Morphology of sol-gel produced composite films for optical oxygen sensors

The results reported concern the characterization of thin layer SiO₂-based matrices with an oxygen sensing component Ru(II)-tris(4,7-diphenyl-1,10-phenanthroline) immobilized, when a sol-gel process along with dip- and spin-coating deposition methods are used.SEM, TEM and AFM study, assisted by X-ray energy dispersive microanalysis reveals the influence of the precursors used, sol treatment and the coating conditions on the films morphology and Ru distribution in the matrices. Uniform and smooth surface is produced from tetraethoxysilane (TEOS). The presence of ormosils (methyltriethoxysilane, MtEOS and octyltriethoxysilane, OtEOS) significantly increases the surface roughness exhibited as dots on the SEM image. Their surface concentration and size depend on the number of immersions and withdrawal speed at the dip coating. Spin deposition leads to rather different morphology of the films, based on TEOS/OtEOS. Following commonly used sol preparation procedure (with 1.25-2.5 g Ru-complex/dm³ sol) microcrystallization of the complex occurs with formation of randomly distributed crystals 100-400 nm in size. The ultrasound treatment of the sol by means of ultrasound disintegrator leads to homogeneous distribution of the complex without observable crystallization and significant improvement of the film sensing properties (increase of Stern-Volmer constant and better linearity of the Stern-Volmer plots both in gaseous and aqueous media).     

The influence of preparative parameters on the adhesion of alumina washcoats deposited on metallic supports

Well-adhered alumina washcoats on FeCrAl metallic supports were prepared using boehmite sols and alumina slurries. The microstructure and the surface performance of the washcoat/support were investigated by SEM, XRD, and ultrasonic vibration. The effects of the main preparative parameters on the coating adherence were studied. The optimal coating conditions are presented as follows: pre-oxidation of the metallic supports was performed at 900 °C for 10 h, the sol layer loadings were 2.0-6.6 wt.%, and the slurry layer loadings were less than 25.3 wt.%. The sol layer drying was performed at 30 °C for 1 h and that for the slurry layer the drying was performed at 120 °C for 2 h, and the coating calcining was performed at 900 °C for 2 h. The SEM photographs of coated samples show that alumina washcoats were well deposited on the metallic supports.     

Preparation and magnetic properties of hexagonal barium ferrite films using BaM nanoparticles

Barium ferrite (BaFe₁₂O₁₉—BaM) thick films have been synthesized using a spinning coating sol-gel process. The coating sol was formed from BaM powders dispersed in the BaM raw sol. XRD, SEM, EDX, vibrating sample magnetometer (VSM), and ac susceptometer, were employed to evaluate the structure, composition and magnetic properties of BaM thick films. The results indicated that a uniform and crack-free coating of BaM with ∼15 μm thickness can be produced with good deal of consistency. The perpendicular and in-plane coercivity had the same value of 5 kOe. The high coercivity is attributed to the magnetocrystalline anisotropy and grain size of the sintered BaM layer. Effective magnetic susceptibility in all measurements have linear variation with increasing dc field.     

Microstructure evolution of sol-gel HA films

Bioactive hydroxyapatite films were fabricated on titanium alloy by a sol-gel method. The samples were firstly precoated at a low drying temperature for many times and then calcined at a relative high temperature. The phase constitution, microstructure and composition analysis were studied by X-ray diffraction (XRD), electronic probe microanalysis (EPMA), and the microstructure evolution was explained by some schematic illustrations. When the samples were precoated only once, hexagonal structure is always observed. After the samples were precoated many times, the hexagonal structure can be preserved only when the drying temperature is 500 °C or above. When the drying temperature is below 500 °C, the dried layer easily redissolved into the next coated sol because of the existence of some water-soluble ions such as NO₃⁻, consequently the hexagonal structure disappeared and a coarse surface with some small pores formed. High calcining temperature can accelerate the atomic diffusion which may integrate the adjacent grains, but excessively high temperature such as 900 °C or above would make the whole film be incinerated completely.     

The preparation of c-axis epitaxial Bi-2212 films on STO(1 0 0) by sol-gel method

Bi₂Sr₂Ca₁Cu₂O_8+δ (Bi-2212) films were grown on (1 0 0) oriented SrTiO₃ (STO) substrate using sol-gel spin-coating method. The effects of heat treatment conditions and coating times on the phase formation and surface morphology were investigated using thermal analysis, optical microscope, X-ray diffraction, and scanning electronic microscopy. Mixed phases were formed from 820 to 840 °C, and Bi-2212 single phase was obtained at 830 °C for 3 h. c-axis epitaxial films with smooth surfaces were obtained by drying at 600 °C and coating for 5 times.     

