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.

Microstructure and corrosion behavior of electroless deposited Ni-P/CeO_2 coating

Electroless Ni-P/nano-CeO2 composite coating was prepared in acidic condition, and its microstructure and corrosive property were compared with its CeO2-free counterpart. Scanning electronic microscopy （SEM） and X-ray diffraction （XRD） spectrometer were used to examine surface morphology and structure of the as-plated coating. Differential scanning calorimeter （DSC） and transmission electronic microscopy （TEM） were used to study the coating＇s phase change at high temperature. The coating＇s corrosive behavior in 3%NaCl ＋ 5%H2SO4 solution was also investigated. The results showed that Ni-P coating had partial amorphous structure mixed with nano-crystals, while the Ni-P/CeO2 coating had perfect amorphous structure. In high-temperature condition, Ni3P precipitation and Ni crystallization took place in both coatings but at different temperatures, while the Ni-P/CeO2 coating had sintered phase of NiCe2O4 spinels. The anti-corrosion property was better in the CeO2-containing coating, and this was due to its less liability to undergo local-cell corrosion than its CeO2-free counterpart. Ni-P/CeO2 coating＇s pure amorphous structure was the result of Ni＇s hindered crystal-typed deposition and P＇s promoted deposition.

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.

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。

An in situ measure method to study deposition mechanism of electroless Ni-P plating on AZ31 magnesium alloy

An in situ method was designed to measure a continuous open circuit potential （OCP） curve of AZ31 magnesium alloy and to observe the morphology variation of Ni-P coating during the process of the electroless plating. The deposition mechanism of the electroless Ni-P plating on AZ31 Mg alloy was studied by OCP curve, scanning electron microscopy （SEM）, and energy dispersion spectroscopy （EDS）. The process of electroless Ni-P plating contains the coating formation stage and the coating growth stage. The formation stage includes three procedures, i.e., the nucleation and growth of Ni crystallites, the extension of the coating in two-dimensional （2D） direction and the coalescence of the coating along three-dimensional （3D） direction. SEM investigations demonstrate that the spherical nodules of the Ni-P coating are not only formed during the coating growth stage, but also generated in the initial deposition stage of electroless Ni-P plating. The variation of the coating rates at different deposition stages corresponds to the deposition mechanism of their respective deposition stage.

Characteristics of microstructure and performance of laser-treated electroless Ni-P/Ni-W-P duplex coatings

Characteristics of microstructures of electroless Ni-P/Ni-W-P duplex coatings were investigated using SEM/EDX and XRD analysis techniques. Microhardness and wear behaviour of the coatings before and after laser crystallization were evaluated by measurements of hardnesses of coating surface and cross-section, and by unlubricated friction and wear experiments. The results indicate that it is possible to prepare electroless Ni-P/Ni-W-P duplex coatings by sequential immersion in two different plating baths. After laser crystallization, the microstructures of electroless Ni-P/Ni-W-P duplex coatings present the characteristics of higher degree of crystallization and larger grain size for outer layer Ni-W-P than inner Ni-P, but outer layer has a higher hardness. The wear resistance of laser-treated duplex coatings in a given process parameter conditions is superior to the as-plated ones. Laser treatment was performed directly in air without argon protection, which provides the possibility for application of industrialized production.

Electroless deposition of Cu on multiwalled carbon nanotubes

Copper has been deposited on the surface of multiwailed carbon nanombes （MWNTs） and inside MWNTs by electroless deposition. The as-prepared Cu-MWNT composite materials have been characterized by X-ray diffractometer （XRD）, transmission electron microscopy （TEM）, and electrochemical measurement. XRD analyses showed that Cu was a face-centered cubic （fcc） structure. The average size of Cu was calculated by Scherrer＇s formula from XRD data, and it was 11 nm. TEM revealed that Cu grains on the surface of MWNTs were uniform with the sizes of about 30-60 nm. The electrochemical measurement indicated that Cu-MWNT composite materials possessed fine electron conductivity.

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.

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.

