十六烷基三甲基溴化铵对镁合金腐蚀行为的影响

采用动电位极化和电化学阻抗等方法检测了十六烷基三甲基溴化铵(CTAB) 对AZ31镁合金在3.5% NaCl溶液中腐蚀行为影响的规律, 用扫描电镜观察表面腐蚀产物膜的形貌并分析其组成. 结果表明, 当NaCl溶液中加入2000~3500 mg/L CTAB时, 镁合金的腐蚀速率降低, 且CTAB浓度为3500 mg/L时, 镁合金的腐蚀速率最低. 这主要是因为CTAB在镁合金表面发生吸附, 使阳极溶解过程受阻, 同时, CTAB减少了腐蚀产物膜内的微观缺陷数量, 减少了腐蚀介质的渗入通道, 增大了电荷转移阻力, 从而使镁合金的耐蚀性得到改善.。     

稀土铈对化学镀复合镀 Ni-P-PTFE 镀层耐蚀性能的影响

为了进一步提高化学镀Ni-P-PTFE复合镀层的耐蚀性能,采用在化学镀液中添加稀土铈的方法在45号碳钢试片表面制备了稀土铈Ni-P-PTFE复合镀层。用扫描电镜观察了镀层的表面形貌,并研究了稀土铈浓度对镀层中PTFE含量的影响,通过浸泡失重法分别研究了在3.5%NaCl和3.5%NaOH溶液中稀土铈浓度对镀层耐蚀性能的影响。结果表明:适量稀土铈的加入提高了镀层中PTFE的含量,降低了镀层的腐蚀速率,提高了复合镀层的耐蚀性能,在铈质量浓度为0.02 g/L时,在3.5%NaCl和3.5%NaOH溶液中镀层的腐蚀速率分别为0.402 mg/cm2和0.235 mg/cm2。     

稀土铈对Ni-P镀层组织和性能的影响

目的研究稀土铈对Ni-P镀层表面组织、沉积速率和耐腐蚀性能的影响,提高沉积速率,改善镀层表面质量,进而提高镀层的耐腐蚀性能。方法采用酸式化学镀方法在50钢基体表面制备了添加稀土铈的Ni-P合金镀层,研究稀土铈的添加量对Ni-P合金镀层表面组织形貌和性能的影响。采用金相显微镜观察镀层表面组织形貌,参照GB/T13913—2008计算镀层沉积速率;使用HV-1000Z型显微硬度计测定合金镀层的硬度,采用均匀腐蚀全浸试验法测试合金镀层在5%NaCl溶液和10%NaOH溶液中的耐蚀性能。结果稀土铈的添加量为40 mg/L时得到的合金镀层组织细小、均匀、平整、致密,沉积速率达到最大值10.4 mg/(cm2·h)。随着稀土铈添加量的增加,镀层硬度明显增大,在稀土铈质量浓度为60 mg/L时,最大硬度值达到487.2HV,硬度提高了13.5%。Ni-P合金镀层在5%NaCl和10%NaOH溶液中耐腐蚀实验结果表明,未添加铈的镀层腐蚀速率最大,添加稀土铈的镀层腐蚀速率呈现先降低后增加的趋势,稀土铈质量浓度为40 mg/L时,镀层的腐蚀速率最低。结论稀土铈可以明显改善镀层表面质量,提高镀层沉积速率、硬度和耐腐蚀性能。     

AZ31镁合金铈转化膜在NaCl溶液中的腐蚀性研究

对AZ31镁合金表面进行稀土铈转化成膜处理,采用扫描电镜、失重法、电化学测试研究了AZ31镁合金铈转化膜在0.05mol/LNa Cl溶液中的腐蚀行为。结果表明:经过成膜处理72 h后,试样的腐蚀速率稳定在0.122 mg·cm~(-2)·h~(-1),而未经成膜处理的镁合金腐蚀速率为0.4583 mg·cm~(-2)·h~(-1)。腐蚀电位先增加后减小,而腐蚀电流密度先减小后增大。腐蚀4h后,腐蚀电位为-1.432 V,腐蚀电流密度为1.393×10~(-1)μA·cm~(-2)。     