Magnetic properties of hexagonal strontium ferrite thick film synthesized by sol–gel processing using SrM nanoparticles

Strontium ferrite SrFe₁₂O₁₉ (SrM) thick films have been synthesized using a spinning coating sol–gel process. The coating sol was formed from SrFe₁₂O₁₉ powders dispersed in the strontium ferrite raw sol. XRD, TEM, SEM, vibrating sample magnetometer (VSM) and ac susceptometer were employed to evaluate the structure, composition and magnetic properties of SrFe₁₂O₁₉ thick films. The results indicated that a uniform and crack-free coating of Strontium ferrite with ∼15 μm thickness can be produced with a good deal of consistency. The magnetization hysteresis loops were almost the same for magnetic fields both applied in parallel and perpendicular.     

Density-modulated alumina-based nanometre films prepared by sol–gel technique

Alumina-based nanometre films produced by a sol–gel method are investigated by wide-angle X-ray scattering and X-ray reflectometry. Every dipping cycle of the sol–gel route results in formation of an X-ray amorphous film exhibiting a density gradient. Both withdrawal speed and drying temperature used as tuning parameters during coating preparation influence the thickness and density of the sol–gel film. An increase of the withdrawal speed results in a thicker film of a lower mean density. An opposite effect is observed with an increase of the drying temperature. The appearance of multilayer Bragg reflections in the reflectivity curves of successive stacked films is discussed in detail. The thermal stability of the density-modulated aluminium oxide-based nanometre multilayers is investigated in a temperature range of 300–1000 °C. Possible applications as X-ray optical elements are outlined. PACS  61.10.Kw; 68.60.Dv; 81.20.Fw     

Optimization of plasma parameters for high rate deposition of titanium nitride films as protective coating on bell-metal by reactive sputtering in cylindrical magnetron device

Nano-structured titanium nitride (TiN) thin film coating is deposited by reactive sputtering in cylindrical magnetron device in argon and nitrogen gas mixtures at low temperature. This method of deposition using DC cylindrical magnetron configuration provides high uniform yield of film coating over large substrate area of different shapes desirous for various technological applications. The influence of nitrogen gas on the properties of TiN thin film as suitable surface protective coating on bell-metal has been studied. Structural morphological study of the deposited thin film carried out by employing X-ray diffraction exhibits a strong (2 0 0) lattice texture corresponding to TiN in single phase. The surface morphology of the film coating is studied using scanning electron microscope and atomic force microscope techniques. The optimized condition for the deposition of good quality TiN film coating is found to be at Ar:N₂ gas partial pressure ratio of 1:1. This coating of TiN serves a dual purpose of providing an anti-corrosive and hard protective layer over the bell-metal surface which is used for various commercial applications. The TiN film's radiant golden colour at proper deposition condition makes it a very suitable candidate for decorative applications.     

Ceramic membrane by tape casting and sol-gel coating for microfiltration and ultrafiltration application

Alumina membrane filters in the form of thin (0.3-0.8 mm) discs of 25-30 mm diameter suitable for microfiltration application have been fabricated by tape-casting technique. Further using this microfiltration membrane as substrate, boehmite sol coating was applied on it and ultrafiltration membrane with very small thickness was formed. The pore size of the microfiltration membrane could be varied in the range of 0.1-0.7 μm through optimisation of experimental parameter. In addition, each membrane shows a very narrow pore size distribution. The most important factor, which determines the pore size of the membrane, is the initial particle size and its distribution of the ceramic powder. The top thin ultrafiltration, boehmite layer was prepared by sol-gel method, with a thickness of 0.5 μm. Particle size of the sol was approximately 30-40 nm. The structure and formation of the layer was analysed through TEM. At 550 °C formation of the top layer was completed. The pore size of the ultrafiltration membrane measured from TEM micrograph was almost 10 nm. Results of microbial (Escherichia coli—smallest-sized water-borne bacteria) test confirm the possibility of separation through this membrane     

Influence of TaCl5 partial pressure on texture structure of TaC coating deposited by chemical vapor deposition

TaC was deposited on graphite substrate with different TaCl₅ partial pressure at 800 °C and 1200 °C by chemical vapor deposition. Microstructures and texture structures of the prepared coatings were researched with X-ray diffraction and scanning electronic microscopy. When the coating deposition process is controlled by surface reaction kinetics (800 °C), TaCl₅ partial pressure had little influence on the microstructure and texture structure of the coating. When the coating formation process is controlled by diffusion kinetics (1200 °C), the microstructure, texture structure of the prepared TaC grains vary greatly with TaCl₅ partial pressure. In the diffusion controlled process, the increasing of TaCl₅ partial pressure will result in the changing of gas supersaturation, and then the occurrence of secondary nucleation, which is the main reason for the changing of coating morphology and texture structure. With the help of competitive growth in (1 0 0) and (1 1 1) directions, the formation mechanism of the different texture coatings are discussed in detail. In addition, a diffusion model of deposition species around step-edge-corner was also proposed to explain the growth mechanism of the texture coatings.     

