镁合金表面化学镀镍前处理工艺的研究进展

镁合金作为最轻的金属结构材料,具有密度低、比强度高、弹性模量大等优势,在航天航空、汽车工业、电子通讯等领域广泛应用,但其化学性质非常活泼,在常温下很容易发生腐蚀,严重限制了其进一步推广应用。化学镀镍具有镀层致密、环境友好等优点,可有效提高镁合金的耐蚀性和耐磨性,但与普通基体相比,镁合金属于难镀金属,化学镀镍前既要去除基体表面原有的疏松多孔的氧化膜,又要生成具有保护和催化作用的新膜层,因此前处理工艺是影响镀层质量及镁合金防腐性能提高的关键因素。以化学镀镍前处理工艺为研究内容,介绍了镁合金化学镀镍前处理工艺的国内外研究现状,从除油、酸洗、活化、浸锌法、预镀层和化学转化膜等方面进行了文献综述和分析,指出相应工艺的优缺点,并探讨了研发方向。根据前处理技术的机理和不同牌号镁合金的特点,研发工艺简单、镀层性能优良、可控性强、环境友好、通用性强的低成本工艺,将是镁合金化学镀镍前处理的研究方向和发展趋势。     

化学镀镍工艺对镀层耐蚀耐磨性的影响

广义的化学镀镍工艺包括镀前预处理工艺,镀镍工艺和后处理工艺,化学镀镍工艺通过对镀层的成分,组织,孔隙率及表面微马形貌的影响而影响镀层的耐蚀,耐磨性,改进预处理工艺可进一步提高镀层的耐蚀性和镀层与基体的结合力,合适的后处理工艺可提高镀层的耐磨性和抗中性盐雾能力。     

镁合金浸锌前处理对化学镀镍层的影响

目的优化出镁合金浸锌前处理的处理液络合剂及工艺条件。方法研究镁合金浸锌前处理处理液的络合剂,确定出适用的络合剂,并在最佳络合剂的条件下,研究前处理液pH值和温度的变化对化学镀镍层的影响。采用电化学测试、扫描电子显微镜(SEM)和X射线衍射(XRD)对化学镀镍层进行耐蚀性评价,并对其微观形貌进行表征,确定出最佳络合剂和工艺条件。结果通过对镀镍层厚度的测量及SEM微观形貌观测,确定最优的前处理液络合剂为苹果酸。在该条件下确定最佳的工艺条件为:pH=10,温度80℃。所制得的化学镀镍层的自腐蚀电位为-0.6 V,与镁合金基体的腐蚀电位-1.47 V相比,提高了0.87 V,腐蚀电流密度由镁合金基体的1.26×10~(-4) A/cm~2下降到1.26×10~(-6) A/cm~2,自腐蚀电流密度降低了2个数量级。镀层的钝化区间在-0.6~0.2 V,且结合力好,外形美观。结论镁合金浸锌前处理处理液的最佳络合剂为苹果酸,最佳工艺条件为pH=10、温度80℃。     

一种无铬低氟的镁合金化学镀镍前处理工艺

为了获得一种更加环保的镁合金化学镀镍前处理工艺,通过多种方法和手段对比研究了3种不同的酸洗活化工艺对镁合金化学镀镍的影响。通过开路电势-时间(OCP-t)曲线解释了不同前处理方法导致不同沉积速度的原因。采用SEM、EDX和XRD分析发现,3种工艺所得镀层均为高磷合金镀层(P含量约为11%),镀层的表面形貌和结构比较接近。动电位极化曲线表明,采用H_3PO_4+HNO_3酸洗,K_4P_2O_7和NH_4HF_2分别活化的前处理工艺所得镀层耐蚀能力略优于传统工艺镀层。新工艺酸洗液对镁合金存在横向的刻蚀,可增强镀层与基底间的机械咬合作用,使得镀层的结合力更强。     

前处理工艺对钛合金化学镀镍层结合力的影响探讨

化学镀镍作为一种经济适用的材料表面处理技术,已经广泛应用于各个领域,钛及钛合金表面化学镀镍可提高其表面硬度、耐蚀性及耐磨性。镀层与基体材料的结合力是衡量化学镀件质量的重要指标之一,而前处理工艺对化学镀镍层结合力起到决定性的影响。本文结合近期研究成果,探讨了除油、酸洗、活化及其它特殊前处理工艺对钛合金化学镀镍层结合力的影响。     

镁及镁合金表面电镀镍工艺的研究

研究了镁及镁合金基体上电镀镍的工艺.通过特殊的前处理工艺,再利用酸性光亮镀镍的方法在镁及镁合金表面获得镍镀层.讨论了前处理工艺、电流密度及添加剂等工艺参数对镀层质量的影响,并利用金相显微镜、扫描电镜、显微硬度计及电子探针对镀层的显微组织及性能进行了研究.结果表明,在此工艺条件下,可以在镁及镁合金表面形成致密度高、孔隙率低、结合强度好且硬度高的合金镀层.镀层镍含量超过96%,镀态硬度为HV370,在250℃时效时,硬度可达HV510,磨损率达到31×10-6mm3/nin,比镁基体有显著提高.     

