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.     

Effect of milling type on the microstructural and mechanical properties of W-Ni-ZrC-Y2O3 composites

This study reports the effect of milling type on the microstructural, physical and mechanical properties of the W-Ni-ZrC-Y₂O₃ composites. Powder blends having the composition of W-1 wt% Ni-2 wt% ZrC-1 wt% Y₂O₃ were milled at room temperature for 12 h using a Spex™ 8000D Mixer/Mill or cryomilled in the presence of externally circulated liquid nitrogen for 10 min using a Spex™ 6870 Freezer/Mill or sequentially milled at room temperature and cryogenic condition. Then, powders were compacted in a hydraulic press under a uniaxial pressure of 400 MPa and green bodies were sintered at 1400 °C for 1 h under Ar/H₂ atmosphere. Phase and microstructural characterization of the milled powders and sintered samples were performed using X-ray diffractometer (XRD), TOPAS software, scanning electron microscope/energy dispersive spectrometer (SEM/EDS), X-ray fluorescence (XRF) spectrometer and particle size analyzer (PSA). Archimedes density and Vickers microhardness measurements, and sliding wear tests were also conducted on the sintered samples. The results showed that sequential milling enables the lowest average particle size (214.90 nm) and it is effective in inhibiting W grain coarsening during sintering. The cryomilled and sintered composite yielded a lower hardness value (5.80±0.23 GPa) and higher wear volume loss value (149.42 µm³) than that of the sintered sample after room temperature milling (6.66±0.39 GPa; 102.50 µm³). However, the sequentially milled and sintered sample had the highest relative density and microhardness values of 95.09% and 7.16±0.59 GPa and the lowest wear volume loss value of 66.0 µm³.     

Oxidation behavior of electrically conductive α/β SiAlON composites with segregated network of TiCN

The oxidation behavior of novel electrically conductive α/β SiAlON composites with a continuous network of 2.5–10 vol% TiCN particulates was investigated. Composites, produced by coating spray dried granules with nano TiCN particles by a simple blending method, were gas pressure sintered at 1990 °C for 1 h under 10 MPa N₂ pressure. Oxidation tests were carried out between 800 °C and 1200 °C in air for 2 and 48 h in atmosphere of dry air. Below 1000 °C, the formation of TiO₂ crystals on the surfaces of TiCN particles was observed. Before the glass transition temperature of intergranular phase (T_g < 1000 °C), it was revealed that oxidation is controlled by the diffusion of oxygen into pre-formed TiO₂ particles. Above T_g, liquid glass dissolves the intergranular phase elements such as Ti, Y, and Si at the interface between TiCN and SiAlON particles. Migration of Ti towards the (opening point of the TiCN network) surface was found to be the main reason for the formation of subsurface porosity that slows down Ti diffusion through the surface. Moreover, it was detected that at high temperatures surface porosity filled by the intergranular glassy phase. Consequently, the oxidation rate was found to be decreased due to the slower oxygen diffusion.     

Effect of the surface microstructure of SiC inner coating on the bonding strength and ablation resistance of ZrB2-SiC coating for C/C composites

The present study has been conducted in order to investigate the effect of the surface morphology of SiC inner coating on the bonding strength and ablation resistance of the sprayed ZrB₂-SiC coating for C/C composites. The microstructure of SiC inner coatings prepared by chemical vapor deposition and pack cementation at different temperatures were analyzed by X-ray diffraction, scanning electron microscopy, and 3D Confocal Laser Scanning Microscope. Tensile bonding strength and oxyacetylene ablation testing were used to characterize the bonding strength and ablation resistance of the sprayed ZrB₂-SiC coating, respectively. Results show that SiC inner coating prepared by chemical vapor deposition has a smooth surface, which is not beneficial to improve the bonding strength and ablation resistance of the sprayed ZrB₂-SiC coating. SiC inner coating prepared by pack cementation at 2000 °C has a rugged surface with the roughness of 72.15 µm, and the sprayed ZrB₂-SiC coating with it as inner layer exhibits good bonding strength and ablation resistance.     