稀土La对汽车用AZ91D镁合金腐蚀行为的影响

以汽车用AZ91D镁合金为研究对象,添加一定量的稀土La元素,利用扫描电镜(SEM)、能谱分析(EDS)、XRD衍射仪、静态腐蚀失重法以及NaCl溶液浸泡等方法分析基体及稀土镁合金显微组织结构、耐腐蚀性、相结构、元素分布,并对稀土La元素改善AZ91D镁合金耐腐蚀性行为机制进行分析与讨论。结果表明:在AZ91D镁合金中w(La)=1.0%时,细化了晶粒,β-Mg_(17)Al_(12)相由较大板块状转变为细片状组织,并广泛密集的分布在基体中;用w(NaCl)=3.5%的溶液浸泡12 h、24 h、36 h、48 h后的静态腐蚀失重结果表明,加入La后AZ91镁合金的腐蚀速率、腐蚀坑均远小于未加La的AZ91D镁合金的腐蚀速率和腐蚀孔洞;分析结果表明合金中晶粒的细化、元素偏析程度的减弱、β-Mg_(17)Al_(12)相数量的增多、β相的密集分布结构以及Al-La、Al-Mn-La新相的出现,提高了基体在NaCl溶液中的自腐蚀电位,从而使基体的耐蚀性有了一定程度的改善。     

含铈AZ91D镁合金的显微组织与腐蚀行为

用盐雾试验、扫描电镜能谱仪、X射线衍射仪等,对加入不同Ce含量的含铈AZ91D镁合金的显微组织和盐雾腐蚀性能进行了分析.结果表明:当加入0.69%Ce时,可使合金铸态组织明显细化,且网状β相呈粒状弥散分布于晶界上,同时有大量针状物Al4Ce相出现;而加入0.93%Ce时,合金铸态组织有粗化趋势,且针状物长大成杆状.12 h腐蚀试验结果表明,加入0.26%Ce和0.93%Ce的合金,腐蚀速率先迅速增加而后又明显降低;而加入0.69%Ce的合金,腐蚀速率保持恒定.随着NaCl溶液浓度的增加,AZ91D合金的腐蚀速率增长较快;加入0.26%Ce后,合金腐蚀速率增长缓慢;加入0.69%Ce后,合金的腐蚀速率随浓度增加逐渐降低;加入0.93%Ce的合金在低浓度下的腐蚀速率略有升高,而在高浓度下的腐蚀速率迅速降低.合金的腐蚀形貌均表现为不均匀腐蚀,腐蚀产物主要由Mg(OH)2组成.含稀土合金的腐蚀产物中还有Al4Ce.稀土Ce提高AZ91D镁合金腐蚀性能的原因归结为Ce对组织的细化作用以及对Al元素偏析程度的降低.     

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。     

含稀土HSn70-1锡黄铜的腐蚀行为研究

通过对Cu-Zn-Sn-Al-Ni-B-Mn-Sb-0.05RE和Cu-Zn-Sn-Al-Ni-B-Mn-Sb-0.1RE锡黄铜分别在NaCl(3.5%)溶液和NaCl(3.5%) NH4Cl(0.5mol/L)溶液中的腐蚀速率测定、腐蚀产物层SEM观察和XRD分析以及X射线能谱分析,研究了含稀土锡黄铜的腐蚀行为.结果表明:含稀土的锡黄铜在NaCl(3.5%)溶液中腐蚀后,腐蚀产物层薄而均匀,与基体之间的结合较好.稀土、硼等元素的添加可以明显改善锡黄铜耐Cl-腐蚀性能;在NaCl(3.5%) NH4Cl(0.5mol/L)溶液中发生了明显的沿晶腐蚀.同时,随稀土含量的增加,锡黄铜在含NH4 的人工海水介质中的耐腐蚀性能有所提高.     

Er对铸态AZ91镁合金显微组织和耐腐蚀性能的影响

利用金相显微镜(OM)、扫描电镜(SEM)、能谱分析(EDS)、X射线衍射分析、集气法及动电位极化曲线研究了微量Er对铸态AZ91镁合金显微组织和腐蚀性能的影响.结果表明:微量Er可细化AZ91镁合金的铸态组织,当AZ91镁合金中加入Er的含量不高于0.7%(质量分数)时,随着Er含量的增加,镁合金中的γ-Mg17Al12相由粗大、连续块状分布逐渐转变为细小、岛状均匀分布,并且有Al3Er相生成;同时,微量Er也可显著提高铸态AZ91的耐腐蚀性能,当Er含量为0.7%时,合金耐蚀性能大幅度提高,在3.5%(质量分数)NaCl水溶液中浸泡的腐蚀速率为0.546 06 mg/(cm2·d),仅为常规AZ91镁合金的1/15;微量Er使得AZ91镁合金在3.5% NaCl溶液中的自腐蚀电位升高,自腐蚀电流降低,从而提高AZ91镁合金的耐腐蚀性能.     

