乙醇胺添加剂对AZ91D镁合金表面磷化膜微观结构的影响研究

以锌系磷酸盐化学转化膜为研究体系,采用SEM,XRD分析方法及检测手段,研究乙醇胺(MEA)添加剂及其浓度对AZ91D镁合金锌系磷酸盐化学转化膜微观结构的影响.研究发现由于锌系磷化液中乙醇胺的添加:(1)改变了AZ91D镁合金锌系磷化膜晶体层的微观结构,促进了晶核的形成和晶粒细化,晶簇间隙中晶核的形成对晶体膜层完整性和致密度起着关键作用;(2)对(Zn_3(PO_4)_2·_4H_2O)晶体的取向有影响,有控制晶簇尺寸使磷化结晶组织更均匀的作用;(3)MEA在1.2g/L时磷化膜层平整致密、晶簇的尺寸均匀缺陷最少;(4)锌系磷化膜有两层结构:(Zn_3(PO_4)_2·_4H_2O)晶体外层和非晶态内层;(5)MEA的不同添加量对晶体层孔隙的影响有3种类型:表面浅孔(a型),晶簇间缝隙或微裂纹(b型),开放缺陷(c型).     

单宁酸对镁合金锆酸盐转化膜耐蚀性能的影响

在钒锆体系基础上添加单宁酸可提高AZ91D镁合金表面锆酸盐转化膜的耐蚀性能,目前研究较少。采用单因素试验的方法,研究单宁酸浓度对转化膜的影响;通过盐雾试验、电化学测试来检测膜层的耐蚀性能;利用扫描电镜(SEM)以及能谱(EDS)分析转化膜的微观形貌和成分变化。结果表明:单宁酸的浓度在0.3~0.5 g/L之间时,膜层晶粒较为细致,膜层均匀,阻抗值弧明显大于其他浓度时的阻抗弧,腐蚀电流密度达2.256×10-5A/cm~2,耐盐雾时间达600 min;在锆酸盐里添加单宁酸后形成的转化膜可以提高AZ91D镁合金表面的耐蚀性能。     

镁合金微弧氧化添加剂的优选

为了获得耐蚀性更优的微弧氧化膜,以NaAlO2-NaOH体系为基础氧化液,考察了EDTA、蒙脱石、阿拉伯树胶等添加剂对AZ91D镁合金微弧氧化膜层耐蚀性能的影响.在3.5%的NaCl水溶液中测定了微弧氧化处理前后镁合金样品的动电位极化曲线,利用腐蚀电阻等参数来判定膜的耐蚀性能.确定了铝酸盐体系中添加剂的最优用量为:3 g/L蒙脱石,0 g/L EDTA,50 mL/L 5%阿拉伯树胶.利用SEM,EDS和XRD等初步研究了陶瓷膜表面的微观结构及成分.结果表明:在该体系中添加最佳用量的添加剂可以得到致密的微弧氧化膜,膜层主要由MgO以及MgAl2O4组成;微弧氧化处理后的镁合金比处理前具有更好的耐蚀性能.     

镁合金铬磷化工艺的试验研究

利用正交试验法和对比实验法研究了一种镁合金铬磷化处理工艺,通过分析计算获得了AZ91D镁合金铬磷化处理液的最佳配方及工艺参数:铬酐12 g/L,次磷酸钠20～30 g/L,室温处理8min.用该工艺方法处理AZ91D镁合金,表面得到了一层致密均匀、附着力和耐蚀性良好、厚度为2.5～3.5 μm的铬磷化膜层,将其用于涂装前的打底层可以大大提高漆膜的附着力和耐蚀性能.该工艺对镁合金的涂装生产具有一定的参考价值.     