AZ91HP镁合金化学镀镍磷及镀层性能研究

目的提高AZ91HP镁合金的耐蚀及耐磨性,扩大其应用范围。方法采用H_3PO_4+Na_3PO_4酸洗液+NH_4HF_2活化的无铬前处理工艺,再直接化学镀,获得镍磷合金镀层,随后对镀层进行了热处理。对施镀前后基体和镀层的形貌、显微硬度和耐蚀性等进行了表征分析。结果 AZ91HP镁合金经H_3PO_4+Na_3PO_4酸洗+NH_4HF_2活化的无铬处理后施镀,形成的细小胞状组织均匀致密,结合力良好,镀层结构以非晶态相为主,耐腐蚀性比基体显著增高。经热处理后,镀层的硬度明显增高且在400℃时获得的镀层硬度最高,但耐蚀性有所下降。结论 H_3PO_4+Na_3PO_4酸洗体系+NH_4HF_2活化为镁合金提供了一种环保而有效的化学镀前处理方法,获得了以非晶态相为主的Ni-P镀层,提高了基体的耐腐蚀性,镀后热处理可进一步提高镀层的硬度。     

镁合金化学镀电镀复合镀层的制备

镁合金具有高的比强度和比刚度、电磁屏蔽性、减震性等优点,广泛应用于航空航天、汽车、电子通讯等领域.然而,由于镁合金的化学活性较高,其耐蚀性能较差,限制了它们的应用.通过改进的镁合金加工工艺可以提高镁合金耐蚀性.另外1种提高镁合金耐蚀性的有效手段就是对镁合金进行表面处理,如化学转化膜、电镀等.这些处理得到的涂层耐蚀性虽然有了很大的提高,但是在长时间处于腐蚀环境中,也容易被腐蚀,因此,研究1种复合镀层来更进一步提高耐蚀性,可以提高镁合金的应用.通过采用以硫酸镍为主盐对镀层进行化学镀镍,在化学镀层基础上电镀锌镍合金,并对化学镀和电镀配方进行优化,得到的复合镀层硬度高、结构致密、光泽性好,在5%的NaCl溶液盐雾试验中,连续喷雾96h无任何腐蚀现象,耐蚀性得到显著的提高.     

AZ91镁合金化学镀镍前处理的工艺

研究了H3PO4+Na2MoO4、H3PO4+KMnO4和H3PO4+Na3PO4三种酸洗工艺以及NH4HF2活化工艺等前处理工艺对AZ91 HP镁合金化学镀的影响.通过金相实验及极化实验,结果表明,AZ91 HP镁合金经H3PO4+ Na3PO4酸洗后再经NH4HF2工艺活化处理后施镀,可获得表面光亮、结合力强和耐蚀性能较好的镍-磷镀层.镁合金酸洗处理后表面的平整程度会影响其化学镀层平整度和光亮度,而活化处理后表面的粗糙程度则影响镀层和基体的结合力.     

前处理对镁合金化学镀镍结合力的影响

研究了镁合金多种前处理工艺对化学镀镍层与基体之间结合力的影响.采用弯曲法、锉刀实验法和划线划格实验3种镀层结合力测试方法,对化学镀镍层与镁合金基体之间结合力的优劣进行了定性评价.结果表明,采用一步法前处理工艺的试样,镀层与基体之间具有良好的结合力,金相显微观察发现镀层与基体之间具有最薄的中间过渡层.用浸锌工艺能较好地改善镀层与基体间的结合力.但镁合金浸锌工艺值得做进一步的研究.     

纯镁超声微弧氧化生物涂层植入体内4周的降解行为

研究纯镁及其超声微弧氧化生物涂层种植体植入动物股骨干内的短期降解过程。利用电化学工作站测定试样在模拟体液中极化曲线。术后4周,取兔股骨干的组织进行扫描电镜观察(SEM)及锥形束检测(CBCT)观察种植体降解状况。结果表明,纯镁与超声微弧氧化生物涂层都发生了降解,在骨组织表面及镁基体的表面几乎同时发生反应,在金属-骨界面形成紧密相邻的降解层、新生骨层,并可见少量的不连续的纤维结缔组织,超声微弧氧化镁生物涂层的腐蚀降解速率及对周围骨组织的刺激明显小于纯镁基体。纯镁基体及超声微弧氧化涂层试样周围的骨组织变化符合正常骨组织的愈合过程,超声微弧氧化生物涂层显示出更好的生物相容性及降解性。     