稀土铈、镧合金化对AZ91腐蚀行为的影响

向AZ91镁合金添加不同含昔的稀土铈或镧,研究了它们对镁合金组织结构和腐蚀性能的影响.结果表明,在AZ9 1镁合金中添加了稀土铈、镧能改善β相分布,起到细化晶粒的作用,并且有少量细小针状的金属间相γ相生成(MgAlRE).少量的稀土铈和镧加入能明显降低AZ91的析氢速率,使AZ91镁合金的自腐蚀电位负移,自腐蚀电流下降,有效提高AZ91镁合金的耐腐蚀性能.     

Corrosion protection of AZ31 magnesium alloy by silane film of partly hydrolysed BTESPT

Abstract

The corrosion protective behaviour of bis-[triethoxysilylpropyl]tetrasulphide (BTESPT) silane film formed by partly hydrolysed BTESPT on AZ31 Mg alloy was investigated. Fourier transform infrared spectroscopy (FTIR) was used for structural characterisation of the silane film. Scanning electron microscope (SEM) and energy dispersive X-ray (EDS) analysis were used for observation of surface morphology and elements analysis of the film. The corrosion behaviours of bare and the silane treated AZ31 Mg alloy in 3·5 wt-%NaCl solution were studied using electrochemical polarisation test, electrochemical impedance spectroscopy (EIS) and immersion test. The results demonstrate that bare AZ31 Mg alloy endures severe corrosion even in NaCl water solution at pH 12, although the corrosion is lighter than that in neutral and acidic NaCl water solution, and that the BTESPT silane film can improve the corrosion protection performances of AZ31 Mg alloy and a lower corrosion rate correlated with higher pH.     

磷酸钠在NaCl溶液中对AZ31镁合金的缓蚀作用

采用电化学阻抗法、动电位极化曲线法、全浸泡失重法和扫描电镜,研究了在3.5%(质量分数)Na Cl溶液中磷酸钠(Na3PO4)对AZ31镁合金腐蚀的抑制作用。结果表明:Na3PO4对3.5%Na Cl溶液中的AZ31镁合金具有缓蚀作用,其缓蚀率随着Na3PO4含量增大逐渐提高,当Na3PO4质量浓度为1.0 g/L时,缓蚀率达到81.5%。结合扫描电镜分析表明,Na3PO4在镁合金表面形成含有Mg(OH)2和Mg3(PO4)2的保护层,这层致密的膜减少了基体与Cl-接触,抑制了镁合金的阳极反应。     

电解液浓度对镁合金微弧氧化层耐蚀性与溶血率的影响

在电解液中加入 (NaPO₃)₆并在镁合金表面制备微弧氧化层,研究 (NaPO₃)₆浓度对镁合金微弧氧化层的影响.结果显示,微弧氧化层中含有MgO,Mg₂SiO₄,Mg₃(PO₄)₂等物质;随 (NaPO₃)₆浓度增加,微弧氧化层厚度增加,表面微孔孔径变大,当 (NaPO₃)₆浓度达到7 g/L时,微弧氧化层截面出现较明显的微裂纹;微弧氧化处理后的镁合金的耐蚀性明显高于基体的.当 (NaPO₃)₆浓度为5 g/L时其耐蚀性最佳;镁合金基体溶血率为72.3%,在不同浓度 (NaPO₃)₆下微弧氧化处理的镁合金溶血率均在1%~2.5%之间,溶血作用消除.     

Formation of a protective layer against corrosion on Mg alloy via alkali pretreatment followed by vanillic acid treatment

Although Mg alloy possesses high specific strength, low density, and good biocompatibility, poor corrosion resistance hinders its further applications. In the present study, an innovative protective layer against corrosion was prepared on the AZ31 Mg alloy via alkali pretreatment followed by vanillic acid treatment. The alkali pretreatment supplied –OH for the AZ31 Mg alloy surface to react with vanillic acid. The vanillic acid treatment played a crucial role in enhancing the corrosion resistance due to the excellent ability to act as a barrier and retard aqueous solution penetration, which effectively isolated the underlying Mg alloy from the corrosive environment. The corrosion current density of alkali and vanillic acid-treated Mg alloy (AZ31V) almost showed two orders of magnitude lower values in comparison with that of the AZ31 Mg alloy, and the corrosion potential of AZ31V Mg alloy increased from −1.41 to −1.25 V. The immersion tests proved that there was no occurrence of severe corrosion. Hence, the alkali pretreatment and vanillic acid treatment may represent a promising method to improve the corrosion resistance of Mg alloy.     