Magneto-optical investigation and hyperfine interactions of copper substituted Fe3O4 nanoparticles

Copper substituted Fe₃O₄ nanoparticles (NPs) (Cu_xFe_1−xFe₂O₄ (0.0≤x≤1.0)) were synthesized by polyol method and the effect of Cu²⁺ substitution on structural, magnetic and optical properties of Fe₃O₄ was investigated. X-ray diffraction (XRD), Transmission electron microscopy (TEM), Scanning electron microscopy (SEM), UV–Visible spectroscopy and Vibrating sample magnetometer (VSM) were used to study the physical properties of the products. The room temperature (RT) magnetization (σ–H) curves revealed the superparamagnetic nature of the products. The extrapolated specific saturation magnetization (σ_s) decreases from 42.69 emu/g to 14.14 emu/g with increasing Cu content (x). The particle size dependent Langevin fit studies were applied to determine the magnetic particle dimensions (D_mag). The average magnetic particle diameter is about 9.89 nm. The observed magnetic moments of NPs are in range of (0.61–1.77) µ_B and rather less than 4 µ_B of bulk Fe₃O₄ and 1 µ_B of bulk CuFe₂O₄. Magnetic anisotropy was assigned as uniaxial and calculated effective anisotropy constants (K_eff) are between 10.89×10⁴ Erg/g and 26.95×10⁴ Erg/g. The average value of magnetically inactive layer for Cu_xFe_1−xFe₂O₄ NPs was calculated as 1.23 nm. The percent diffuse reflectance spectroscopy (DR%) and Kubelka–Munk theory were applied to determine the energy band gap (E_g) of NPs. The extrapolated optical E_g values from Tauc plots are between minimum 1.98 eV to 2.31 eV. From 57Fe Mössbauer spectroscopy data, the variation in line width, isomer splitting, quadrupole splitting and hyperfine magnetic field values on Cu⁺² ion substitution have been determined. Although, the Mössbauer spectra for the sample x=0.2 and 0.8 are composed of paramagnetic doublets, ferromagnetic sextets were also formed for other products.     

Comparison of the anti-coking performance of CVD TiN,TiO2 and TiC coatings for hydrocarbon fuel pyrolysis

Previous work has shown that both TiN and TiO₂ coatings can inhibit the metallic catalytic coking effectively, but both of them have their own shortage. In this work, TiC coating was prepared on the surface of SS304 tube using TiCl₄-CH₄-H₂ by CVD method. Its morphology, elemental composition, thickness and oxidation resistance were characterized by SEM, EDX, metalloscopy and TPO tests, respectively. The results show that CVD TiC coating is gray, homogeneous, and dense without cracks or holes. The TiC coating presents a cuboid particle structure with the sizes of about 1.0 µm for the cuboid crystals, and the Ti/C ratio close to 1:1, while the average thickness is about 11.62 µm. TPO results show that the TiC coating begins to react with O₂ and release CO₂ at about 810 °C. Compared with the TiN coating (The initial oxidation temperature of TiN is about 350 °C), the oxidation resistance of TiC coating is improved substantially. As a conclusion, the high oxidation resistance order is TiO₂ coating>TiC coating>TiN coating. Furthermore, the temperature programmed cracking of RP-3 Chinese jet fuel was employed to compare the anti-coking performance of TiN, TiO₂ and TiC coatings. The results show that each of TiN, TiO₂ and TiC coating has obvious anti-coking effect, and the anti-coking performance order is TiN coating=TiC coating>TiO₂ coating.     