镁合金高压阳极氧化工艺研究

为开发耐蚀性能优良的镁合金阳极氧化工艺,用正交试验对AZ91D镁合金高压阳极氧化成膜工艺进行了研究,并利用扫描电镜(SEM)、X射线衍射(XRD)、X射线光电子能谱(XPS)、全浸腐蚀试验和极化曲线等分别研究了镁合金阳极氧化膜层的表面形貌、相成分、元素成分、价态和膜层的耐蚀性等.获得了AZ91D镁合金高压阳极氧化的最佳成膜工艺参数为:10 g/L KOH,5 g/L NaF,5 g/L Na2SiO3,0.5 g/L Na2B4O7, 100 mL/L乙二醇, 75 mL/L丙三醇, 50 mL/L组分G;电流密度 8.9 mA/cm2,氧化时间 30 min.在最佳工艺下所得阳极氧化膜层呈多孔结构,孔洞分布比较均匀,孔径尺寸约为1～2 μm;氧化膜层主要由Al2SiO5、MgF2和MgAl2O4相组成;氧化膜层的耐蚀性明显优于传统含铬DOW17工艺所得氧化膜层的耐蚀性.     

AZ91镁合金磷化液配方及优选

为了进一步提高镁合金表面磷化膜的耐腐蚀性能,采用锌系磷化液对AZ91镁合金进行磷化处理。采用扫描电镜及能谱仪分析磷化膜的形貌及成分;采用浸泡试验和极化曲线分析磷化膜的耐腐蚀性能。通过正交试验优选磷化液配方。结果表明:最优磷化工艺为2.0 g/L氧化锌,5 m L/L磷酸,0.2 g/L十二烷基磺酸钠,0.1 g/L酒石酸,0.2 g/L钼酸铵,0.3 g/L氟化钠,时间40 min,温度40℃,pH值2.5;优化工艺下所得磷化膜微观形貌均匀细致、厚度均匀、腐蚀失重小、腐蚀电流密度低,可有效地抑制镁合金的腐蚀。     

AZ91D镁合金钡基磷酸盐转化膜的形貌、组构及其耐腐蚀性能

采用钢铁、铝改进型磷化技术对AZ91D镁合金进行磷化,膜薄,不耐蚀。利用扫描电镜(SEM)、X射线衍射(XRD)技术,研究了镁合金预处理后的表面形貌、组构及钡基磷酸盐转化膜的表面形貌及相组成。采用电化学、盐雾和湿热技术测试了磷酸盐转化膜的抗腐蚀性能。结果表明:AZ91D镁合金预处理前后表面的相组成基本不变,酸洗后表面在相界处出现了较深的狭缝;磷酸盐转化膜主要由Mg,MgO和一些无定形的相组成;钡基磷酸盐转化膜可以明显提高AZ91D镁合金的抗腐蚀性能。     

镁合金阳极氧化电解液组分的优化探讨

为了改进镁合金的耐蚀性,促进其进一步应用,用优化工艺在AZ31镁合金表面制得了具有良好耐点蚀性能的阳极氧化膜,采用正交设计方法分析研究了电解液组分对镁合金氧化成膜及抗蚀性的影响,获得最优工艺参数为:45 g/L NaOH,80 g/L Na2SiO3,5 g/L柠檬酸钠,40 mL/L添加剂D(一种有机缓蚀剂);氧化温度10～30℃,时间10～40 min,电流密度1～20 mA/cm2,阴阳极面积比2:6.用该优化工艺在AZ31镁合金表面生成的氧化膜具有良好的耐点蚀性能,经浸泡耐蚀试验评定为9级.     

硅酸钠浓度对镁合金阳极化的影响

采用电压-时间曲线、全浸腐蚀实验、极化曲线法、X射线衍射法(XRD)、扫描电镜(SEM)、能量色散谱仪(EDS)和X射线光电子能谱法(XPS)等方法研究了AZ91D镁合金在含不同浓度硅酸钠的阳极化溶液中的阳极氧化行为和膜层的成分、结构.结果表明:在本文给定工艺中,AZ91D镁合金的阳极化过程可分为三个阶段:电火花出现之前的致密层生成阶段,少量小电火花出现的多孔层生成阶段,出现较大电火花的多孔膜层稳定生长阶段.阳极氧化过程中,随着阳极氧化溶液Na2SiO3浓度的升高,出现电火花的时间缩短,出现电火花时的电压值降低;阳极化膜的颗粒度变大甚至膜层出现裂纹,膜层厚度基本不变.阳极化膜层中主要含有Mg2 、O2-、Si4 和B3 ,主要相结构为MgO、MgSiO3和Mg3B2O6.硅酸钠浓度对阳极化膜的耐蚀性影响较大,当硅酸钠浓度为120g/L时,膜层耐蚀性能最好.     

