Deposition of alumina coatings on monocrystalline diamonds by sol–gel techniques

Machining of steel or iron-based alloys with diamond tools leads to rapid tool failure — probably due to chemical wear. The use of monocrystalline diamond tools has, up to now, been obligatory for precision machining. Coating the diamonds with a thin but hard and chemically inert alumina film may overcome the problem. Alumina coatings were deposited by sol–gel techniques. It was shown that a very thin TiN intermediate layer, deposited by reactive sputtering, results in a good adhesion of the alumina coatings to the monocrystalline diamonds. The microstructure of the coatings was characterized by field-emission scanning electron microscopy (FE-SEM) and by transmission electron microscopy (TEM). The deposited coatings showed a nanocrystalline, dense microstructure. The hardness of the coatings was investigated by ultramicrohardness measurements (UMH).     

Magnetothermal study of nanocrystalline particle formation in amorphous electroless Ni–P and Ni–Me–P alloys

The microstructure of amorphous Ni–P and Ni–Me–P materials and especially its change during the heat treatment is of great importance for their magnetic, mechanical and corrosion behavior. A new magnetic phase analysis method (magnetothermal) is presented that reveals the precipitation of nanoparticles with strong magnetic properties during phase transformation upon heat treatment. It is applied to electroless Ni–P, Ni–Cu–P and Ni–Sn–P amorphous alloys. The results acquired by this method are compared with data obtained by differential scanning calorimetry, as well as by microhardness measurements using identical heat treatment in all three cases. Due to the high sensitivity of the magnetothermal method a more detailed picture of the precipitation processes in Ni–P alloys is obtained and the new information is discussed. Magnetothermal measurements reveal several stages of precipitation of a phase with strong magnetic properties. This phase is Ni in the Ni–P alloy, and Ni(Me) solid solution in the Ni–Me–P alloys. Though Sn has a stronger effect on the Ni magnetization, Cu is more effective in preventing the appearance of high magnetization in a thermally treated Ni–Cu–P alloy. This is due to Cu incorporation in Ni particles in a quantity above four times larger than Sn.     

Effects of saccharin on the electrodeposition of Ni–Co nanocrystalline coatings

Nickel–Co nanocrystalline coatings were electrodeposited onto a carbon steel substrate with and without saccharin addition. In the absence of saccharin, current density and adsorption of hydrogen complexes and/or intermediate components were distinguished as two effective parameters causing nanocrystalline electrodeposits. In the latter case, the growth active sites can be blocked easily at low current densities. By increasing the current density, a lower degree of adsorption was associated by a significant increase in surface diffusion of adions resulting in grain growth. Although, the nucleation rate is expected to increase with current density, it seems that the Ni–Co grain size is not reduced by the nucleation rate. Adsorption of saccharin molecules and/or decomposed sulfide species occurred in the saccharin contained bath, resulting in slow surface diffusion of adions. Therefore, finer grains were obtained which produced a smooth morphology instead of the pyramidal forms obtained in the absence of saccharin.     

Electrochemical characterization of Ni–P and Ni–Co–P amorphous alloy deposits obtained by electrodeposition

Ni–P and Ni–Co–P amorphous alloy deposits were obtained by electrodeposition at 80 °C on carbon steel substrates. The influence of the electrolyte Co²⁺ concentration and of applied current density was investigated. The corrosion behaviour of amorphous and crystalline deposits was evaluated by polarization curves and electrochemical impedance spectroscopy in NaCl 0.1 M solution at room temperature. Impedances were measured for samples under total immersion (free potential against time) and for polarized samples in predefined regions of the polarization curves. It was found that the alloy deposit composition is highly affected by the composition of the electrolyte but displays no significant dependence on applied current density. The results showed that the presence of Co on Ni–P amorphous alloys improves the deposit performance in the studied corrosive medium. It was also verified that the amorphous structure provides higher corrosion resistance to both Ni–P and Ni–Co–P alloys.     

