Comparative study of microstructure and corrosion resistance of electroless Ni-W-P coatings treated by laser and furnace-annealing

A comparative study of amorphous electroless Ni-W-P coatings on mild steel substrate treated by a high power diode laser and furnace annealing was presented.Effects of different laser operating parameters and furnace-annealing conditions on microstructures,in terms of crystallisation,pores formation and grain growth,were investigated using SEM/EDX and XRD. Corrosion behaviours of these coatings before and after various treatments were evaluated with anodic polarisation in 0.5 mol/L H2SO4 solution.The results show that the furnace-annealing produces either a mixture of nanocrystallined Ni and amorphous phases or precipitated Ni3P phase distributed in nanocrystallined Ni-based matrix,depending on annealing temperatures,whilst the laser treatment under the operating conditions only produces nanocrystallined Ni-based matrix with Ni3P precipitates.Corrosion performance of the coatings treated by both the laser and the furnace-annealing is dependent on the annealing temperature and laser operating conditions.Corrosion mechanisms of various treated-coatings were discussed in the consideration of phase constitutes and proportion,grain sizes of both Ni and Ni3P phases,pores formation and residual stresses.

The study of electroless Ni-W-P alloy plating on glass fibers

Ni-W-P coatings were deposited on the surface of glass fibers by the electroless plating process. The bath was very stable through the palladium salt test. There was no phenomenon of peeling and blistering on the surface of the Ni-W-P alloy glass fibers in the thermal shock test. It showed that the deposit had high impact strength and good adhesion. The morphology of the coatings was observed by scanning electron microscope （SEM）. The elements and their contents were tested and analyzed by energy dispersion spectrometer （EDS）. The tungsten content reached up to 12.1 wt.%. The effects of the concentrations of NiSO4, Na2WO4, and NaH2PO2.H20 on the conductivity of the coatings were studied. The resistivity of the Ni-W-P alloy glass fibers reached 7.39 × 10^-3 Ωcm. The alloy coatings on glass fibers were analyzed by XRD. The results indicated that the deposit had an amorphous structure and good heat stability. The suitable work temperature range was lower than 190℃. Finally, the electromagnetic parameters of the Ni-W-P alloy glass fibers were tested and analyzed primarily. The magnetic loss reached 0.04023 and the dielectric loss reached -5.80239. The plated alloy is a kind of soft magnetic material.

Significant Inhibition of IMCs Growth between an Electroless Ni-W-P Metallization and SAC305 Solder During Soldering and Aging

The formation and growth behavior of intermetallic compound(IMC) layers after introducing an electroless Ni-W-P metallization into the Sn-3.0Ag-0.5Cu(SAC305) solder joint during soldering and aging were investigated. The soldering was performed at 250 ℃ for 10 min, followed by air cooling and aging treatment at 150 ℃ up to 15 days. The results show that the scallop-like Cu_6Sn_5 IMC layer and planar-like Cu_3Sn formed between solder and Cu substrate during soldering and aging. The Ni_3P and(Ni,Cu)_3Sn_4 compounds were formed between electroless Ni-W-P layer and solder, and Cu substrate was not damaged and kept a smooth interface. When the isothermal aging treatment was applied, the total thickness of IMCs which formed at the SAC305/Cu and SAC305/Ni-W-P/Cu interface increased with increasing aging time. Kirkendall voids emerged at the Cu_3Sn and the Ni_3P layers, but the voids emerged at the Ni_3P layer in the form of crack. The amount of Kirkendall voids increased and the crack elongated with increasing aging time. The Cu_6Sn_5 and(Ni,Cu)_3Sn_4grains grew by merging adjacent grains. In the process of growth, the growing interfacial compounds filled the free space, and new columnar dendrite grain of(Ni,Cu)_3Sn_4 constantly generated during aging treatment. After 15 days aging, the Ni-W-P barrier layer was still remained, which indicated that the Ni-W-P layer can be a good barrier layer between the solder alloys and Cu substrate.

