Electroless Nickel Plating Solution Research Articles

Electrochemical activity of electroless Ni-P coatings in the hydrogen evolution reaction

The purpose of this study was investigation of the electrochemical activity of Ni-P coatings, differing in phosphorus content and structure, in the hydrogen evolution reaction (HER) and the identification of the reasons for their high activity in the reaction being studied. The coatings were deposited from an electroless nickel plating solution, the phosphorus content in the coatings (from 4.8 to 8.0 wt. %) varied by changing the pH of the solution. It was found that during cathodic polarization in 0.5 M H2SO4 additional surface activation occurs as a result of dissolution of the surface layer of the coating, removal of phosphorus from the surface layer, and development of the electrode surface. Of all the coatings studied coatings containing 4.8% phosphorus were most susceptible to cathodic activation. Coatings with a phosphorus content of 8.0% were least susceptible to cathodic activation. The similar electrochemical activity of the studied coatings (taking into account the roughness factor) in HER indicates that, as a result of cathodic polarization, the composition of the thin surface layer on which the cathodic reaction occurs is approximately the same, regardless of the initial phosphorus content

High-efficiency nickel recovery from spent electroless nickel plating solution: effective degradation of high-concentration nickel complexes to form a nickel ferrite nanomaterial via Fe3O4 catalytic oxidation

High-concentration organic nickel complexes were efficiently degraded and converted into NiFe2O4 nanomaterials via Fe3O4 catalytic oxidation under alkaline conditions, with high removal efficiency of nickel (99.99%) and TOC (81.94%), respectively.

Integrating multi-method approaches for the green separation and retrieval of nickel and phosphorus from spent electroless nickel plating solutions

The spent electroless nickel plating (SENP) solution comprises abundant complexed nickel, hypophosphite, and phosphite ions, alongside scant organic additives.

Design of a scheelite production pilot plant for the treatment of spent electroless nickel plating solutions in Field Service Solution S.A.S.: an alternative source for tungsten recycling

In this contribution, the design considerations to assemble a pilot-plant for tungsten recovery and further conversion into synthetic scheeliteas raw material, as an eco-friendly improvement for the current electroless nickel process in Field Service Solution (FES) S. A. S., arepresented. This low-cost methodology scale-up aims to provide an alternative treatment for spent electroless nickel solutions (Ni-P-W) asa secondary tungsten source. The plant is projected to treat up to 750 L of industrial waste per week, achieving a maximum scheeliteproduction of 9.1 kg per week. This prototype serves as a model of eco-sustainability in the nickel-plating industry by controlling thedisposal of heavy metals and by facilitating the production of other tungsten derivatives and their feasible reuse in the process.

Исследование и моделирование процесса подавления биодеградации растворов для химического никелирования

The paper considers proliferation of filamentous fungi in electroless nickel plating baths. We determined that it leads to decomposition of processing media and decreased coating deposition rates. We developed a mathematical model for suppressing filamentous fungi growth in electroless nickel plating solutions in the presence of various inhibitors. The model allows us to predict microorganism proliferation rate under the conditions specified. We used experimental data and mathematical simulation as the basis for investigating processing media biodegradation in electroless nickel plating. Our mathematical simulation showed that it is possible to use the Verhulst model to describe the growth kinetics of filamentous fungi colonies. It also allowed us to determine the parameters of the process kinetics, to predict bath electrolyte stability and select efficient inhibitors. We validate our selection of inhibitor substances (copper sulphate, sodium tetraborate, lactic acid, sodium propionate, chloroform) that have a fungistatic or fungicidal effect on biological object proliferation. We developed a mathematical model for the process of inhibiting processing media biodegradation in electroless nickel plating by means of various substances. We substantiate the ambiguity of selecting the initial condition for stating the Cauchy problem in the mathematical description of the process. We present and analyse the results of mathematically simulating the process under consideration. We found sodium tetraborate to be the most efficient biological object proliferation inhibitor, since, as its concentration increases to 50 mmol/l, there is no deterioration in the coating quality; at the same time, the coating deposition rate increases and the necessary fungicidal effect

Effect of Na4P2O7·10H2O as complexing agent on deposition behavior and property of electroless Ni-P coating on ZK61M magnesium alloy

The electroless Ni-P coating was prepared on ZK61M magnesium alloy by using Na4P2O7·10H2O as main complexing agent and NiSO4·6H2O as main salt in the electroless nickel plating solution. The effects of Na4P2O7·10H2O on deposition rate, growth progress and corrosion resistance of the Ni-P coating were investigated systematically in this study. The properties of the plating were characterized by the measurements including, scanning electronic microscope (SEM), energy dispersive spectrometer (EDS), x-ray diffraction (XRD), electrochemical polarization and immersion tests in 5% NaCl solution. The results showed that the initial uniform deposition of the plating on the HF-activated substrate was achieved by using Na4P2O7·10H2O as the main complexing agent. The deposition rate showed an obvious upward trend with the increment on the concentration of Na4P2O7·10H2O. It was worth noting that the content of phosphorus reached more than 7 wt% in Ni-P coating while the concentration of Na4P2O7·10H2O was higher than 40 g L−1. Most importantly, the plating with an obvious microcrystal structure had excellent corrosion resistance. Moreover, no corrosion on the surface was observed while the sample was immersed into 5% NaCl solution for 12 h. The self-corrosion potential of the Ni-P coating exceeded −0.5 V. The self-corrosion current could be reduced about 2 orders of magnitude comparing to magnesium alloy substrate.