Pulse current electrodeposition and corrosion properties of Ni–W alloy coatings

Ni–W alloy coatings were prepared on a mild steel substrate by means of pulse current (PC) and compared to the coatings electrodeposited by direct current (DC). In particular the study dealt with the influence of the frequency using pulse current on the surface morphology while maintaining a constant duty cycle. A constant charge for DC and PC electrodeposition of Ni–W alloy coatings was used. The morphology of the coatings was explored by scanning electron microscopy and the composition of the coatings was analysed by X-ray powder diffraction and energy dispersive X-ray analysis. Corrosion resistance of Ni–W alloy coatings was investigated by potentiodynamic polarization in a chloride medium. The corrosion products were analysed by Raman spectroscopy. It was found that the temperature of the electrolysis affects current efficiency of the DC and PC electrodeposition. The frequency of pulse electrodeposition alters the morphology of the Ni–W alloy coatings. There was evidence of the positive influence of increased tungstate concentration in the electrolyte on corrosion resistance of the Ni–W alloy coatings.     

Preparation and characterization of Ni–P/nanodiamond coatings: Effects of surfactants

In this study, the effects of different concentrations of surfactants on the properties of the Ni–P/nanodiamond (ND) coatings were investigated. Sodium dodecyl sulfate (SDS) and cetyltrimethyl ammonium bromide (CTAB) were used as the surfactants. Morphology, microhardness and some tribological properties of the coatings were evaluated and compared. Results showed that the composite coatings modified with high concentrations of SDS had smoother surface morphologies than the ones modified with CTAB and low concentrations of SDS. Moreover, it was observed that these coatings had the highest microhardness and wear resistance as well as the lowest friction coefficient (FC) among the coatings. It was found that the effect of NDs on the microhardness of as-plated composite coatings and the ones annealed at 200 °C/3 h was not significant, but became significant when heat treated at 300 °C/1 h and 400 °C/1 h.     

Preparation and characterization of nanocrystalline Fe–Ni–Cr alloy electrodeposits on Fe substrate

Fe–Ni–Cr alloy layers were prepared by electrodeposition from trivalent chromium plating bath in chloride-sulfate based solution. The influences of bath composition and plating parameters on the alloy electrodeposition process and the properties of deposited alloy were studied. The effects of plating parameters and bath composition such as current density, bath pH, bath temperature, the concentrations of FeSO₄ · 7H₂O and CrCl₃ · 6H₂O on the contents of Fe and Cr in Fe–Ni–Cr alloy layer were investigated. Electrodeposited Fe–Ni–Cr alloy layers on Fe substrate were characterized by X-ray diffraction (XRD), Electronic Differential System (EDS) and a CHI600B electrochemistry workstation. The composition of the Fe–Ni–Cr coatings depends on bath composition and plating conditions including pH, current density, and temperature. The internal structure of the alloy is nanocrystalline, the average grain size is 87 nm, and the corrosion resistance of the alloy layers is better than that of pure nickel layers.     

Synthesis and characterization of microporous silica–alumina membranes

The development of microporous ceramic thin layers is of prime interest for sensors or gas separation membranes working at high temperature. Microporous silica membranes can be easily prepared by the sol–gel process. However the microporosity of pure silica is rapidly modified by steam at high temperature. One way to improve hydrothermal stability is to use mixed-oxide membranes. In this work, microporous silica–alumina membranes were prepared by a simple and robust sol–gel method. Tetraethoxysilane was mixed with an acidic alumina hydrosol. Urea was added for preparing the alumina hydrosol, for controlling the mixed-oxide network polycondensation and also as porogen agent. FTIR and ²⁷Al NMR spectroscopic analyses showed that for Si/Al molar ratios up to 6/1, homogeneous mixed oxides were obtained with a random distribution of Al and Si atoms in the oxide lattice based on tetrahedral units. The derived supported layers were crack-free as demonstrated by scanning electron microscopy (SEM) observations. Their microporosity was investigated using ellipsoporosimetry (EP) with films supported on flat dense substrates. He, N₂ and CO₂ permeance measurements were performed for membranes deposited on porous tubular substrates. The measured values of He/N₂ and He/CO₂ ideal selectivities are in agreement with the microporous nature of the prepared layers.     

