E. Valova

Electroless deposited Ni-Re-P, Ni-W-P and Ni-Re-W-P alloys

Coatings of electroless Ni–W–P, Ni–Re–P and Ni–W–Re–P alloys were plated in alkaline citrate baths containing amino alcohols, but not free ammonia ions. The reference Ni–P alloy was used as an intermediate layer in the sandwich: Ni–Me–P/Ni–P/substrate. An extremely homogeneous thickness distribution of all alloy components was found by applying scanning Auger electron spectroscopy (SAES(. The inclusion of refractory metals at the expense of nickel and without substantial change in phosphorus content was established. A non-oxidized state of the codeposited Re and W in Ni–W–P, Ni–Re–P and Ni–W–Re–P alloys was determined by means of X-ray photoelectron spectroscopy examination, as well as by SAES profiles, revealing the absence of oxygen throughout the coatings. All alloy films are amorphous and paramagnetic.

Incorporation of Zinc in Electroless Deposited Nickel-Phosphorus Alloys I. A Comparative Study of Ni-P and Ni-Zn-P Coatings Deposition, Structure, and Composition

The impact of zinc incorporation on the chemical composition of electroless Ni-Zn-P coatings and the elements distribution through the thickness was studied. Ni-Zn-P alloy was deposited on various metal substrates (Al, Fe, Au) with and without electroless Ni-P underlayer. The employed bath formulation and the substrates with a Ni-P intermediate layer allowed direct comparison between the binary Ni-P and Ni-Zn-P alloy coatings. A reduction in phosphorus content and deposition rate due to zinc inclusion was observed. Some physical characteristics (morphology, structure, magnetic properties) of Ni-Zn-P coatings were assessed in parallel with those of Ni-P. The localization of Zn mainly at the grain boundaries together with P was proved by transmission electron microscopy combined with energy dispersive X-ray analysis system, The particular role of the steel substrate is discussed as a source of iron, subsequently included in electroless Ni-P and Ni-Zn-P coatings.

Crystalline and Amorphous Electroless Co-W-P Coatings

Electroless deposition onto polycrystalline (Cu, Au) and amorphous (Ni-P) substrates was applied to prepare Co-W-P coatings of two types: crystalline (hexagonal close packed, hcp), with low phosphorus content about 2.4-2.7 atom %, and amorphous, with P concentration within 7.4-8.3 atom %. Tungsten content varied typically in the narrow range of 2.9-3.7 atom % in both types of coatings. Atomic force microscopy revealed substantial difference in their morphology. Polycrystalline Co-W-P coatings consist of grains of stacked plates (lamellas), confirmed by transmission electron microscopy also. Amorphous films are smoother and uniform. The crystalline structure promotes the surface oxidation to a higher extent than the amorphous structure, as shown by the X-ray photoelectron spectroscopy (XPS). Auger electron spectroscopy depth profiles display oxidation, smoothly diminishing toward the inside of the crystalline films. Amorphous coatings are oxidized only at the surface. Inside both types of coatings, however, all alloy components are in nonoxidized form, according to XPS data. Differential scanning calorimetry (DSC) studies of amorphous coatings revealed three transformation peaks, ascribed to a crystallization of hypoeutectic alloy and a transition of Co-based hcp phase into face-centered cubic. Magnetic properties variation with temperature is in agreement with DSC results.

Morphology, Structure and Photoelectrocatalytic Activity of TiO2 / WO3 Coatings Obtained by Pulsed Electrodeposition onto Stainless Steel