Novel technology of electroless Ni-W-P on plastics and its interface behavior

The electroless Ni-W-P coatings on polyoxymethylene(POM) were prepared. The POM was pretreated by hot spraying Al powder on it. Before the electroless Ni-W-P deposition, the POM with Al coating was flash plated in alkaline bath. The mechanism of Ni-W-P deposition was studied and the technology was optimized. The XRD analysis shows that the "as-deposited" Ni-W-P plating has mixed crystalline structure. The hardness value of deposits is more than HV700. The abrasion resistance of deposits is six times more than that of POM. Bending test was used to determine the cohesion between the deposits and the substrates. SEM was used to study the behavior of surface abrasion and interface bonding condition. The reason for the excellent cohesion was interpreted.

表面活性剂对Ni-W-P化学镀层沉积行为及性能的影响

Ni-W-P化学镀层因具有良好的耐蚀、耐磨性能而成为重要的“代铬”镀层。表面活性剂可以增强镀液对基体润湿能力,加快界面处H2逸出速率,减少镀层针孔数量或氢缺陷,从而提高镀层质量。本论文探究了十二烷基磺酸钠(SDS)、十六烷基三甲基溴化铵(CTAB)以及聚乙二醇-200(PEG-200)三种典型表面活性剂对Ni-W-P镀层沉积行为及性能的影响。借助扫描电子显微镜、X射线衍射以及电化学方法对Ni-W-P镀层的表面微观形貌、物相、气孔率和耐蚀性能进行了表征,并通过接触角、沉积电位阐述了表面活性剂在化学镀Ni-W-P过程中的作用机理。研究结果表明,表面活性剂可改善镀层表面质量以及颗粒尺寸均匀性,并显著降低镀层内部针孔数量,优先顺序为PEG-200>SDS>CTAB。XRD衍射结果显示,表面活性剂可提高镀层内合金元素W和P含量,有利于形成耐蚀性能良好的Ni-W-P非晶镀层。此外,三种表面活性剂均能改善镀液对基体的润湿能力,其中PEG-200对基体的润湿角最小(65°),说明PEG-200对于提高界面处H2逸出速度,降低化学镀过程中电位波动效果更为明显。论文研究结果可以为制备内部缺陷较少、耐蚀性能优良的Ni-W-P化学镀层提供一定的理论基础。

软装设计用铜合金的表面Ni-W-P镀层与性能研究

针对软装设计用铜合金复杂服役环境的使用需求,为解决铜合金表面硬度低、耐腐蚀性能差等问题,采用化学镀的方法在软装设计用铜合金表面制备了Ni-W-P镀层。研究了Na_(2)WO_(4)浓度对化学镀层沉积速率、表面形貌、物相组成、硬度和耐腐蚀性能的影响。结果表明:随着Na_(2)WO_(4)浓度从15 g/L增加至65 g/L,铜合金表面镀层的沉积速率先增后减,在Na_(2)WO_(4)浓度为35 g/L时取得最大值。镀层中P元素含量逐渐减小,W元素含量先增加后减小。不同Na_(2)WO_(4)浓度的镀层中都可见Ni和Ni_(5)P_(4)衍射峰,镀层硬度高于未添加Na_(2)WO_(4)的镀层。且随着Na_(2)WO_(4)浓度增加,镀层硬度先增后减,在Na_(2)WO_(4)浓度为35 g/L时取得最大值。随着Na_(2)WO_(4)浓度从15 g/L上升至65 g/L,铜合金表面镀层的腐蚀电位先正向移动后负向移动,腐蚀电流密度先减小后增大。在Na_(2)WO_(4)浓度为35 g/L时,取得腐蚀电流密度最小值和电荷转移电阻最大值。电化学阻抗谱与极化曲线测试结果相吻合,Na_(2)WO_(4)浓度为35 g/L时具有最佳的耐腐蚀性能。

High corrosion and wear resistant electroless Ni–P gradient coatings on aviation aluminum alloy parts