HARDNESS AND WEAR RESISTANCE OF ELECTROLESS NICKEL DEPOSITS

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Activator-assisted electroless deposition of copper nanostructured films

This paper showed simple and effective synthesis of copper nanoparticles within controlled diameter using direct electroless deposition on glass substrates, following the sensitization and activation steps. Electroless-deposited metals, such as Cu, Co, Ni, and Ag, and their alloys had many advantages in micro- and nanotechnologies. The structural, morphological, and optical properties of copper deposits were characterized using X-ray diffraction （XRD）, atomic force microscopy （AFM）, and UV-Vis spectroscopy. The structural data was further analyzed using the Rietveld refinement program. Structural studies reveal that the deposited copper prefers a （111） orientation. AFM studies suggest the deposited materials form compact, uniform, and nanocrystalline phases with a high tendency to self-organize. The data show that the particle size can be controlled by controlling the activator concentration. The absorption spectra of the as-deposited copper nanoparticles reveal that the plasmonic peak broadens and exhibits a blue shift with decreasing particle size.

Online evaluation of electroless deposition rate by electrochemical noise method

Continuous noise resistance calculation(CNRC)technique was used for online determination of the electroless nickel deposition rate on zirconium pretreated magnesium alloy.For this purpose,the noise resistance(R_n) variation with time was calculated for the pretreated alloy surface in the electroless plating solution.The CNRC results were described by energy dispersive X-ray spectroscopy(EDS)and scanning electron microscopy(SEM)techniques.Also,potentiodynamic polarization and gravimetric measurements were used for determination of the electroless deposition rate at the same time period and the results were compared with the CNRC results.The Rn variation with plating time shows that the electroless plating consists of different stages with various deposition rates.The results of the CNRC and polarization methods were not in acceptable agreement due to the limitations of the polarization method for online monitoring of the deposition rate.However,the results of the gravimetric measurements were in complete agreement with the CNRC technique and so,the CNRC can be considered as suitable tool for online evaluation of the electroless deposition rate.

Fabrication of multi-shell coated silicon nanoparticles via in-situ electroless deposition as high performance anodes for lithium ion batteries

Si-based materials have been extensively studied because of their high theoretical capacity,low working potential,and abundant reserves,but serious initial irreversible capacity loss and poor cyclic performance resulting from large volume change of Si during lithiation and delithiation processes restrict their widespread application.Herein,we report the preparation of multi-shell coated Si(DS-Si)nanocomposites by in-situ electroless deposition method using Si granules as the active materials and copper sulfate as Cu sources.The ratio of Si and Cu was readily tuned by varying the concentration of copper sulfate.The multi-shell(Cu@CuxSi/SiO2)coating on Si surface promotes the formation of robust and dense SEI films and the transportation of electron.Thus,the obtained DS-Si composites exhibit an initial coulombic efficiency of 86.2%,a capacity of 1636 mAh g^-1 after 100 discharge-charge cycles at 840 mA g^-1,and an average charge capacity of 1493 mAh g^-1 at 4200 mA g^-1.This study provides a low-cost and large-scale approach to the preparation of nanostructured Si-metal composites anodes with good electrochemical performance for lithium ion batteries.

Study of the Corrosion Resistance of Electroless Ni-P Deposits in a Sodium Chloride Medium

The corrosion resistance of electroless Ni-P deposits with phosphorous contents from 12% to 14% in sodium chloride solutions was studied. The deposits were immersed in 3.5% NaCl solutions for 29 d to obtain the electrochemical parameters and were examined in a standard salt spray test for 15 d respectively. The corrosion resistance of the deposits was studied by poten- tio-dynamic scan, electrochemical impedance spectroscopy (EIS), X-ray diffraction (XRD) and cold-field emission scanning electron microscopy (FE-SEM) equipped with an energy dispersive X-ray detector (EDX). The patterns of XRD and the results of FE-SEM showed that the prepared deposits were amorphous. But after a 15 d standard salt spray test, a few pinholes appeared on the surface of the deposit and the weight content of phosphorus on the surface of the deposit was higher (which was beneficial to the formation of the passivation films) than that before the standard salt spray test when the nickel content was lower because the dissolved weight of nickel was greater than that of phosphorus. The results from potentio-dynamic scan and EIS showed that passivation films formed on the Ni-P deposit after immersion in the NaCl solutions, which decreased the corrosion rate of Ni-P samples. The results of this work show their potential applications in marine corrosion.