Enhanced corrosion performance of magnesium phosphate conversion coating on AZ31 magnesium alloy

Magnesium phosphate conversion coating (MPCC) was fabricated on AZ31 magnesium alloy for corrosion protection by immersion treatment in a simple MPCC solution containing Mg²⁺ and PO^3?₄ ions. The MPCC on AZ31 Mg alloy showed micro-cracks structure and a uniform thickness with the thickness of about 2.5 µm after 20 min of phosphating treatment. The composition analyzed by energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy revealed that the coating consisted of magnesium phosphate and magnesium hydroxide/oxide compounds. The MPCC showed a significant protective effect on AZ31 Mg alloy. The corrosion current of MPCC was reduced to about 3% of that of the uncoated surface and the time for the deterioration process during immersion in 0.5 mol/L NaCl solution improved from about 10 min to about 24 h.     

Characterization of the corrosion performances of as-cast Mg–Al and Mg–Zn magnesium alloys with microarc oxidation coatings

In the present study, corrosion-protective microarc oxidation (MAO) coatings were prepared on AZ31B, AZ80, and ZK60 cast magnesium alloy substrates in an alkaline silicate electrolyte. The corrosion performances of the uncoated and MAO-coated alloys were investigated using electrochemical and salt spray chamber corrosion tests. The microstructure characterization and experimental results show that among the three alloys studied, the ZK60 Mg alloy exhibited the best and AZ31B the least corrosion resistance under the salt spray conditions. The MAO coating provided robust corrosion protection of the Mg substrates and resulted in a significant decrease in the corrosion rate of the alloys by 3–4 orders of magnitude. The MAO coating on ZK60 alloy showed better corrosion protectiveness than that on the AZ series alloys due to the incorporation of different alloying elements in the coating, especially the Zn and Al elements, which are from the Mg substrate. The corrosion performances and mechanisms of the uncoated and MAO-coated Mg alloys are interpreted in terms of the microstructure and phase/chemical compositions of both the substrates and coatings.     

AZ31镁合金沉积类金刚石薄膜的表面形貌和腐蚀行为

为了改善镁合金的耐蚀性,扩展其应用范围,采用等离子全方位离子镀膜技术在AZ31镁合金表面沉积了含有Si-N和Si-O的2种类金刚石(Diamond-like carbon,DLC)薄膜,研究了其表面形貌及其在3.5%NaCl溶液中的腐蚀行为,探究了DLC薄膜对AZ31镁合金腐蚀行为的影响。利用SEM和AFM观察了AZ31镁合金表面沉积DLC薄膜的表面形貌,采用电化学法测试表面沉积DLC薄膜的AZ31镁合金在3.5%NaCl溶液中的极化曲线和开路电位,通过拉伸试验测试其在空气和3.5%NaCl溶液中的应力应变。结果表明:镁合金试样表面的DLC薄膜光滑致密,在3.5%NaCl溶液中表面沉积DLC薄膜AZ31镁合金的极化行为与表面未沉积DLC薄膜AZ31镁合金相似,表面沉积DLC薄膜AZ31镁合金电位正向移动,耐蚀性提高;与表面未沉积DLC薄膜AZ31镁合金相比,在空气中,表面沉积DLC薄膜AZ31镁合金极限抗拉强度与其接近,延伸率略低;在3.5%NaCl溶液中,表面沉积DLC薄膜AZ31镁合金极限抗拉强度略有降低,延伸率略高。     

Improvement of corrosion resistance of AZ31 Mg alloy by anodizing with co-precipitation of cerium oxide

Anodizing of AZ31 Mg alloy in NaOH solution by co-precipitation of cerium oxide was investigated. The chemical composition and phase structure of the coating film were determined via optical microscopy, SEM and XRD. The corrosion properties of the anodic film were characterized by using potentiodynamic polarization curves in 17 mmol/L NaCl and 0.1 mol/L Na₂SO₄ solution at 298 K. The corrosion resistance of AZ31 magnesium alloy is significantly improved by adding cerium oxide to alkaline solution. In addition, the surface properties are enhanced and the film contains no crack.     

CeCl3对含Ce镁合金精炼过程中Ce损耗量的影响

采用含CeCl3的净化熔剂对含Ce的镁合金进行精炼,研究了CeCl3对合金中Ce损耗量的影响规律.结果表明:当熔剂中不含CeCl3时,合金中的Ce损失高达27.7%;而当CeCl3的含量达到15%时,合金中的Ce损失仅为4.5%,CeCl3处理使镁合金中稀土相均匀分布,使Mg17Al12相细化,但相组成没有明显变化;随着CeCl3含量的增加,合金力学性能提高,但过多的CeCl3会在合金中引入熔剂夹杂.并从热力学方面探讨了熔剂与镁液的作用机理,计算了镁熔体中Mg和Ce的活度及熔剂熔体中MgCl2和CeCl3的活度.结果表明,由于CeCl3抑制了合金中Ce与熔剂中MgCl2的反应,从而降低了Ce的损耗.