Nanostructure,mechanical and tribological properties of reactive magnetron sputtered TiCx coatings

This study describes the correlation between microstructure, mechanical and tribological properties of TiC_x coatings (with x being in the range of 0–1.4), deposited by reactive magnetron sputtering from a Ti target in Ar/C₂H₂ mixtures at ~ 200 °C. The mechanical and tribological properties were found to strongly depend on the chemical composition and the microstructure present. Very dense structures and high hardness, combined with low wear rates and friction coefficients, were observed for coatings with chemical composition close to TiC. X-ray diffraction and X-ray photoelectron spectroscopy analysis, used to evaluate coating microstructure, composition and relative phase fraction, showed that low carbon contents in the coatings lead to sub-stoichiometric nanocrystalline TiC_x coatings being deposited, whilst higher carbon contents gave rise to dual phase nanocomposite coatings consisting of stoichiometric TiC nanocrystallites and free amorphous carbon. Optimum performance was observed for nanocomposite TiC_1.1 coatings, comprised of nanocrystalline nc-TiC (with an average grain size of ~ 15 nm) separated by 2–3 monolayers of an amorphous a-DLC matrix phase.     

Significance of hot pressing parameters and reinforcement size on sinterability and mechanical properties of ZrB2–25 vol% SiC UHTCs

The influences of hot pressing parameters and SiC particle size on the bulk density, the average ZrB₂ grain size and Vickers hardness of ZrB₂–25 vol% SiC ultrahigh temperature ceramic composites were investigated. In this paper, the Taguchi methodology (An L9 orthogonal array) was used to specify the contributions of four parameters: the hot pressing temperature, holding time, applied pressure and SiC particle size. The experimental procedure included nine tests for four parameters with three levels which were employed to optimize the process parameters. The statistical analyses recognized the hot pressing pressure and temperature as the most consequential parameters affecting the density and hardness of ZrB₂–SiC composites. The SiC particle size and holding time were specified as the most effective parameters on the average ZrB₂ grain size. The bulk density, average ZrB₂ grain size, Vickers hardness and fracture toughness of the sample, hot pressed at optimal conditions (1850 °C, 90 min, 16 MPa and 200 nm), reached about 5.36 g/cm³, 10.03 µm, ~17.1 GPa and 5.9 MPa m^1/2, respectively. The confirmation test, carried out under optimum conditions, showed that the experimental results were relatively equal to the predicted values from the Taguchi prediction model. Finally, the mechanisms of enhanced fracture toughness of the hot pressed ZrB₂–SiC ceramic composites were discussed.     

Synthesis,characterization and evaluation of titanium carbonitride surface layers with varying concentrations of carbon and nitrogen

Titanium carbonitride (TiCN) surface layers were grown by direct exposure of Ti to a gas mixture of ammonia and methane at 1050 °C. TiC_xN_1?x coatings with varying C/N ratio were synthesized by appropriately changing the content of methane and ammonia in the reactive gas mixture. The resultant layers were subjected to various characterization and evaluation techniques to study the variation of properties with respect to change in C/N ratio. A systematic change in lattice parameter and microstructure was observed as a function of the composition of active gas mixture. Friction coefficient of TiC was found to be extremely low (0.078). Reaction mechanisms for the growth of TiN and TiC were found to be entirely different. The effect of composition of the gas mixture on growth kinetics of TiCN is elucidated.     

Effect of PyC interphase thickness on mechanical and ablation properties of 3D Cf/ZrC–SiC composite

Three-dimensional (3D) C_f/ZrC–SiC composites were successfully prepared by the polymer infiltration and pyrolysis (PIP) process using polycarbosilane (PCS) and a novel ZrC precursor. The effects of PyC interphase of different thicknesses on the mechanical and ablation properties were evaluated. The results indicate that the C_f/ZrC–SiC composites without and with a thin PyC interlayer of 0.15 µm possess much poor flexural strength and fracture toughness. The flexural strength grows with the increase of PyC layer thickness from 0.3 to 1.2 µm. However, the strength starts to decrease with the further increase of the PyC coating thickness to 2.2 µm. The highest flexural strength of 272.3±29.0 MPa and fracture toughness of 10.4±0.7 MPa m^1/2 were achieved for the composites with a 1.2 µm thick PyC coating. Moreover, the use of thicker PyC layer deteriorates the ablation properties of the C_f/ZrC–SiC composites slightly and the ZrO₂ scale acts as an anti-ablation component during the testing.     