AZ31镁合金钕基转化膜工艺与耐蚀性能研究

研究了AZ31镁合金钕基转化膜的制备工艺,并对膜层形貌、化学组成和耐腐蚀性能进行了分析。通过正交优化得到了钕基转化膜的4个工艺条件的最佳水平组合为Nd(NO3)3浓度为5g/L,H2O2浓度为5mL/L,成膜时间9min,成膜温度40℃。结果表明,采用最佳工艺得到的钕基转化膜层均匀且致密,其主要成分是Nd2O3和少量MgO。通过动电位极化曲线和析氢实验研究了钕基转化膜层对AZ31镁合金在3.5%(质量分数)NaCl溶液中耐蚀性能的影响,结果表明,钕基转化膜可以大大降低AZ31镁合金的腐蚀速率,当Nd(NO3)3浓度为5g/L时,钕基转化膜的腐蚀电流密度最小,耐腐蚀性能最好。     

镁合金微弧氧化陶瓷膜的微观结构、相成分和耐腐蚀性能

为获得耐腐蚀性优良的镁合金表面膜层,在含5 g/L硅酸钠、2 g/L磷酸钠和1 g/L氢氧化钠的复合溶液中,用自制设备对AZ91D镁合金进行了微弧氧化.利用扫描电镜和X射线衍射分析了AZ91D 镁合金表面微弧氧化陶瓷膜的表面形貌、截面结构和相组成.结果表明:AZ91D 微弧氧化陶瓷膜由疏松层和致密层组成,疏松层陶瓷膜疏松,厚度较大,且存在一些孔洞;致密层陶瓷膜与基体金属结合紧密,陶瓷膜主要由MgO,Mg2SiO4,Mg3(PO4)2和MgAl2O4组成.在3.5%的NaCl溶液中,微弧氧化陶瓷膜的自腐蚀电位为-1 390 mV,而镁合金基体的为-1 540 mV,表明经微弧氧化处理后AZ91D 镁合金的耐蚀性有较大提高.     

Fabrication of anticorrosive multilayer onto magnesium alloy substrates via spin-assisted layer-by-layer technique

To improve the corrosion resistance of magnesium alloy, we reported a novel approach for the fabrication of anticorrosive multilayers onto AZ91D substrates. The multilayers were composed of poly(ethylene imine) (PEI), poly(styrene sulfonate) (PSS) and 8-hydroxyquinoline (8HQ). They were deposited onto AZ91D substrates via a spin-assisted layer-by-layer (LbL) technique. The multilayered structure was stabilized with glutaraldehyde (GA) as crossing linker. It was confirmed by Fourier transform infrared spectroscopy (FT-IR). Surface morphologies and elemental compositions of the formed anticorrosive multilayers were characterized with scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS), respectively. The corrosion performance of the multilayer coated AZ91D substrates was characterized by hydrogen evolution. The results of electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization measurements suggested that the multilayered coating improved the corrosion resistance of AZ91D substrates. In vitro study revealed that the multilayered coating was cytocompatible. The study provides a potential alternative for the fabrication of corrosion resistant magnesium alloy-based implants.     

AZ91D镁合金锌系磷化膜成膜机理和生长过程的研究

以磷酸盐化学转化膜为研究体系,采用SEM、XRD、OCP等分析方法及检测手段,研究AZ91D镁合金系磷酸盐化学转化膜的成膜机理、膜层结构及生长过程。研究发现AZ91D镁合金在磷化液中成膜过程分5个阶段:初始成核(1～5s)、基体快速溶解(5～60s)、晶体快速生长(1～2min)、膜层稳态生长(2～10min)和膜层沉积溶解平衡阶段(10min以后)。AZ91D镁合金表面的磷酸盐晶核的形成并非在金属进入溶液的最初时刻一次形成,是分批形成。最先形成的晶核逐渐长大,新的晶核不断生成,磷酸盐晶粒对其表面的覆盖度逐渐增大,直至各个晶粒逐渐长大相互接界,将其表面完全覆盖,结晶过程结束。晶核的形成未优先发生在基体金属的晶界上,随着晶核的生长和外延而形成磷化膜。     