Micro-thermal analysis of polyester coatings

The application and suitability of micro-thermal analysis to detect changes in the chemical and physical properties of coating due to ageing and especially photo-degradation is demonstrated using a model polyester coating based on neopentyl glycol isophthalic acid. The changes in chemical structure like chain scission and cross-linking are manifested by a shift of the LTA detectable T_g and by a change of the slope of the part of the LTA graph responsible for the penetration of the hot sensor into the material after passing the glass transition temperature. As such LTA is a valuable tool to have a quick look into coating surfaces and especially their ageing. The photo-degradation of polyester in air leads to the formation of a cross-linked network at a surface layer of about 3-4 μm coupled with an increase in hardness and of the glass transition temperature by ∼90 K, the effect is less drastic for a photo-degradation in a nitrogen environment. Moreover, the presence of a non-equilibrium dense surface layer with a higher T_g formed during the drying of the coating formulation and the film solidification can be shown.     

Effect of Fe/Sr mole ratios on the formation and magnetic properties of SrFe12O19 microtubules prepared by sol-gel method

The sol was obtained by sol-gel method. Then, the sol was dripped onto the absorbent cotton template. The gel was obtained after the evaporation of water. Strontium ferrite microtubules were prepared after carrying out calcination process at different temperatures. The phase, morphology and particle diameter and the magnetic properties of samples were studied by X-ray diffraction (XRD), scanning electron microscopy (SEM) and vibrating sample magnetometer (VSM), respectively. The effects of Fe³⁺/Sr²⁺ mole ratio and calcination temperature on the crystal structure, morphology and magnetic properties of ferrite microtubules were studied. The external diameters of obtained SrFe₁₂O₁₉ microtubules were found to range between 8 and 13 μm; the wall thicknesses ranged between 1 and 2 μm. When the Fe³⁺/Sr²⁺ mole ratio and the calcination temperature were 11.5 and 850 °C, respectively, the coercivity, saturation magnetization and remanent magnetization for the samples were 7115.1 Oe, 70.1 and 42.4 emu/g, respectively. The mechanism of the formation and variation in magnetic properties of the microtubules were explained.     

In situ formation of low friction ceramic coatings on carbon steel by plasma electrolytic oxidation in two types of electrolytes

In situ formation of ceramic coatings on Q235 carbon steel was achieved by plasma electrolytic oxidation (PEO) in carbonate electrolyte and silicate electrolyte, respectively. The surface and cross-section morphology, phase and elemental composition of PEO coatings were examined by means of scanning electron microscopy (SEM), X-ray diffraction (XRD) and energy-dispersive X-ray spectroscopy (EDS). The bond strength of the coating was determined using a direct pull-off test. The hardness as well as tribological properties of the ceramic coating was primarily studied. The results indicated that the coating obtained in carbonate electrolyte was Fe₃O₄, while the coating achieved from silicate electrolyte was proved to be amorphous. Both kinds of coatings showed coarse and porous surface. The Fe₃O₄ coatings obtained in carbonate electrolyte showed a high bonding strength to the substrate up to 20 ± 2 MPa and the value was 15 ± 2 MPa for the amorphous coatings obtained in carbonate electrolyte. The micro hardness of the amorphous coating and the Fe₃O₄ coating was 1001 Hv and 1413 Hv, respectively, which was more than two and three times as that of the Q235 alloy substrate (415 Hv). The friction coefficient exhibited by amorphous coating and Fe₃O₄ coating was 0.13 and 0.11, respectively, both lower than the uncoated Q235 substrate which ranged from 0.17 to 0.35.     