Floating zone partial re-melting of B4C infiltrated with molten Si

Green compacts of B₄C or B₄C added with 1 vol% graphite were infiltrated with molten Si and subsequently were subject of processing by floating zone partial re-melting (FZPR). In FZPR only the low temperature fusible component, in this case Si, is melted. A fully dense B₄C-based ceramic is obtained. It contains free-Si, SiC and B₄C. In the center of the FZPR ceramic without graphite addition, the amount of Si is decreased when compared to the infiltrated material. Some impurity elements such as Al, Fe, or Ti detected in the raw B₄C powder are preferentially gathered at the edges of the sample. In the sample added with graphite, formation of a high amount of SiC in the infiltrated material hinders Si shift from the center to the edges. The pulling rate and the particle size of the B₄C raw powders are also important. It is recognized that sintering of powders larger than 10–20 µm is usually difficult: our approach is demonstrated to be suitable for processing of B₄C powders with a very different particle size, from 10 to 250 µm. The FZPR ceramic had a Vickers hardness of 9–38 GPa depending on location of the indentation imprint and on the sample. A tensile strength of 114–188 MPa that is up to about 2–3 times higher than for the infiltrated material was recorded. Work indicates that the proposed processing approach offers extended control possibilities towards fabrication of new composite materials not available by traditional technologies.     

New vacancied and Gd3+-doped lead molybdato-tungstates and tungstates prepared via solid state and citrate-nitrate combustion method

New Pb_1-3x⌷_xGd_2x(MoO₄)_1-3x(WO₄)_3x (0<x≤0.1774) and Pb_1-3x⌷_xGd_2xWO₄ (0<x≤0.1154, ⌷ denotes vacancy) solid solutions were synthesized via solid state reaction route and citrate-nitrate combustion method. XRD and SEM data showed that as-prepared ceramics crystallize in the tetragonal scheelite type symmetry (space group I4₁/a) with the crystallite size varying between ~10 and ~40 µm (solid state method) or ~500 nm and 2 µm (combustion synthesis). A change in lattice constants (a and c), lattice parameter ratio c/a and progressive deformation of MoO₄/WO₄ tetrahedra with an increase of Gd content was observed. The melting point of each Gd-doped sample is lower than the melting point of adequate scheelite matrix. Ceramics under study are insulators with indirect band gap (E_g)>3 eV. EPR investigation revealed a difference among spectra obtained for varied gadolinium content, whereas synthesis method has no influence on EPR results.     

The influence of pulse plating parameters on microstructure and properties of Ni-W-Si3N4 nanocomposite coatings

Nanosized silicon nitride (Si₃N₄) particles reinforced Nickel-tungsten composite coatings were deposited on the surface of C45 steel sheet by pulse electrodeposition. The effect of duty cycle, frequency, current pattern and presence of Si₃N₄ nanoparticles on microstructure, phases and corrosion resistance and mechanical properties of the coatings were investigated. The Si₃N₄ phase was incorporated into Ni-W alloy matrix uniformly and the inclusion content of in the coating was analyzed by energy dispersive x-ray spectrometer (EDS). The structure, microhardness and surface roughness of the coatings was analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), Vickers micro-indenter and atomic force microscopy (AFM). The corrosion protection of steel by the coatings was evaluated by weight loss and electrochemical impedance spectroscopy (EIS). Corrosion rates of the coatings were determined using the Tafel polarization test. The results indicated that the duty cycle of 60%, pulse frequency of 1000 Hz, average current density of 5 A/dm⁻², and Si₃N₄ nanoparticles concentration of 30 g/L were the optimal plating conditions. The amount of Si₃N₄ particles incorporated into the coating that were produced under the optimum plating conditions was 2.1 wt%, and the microhardness was 1031 Hv as well as the crystallite size of this coating was 27 nm.     