Molybdenum-on-chromium dual coating on steel

Molybdenum and chromium coatings were deposited on AISI 4130 steel using the Laser Induced Surface Improvement¹ (LISI™) process. In this process a mixture of precursor material is pre-placed on the substrate and then laser melted, resulting in the formation of a thin surface layer of alloy on the underlying material. First, a chromium coating was deposited on steel using the Cr-CrB₂ eutectic composition, and subsequently a molybdenum coating using the Mo-MoB eutectic composition was deposited on the chromium layer. Both the coatings have been individually characterized and compared using scanning electron microscope, energy dispersive spectrometry, Vicker’s hardness, X-ray diffraction, wear and erosion. The chromium layer exhibited superior erosion resistance (ASTM G76) while the molybdenum-on-chromium coating performed better in sliding wear (ASTM G77).     

电流密度对ZK60镁合金表面超疏水涂层的制备及耐腐蚀性的影响

为了提高镁合金的耐腐蚀性能,基于层状双氢氧化物（LDHs）膜在ZK60镁合金表面制备了超疏水（SH）涂层。涂层制备过程中引入电场辅助,研究了工作电流密度对涂层性能的影响。结果表明,工作电流密度显著影响LDHs膜的微观结构,这对SH涂层的疏水性具有重要影响。当工作电流密度为25 mA/cm²时,SH涂层表面呈现均匀的微纳米结构,并表现出超疏水性。超疏水涂层的腐蚀电流密度（I_corr=9×10^-7 A·cm^-2）比ZK60基体的腐蚀电流密度（I_corr=3×10^-5 A·cm^-2）低了2个数量级,表现出优异的耐腐蚀性。     

纳米石墨改性ZM5镁合金微弧氧化陶瓷层摩擦磨损性能

添加纳米石墨颗粒的硅酸盐溶液中制备ZM5合金微弧氧化陶瓷层,利用SEM、EDS和XRD分析了涂层的微观形貌、成分及物相组成,用球-盘干磨损试验对涂层的室温摩擦磨损行为进行研究。结果表明,纳米石墨改性微弧氧化陶瓷层主要由Mg2SiO4、少量的MgO、Mg和C相组成,石墨以机械形式分散于陶瓷层中并起到减摩作用。4.9N载荷下体积磨损率为9.19×10-5 mm3/Nm,是无石墨微弧氧化陶瓷层的1/3,ZM5基体的1/14;9.8N载荷下体积磨损率为1.44×10-4 mm3/Nm,是无石墨微弧氧化陶瓷层的2/5,ZM5基体的1/8,与无石墨微弧氧化陶瓷层相比显著提高了镁合金基体的耐磨性,且其室温干摩擦磨损机理为疲劳磨损,磨痕呈疲劳剥落形貌。     

Wear and corrosion resistance of AZ91 magnesium alloy coated by pulsed current electrodeposited Ni–Al2O3 nanocomposite

In this work, Ni and Ni–Al₂O₃ nanocomposite coatings were applied on AZ91 magnesium alloy using a pulse plating process and the corrosion resistance of coated samples was evaluated by means of the potentiodynamic polarisation method in 3.5?wt-% NaCl solution. Field emission scanning electron microscopy was employed to identify microstructure and morphology of the coatings. Vickers microhardness and pin-on-disc wear tests were also used to investigate mechanical properties of the coatings. The polarisation test revealed that the pure Ni coating on AZ91 along with the presence of nanoparticles were key factors leading to a reduction in the corrosion current density and the improvement of corrosion resistance so that the corrosion current density of 210.45?µA?cm^?2 for the substrate (AZ91) decreases to 31.92 and 1.54?µA?cm^?2 by applying pure Ni and Ni–Al₂O₃ nanocomposite coatings, respectively. Furthermore, Ni–Al₂O₃ nanocomposite coating increased the microhardness and wear resistance compared to the substrate up to 435 and 340%, respectively.     

Investigation of wear and corrosion resistance of nanocomposite coating formed on AZ31B Mg alloy by plasma electrolytic oxidation

Ceramic-WC coatings were prepared on AZ31 B Mg alloy by plasma electrolytic oxidation (PEO) from a phosphate based bath containing suspended tungsten carbide nanoparticles at various process times. Scanning electron microscope results indicated that increase of coating time and incorporation of tungsten carbide into the ceramic coating during the PEO process led to a decrease in the number and diameter of coating pores. Phase analysis showed that the nanocomposite coating was composed of MgO, Mg₃(PO₄)₂ and WC. Tribological properties and corrosion behaviour of uncoated AZ31 B Mg alloy and ceramic coatings were evaluated using a pin-on-disc tribometer and potentiodynamic polarisation technique in 3.5% NaCl solution, respectively. The wear and electrochemical tests showed that wear and corrosion resistance of ceramic-WC nanocomposite coatings were better than ceramic only ones. In addition, wear and corrosion behaviour of coatings improved with increasing the coating time.     