A Ni–P alloy gradient coating consisting of multiple electroless Ni–P layers with various phosphorus contents was prepared on the aviation aluminum alloy. Several characterization and electrochemical techniques were used to characterize the different Ni–P coatings’ morphologies, phase structures, elemental compositions, and corrosion protection. The gradient coating showed good adhesion and high corrosion and wear resistance, enabling the application of aluminum alloy in harsh environments. The results showed that the double zinc immersion was vital in obtaining excellent adhesion (81.2 N). The optimal coating was not peeled and shredded even after bending tests with angles higher than 90°and was not corroded visually after 500 h of neutral salt spray test at 35℃. The high corrosion resistance was attributed to the misaligning of these micro defects in the three different nickel alloy layers and the amorphous structure of the high P content in the outer layer. These findings guide the exploration of functional gradient coatings that meet the high application requirement of aluminum alloy parts in complicated and harsh aviation environments.

XPS Studies on Electroless As-Deposited and Annealed Ni-P Films

Electroless deposition has been used to deposit Ni-P films on glass slides using the reducing agent sodium hypophosphite. This has been done with a purpose to use Ni-P films as back contact for silicon carbide radiation detectors. By keeping deposition time, temperature, pH and concentration of the precursor solution constant, the film deposition has been done. XPS studies were done to analyze the composition and stoichiometry of Ni-P thin films.

Deposition of electroless Ni-P/Ni-W-P duplex coatings on AZ91D magnesium alloy

The electroless Ni-P/Ni-W-P duplex coatings were deposited directly on AZ91D magnesium alloy by an acid-sulfate nickel bath.Nickel sulphate and sodium tungstate were used as metal ion sources and sodium hypophosphite was used as reducing agent.The coating was characterized for its structure,morphologies,microhardness and corrosion properties.The presence of dense and coarse nodules in the duplex coatings was observed by SEM and EDS.Tungsten content in Ni-P/Ni-W-P alloy is about 0.65%(mass fraction) and the phosphorus content is 8.18%(mass fraction).The microhardness of the coatings is 622 VHN.The coating shows good adhesion to the substrate.The results of electrochemical analysis,the porosity and the immersion test show that Ni-P/Ni-W-P duplex coatings possess noble anticorrosion properties to protect the AZ91D magnesium alloy.

活化处理对高速钢Ni-W-P化学镀层结合力影响

为提高Ni-W-P化学镀层与高速钢基体之间的结合力,重点研究了高速钢化学镀前的表面活化处理工艺。以不同浓度的盐酸、硫酸、氢氟酸和活化时间为研究对象,以Ni-W-P镀层与高速钢基体的结合力为研究指标,通过正交试验对活化剂组分和活化时间进行优化。结果表明,在试验条件下,当活化剂中添加8%的浓盐酸和2.5%的氢氟酸(其余为水)并对高速钢基体进行3 min活化处理时,制备的Ni-W-P镀层与基体的结合力最大。

Synergistic Effect between Nano-ceramic Lubricating Additives and Electroless Deposited Ni-W-P Coating

The major solving ways for the material wear are surface modification and lubrication. Currently, the researches at home and abroad are all limited to the single study of either nano-lubricating oil additive or electroless deposited coating. The surface coating has high hardness and high wear resistance, however, the friction reduction performance of the coating with high hardness is not good, the thickness of the coating is limited, and the coating can not regenerate after wearing. The nano-lubricating additives have good tribological performance and self-repair function, but under heavy load, the self-repair rate to the worn surface with the nano-additives is smaller than the wearing rate of the friction pair. To solve the above problems, the Ni-W-P alloy coating and deposition process with excellent anti-wear, and suitable for industrial application were developed, the optimum bath composition and process can be obtained by studying the influence of the bath composition, temperature and PH value to the deposition rate and the plating solution stability. The tribological properties as well as anti-wear and friction reduction mechanism of wear self-repair nano-ceramic lubricating additives are also studied. The ring-block abrasion testing machine and energy dispersive spectrometer are used to explore the internal relation between the coating and the nano-lubricating oil additives, and the tribology mechanism, to seek the synergetic effect between the two. The test results show that the wear resistance of Ni-W-P alloy coating （with heat treatment and in oil with nano-ceramic additives） has increased hundreds times than 45 steel as the metal substrate in basic oil, the friction reduction performance is improved. This research breaks through the bottleneck of previous separate research of the above-mentioned two methods, and explores the combination use of the two methods in industrial field.