New industrial application of forward osmosis (FO): Precious metal recovery from printed circuit board (PCB) plant wastewater

As a promising industrial application of forward osmosis (FO), an FO-based concentration system for precious metal recovery from printed circuit board (PCB) wastewater has been newly suggested. This novel FO concentration process utilizes a dilution-needed waste solution possessing high conductivity as a draw solution, and thus an external supply of draw solution as well as a re-concentration process for the diluted draw solution are not required. An electroless (E’less) nickel (Ni) plating solution was evaluated as dilution-needed waste stream-based draw solution, and the test results confirmed that the selected Ni solution could produce an acceptable FO performance, i.e., water flux of 39.4 LMH (active layer facing draw solution (AL-DS) mode with deionized feed solution). From a series of FO experiments conducted with a palladium (Pd) catalyst as a concentration-needed feed solution, the Pd solution was effectively concentrated under an active layer facing feed solution (AL-FS) mode with a slight impact from Pd scaling. The modeling prediction based on our experimental results showed that theoretically Pd can be concentrated 17.2-times-high. The overall performance of our Pd concentration tests indicated that the FO process is promising for concentrating Pd, thereby improving the efficiency of its recycling. The newly proposed system, a recovery-free FO driven by a waste stream, offers attractive economic advantages including (1) zero cost for the supply and re-concentration of the draw solution and (2) enhanced energy efficiency in the precious metal recycling process.

Operation of Electroless Nickel Plating Solution TsKN 111 at High Specific Loading Area

Operation of Electroless Nickel Plating Solution TsKN 111 at High Specific Loading Area

Inexpensive and green synthesis of multi-doped LiFePO4/C composites for lithium-ion batteries

Multi-doped LiFePO4/C has been successfully synthesized using iron powder as an iron source and spent electroless nickel plating solution (SENPS) as phosphorus, carbon and dopants sources. A possible liquid-phase and solid-phase mechanisms for the formation of multi-doped LiFePO4/C are also proposed. The structure, morphology, elemental composition and particle size distribution of the powder are characterized by X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectroscopy and laser particle size analyzer, respectively. The charge-discharge tests demonstrate that the electrochemical properties of the material are comparable to that of the similar material prepared from SENPS and ferric oxide or ferrous oxalate, with the initial discharge capacities of 165.1, 158.8, 152, 145.8, 133.1 and 120.2 mAhg−1 at 0.1, 0.5, 1, 2, 5 and 10C, respectively, and excellent cycling performance at 1C.

Development of Novel Electrode Using Nickel-Based Film with Bi2-XRu2O7-Z Nano-Particles on Resin for Air Secondary Battery

An air secondary battery has a gas diffusion electrode as the positive electrode, so that the battery has no need to store the active mass in the electrode and the capacity of the positive electrode is not limited. This also means that the weight of the air electrode can be reduced and is independent of the battery capacity. For this purpose, we have been developing the air electrode’s material which consists of nickel-based film co-deposited with pyrochlore-type oxide on resin by electroless nickel plating [1]. In this work, we present a novel preparation method to obtain the nickel-based film which contains Bi2-xRu2O7-z nano-particles in the outermost surface on resin and the results of the polarization measurements for oxygen reduction and evolution in KOH solutions. The precipitate obtained from the metal salt solution containing Bi(III) and Ru(III) after adding NaOH solution was calcined to obtain Bi2-xRu2O7-z nano-particles, which were added into the electroless nickel plating solution. The oxide particles on the outermost surface of the nickel-based film formed on ABS resin were obtained by electroless nickel plating with using the rotating disk electrode (RDE). The obtained sample was analyzed by SEM and EDX and used as the rotating disk electrode in a three-electrode cell to measure the polarization behaviors for oxygen reduction and evolution in 0.1 mol/L KOH solutions. The SEM and EDX results revealed that more Bi2-xRu2O7-z particles were deposited on the outermost surface of the nickel-based film formed on ABS resin than those in our previous work [1], although the oxide particles seemed to be aggregated. This surface modified resin electrode was set as the RDE in KOH solution, and cyclic voltammetry was carried out for ORR and OER, in which the measurement for oxygen reduction was performed with the solutions under O2 or N2 atmosphere and the net current was obtained by subtracting the current in N2 from that in O2. The results indicated that the oxygen reduction and evolution on the electrode were observed and the current density for both reactions was higher than that obtained in our previous work [1], because more oxide catalysts were contained in the nickel-based film and were seen on the outermost surface, resulting in the increase in surface area. The results also indicated a possibility of a light air electrode based on 3D-structured resin of which the surface is modified with a conductive nickel-based film containing a bi-functional oxide catalyst such as bismuth ruthenium oxide. More detailed results will be shown in this paper. Reference [1]Y. Tamura, M. Morimitsu, PRiME 2016, Abs#0787, Honolulu (2016).

