镀覆Ti N、Zr N薄膜,以提高其切削性能。方法采用磁控溅射技术,调整沉积时间、基片偏压、占空比等工艺参数在不锈钢根管锉上分别沉积Ti N、Zr N薄膜。对Ti N、Zr N膜层进行SEM断面分析、XRD相组成分析、表面硬度测试、膜层附着力测试,考查了Ti N、Zr N薄膜的厚度、相组成、硬度以及附着力。通过对镀膜后的根管锉进行电化学腐蚀试验、模拟临床切削试验,分析了镀膜后根管锉的耐蚀性和切削性能。结果随着工艺参数的变化,Ti N、ZrN薄膜的厚度、相结构以及硬度均显示了规律性的变化。镀覆Ti N、Zr N薄膜的不锈钢根管锉的自腐蚀电流密度相对于未镀膜的根管锉均明显降低。确定了Ti N膜层和Zr N膜层的优化沉积工艺分别为沉积时间1 h、负偏压100 V、占空比60%和沉积时间1h、负偏压150V、占空比60%。优化工艺下镀膜的不锈钢根管锉的切削数量和切削效率显著提高。结论和未镀膜不锈钢根管锉相比,镀覆Ti N、ZrN薄膜的不锈钢根管锉的表面硬度、耐蚀性能均有显著提高。最优工艺下制备的镀覆Ti N、Zr N薄膜的不锈钢根管锉兼具切削数量、切削效率以及切削稳定性等方面的综合优势,和未镀膜不锈钢根管锉相比,切削效率提高60%～75%,切削树脂模拟根管数量达到1.7～2倍,实现了切削性能的显著提升。     

Anticorrosive performance of epoxy/clay nanocomposites pretreated by hexafluorozirconic acid based conversion coating on St12

Abstract

In this research, epoxy composites were prepared using different loadings (0.5, 0.8, 1, 2 and 3 wt-%) of clay nanoparticles. Fourier transform infrared spectroscopy was utilised to investigate the curing behaviour of epoxy resin. The quality of dispersion and the distribution structure of nanoclays in coating were studied by visual observations and X-ray diffraction in detail. Corrosion resistance behaviour of epoxy coating containing various clay percentages was investigated on steel by electrochemical impedance spectroscopy. Moreover, the modification of substrate was accomplished using conversion coating based on hexafluorozirconic acid. The electrochemical results revealed that the pretreated coating with 3 wt-% nanoclays possesses the best anticorrosive performance (2.5×10⁸ Ω cm²) after 2 weeks immersion in 3.5 wt-%NaCl solution. The morphological properties of conversion coating were observed by a field emission scanning electron microscope. In addition, pull-off technique was employed to measure the adhesion strength of coatings to metallic substrate. Experimental results exhibited that optimum clay loadings and conversion coating impressively increased the corrosion resistance and coating adhesion as well.     

The EIS investigation of powder polyester coatings on phosphated low carbon steel: The effect of NaNO2 in the phosphating bath

The effect of different type of iron-phosphate coatings on corrosion stability and adhesion characteristic of top powder polyester coating on steel was investigated. Iron-phosphate coatings were deposited on steel in the novel phosphating bath with or without NaNO₂ as an accelerator. The corrosion stability of the powder polyester coating was evaluated by electrochemical impedance spectroscopy (EIS), adhesion by pull-off and NMP test, while surface morphology of phosphate coatings were investigated by atomic force microscopy (AFM).The adhesion and corrosion stability of powder polyester coatings were improved with pretreatment based on iron-phosphate coating deposited from NaNO₂-free bath.     

Electrochemical and In Vitro Behavior of Nanostructure Sol-Gel Coated 316L Stainless Steel Incorporated with Rosemary Extract

The corrosion resistance of AISI 316L stainless steel for biomedical applications, was significantly enhanced by means of hybrid organic-inorganic sol-gel thin films deposited by spin-coating. Thin films of less than 100 nm with different hybrid characters were obtained by incorporating rosemary extract as green corrosion inhibitor. The morphology, composition, and adhesion of hybrid sol-gel coatings have been examined by SEM, EDX, and pull-off test, respectively. Addition of high additive concentrations (0.1%) did not disorganize the sol-gel network. Direct pull-off test recorded a mean coating-substrate bonding strength larger than 21.2 MPa for the hybrid sol-gel coating. The effect of rosemary extract, with various added concentrations from 0.012 to 0.1%, on the anticorrosion properties of sol-gel films have been characterized by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization tests in simulated body fluid (SBF) solution and has been compared to the bare metal. Rosemary extract additions (0.05%) have significantly increased the corrosion protection of the sol-gel thin film to higher than 90%. The in vitro bioactivity of prepared films indicates that hydroxyapatite nuclei can form and grow on the surface of the doped sol-gel thin films. The present study shows that due to their excellent anticorrosion properties, bioactivity and bonding strength to substrate, doped sol-gel thin films are practical hybrid films in biomedical applications.     