Cr12MoV模具钢化学镀Ni-W-P/PTFE复合镀层及耐磨性能研究

以Cr12MoV模具钢作为基体化学镀Ni-W-P/PTFE复合镀层,以期提高模具的耐磨性能。通过改变PTFE颗粒添加量获得不同Ni-W-P/PTFE复合镀层,并对复合镀层的表面形貌、化学成分、晶相结构、硬度及耐磨性能进行表征。结果表明:不同复合镀层表面都存在尺寸不同、分布不均匀的胞状物,还附着白色PTFE颗粒,但是晶相结构无显著性差异。随着PTFE颗粒添加量从2 g/L增至14 g/L,复合镀层中PTFE颗粒含量呈现先升高,后降低趋势,并且颗粒分散状况不同,硬度呈现减小趋势,而耐磨性能逐步提高,然后变差。当PTFE颗粒添加量为8 g/L获得的Ni-WP/PTFE复合镀层中PTFE颗粒含量达到3.63%,并且颗粒分布趋于均匀,具有优良的耐磨性能,其摩擦系数仅为0.41,表面磨痕宽度和深度分别为500μm和14.7μm,作为表面改性层能有效减轻Cr12MoV模具钢的磨损程度。

The Effect and Mechanism of Nano-Cu Lubricating Additives on the Electroless Deposited Ni-W-P Coating

The coating and deposition process with excellent anti wear and suitable for industrial application were developed, and the optimum bath composition and process were obtained by studying the influence of the bath composition, temperature and pH value on the deposition rate and the plating solution stability. Moreover, the tribological properties of nano-Cu lubricating additives and electroless deposited Ni-W-P coating as well as their synergistic effect are researched using ring-block abrasion testing machine and energy dispersive spectrometer. Research results show that Ni-W-P alloy coating and nano-Cu lubricating additive have excellent synergistic effect, e g, the wear resistance of Ni-W-P alloy coating （with heat treatment and the oil with nano-Cu additives） has increased hundreds times than 45 steel as the metal substrate with the basic oil, and zero wear is achieved, which breaks through the bottleneck of previous separate research of the above-mentioned two aspects.

XPS Study of Electroless Deposited Sb2Se3 Thin Films for Solar Cell Absorber Material

As a thin film solar cell absorber material, antimony selenide (Sb2Se3) has become a potential candidate recently because of its unique optical and electrical properties and easy fabrication method. X-ray photoelectron spectroscopy (XPS) was used to determine the stoichiometry and composition of electroless Sb2Se3 thin films using depth profile studies. The surface layers were analyzed nearly stoichiometric. But the abundant amount of antimony makes the inner layer electrically more conductive.

Depth Profile Study of Electroless Deposited Sb2S3 Thin Films Using XPS for Photovoltaic Applications

Sb2S3 has gained tremendous research recently for thin film solar cell absorber material because of their easy synthesis, unique electrical and optical properties. The stoichiometry and composition of electroless Sb2S3 thin films were analyzed using XPS depth profile studies. The surface layers were found nearly stoichiometric. On the other hand, the inner layer was rich in antimony composition making it more conductive electrically.