EFFECT OF ELECTROLESS DEPOSITION CONDITIONS ON THE STRUCTURES AND THE MAGNETIC PERFORMANCES OF THE Co-Fe-P ALLOY

Electroless Co-Fe-P alloys were deposited from an alkaline bath, containing boric acid as a buffer agent and sodium citrate as a complexing agent. As a result, with the increase of pH of the bath, the iron content of the deposit increased, whereas the cobalt and phosphorus contents decreased. The structure of the deposit was investigated using X-ray diffraction （XRD） and transmission electron microscope （TEM）. The deposit consisted of hexahedron phase Co, cubic phase Fe-Co, and amorphous phase （crystalline）. The magnetic performances of the deposit were studied using vibrating sample magnetometer （VSM）. The more the content of Fe and the less the content of P （the content of Co being less）, the better the magnetic performances of the deposit. The Co-Fe-P deposit was suitable for use as soft magnetic material.

Electroless Ni-P Deposition on Magnesium Alloy from a Sulfate Bath

A technology for electroless Ni-P deposition on AZ91D from a low cost plating bath containing sulfate nickel was proposed. The seal pretreatment was employed before the electroless Ni-P deposition for the sake of occluding the micro holes of the cast magnesium alloy and interdicting the bubble formation in the Ni-P coating during plating process. And pickling pretreatment can provide a better adhesion between the Ni-P deposition and AZ91D substrate. The deposition speed of the Ni-P coating is 29 μm/h. The technology is employed to AZ91D magnesium alloy automobile parts and can provide high hardness and high wear-resistant. The weight losses of Ni-P plated and heat-treated Ni-P plated magnesium alloy specimen are only about 1/6 and 1/10 that of bare magnesium alloy specimen after 10 min abrasion wear, respectively. The hardness of the electroless Ni-P plated brake pedal support brackets is 674.1 VHN and 935.7 VHN after 2 hours heat treatments at 180 C. The adhesion of Ni-P coatings on magnesium alloy substrates meets the demands of ISO Standards 2819. The technology is environment friendly and cannot cause hazard to environment because of absence of chromate in the whole process.

Effect of initial deposition behavior on properties of electroless Ni-P coating on ZK60 and ME20 magnesium alloys

The composition of magnesium alloys is greatly associated with initial deposition behavior of electroless Ni-P coatings.Thus,the initial deposition behavior of electroless Ni–P coatings on ZK60 and ME20 alloys was investigated.The results indicated that differences in the alloy compositions significantly influenced the initial deposition process and the adhesive strength,corrosion resistance,and crystal structure.The initial deposition of coatings on ZK60 and ME20 alloys preferentially occurred on the precipitates.The precipitates in ZK60 alloy had higher chemical activity after HF activation and controlled the initial deposition rate of the coating.The initial deposition rate of the coating on ME20 alloy mainly depended on the density of the Mg F2 film formed by HF activation rather than on the precipitates.Owing to differences in the initial deposition process,the coating on ZK60 alloy had higher adhesive strength and better corrosion resistance than that on ME20 alloy.The coatings on ZK60 and ME20 alloys mainly had crystalline structures,and the coating on ME20 alloy had also a slight microcrystalline structure.

Fabrication of anatase titanium dioxide nanotubes by electroless deposition using polycarbonate for separate casting method

Titanium dioxide nanotubes(TNTs)were prepared by electroless deposition using ion track etched polycarbonate templates.The ion tracks were prepared to the desired diameter of the TNTs outer diameter.Titanium dioxide nanotubes with a diameter of minimum 80 nm having a wall thickness of minimum 10 nm can be fabricated using this method.To achieve nanotubes with thin walls and small surface roughness the tubes were generated by a several steps procedure under aqueous conditions at nearly room temperature.The presented approach will process open end nanotubes with well defined outer diameter and wall thickness.Using this method TNT arrays up to 109 tubes per cm2having a tube length up to 30μm can be produced,single tubes are also possible.The structural properties of the grown TNTs were investigated by using various analytical techniques,i.e.scanning electron microscopy(SEM),energy dispersive X-ray fluoresence spectrometer(EDX),X-ray photoelectron spectroscopy(XPS),X-ray diffraction(XRD),Raman spectroscopy and Photoluminescence.

Electroless Deposition of Fe-Mo-W-B Amorphous Alloys

The preparation, formation mechanism, surface appearance and structure of electroless plating Fe-Mo-W-B amorphous alloys were systematically studied. The deposition rates of the deposits in different bath composition as plated were measured. The formation mechanism of the deposits was discussed. The parameter for amorphous structures formation was suggested for the deposits.

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.