A simple two-step pulsed electrodeposition/ electrosynthesis technique is employed for the preparation of a bicomponent photocatalyst, TiO2/WO3, onto metal substrates. TiO2 can be activated under UV light illumination and is well known for its water detoxification capabilities. The coupling between this wide band-gap semiconductor with a suitable narrow band-gap one, WO3, is used for effective separation of the photogenerated charge carriers. Besides the reduced surface recombinetion due to directional charge transfer, the combination with the visible light (Vis)-activated WO3 entails an extended photoactivity towards Vis wavelengths. In addition, the photocatalytic decomposition of organic water pollutants at TiO2/WO3 layers supported on conductive substrates can be further enhanced by applying a positive bias in an appropriate electrochemical cell. Drawing the electrons away from the surface through the external circuit reduces surface recombination rates of photogenerated electron-hole pairs. Recently, bilayer TiO2/WO3 photocatalysts were prepared onto stainless steel substrates by continuous cathodic electrodeposition of WO3 followed by TiO2 electrosynthesis [1, 2]. Their photoelectrocatalytic efficiency is very promising and superior to both their single-component counterparts. Also, there have been indications of the considerable impact of composition, morphology and structure on photoelectrocatalytic activity [3]. This implicates the necessity for appropriate monitoring and design of these factors. By applying a consecutive pulsed electrodeposition/electrosynthesis method for WO3 and TiO2, a favorable modification of the electronic properties at the TiO2-WO3 junction and an increased catalyst surface area has been sought. The morphology, structure and related composition distribution of the pulsed-deposited films onto metal substrates have been characterized by high resolution Field Emission SEM (FE SEM) (Fig. 1), SEMEDS and Raman spectroscopy. The photocurrents at photoanodes with various loadings, structure and morphology have been evaluated in the presence and absence of the model pollutants Na-oxalate and 4chlorophenol under UV and Vis light illumination. Similar to the case of continuous electrodeposition [3], a trend was observed of the impact and the need for optimization of the TiO2/WO3 loading ratio, surface morphology, structure and composition distribution to design high-performance photocatalysts. The performance for bulk photo-decomposition of 4-chlorophenol has been evaluated at photoanodes WO3 and TiO2/WO3 prepared by continuous electrodeposition and compared with that at pulsed-plated TiO2/WO3. Long-term photoelectrolysis at constant potential was applied, using spectrophotometry to monitor the variation of the pollutant concentration.

Pt-Ni carbon-supported catalysts for methanol oxidation prepared by Ni electroless deposition and its galvanic replacement by Pt

Pt–Ni particles supported on Vulcan XC72R carbon powder have been prepared by a combination of crystalline Ni electroless deposition and its subsequent partial galvanic replacement by Pt upon treatment of the Ni/C precursor by a solution of chloroplatinate ions. The Pt-to-Ni atomic ratio of the prepared catalyst has been confirmed by EDS analysis to be ca. 1.5:1. No shift of Pt XPS peaks has been observed, indicating no significant modification of its electronic properties, whereas the small shift of the corresponding X-ray diffraction (XRD) peaks indicates the formation of a Pt-rich alloy. No Ni XRD peaks have been observed in the XRD pattern, suggesting the existence of very small pockets of Ni in the core of the particles. The surface electrochemistry of electrodes prepared from the catalyst material suggests the existence of a Pt shell. A moderate increase in intrinsic catalytic activity towards methanol oxidation in acid has been observed with respect to a commercial Pt catalyst, but significant mass specific activity has been recorded as a result of Pt preferential confinement to the outer layers of the catalyst nanoparticles.

Comparison of the Structure and Chemical Composition of Crystalline and Amorphous Electroless Ni-W-P Coatings

Electroless deposition was applied to prepare Ni-W-P coatings of two types: crystalline, with low P and W, and amorphous with high W content. Their morphology was studied by atomic force microscopy. Polycrystalline Ni-W-P alloys consist of grains of stacked plates (lamellas), as it was revealed by transmission electron microscopy. The coatings exhibit a (100) texture. X-ray diffraction and electron diffraction analysis demonstrated the unit cell parameter of the crystalline phase in Ni-W-P is practically equal to that of pure Ni. This implies W and P are localized along the grain boundaries. The Warren/Averbach method was applied to determine microstrain and size of coherent scattering domains. The crystalline structure promotes the surface oxidation of Ni-W-P to higher extent in comparison with the amorphous structure. X-ray photoelectron spectroscopy analysis demonstrated the presence of oxygen and carbon in the bulk of the crystalline Ni-W-P coatings in larger quantities than in the amorphous. In the crystalline coatings in addition to oxygen and carbon, scanning Auger electron spectroscopy showed the presence of nitrogen. It is supposed that all these elements come from ligand residues adsorbed at the grain boundaries during coating growth. Nanoindentation tests indicated that amorphous Ni-W-P samples display more uniform surface mechanical properties at the nanometer scale than the crystalline ones.