Young's modulus and adhesion coefficient of amorphous Ni–P coatings on a metal substrate

In the present paper the Young's modulus and adhesion coefficient of amorphous Ni–P coatings obtained from aqueous solutions were determined. The measurements were carried out using a vibrating reed apparatus. In the temperature range 550–590 K, crystallization of Ni and formation of nickel phosphide Ni₃P were observed. The Young's modulus of Ni–P amorphous layers on stainless steel at room temperature was found to be about 112 GPa. The adhesion coefficient γ of the examined layers depends on the layer thickness a _f and strongly decreases for a _f > 8 μm. This dependence corresponds to the change of the relative adhesion coefficient of about 40% for 8 μm < a _f < 15 μm. It was also shown that the adhesion coefficient does not depend on the temperature, at least in the range 300–550 K.     

The effect of ceramic nanoparticles on tribological properties of alumina sol–gel thin coatings

Thin alumina coatings containing zirconia or alumina nanoparticles having diameter of ～20–30 nm were deposited by the sol–gel dip-coating process on silicon wafers. The mass content of nanoparticles in the alumina coating was fixed at 15% in relation to the theoretical mass of alumina matrix resulted from the amount of the applied precursor. Atomic force microscopy (AFM) was used to image the surface topography of as-made coatings and find out the wear level after frictional tests. Tribological tests were performed with the use of a microtribometer operating in the load range of 30–100 mN. It was found that the presence of α-alumina (corundum) or zirconia nanoparticles enhances the tribological performance of alumina layers annealed at 100 °C by decreasing the average wear rate by 20% and 63% for zirconia and corundum nanoparticles, respectively. No wear was observed for samples containing both types of nanoparticles annealed at 500 °C.     

Fabrication and characterization of ceramic coatings with alumina–silica sol-incorporated α-alumina powder coated on woven quartz fiber fabrics

The formation and properties of dense silica/α-alumina coatings derived from alumina–silica sol-incorporated coarse alumina powder (median particle size d₅₀=0.509 μm) using Al(NO₃)₃·9H₂O and tetraethyl orthosilicate as precursors have been investigated. Phase compositions and thermal evolution analysis of the coatings as well as interface microstructure between the coatings and the matrix were characterized by means of XRD, XRF, DSC-TG, TEM, SEM supplemented with EDS, and tensile strength tester. Silica/α-alumina coatings combined with quartz fiber matrix are homogeneously integrated with distinct inter-diffusion near the interface. The heat conduction mechanism of the quartz fiber matrix was influenced by the dense silica/α-alumina ceramic coatings, and the prepared coatings provide practical thermodynamic stability and desired mechanical strength for the woven quartz fiber fabrics.     

Chemical synthesis of TiO2 nanoparticles and their inclusion in Ni–P electroless coatings

The work addresses the preparation of Ni3P3TiO₂ nanocomposite coatings on mild steel substrate by the electroless technique. Nanosized TiO₂ particles were first synthesized by the precipitation method and then were codeposited (4 g/l) into the Ni3P matrix using alkaline hypophosphite reduced EL bath. The surface morphology, particle size, elemental composition and phase analysis of as-synthesized TiO₂ nanoparticles and the coatings were characterized by field emission scanning electron microscopy (FESEM), energy-dispersive analysis of X-ray (EDAX) and X-ray diffraction (XRD). Coatings with 20 µm thickness were heat treated at 400 °C for 1 h in argon atmosphere. The morphology, microhardness, wear resistance and friction coefficient characteristics (ball on disc) of electroless Ni3P3TiO₂ nanocomposite coatings were determined and compared with Ni3P coatings. The results show that as-synthesized TiO₂ nanoparticles are spherical in shape with a size of about12 nm. After heat treatment, the microhardness and wear resistance of the coatings are improved significantly. Superior microhardness and wear resistance are observed for Ni3P3TiO₂ nanocomposite coatings over Ni3P coatings.     