Jet pulse electrodeposition and characterization of Ni–AlN nanocoatings in presence of ultrasound

In current study, Ni–AlN nanocoatings were successfully prepared by adopting the jet pulse electrodeposition (JPE) technique with ultrasound. The scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Vickers microhardness test, electrochemical workstation and friction wear tests were utilized to investigate the microstructure, mechanical properties, corrosion degree and wear resistance of the coatings. The results indicated that the Ni–AlN nanocoatings deposited by using ultrasound demonstrated the minimum and most compact surface structure compared to the other coatings. The thicknesses of Ni coating and Ni–AlN nanocoatings were approximately 56 µm. The average atomic percent of Al and Ni elements in the Ni–AlN nano-coating prepared by using ultrasound, were approximately 21.4 at% and 47.5 at%, respectively. The maximum kinetic energy of the jet plating solution was 916 m²/s² during JPE-deposited Ni-AlN nanocoatings including ultrasound. The average micro-hardness value of the nano-coating prepared by using ultrasound equaled 767.9 HV. The Ni–AlN nanocoatings prepared using ultrasound had the minimum E_corr and I_corr values of ? 0.167 V and 6.363 × 10^?6 mA/cm², respectively. In this case, the demonstrated corrosion resistance was the most efficient. The Ni–AlN nanocoatings prepared using ultrasound sustained the minimum friction coefficients and the average friction coefficient was approximately 0.52. In contrast, the JPE-deposited Ni coating presented the maximum friction coefficient, while the average friction coefficient was approximately 1.43.     

High-frequency induction heated sintering of High-energy ball milled TiC0.5N0.5 powders and mechanical properties of the sintered products

Commercial TiC_0.5N_0.5 powders were high-energy ball milled for various durations and consolidated without binder using the high-frequency induction heated sintering method (HFIHS). The effect of milling on the sintering behavior, crystallite size and mechanical properties of TiCN powders were evaluated. A nanostructured dense TiCN compact with a relative density of up to 98% was readily obtained within 3 min. The ball milling effectively refined the crystallite structure of TiCN powders and facilitated the subsequent densification. The sinter-onset temperature was reduced appreciably by the prior milling for 10 h from 1170 °C to 820 °C. Accordingly, the relative density of TiCN compact increased as the milling time increases. The microhardness of sintered TiCN was linearly proportional to the density while its toughness did not show any correlation with the crystalline size or density. It is clearly demonstrated that a quick densification of nano-structured TiCN bulk materials to near theoretical density could be obtained by the combination of HFIHS and the preparatory high-energy ball milling processes.     

Synthesis and characterization of Ba1−xSrxTiO3 nanopowders by citric acid gel method

Stoichiometric and monophasic Ba_1−xSr_xTiO₃ (x = 0.3) nanopowders were successfully prepared by the citric acid gel method using barium nitrate, strontium nitrate and tetra-n-butyl titanate as Ba, Sr, Ti sources and citric acid as complexing reagent. Thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), infrared (IR) spectroscopy, X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to characterize the thermal decomposition behavior, the crystallization process and the particle size and morphology of the calcined powders. The results indicated that single-phase and well-crystallized Ba_1−xSr_xTiO₃ (x = 0.3) nanopowders with particle size around 80 nm could be obtained after calcining the dried gel at 950 °C for 2 h.     

Investigation of the structural and mechanical properties of micro-/nano-sized Al2O3 and cBN composites prepared by spark plasma sintering