铁基粉末冶金零件电镀前二次水基防锈溶液的封孔技术研究

目的铁基粉末冶金零件具有特殊的疏松和多孔结构,在前处理、电镀、钝化等过程中易造成零件孔隙的酸、碱、盐等残留,镀后零件在使用过程中也易出现耐腐蚀性能下降或镀层脱落的现象。因此,对铁基粉末冶金零件孔隙进行封闭是一种提高镀层防腐蚀性能和结合性能的有效方法。方法采用一种专用的粉末冶金零件水基防锈封闭溶液,对零件孔隙进行前处理前的第一次封闭和前处理后的第二次封闭。其孔隙封闭原理是在镀前处理前,利用水基防锈溶液中的缓蚀剂、钝化剂等成分的扩散、渗透,在孔隙处发生吸附、钝化及沉淀等反应,来减轻或避免前处理过程中接触到的酸、碱等成分在孔隙的残留;再在电镀前处理后,进行第二次防锈水溶液的封闭处理,可进一步强化粉末冶金零件的钝化封闭效果。结果没有经过防锈水溶液封闭处理的白钝化锌镍合金镀层(滚镀零件),在96 h盐雾试验后,表面出现了轻微的腐蚀;经过一次防锈水溶液封闭处理的锌镍合金镀层,在120 h后出现了轻微的腐蚀;经过二次防锈水溶液封闭处理的锌镍合金镀层,在240 h后未出现腐蚀。结论粉末冶金零件经过这二次封闭处理,再进行电镀Zn-Ni合金及镀层钝化处理,可以有效提高零件表面镀层的耐腐蚀性能和结合性能。     

An evaluation of the corrosion resistance and adhesion properties of an epoxy-nanocomposite on a hot-dip galvanized steel (HDG) treated by different kinds of conversion coatings

Hot-dip galvanized steel (HDG) samples were chemically treated by Cr(III), Cr(VI), Cr(III)-Co(II) and Cr(III)-Ni(II) conversion coatings. Epoxy nanocomposites were prepared using 2 wt.%, 3.5 wt.%, 5 wt.% and 6.5 wt.% nano-ZnO. Electrochemical impedance spectroscopy (EIS), pull-off adhesion tester and scanning electron microscope (SEM) were utilized to evaluate epoxy coatings properties on the surface of pre-treated HDG samples. Results showed that addition of nano-ZnO particles (specially 3.5 wt.%) can significantly improve the corrosion resistance of the epoxy coating on HDG. Decrease of contact angle (φ) and increase of surface roughness (Ra) of the pre-treated HDG samples were obtained. Decrease of the value of φ was more pronounced when the Cr(III) pre-treated samples were post-treated by Cr(III)-Co(II) and Cr(III)-Ni(II) conversion coatings (CCs). The dry and wet adhesion strengths of the epoxy coating to HDG were significantly increased after the surface treatment of the samples. Increase of the adhesion strength and decrease of the adhesion loss were more pronounced on Cr(III)-Co(II) and Cr(III)-Ni(II) post-treated samples. The corrosion resistance of epoxy coating was also increased on the surface of pre-treated HDG samples. Increase of the corrosion resistance of the Cr(III) pre-treated HDG samples was more pronounced on the samples which were post-treated by Co(II) and Ni(II).     

铝合金稀土磷化与铬磷化比较

采用电化学测试、全浸腐蚀试验和结合力测试,研究了6061铝合金铬磷化处理和以稀土为添加剂的磷酸盐处理所形成的化学转化膜的工艺性能。动力学研究表明,两者的成膜过程是不相同的。极化曲线测试结果显示,在弱极化区范围内,两者抗蚀性能相近,而在强极化区,铬磷化转化膜的抗蚀性优于以稀土为添加剂的磷酸盐化学处理所形成的转化膜,全浸腐蚀试验有类似的结果。结合力测试结果则表明,以稀土为添加剂的磷酸盐化学处理所形成的转化膜与有机涂层间的结合力要优于铬磷化转化膜。     

镀锌板硅烷-硝酸锆复合转化膜的性能与表征

目的获得一种防腐性能优越的转化膜。方法将KH560和KH791两种硅烷复合后水解,添加硝酸锆,得到KH560-KH791-硝酸锆复合钝化液,采用该钝化液对镀锌钢板进行钝化处理,通过盐水浸泡实验、中性盐雾试验和附着力测试,与添加硝酸锆前的转化膜进行性能对比。结果盐水浸泡和中性盐雾腐蚀72 h的实验中,添加硝酸锆后的转化膜性能都明显优于添加前,二者的附着力测试均能达到一级。结论加入的硝酸锆填充了膜层空隙,更加有效地阻挡了腐蚀介质的渗透,使得钝化膜的防腐性能提高。