Pd-ZSM-5复合膜的制备及其氢气分离性能

为了能够在大孔氧化铝载体表面得到透氢性能良好的钯膜,利用二次生长法在多孔Al_(2)O_(3)载体上生长出一层连续完整的ZSM-5沸石分子筛修饰层,通过化学镀过程在ZSM-5沸石分子筛修饰的载体上沉积一层钯膜,从而得到Pd-ZSM-5复合膜。利用扫描电子显微镜(SEM)对载体、ZSM-5沸石分子筛修饰后的载体和Pd-ZSM-5复合膜的形貌进行详细分析,并通过X线能量色散光谱(EDX)对Pd-ZSM-5复合膜的表面和截面元素分布进行了研究。而且,为了确定该Pd-ZSM-5复合膜的H_(2)渗透性能,在623~773 K范围内,研究了操作温度、操作时间和测试压力对Pd-ZSM-5复合膜透氢性能的影响。研究结果表明,ZSM-5沸石分子筛修饰层能够有效改进载体的表面粗糙度和降低其表面孔径,有助于Pd膜的沉积。所制备的Pd-ZSM-5复合膜表面完整、致密,Pd膜层厚度约为5μm, ZSM-5沸石修饰层厚度约为3μm。当操作温度为773 K、渗透压力为0.1 MPa时,Pd-ZSM-5复合膜的H_(2)渗透通量和H_(2)/N_(2)渗透选择性分别为0.113 mol/(m·s)和468。而且,该Pd复合膜在773 K下,连续操作300 h后,其H_(2)渗透性能保持相对稳定。

热致液晶高分子膜的表面处理及化学镀铜

论文采用氢氧化钠(NaOH)溶液对Vecstar型热致液晶高分子(TLCP)膜表面进行刻蚀粗化,然后通过3-氨丙基三乙氧基硅烷(KH550)在膜表面引入氨基,利用氨基络合银离子使膜表面活化,再进行无钯化学镀铜,提升了TLCP膜与金属铜之间的黏附力。借助扫描电子显微镜(SEM)、接触角测量仪、X射线衍射仪(XRD)和剥离测试等对经表面处理及化学镀铜后的TLCP膜进行表征,探讨了NaOH溶液浓度、表面粗化温度和时间、活化溶液组成等对TLCP表面化学镀铜的影响。结果表明,经表面处理后TLCP膜表面产生均匀的孔洞,接触角下降至29.30°,亲水性大幅提高;所镀铜层呈光亮的粉色,带有金属光泽,致密平滑,纯度高,镀层厚度可达2.78μm,与TLCP膜间的附着力等级达到了5B。

稀土对化学镀Ni-W-P镀液及镀层性能的影响

研究了4种稀土元素Nd、Pr、Ce、La的硫酸盐及其氧化物对化学镀Ni W P镀液的沉积速度和镀层耐硝酸滴定变色时间的影响。结果表明,4种稀土的硫酸盐均降低了镀液的沉积速度,并使镀层的耐蚀性能下降;Nd、Ce、La的氧化物亦使镀层的耐蚀性下降,而当ρ(Pr2O3)为4mg/L时,镀液的稳定性为未加Pr2O3时的2倍,其沉积速度明显加快,镀层的耐硝酸滴定变色时间超过2000s,硬度明显增大,SEM图表明该镀层呈现致密而均匀的胞状形貌,表面质量优于未加稀土的镀层,X-射线衍射图也表明Pr2O3促进了镀层的非晶态化程度,从而提高其耐蚀性能。

AZ91D镁合金Ni-W-P多层化学镀层的摩擦磨损及耐腐蚀性能

采用多层化学镀工艺在AZ91D镁合金表面成功制备了Ni-W-P多层化学镀层。通过XRD、SEM、摩擦磨损实验以及电化学分析测试等方法,对比研究了普通单层化学镀试样与多层化学镀试样的显微结构、摩擦磨损性能以及耐腐蚀性能。结果表明:多层化学镀层的摩擦因数、维氏硬度及磨损速率与单层化学镀层大体相当,分别为0.33、933 HV和1.46 mg/Km,保留了单层化学镀层优异的耐磨损性能。此外,多层化学镀层的孔隙率较单层化学镀层降低了2个数量级,涂层更为致密。与普通单层化学镀层相比,多层化学镀层的耐蚀性能显著提高,其腐蚀电位和击破电位分别提高了168和209 mV,钝化电流密度由4.212μA·cm−2降低至1.306μA·cm−2。因此,多层化学镀层有望成为AZ91D镁合金更有前景的耐磨耐蚀防护涂层。