Alumina-cubic boron nitride (cBN) composites were prepared using the spark plasma sintering (SPS) technique. Alpha-alumina powders with particle sizes of ∼15 µm and ∼150 nm were used as the matrix while cBN particles with and without nickel coating were used as reinforcement agents. The amount of both coated and uncoated cBN reinforcements for each type of matrix was varied between 10 to 30 wt%. The powder materials were sintered at a temperature of 1400 °C under a constant uniaxial pressure of 50 MPa. We studied the effect of the size of the starting alumina powder particles, as well as the effect of the nickel coating, on the phase transformation from cBN to hBN (hexagonal boron nitride) and on the thermo-mechanical properties of the composites. In contrast to micro-sized alumina, utilization of nano-sized alumina as the starting powder was observed to have played a pivotal role in preventing the cBN-to-hBN transformation. The composites prepared using nano-sized alumina reinforced with nickel-coated 30 wt% cBN showed the highest relative density of 99% along with the highest Vickers hardness (H_v2) value of 29 GPa. Because the compositions made with micro-sized alumina underwent the phase transformation from cBN to hBN, their relative densification as well as hardness values were relatively low (20.9–22.8 GPa). However, the nickel coating on the cBN reinforcement particles hindered the cBN-to-hBN transformation in the micro-sized alumina matrix, resulting in improved hardness values of up to 24.64 GPa.     

Graphene oxide/hydroxyapatite composite coatings fabricated by electrophoretic nanotechnology for biological applications

Graphene oxide (GO) was firstly employed as nanoscale reinforcement fillers in hydroxyapatite (HA) coatings by a cathodic electrophoretic deposition process, and GO/HA coatings were fabricated on pure Ti substrate. The transmission electron microscopy observation and particle size analysis of the suspensions indicated that HA nanoparticles were uniformly decorated on GO sheets, forming a large GO/HA particle group. The addition of GO into HA coatings could reduce the surface cracks and increase the coating adhesion strength from 1.55 ± 0.39 MPa (pure HA) to 2.75 ± 0.38 MPa (2 wt.% GO/HA) and 3.3 ± 0.25 MPa (5 wt.% GO/HA), respectively. Potentiodynamic polarization and electrochemical impedance spectroscopy studies indicated that the GO/HA composite coatings exhibited higher corrosion resistance in comparison with pure HA coatings in simulated body fluid. In addition, superior (around 95% cell viability for 2 wt.% GO/HA) or comparable (80–90% cell viability for 5 wt.% GO/HA) in vitro biocompatibility were observed in comparison with HA coated and uncoated Ti substrate.     

The crystallization behaviours of reactive-plasma-sprayed TiCN coatings with different Ti/graphite powder ratios

TiCN coatings were reactive plasma sprayed with different Ti/graphite powder ratios. Their crystallization behaviours were investigated. The results showed that the TiN coating consisted of TiN and TiN_0.3O phases. With the decrease in the Ti/graphite ratios, the phases in the coatings changed from TiC_0.7N_0.3+TiC_0.3N_0.7+amorphous (Ti:graphite = (6-10):1) to TiC_0.3N_0.7 + TiC + amorphous (Ti:graphite = 4:1). The surface of the TiN coating exhibited the columnar crystals. With the decrease in the Ti/graphite ratios, the columnar crystals gradually skewed towards the surface. The cross-section crystalline morphologies of all the coatings exhibited the layer-layer columnar crystals with better bonding interfaces between the layers. The micro-hardness of the sprayed TiN coating was 1000 HV_0.1. The micro-hardness of the TiCN coatings increased with the decrease in the Ti/graphite ratios. The maximum microhardness (1315 HV_0.1) was observed at a Ti/graphite ratio of 4:1, approximately 30% higher than that of the TiN coating. The increase in the micro-hardness was correlated with the phase composition and crystalline morphologies.     

Sol-gel coated enamel for steel: 250 days of continuous high-temperature stability

Two types of thermally durable and heat-resistant enamel coatings were applied to steel alloys. Three-layer TiO₂-SiO₂ sol-gel films were grown by a dip-coating method on an enamelled metal alloy to maintain and protect their properties from undesired environmental impact.The enamel coatings withstood 6000 h at 600 °C, retaining their colour while staying hard and adhering firmly to the metal surface. A three-layer sol-gel coating improved the chemical resistance of the enamelled metal by 6% (0 h), 29% (3000 h), and 28% (6000 h) at 600 °C. Throughout the whole treatment at 600 °C, the enamel coatings maintained their microhardness and even increased it from 3.6 to 4.4 GPa.