Thermoset–thermoplastic hybrid nanoparticles and composite coatings

Structured thermoset–thermoplastic hybrid nanoparticles and composite coatings were successfully synthesized through a novel one-pot approach. Both the polyaddition of epoxy curing and the free radical polymerization of various vinyl monomers were performed in sequence in miniemulsion droplets. Benefiting from the precise control of the compatibility between thermoset phase (epoxy monomer/amine curing agent) and vinyl phase (vinyl monomers/polymers), colloidally stable, core–shell structured thermoset–thermoplastic hybrid nanoparticles between 100 and 200 nm were obtained through chemically induced phase separation. The influence of the compositions on the colloidal stability and morphology of the final hybrid latexes and films was studied in detail. Meanwhile, the mechanical properties of thermoset–thermoplastic coatings and corresponding thermoplastic coatings were investigated. It is found that the thermoset–thermoplastic composite coatings showed significantly improved film properties in terms of hardness compared to the analogous thermoplastic coatings. Furthermore the thermoset–thermoplastic hybrid films were highly transparent even with 33 wt% of epoxy thermoset domains embedded.     

Deposition,structure and tribological behavior of silver–carbon nanocomposite coatings

Silver–carbon nanocomposite coatings were deposited by plasma-enhanced chemical vapor deposition and d.c. magnetron sputtering of a silver target. Coatings with various metal concentrations were prepared by changing of acetylene and argon gas mixture ratio (C₂H₂/Ar), and concentrations of more than 40 at.%Ag was achieved in this study. Transmission electron microscope revealed that silver metallic grains with typically 15 nm were dispersed in amorphous carbon host matrix. Size of the grains increased with decrease of the gas mixture ratio due to secondary or triangularly formed metal grains. Tribological behavior of the coatings was investigated using reciprocating tribometer with in-situ electrical contact resistance measurement. Low and stable friction coefficient was achieved in the specimen with relatively low Ag concentration. Elemental mapping results on the ball after the friction tests reveal that tribofilm was formed on the ball when low and stable friction was achieved, and the tribofilm was mainly composed of C and Ag. It can be concluded that formation of the tribofilm is necessary for achieving low and stable friction.     

Isotropic magnetization response of electrodeposited nanocrystalline Ni–W alloy nanowire arrays

Isotropic magnetization response was demonstrated in electrodeposited nanocrystalline Ni–15 % W alloy nanowire arrays, which can be applied to nanoscale magnetic field sensors. The Ni–W alloy nanowire arrays were electrochemically synthesized on a nanochannel template electrode from an aqueous electrolytic solution. X-ray and electron diffraction patterns revealed that Ni–15 % W alloy deposits were composed of ultrafine crystal grains with a supersaturated solid solution phase. The magnetization of the Ni–15 % W alloy thin films reached saturation at around 2.5 kOe in a perpendicular direction to the film plane, whereas the pure Ni thin films hardly magnetized in the perpendicular direction. On the contrary, Ni–15 % W alloy nanowire arrays were easily magnetized, and reach saturation at around 1.0 kOe, even in a perpendicular direction to the array film plane that corresponds to the long-axis direction of the alloy nanowires.     

Direct and pulse current electrodeposition of Ni–W–TiO2 nanocomposite coatings

Ni–W–TiO₂ nanocomposite coatings have been obtained on mild steel surface by direct current (DC) and pulse current (PC) electrodeposition from Watts bath containing an ammonical citrate complexing agent. The morphology of the coatings was explored by scanning electron microscopy (SEM), atomic force microscopy (AFM) and the composition of the electrodeposits was analyzed by energy dispersive X-ray analysis (EDX). Surface morphology studies revealed that Ni–W alloy surface was covered by long needle like crystals and Ni–W–TiO₂ composite coatings with smaller spherical sized grains. The coated surface contained 25.55% W and 5.55% Ti. XRD studies revealed that (111) plane was predominant in both Ni–W alloy deposits and Ni–W–TiO₂ composite coatings. The patterns of the electrodeposits confirmed only fcc frame work structure. Microhardness values increased with TiO₂ addition in the alloy. The corrosion resistance of Ni–W alloy deposit and TiO₂ incorporated coatings was evaluated by Potentiodynamic polarization studies in 3.5% NaCl solutions. Corrosion current densities decreased with TiO₂ inclusion in the alloy deposit. Electrochemical impedance studies revealed that the charge transfer resistance increased with TiO₂ inclusion in the alloy deposits while the double layer capacitance decreased. The PC composites coatings offer uniform surface, high microhardness and enhanced corrosion resistance than DC composites coatings.     