Influence of reactive gas and temperature on structural properties of magnetron sputtered CrSiN coatings

CrSiN coatings were deposited on stainless steel (Grade: SA304) and silicon Si(1 0 0) substrates, with varying argon-nitrogen gas proportions and deposition temperature, using reactive magnetron sputtering technique in the present work. The influence of sputtering (Ar) and reactive gas proportions (N₂) and temperature on the structural properties of the CrSiN coating was investigated. A small amount of silicon content (3.67 at.% Si) plays a crucial role in addition to the nitrogen content for the formation of different phases in the CrSiN coatings as observed in the present work. For example, the coating with comparatively low nitrogen content, 40% N₂, during deposition, formed a crystalline structure consisting of nano-crystalline CrN which is separated by an amorphous SiN phase, as evident from X-ray diffraction (XRD) and transmission electron microscopy (TEM), respectively. The formation of CrN(1 1 1) and Cr₂N(1 1 1) phases has occurred at 30% N₂ with 3.67% Si content, which transformed in to CrN(1 1 1) and CrN(2 0 0) with increase in N₂ content but with same Si content. The surface topography and morphology of the coatings were analyzed by atomic force microscopy (AFM) and field emission scanning electron microscopy (FESEM), respectively. A less columnar growth is observed in CrSiN coatings deposited at low argon content, Ar:N₂ (20:80), and with 3.67 at.% Si in the coatings. However, it becomes dense with increase in nitrogen content and temperature. The XRD analysis showed that the intensity of a dominating peak (1 1 1) is decreasing from (80:20) to (60:40) argon:nitrogen environment. With a further increase of nitrogen content, from (60:40), in the sputtering gas mixture, to (40:60) argon-nitrogen, there is a sudden increase in (1 1 1) peak and above (40:60), the peak reduction rate is very slow than the previous one. The (1 1 1) and (2 0 0) peak intensity variations are very limited due to high nitrogen content, above 50%, and considerable amount of Si atoms, 3.67 at.%, present in the CrN coatings.     

Structural, optical, and electrical properties of p-type NiO films and composite TiO2/NiO electrodes for solid-state dye-sensitized solar cells

p-Type nickel oxide thin films were prepared by sol-gel method, and their structural, optical and electrical properties were investigated. The Ni(OH)₂ sol was formed from nickel (II) acetate tetrahydrate, Ni(CH₃COO)₂·4H₂O, in a mixture of alcohol solution and poly(ethylene glycol), and deposited on an ITO substrate by spin coating followed by different heat treatments in air (50-800 °C). The formation and composition of NiO thin film was justified by EDX analysis. It is found that the thickness of the NiO film calcined at 450 °C for 1 h is about 120 nm with average particle size of 22 nm, and high UV transparency (∼75%) in the visible region is also observed. However, the transmittance is negligible for thin films calcined at 800 °C and below 200 °C due to larger particle size and the amorphous characteristics, respectively. Moreover, the composite electrode comprising n-type TiO₂ and p-type NiO is fabricated. The current-voltage (I-V) characteristics of the composite TiO₂/NiO electrode demonstrate significant p-type behavior by the shape of the rectifying curve in dark. The effect of calcination temperature on the rectification behavior is also discussed.     

High specific surface area TEOS-based aerogels with large pore volume prepared at an ambient pressure

The experimental results on the synthesis of tetraethoxysilane (TEOS)-based silica aerogel with high specific surface area and large pore volume, via ambient pressure drying (APD) route, are reported. The silica aerogels were prepared by the acid-base sol-gel polymerization of TEOS precursor followed by the drying of the alcogels at an ambient pressure. The solvent present in the alcogel (i.e. ethanol) was replaced by a non-polar solvent such as hexane prior to the surface modification step. In order to minimize the drying shrinkage, the surface of the gels was modified using trimethylchlorosilane (TMCS) before the APD. The FTIR spectra of the surface modified aerogels showed Si-CH₃ peaks at 2965 and 850 cm⁻¹. The effect of the base catalyst (NH₄OH) addition to the sol, at different time intervals (T), on the physical and textural properties of the resulting aerogels has been investigated. It has been observed that the surface area and the cumulative pore volume of the aerogels enhanced considerably from 819 to 1108 m² g⁻¹ and 2.65 to 4.7 cm³ g⁻¹, respectively with an increase in the T value from 6 to 48 h. Silica aerogels with very low bulk density (0.06 g cm⁻³), extremely high specific surface area (1108 m² g⁻¹) and large cumulative pore volume (4.7 cm³ g⁻¹) could be synthesized by drying the alcogels at the ambient pressure. The aerogels were mesoporous solids with the average pore size ranging from 12 to 17 nm. The results have been discussed by taking into consideration the hydrolysis and condensation reactions during the sol-gel polymerization of the TEOS precursor.     