Intensification of the Process of Utilization of Spent Electroless Nickel Plating Solutions

Intensification of the Process of Utilization of Spent Electroless Nickel Plating Solutions

LiFe1-x(Ni0.98Co0.01Mn0.01)xPO4/C (x = 0.01, 0.03, 0.05, 0.07) as cathode materials for lithium-ion batteries

LiFe1-x(Ni0.98Co0.01Mn0.01)xPO4/C (x=0.01, 0.03, 0.05, 0.07) is prepared by using spent electroless nickel plating solution as a raw material. The mechanism of the reaction is investigated by the analyses of thermogravimetric and differential scanning calorimeter (TG/DSC) and X-ray diffraction (XRD). It is found that the formation of LiFe1-x(Ni0.98Co0.01Mn0.01)xPO4/C starts at 300°C, and above 500°C, the product can be ascribed to LiFe1-x(Ni0.98Co0.01Mn0.01)xPO4/C. The structure, morphology and electrochemical properties of the samples are characterized by XRD, scanning electron microscope (SEM), electrochemical impedance spectroscopy(EIS) and charge/discharge tests. The results show that the Ni, Co and Mn multi-doping does not destroy the olivine structure of LiFePO4 and is beneficial to the uniform distribution of particles, which improves the electrochemical properties of the samples. Especially, LiFe0.97(Ni0.98Co0.01Mn0.01)0.03PO4/C exhibits the best cycling stability and rate capability among all the samples. Its initial discharge capacity is 150.6mAhg−1 with the capacity retention of 98.8% after 100 cycles at 1C. Even at 10C, it still shows a high discharge capacity of 116.5mAhg−1.

고도산화공정을 이용한 고농도 무전해 니켈도금 폐액 처리방안 연구

본 연구에서는 고농도 무전해 니켈도금 폐액을 처리하기 위한 고도산화공정 기술을 개발하였다. 추출, 농축 공정을 이용한 니켈 금속 회수보다는 폐수를 방류수 수준으로 처리할 수 있는 기술 개발을 위하여 차아인산염과 아인산염을 침전이 용이한 인산염으로 효과적으로 전환시킬 수 있는 공정 개발에 초점을 맞추었다. 광화학적 방법인 <TEX>$UV/H_2O_2$</TEX> 방식을 채택하여 COD, <TEX>$PO_4-P$</TEX> 변화 효율 및 과산화수소의 소모량을 분석함으로써 고농도 무전해 니켈도금 폐액의 고도산화처리 특성을 평가하였다. 특히, <TEX>$UV/H_2O_2/O_3$</TEX> 방식으로 오존산화법을 추가함으로써 과산화수소 사용량을 30% 가량 절감하고 처리시간을 약 6 h 단축시킬 수 있었다. We develop advanced oxidation processes for the treatment of spent electroless nickel plating solution. Apart form recovering nickel by leaching and enrichment, more emphasis is placed on rendering the waste water recyclable via oxidizing phosphite and hypophosphite into phosphate which can then be precipitated easily. <TEX>$UV/H_2O_2$</TEX> process is employed and the conversion efficiency of COD and <TEX>$PO_4-P$</TEX>, and <TEX>$H_2O_2$</TEX> consumption are analyzed. Furthermore, the <TEX>$UV/H_2O_2/O_3$</TEX> process in conjunction with <TEX>$O_3$</TEX> generator enables us to not only save the treatment time by 6 hours but also reduce <TEX>$H_2O_2$</TEX> consumption by 30%.