几种添加剂作用的微弧氧化膜表面结构及防腐性能

为定性比较添加剂对涂层防腐性能的作用,通过恒压微弧氧化(MAO)方法在AZ31B镁合金表面制备氧化陶瓷膜,采用扫描电子显微技术(SEM)、中性盐雾试验(NSS)等手段,考察了KOH及添加剂Na_2B_4O_7、C_6H_5Na_3O_7和EDTA-2Na浓度(质量浓度)对MAO膜表面形貌、防腐性能、粗糙度和厚度的影响。结果表明:单一组分Na_2SiO_3电解液因较高起弧电压而未能在260 V恒压条件下获得具有"火山口"形貌特征的MAO膜,其防腐性能较差。适量KOH因较低微弧等离子体诱发电压和OH-较快的放电作用,提高了涂层的防腐性能。在优化的Na_2SiO_3-KOH体系中引入10~15 g/L Na_2B_4O_7,因其特殊的形成过程及其"火山喷射状"的微结构,且获得的MAO膜具有自封孔结构,提高了其对镁合金的点腐蚀防护性能。C_6H_5Na_3O_7和EDTA-2Na具有抑弧效应,获得的MAO膜表面微孔分布均匀,但降低了MAO膜的厚度、粗糙度以及防腐性能。     

Corrosion and wear resistance of AZ31 Mg alloy treated by duplex process of magnetron sputtering and plasma electrolytic oxidation

In order to improve the wear and corrosion resistance of AZ31 magnesium alloy, a magnetron-sputtered Al layer with a thickness of 11 μm was firstly applied on the alloy, and then treated by plasma electrolytic oxidation (PEO) in an aluminate and silicate electrolytes, respectively. The performance of PEO coatings was investigated by dry sliding wear and electrochemical corrosion tests. The aluminate coating exhibits excellent wear resistance under both 10 and 20 N loads. The silicate coating only shows low wear rate under 10 N, but it was destroyed under 20 N. Corrosion tests show that the Al layer after magnetron sputtering treatment alone cannot afford good protection to the Mg substrate. However, the duplex layer of PEO/Al can significantly improve the corrosion resistance of AZ31 alloy. Electrochemical tests show that the aluminate and silicate coatings have corrosion current densities of ∼1.6×10⁻⁶ and ∼1.1×10⁻⁶ A/cm², respectively, which are two orders lower than that of the un-coated AZ31 alloy. However, immersion tests and electrochemical impedance spectroscopy (EIS) show that the aluminate coating exhibits better long-term corrosion protection than silicate coating.     

HVAF工艺参数对铝基非晶合金涂层性能的影响

针对铝基非晶合金形成能力弱的问题,采用超音速火焰喷涂(HVAF)工艺制备出铝基非晶合金涂层,研究了优化工艺参数对涂层孔隙率和非晶含量的影响,并评价了涂层的耐蚀和耐磨性能。 结果表明:在合适的喷涂厚度下,提高喷枪移动速率及降低送粉速度,可有效提高涂层的致密度与非晶含量,进而明显提升了涂层的耐蚀和耐磨性能。 在优化的工艺参数下得到的铝基非晶涂层孔隙率为 0. 12%,非晶含量为 83. 7%时,点蚀电位可提高到-0. 3 V_SCE ,腐蚀电流密度降低一个数量级,磨损速率仅为 5. 6×10 ^-4 mm ³N ^-1m ^-1 。     

A Study of Wear and Corrosion Resistance of Arc-Sprayed Ni-Ti Composite Coatings

In this study, the corrosion and wear performance of Ni-Ti composite coatings with distinct parameters were investigated. The coatings were prepared by arc spraying with Ti and Ni wires fed synchronously. Structural, surface morphological, and compositional analyses of the Ni-Ti composite coatings were performed using microhardness, SEM/EDS, XRD, and DTA analysis. Electrochemical AC impedance and potentiodynamic polarization tests were carried out to examine the anticorrosion performance of the coating. Ball-on-disc dry wear tests based on the ASTM G99 standard were performed at room temperature to evaluate the antiwear properties. The DTA and XRD analysis results indicated that some intermetallic compounds such as TiNi₃ and Ni-Ti alloy were present within the Ni-Ti coating. The wear resistance of the Ni-Ti composite coating is superior to that of the Ni-sprayed coating but slightly inferior to that of the Ti-sprayed coating. The corrosion resistance of the arc-sprayed Ni-Ti coating is superior to that of Ti but inferior to that of Ni. The corrosion and wear performance of the composite coating are greatly influenced by the coating microstructure and thickness.