Synthesis and characterization of thermosensitive core–shell polymeric nanoparticles

Thermosensitive core–shell nanoparticles were synthesized by semicontinuous heterophase polymerization of styrene, followed by a seeded polymerization for forming a shell of poly(N-isopropyl acrylamide) (PNIPAM). Nanoparticles characterization by scanning transmission electronic microscopy showed core–shell morphology with average particle diameters around 40 nm. An inverse dependence of the particle size with temperature in the range 20–55 °C was identified by quasielastic light scattering measurements. As was expected for core–shell particles with PNIPAM as the shell, a volume phase transition near 32 °C was detected. In spite of thermosensitive properties of core–shell nanoparticles synthesized here, the volume percentage loss values were not so high, probably due to their relatively low content of PNIPAM.     

Synthesis,characterization, and infrared-emissivity study of Ni–P–CB nanocomposite coatings by electroless process

The Ni–P–CB (carbon black) nanocomposite coatings have been successfully deposited on an ABS plastic matrix via electroless plating process. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) spectrometry techniques were employed to examine the surface morphology and structure of the as-plated coating. Energy dispersive spectroscopy (EDS) was adopted to obtain the component analysis of the Ni–P–CB composite coating, and the infrared emissivity of the coating was determined by the IRE-I Infrared Emissometer. SEM and XRD results indicated that the nanoparticles were dispersed homogeneously in the Ni–P coating; the result of EDS showed that the increased rate of CB content is in correspondence with its concentration. In the case that CB concentration is lower than 4 g/L, the increase rate is sharp, whereas when the concentration is higher than 4 g/L, the increase rate is reduced significantly. Furthermore, study of infrared emissivity shows that the nanocomposite coatings possessed low emissivity value. A comparison of the infrared emissivity dependence on surface resistivity obtained from the analysis of the experimental results and those calculated using the Hagen–Rubens relation indicates that the Hagen–Rubens relation is good for modeling the infrared emissivity of the Ni–P–CB nanocomposite coatings.     

Synthesis and characterization of sol–gel derived continuous spinning alumina based fibers with silica nano-powders

Silica nano-powders were used as the Si source to substitute acidic silica sol in the SiO₂–Al₂O₃ sol mixture for benefiting the sintering of the fibers at 1250 °C. With the increase of nano-silica, grain diameter and porosity of the fibers decreased firstly and increased subsequently, a minimum value of 35.86 nm and 0.86% was exhibited at the nano-silica content of 20%. The solid content, linear growth model and homogeneity of the precursor sol were not affected by the presence of nano-silica, although the continuous spinning length became low. NMR Analysis of ²⁷Al indicated that polymerization degree of the sol was enhanced by nano-silica. The nano-particle contributed to the reduced intermolecular distance of gel, so the appropriate content existed for resulting the reduced grain size and compact structure of the fibers.     

Preparation and dielectric properties of dense and amorphous alumina film by sol–gel technology

Dense and crack-free aluminum oxide films were fabricated by sol–gel spin-coating technology. Aluminum nitrate (Al(NO₃)₃.9H₂O) was used as the precursor material. X-ray diffraction shows that the fabricated films are amorphous. X-ray photoelectron spectroscopy confirms that the thin films are alumina (Al₂O₃). Field-emission scanning electron microscopy images of the films reveal that the films are compact with a dense cross section. Dielectric measurements were carried out on samples with a metal–insulator–metal structure. The electrical characteristics of the films were affected by the thermal sintering temperature of the films. The leakage current density of the films decreases with the increase in the sintering temperature and increases with the increase in the measuring temperature. The leakage current shows a linear dependence on the voltage in the low-electric field-regime. The current density ascends to higher values due to the effect of space charges in the high-electric-field regime. The ionization energy of the top-electrode metals (Au, Pt or Ti–Au) has a strong effect on the leakage current.