A novel method for nickel recovery and phosphorus removal from spent electroless nickel-plating solution

A new approach to nickel recovery from spent electroless nickel-plating (ENP) solution was investigated using ion-exchange method with brown coal. Nickel ion-exchange was influenced by the solution pH, with the optimum values of pH 9.0–10.0, and was hindered by the anion species existing in the spent solution, especially for the high concentrations of phosphorus compounds. Calcium hydroxide precipitated most of the phosphorus from spent ENP solution, with the highest phosphorus removal efficiency of 98.2%. At the same time, pH control is required to prevent the co-precipitation of nickel hydroxide. Phosphorus removal with CaCO3 and CaCl2 showed strong pH dependence. The solution pH dropped with CaCl2 addition. As a result, the formation of calcium sulphate occurred prior to that of P–Ca compounds. In contrast, CO32− anions from CaCO3 dissolution reacted with the H+ ions to neutralize the solution and decrease CaCO3 solubility at last, the phosphorus removal reached its maximum of 51%. Combined use of calcium carbonate and calcium chloride improved phosphorus removal, maximizing the phosphorus removal efficiency at 94.8%, and enabling 62% of nickel in the ENP solution to be ion-exchanged into brown coal.

Solution-processed copper-nickel nanowire anodes for organic solar cells.

This work describes a process to make anodes for organic solar cells from copper-nickel nanowires with solution-phase processing. Copper nanowire films were coated from solution onto glass and made conductive by dipping them in acetic acid. Acetic acid removes the passivating oxide from the surface of copper nanowires, thereby reducing the contact resistance between nanowires to nearly the same extent as hydrogen annealing. Films of copper nanowires were made as oxidation resistant as silver nanowires under dry and humid conditions by dipping them in an electroless nickel plating solution. Organic solar cells utilizing these completely solution-processed copper-nickel nanowire films exhibited efficiencies of 4.9%.

Selective Plating on Photopatterned Titanium Oxide Films

A method for direct formation of patterned metal film on glass without resist use or etching was investigated. Palladium, which functions as an initiation catalyst for auto-catalytic metal deposition reactions, was selectively adsorbed onto solution processed nano-porous titanium oxide films on glass from an ionic palladium solution. After selective palladium catalyst grafting onto the titanium oxide, exposure of the films to an electroless nickel, copper or gold plating solution resulted in metal deposition selectively on the titanium oxide surface. Photo-active titanium complex films were photo-patterned then pyrolyzed to give the respective pattern preserved titanium oxide films that could then be selectively plated. Correlations between titanium oxide film characteristic and palladium adsorption were analyzed by ellipsometry and inductively coupled plasma mass spectroscopy. Cross section observation of metalized glass showed penetration of palladium catalyst into and elucidated the structure of plated metal on the patterned titanium oxide films.

Separation and Recovery of Nickel from Spent Electroless Nickel-Plating Solutions with Hydrometallurgical Processes

A method of recovering nickel from spent electroless nickel-plating solutions has been investigated through the electrowinning method, following the precipitation of nickel by adding alkali and then dissolving this nickel precipitate with sulfuric acid. When sufficient caustic soda was added to a spent electroless nickel-plating solution to increase the pH to higher than 13, fine nickel particles, below 4 microns in size, along with nickel hydroxide were formed. After filtering the nickel precipitate, it was dissolved with a sulfuric acid solution of over 2 vol%, with which more than 95% of the nickel precipitate could be dissolved. For nickel recovery by electrowinning, the pH of the nickel solution required an adjustment of nearly 2.0.

Possible reasons for the appearance of metallic phase in electroless nickel plating solutions

The growth of Ni-P coatings was studied in the “stable” electroless nickel plating solution and in the “decomposed” solution containing in its bulk a sufficient amount of the metallic phase particles.

Direct Formation of Patterned Nickel Film on Polymer Using Selective Electroless Deposition and Electroless Anisotropic Growth Plating

Plating on plastic technology is widely applied in electronics-related fields. Conventionally, good adhesion strength between metal and resin has been obtained from the anchoring effect of a roughened surface. However, as the frequency increases, detrimental influences arise from the skin effect in the high-speed transmission. Therefore, the interface of the conductor and substrate should be as smooth as possible. A metal film with high adhesion strength and surface smoothness can be formed by surface modification with UV irradiation. This led us to the examination of selective deposition with the UV irradiation technique. In addition, anisotropic growth has been obtained by the addition of inhibitors to the electroless plating bath where pattern formation was possible without using resist by controlling the horizontal growth during plating. Anisotropic growth on selectively UV-irradiated regions has been obtained by the addition of inhibitors to the electroless nickel-plating solution and in this study, direct nickel-pattern formation was accomplished without using resist by controlling the plating growth in the horizontal direction in a technique combining selective deposition and anisotropic growth.

ChemInform Abstract: The Mechanism of Electroless Ni-P Deposition Studied by Electrochemical Mass Spectrometry.

Abstract An acetate electroless nickel plating solution containing H2PO2− as a reducing agent and D2O as a solvent at pH 4.5 and t0 = The isotopic composition of the evolved gas and rates of light and heavy hydrogen formation were determined to depend on electrode potential and on bot hypophosphite oxidation was found to increase in the cathodic region and to decrease in the anodic region in the presence of nickel(II). Nickel(II) was from water. The data obtained are discussed in terms of an electrochemical mechanism of electroless plating.