Carbon-supported Pt(Cu) electrocatalysts for methanol oxidation prepared by Cu electroless deposition and its galvanic replacement by Pt

Bimetallic Pt–Cu carbon-supported catalysts (Pt(Cu)/C) were prepared by electroless deposition of Cu on a high surface area carbon powder support, followed by its partial exchange for Pt; the latter was achieved by a galvanic replacement process involving treatment of the Cu/C precursor with a chloroplatinate solution. X-ray diffraction characterization of the Pt(Cu)/C material showed the formation of Pt-rich Pt–Cu alloys. X-ray photoelectron spectroscopy revealed that the outer layers are mainly composed of Pt and residual Cu oxides, while metallic Cu is recessed into the core of the particles. Repetitive cyclic voltammetry in deaerated acid solutions in the potential range between hydrogen and oxygen evolution resulted in steady-state characteristics similar to those of pure Pt, indicating the removal of residual Cu compounds from the surface (due to electrochemical treatment) and the formation of a compact Pt outer shell. The electrocatalytic activity of the thus prepared Pt(Cu)/C material toward methanol oxidation was compared to that of a commercial Pt/C catalyst as well as of similar Pt(Cu)/C catalysts formed by simple Cu chemical reduction. The Pt(Cu)/C catalyst prepared using Cu electroless plating showed more pronounced intrinsic catalytic activity toward methanol oxidation than its counterparts and a similar mass activity when compared to the commercial catalyst. The observed trends were interpreted by interplay between mere surface area effects and modification of Pt electrocatalytic performance in the presence of Cu, both with respect to methanol oxidation and poisonous CO removal.

Investigation of the primary crystallization of Ni-17 at. % P alloy by ASAXS

Primary crystallization of Ni(P) particles in hypoeutectic Ni-P amorphous alloy obtained by electroless deposition has been investigated with ASAXS. The particle size distribution, the size dependence of the particle composition and the amorphous matrix composition were found simultaneously. The size distribution consists of a peak at particle radius of ∼1 nm and a tail spanning from ∼2 to 15 nm. The composition of the particles of the peak changes from ∼14 to ∼2 at.% P as their radius grows from 0.7 to about 3 nm. The particles in the tail of the size distribution (2-15 nm) have nearly constant P content in the range of 0-2 at.%. The matrix composition tends to the eutectic one at the end of the primary crystallization process.

Interface with Substrates of High‐Phosphorus Electroless NiP and NiCuP Deposited from Nonammonia Alkaline Solutions

Electroless NiP and NiCuP alloys with high phosphorus content (11 to 13 weight percent) are plated from nonammonia alkaline baths onto aluminum and iron substrates. Energy-dispersive spectroscopy analysis is used to examine the chemical composition of the coatings. Scanning Auger electron spectroscopy is applied to study elemental profiles and the interface with the substrates. The zincate layer transformation at the interface with the aluminum substrate is investigated at two bath temperatures. Nickel, phosphorus, and copper concentration is plotted against the coating thickness to examine the chemical homogeneity and to obtain information about the mechanism of electroless ternary alloy formation on both types of substrates.

Electroless Deposition of Ni–Sn–P and Ni–Sn–Cu–P Coatings

The surface morphology and the elemental distribution of low- and high-tin Ni-Sn-P coatings have been investigated. It is shown that in low-tin Ni-Sn-P coatings there is a uniform distribution of the alloy components, both on the surface and through the thickness. The main mechanism of electroless alloy deposition in this case is based on the well-known hypophosphite oxidation as a source of electrons for the metals (Ni and Sn) and phosphorus reduction. In high-tin coatings, a nonuniform distribution of the components is observed, both on the surface and through the coating thickness. Three-dimensional areas enriched in tin and impoverished in Ni and especially in P have been observed using scanning electron microscopy with energy-dispersive X-ray spectroscopy, scanning Auger electron spectroscopy, and Auger electron spectroscopy. The disproportionation reaction of Sn(II) is suggested as being predominant over the hypophosphite oxidation in these three-dimensional areas and is responsible for their formation. The introduction of copper in the solution is giving an additional opportunity to reveal the role of the oxidation of Sn(II) into Sn(IV) as a source of electrons.