Effects of Ca combined with Sr additions on microstructure and mechanical properties of AZ91D magnesium alloy

Abstract

Weight reduction to improve automobile fuel economy has triggered renewed interest in magnesium. The effects of Ca/Sr separate and composite additions to AZ91D magnesium alloy on its microstructure and mechanical properties have been investigated. The results indicate Ca can refine both the grain and eutectic phase of AZ91D magnesium alloy. Sr hampers microstructure refinement when composite Ca/Sr additions are made. In addition, separate Ca additions to AZ91D magnesium alloy increase yield strength but decrease elongation of this alloy. By adjusting the Ca/Sr composite proportions, additions to AZ91D magnesium alloy are able to improve both microstructure and mechanical properties of the alloy.     

Laser cladding of Zr-based coating on AZ91D magnesium alloy for improvement of wear and corrosion resistance

To improve the wear and corrosion resistance of AZ91D magnesium alloy, Zr-based coating made of Zr powder was fabricated on AZ91D magnesium alloy by laser cladding. The microstructure of the coating was characterized by XRD, SEM and TEM techniques. The wear resistance of the coating was evaluated under dry sliding wear test condition at room temperature. The corrosion resistance of the coating was tested in simulated body fluid. The results show that the coating mainly consists of Zr, zirconium oxides and Zr aluminides. The coating exhibits excellent wear resistance due to the high microhardness of the coating. The main wear mechanism of the coating and the AZ91D sample are different, the former is abrasive wear and the latter is adhesive wear. The coating compared to AZ91D magnesium alloy exhibits good corrosion resistance because of the good corrosion resistance of Zr, zirconium oxides and Zr aluminides in the coating.     

Investigation on a Non-cyanide Plating Process of Ni-P Coating on Magnesium Alloy AZ91D

In this research we presented a non-cyanide plating process of Ni-P alloy coating on Mg alloy AZ91D. By applying a new process flow of electroless nickel plating in which zinc coating is used as transition of Ni-P coating on Mg alloy AZ91D, the process of copper transition coating plated in the cyanides bath can be replaced. A new bath composed of NiSO4 was established by orthogonal test. The results show that zinc transition coating can increase the adhesion and pH 4.0 and 95℃, respectively. The present process flow is composed of ultrasonic cleaning→alkaline cleaning→acid pickling→activation→double immersing zinc→electroplating zinc→electroless nickel plating→passivation treatment.The present non-cyanide process of electroless nickel plating is harmless to our surroundings and Ni-P coating on Mg alloy AZ91D produced by present process possesses good adhesion and corrosion resistance.     

镁合金表面喷铝防腐蚀层的微观组织分析

在AZ91D镁合金表面热喷铝，用以提高其表面的耐腐蚀性能。采用SEM，EPMA等方法对AZ91D表面喷铝扩散层的组织进行了仔细的观察与分析，发现在防腐蚀层上有大量的Mg17Al12相存在，且呈决状及非连续片状分布。经显微硬度测定，喷铝层硬度较镁合金基体高；腐蚀后这种相凸出于基体，比镁合金基体有较好的耐腐蚀性能。     

电解液组成对AZ91D镁合金微弧氧化的影响

在含有NaAlO2、KF的电解质溶液中,采用恒电流方式对AZ91D镁合金进行微弧氧化获得陶瓷膜.研究了电解液组分及浓度对陶瓷氧化膜厚度及表面形貌的影响,同时,采用动电位极化曲线及电化学交流阻抗评价了陶瓷氧化膜的耐蚀性.研究发现:NaAlO2单独存在时即可产生火花放电现象,但得到的氧化膜较薄;氟化钾的加入可以显著增加氧化膜厚度,膜厚的增长速度与氟化钾的加入量呈线性关系.SEM表面形貌分析表明:电解质浓度较低时产生的氧化膜宏观上较粗糙、微观上颗粒结合紧密;高浓度时得到的氧化膜宏观上细致光滑,微观上存在明显的孔洞和放电隧道,呈熔融状态结合在一起.动电位极化曲线及电化学交流阻抗的测试一致表明,经微弧氧化处理后的镁合金耐蚀性显著提高.