Process and performance of hot dip zinc coatings containing ZnO and Ni-P under layers as barrier protection

A new coating system of under layer for hot dip zinc coating was explored as an effective coating for steel especially for application in relatively high aggressive environments. The influence of different barrier layers formed prior to hot dip galvanization was investigated to optimize high performance protective galvanic coatings. The deposition of ZnO and Ni-P inner layers and characteristics of hotdip zinc coatings were explored in this study. The coating morphology was characterized by scanning electron microscope (SEM) analysis. The hot dip zinc coatings containing under layer showed substantial improvement in their properties such as good adhesion, and high hardness. In addition, a decrease in the thickness of the coating layer and an enhancement of the corrosion resistance were found. Open circuit potential (OCP) of different galvanized layers in different corrosive media viz. 5% NaCl and 0.5 M H₂SO₄ solutions at 25 ± 1 °C was measured as a function of time. A nobler OCP was exhibited for samples treated with ZnO and Ni than sample of pure Zn; this indicates a dissolution process followed by passivation due to the surface oxide formation. The high negative OCP can be attributed to the better alloying reaction between Zn and Fe and to the sacrificial nature of the top pure zinc layer.     

Microstructure and wear behaviors of laser clad NiCr/Cr3C2-WS2 high temperature self-lubricating wear-resistant composite coating

The high temperature self-lubricating wear-resistant NiCr/Cr₃C₂-30%WS₂ coating and wear-resistant NiCr/Cr₃C₂ coating were fabricated on 0Cr18Ni9 austenitic stainless steel by laser cladding. Phase constitutions and microstructures were investigated, and the tribological properties were evaluated using a ball-on-disc wear tester under dry sliding condition at room-temperature (17 °C), 300 °C and 600 °C, respectively. Results indicated that the laser clad NiCr/Cr₃C₂ coating consisted of Cr₇C₃ primary phase and γ-(Fe,Ni)/Cr₇C₃ eutectic colony, while the coating added with WS₂ was mainly composed of Cr₇C₃ and (Cr,W)C carbides, with the lubricating WS₂ and CrS sulfides as the minor phases. The wear tests showed that the friction coefficients of two coatings both decrease with the increasing temperature, while the both wear rates increase. The friction coefficient of laser clad NiCr/Cr₃C₂-30%WS₂ is lower than the coating without WS₂ whatever at room-temperature, 300 °C, 600 °C, but its wear rate is only lower at 300 °C. It is considered that the laser clad NiCr/Cr₃C₂-30%WS₂ composite coating has good combination of anti-wear and friction-reducing capabilities at room-temperature up to 300 °C.     

The effect of heat treatment on the performance of the Ni/(Zr-Sm oxide) catalysts for carbon dioxide methanation

The active catalysts for methane formation from the gas mixture of CO₂ + 4H₂ with almost 100% methane selectivity were prepared by reduction of the oxide mixture of NiO and ZrO₂ prepared by calcination of aqueous ZrO₂ sol with Sm(NO₃)₃ and Ni(NO₃)₂. The 50 at%Ni-50 at%(Zr-Sm oxide) catalyst consisting of 50 at%Ni-50 at%(Zr + Sm) with Zr/Sm = 5 calcined at 650 or 800 °C showed the highest activity for methanation. The active catalysts were Ni supported on tetragonal ZrO₂, and the activity for methanation increased by an increase in inclusion of Sm³⁺ ions substituting Zr⁴⁺ ions in the tetragonal ZrO₂ lattice as a result of an increase in calcination temperature. However, the increase in calcination temperature decreased BET surface area, metal dispersion and hydrogen uptake due to grain growth. Thus, the optimum calcination temperature existed.     

The characteristics of chromized 1020 steel with electrical discharge machining and Ni electroplating pretreatments

A uniform and continuous chromized coating on AISI 1020 steel is produced by low-temperature pack chromization (LTPC) with electrical discharge machining and Ni electroplating pretreatments. The anticorrosive performance of the chromized steels is investigated in a 0.5 M H₂SO₄ solution at room temperature. The testing results indicate that the chromized specimen with electrical discharge machining and Ni electroplating pretreatments exhibits the lowest corrosion current density, 2.16 × 10⁻⁸ A cm⁻², among the tested specimens. The corrosion resistance of all tested specimens are in the order of bare 1020 < 1020-Cr(700-2) < 1020-Ni-Cr(700-2) < 1020-EDM-Ni-Cr(700-2). Moreover, the 1020-Ni-Cr(700-2) specimen have the best conductivity as a result of the less amount of oxides in the superficial coating.