Effect of suspension stability on bonding strength and electrochemical behavior of electrophoretically deposited HA–YSZ nanostructured composite coatings

In the present study, HA–YSZ nanostructured composites were deposited on Ti–6Al–4 V substrates by electrophoretic deposition of suspensions containing 0, 10, 20 and 40 wt% YSZ. The stability of each suspension was determined by applying response surface methodology, DLVO theory and zeta potential measurement for different YSZ contents and dispersant concentrations. The maximum zeta potential and electromobility of suspended particles was obtained for the suspension with 20 wt% YSZ. The electrophoretic deposition of HA–YSZ nanostructured composites was carried out at a constant voltage of 20 V for 120 s. The deposition kinetics was studied based on a mass-charge correlating approach under ranges of voltage (20–60 V), time (30–300 s) and wt% YSZ (0–40). The as–deposited and sintered HA–YSZ coatings were characterized by SEM, XRD, DSC–TG and FT–IR analyses. The micro-scratch behavior of coated samples indicated the highest critical contact pressures of crack initiation, P_c1 = 4.50 GPa, crack delamination, P_c2 = 5.14 GPa and fracture toughness, K_IC = 0.622 MPa m^1/2 for HA-20 wt% YSZ sample. The results of potentiodynamic polarization measurements showed that the implementation of 20 wt% YSZ could efficiently decrease the corrosion current density and corrosion rate of coated samples, while corrosion potential and linear polarization resistance were increased.     

Corrosion stability of polyester coatings on steel pretreated with different iron–phosphate coatings

The influence of steel surface pretreatment with different types of iron–phosphate coatings on the corrosion stability and adhesion characteristics of polyester coatings on steel was investigated. The phosphate coating was chemically deposited either from the simple novel plating bath, or with the addition of NaNO₂, as an accelerator in the plating bath. The morphology of phosphate coatings was investigated using atomic force microscopy (AFM). The corrosion stability of polyester coatings on steel pretreated by iron–phosphate coatings was investigated by electrochemical impedance spectroscopy (EIS) in 3% NaCl solution, while “dry” and “wet” adhesion were measured by a direct pull-off standardized procedure. It was shown that greater values of pore resistance, R_p, and smaller values of coating capacitance of polyester coating, C_c, on steel pretreated with iron–phosphate coating were obtained, as compared to polyester coating on steel phosphated with accelerator, and on the bare steel. The surface roughness of phosphate coating deposited on steel from the bath without accelerator is favorable in forming stronger bonds with polyester coating. Namely, the dry and wet adhesion measurements are in accordance with EIS measurements in 3% NaCl solution, i.e. lower adhesion values were obtained for polyester coating on steel phosphated with accelerator and on the bare steel, while the iron–phosphate pretreatment from the novel bath enhanced the adhesion of polyester coating on steel.     

Synthesis and hydrothermal stability of U doped zirconolite–sphene composite materials

Two series of U doped zirconolite–sphene composite materials were prepared by solid state reaction method: CaZr_(1?m)U_mTi₂O₇?(1?m) Ca_(1?x)U_xAl_2xTi_(1?2x)SiO₅ (m?=?7x) and Ca_(1?n)U_6nZr_(1?5n)Al_2nTi_(2?2n)O₇?(1?5n) Ca_(1?y)U_yAl_2yTi_(1?2y)SiO₅ (n?=?5y/6). The effects of U content on the phase structure of the composite materials were mainly investigated. The results show that the optimal synthesis temperature of the composite material is ～1230°C. In comparison with the incorporation of U in the Zr site of zirconolite, U incorporation in the Ca site of zirconolite using Al as charge compensating ions was not very efficient. Hydrothermal stability of the U doped zirconolite–sphene composite material was examined by modified product consistency test method at 90°C in deionised water (pH 7). The normalised U leach rate is fairly constant in a low value below 10^?5 g m^?2 day^?1 after 28 days.     

Microwave- or conventional–hydrothermal synthesis of Co-based materials for electrochemical energy storage

Crystalline Co₃O₄ and Co(OH)₂ were synthesized using Co(NO₃)₂ as a precursor by conventional–hydrothermal and microwave–hydrothermal routes, respectively. The Co₃O₄ phase showed cubic morphologies while the β-Co(OH)₂ phase exhibited plate-like shapes. The electrochemical performances of Co₃O₄ and Co(OH)₂ phases were evaluated as electrode materials for lithium-ion battery anodes, cathodes and supercapacitors. Both Co₃O₄ and Co(OH)₂ phases showed pseudocapacitive performances in Li₂SO₄ and KOH electrolytes. The Co₃O₄ and Co(OH)₂ phases were found to be more promising as anodes than as cathodes in lithium-ion batteries. The Co(OH)₂ electrodes showed higher specific capacitances than those of Co₃O₄ materials.     

Atmospheric plasma sprayed silica–hydroxyapatite coatings on magnesium alloy substrates

Silica-doped hydroxyapatite as a bioactive coating presents some advantages compared to the pure one, such as: increased in vivo bioactivity and early bone ingrowth. The aim of this study is to obtain a deposition of silica-doped hydroxyapatite on magnesium alloy plates by atmospheric plasma spraying. The coating material was prepared by a precipitation method with sodium silicate addition as a source of silica, and various methods were used to characterize it. Spraying conditions including powder feed rate and current values were varied. The coating properties were defined by determining the purity, phase composition, morphology and corrosion protection of the HAP–Si deposits on the magnesium plates.     

Deposition of zinc–zinc phosphate composite coatings on steel by cathodic electrochemical treatment

The present work aims at the development of an energy-efficient and eco-friendly approach for the deposition of zinc phosphate coatings on steel. The study describes the possibility of preparing zinc–zinc phosphate composite coatings by cathodic electrochemical treatment using dilute phosphoric acid as an electrolyte and zinc as an anode. The methodology enables the preparation of coatings with different proportions of zinc and zinc phosphate by suitably varying the applied current density, pH, and treatment time. Adhesion of the coating on mild steel and adhesion of paint film on the phosphate coating were found to be good. The surface morphology of the coatings exhibited platelet-type features and small white crystals (agglomerated at some places) which represented zinc and zinc phosphate, respectively. An increase in current density (from 20 to 50 mA/cm²) increased the size of the zinc crystals, and coatings prepared at 40 and 50 mA/cm² resembled that of electrodeposited zinc. Since the proportions of zinc and zinc phosphate could be varied with applied current density, pH, and treatment time, it would be possible to use this methodology to prepare coatings that would offer different degrees of corrosion protection.     

Effect of pH and carbon nanotube content on the corrosion behavior of electrophoretically deposited chitosan–hydroxyapatite–carbon nanotube composite coatings

In the first stage, chitosan (CH)–hydroxyapatite (HA)-multiwalled carbon nanotube (MWCNT) composite coatings were synthesized by electrophoretic deposition technique (EPD) on 316L stainless steel substrates at different levels of pH and characterized by X-ray diffraction (XRD), Raman spectroscopy, FTIR and field emission scanning electron microscopy (FESEM). A smooth distribution of HA and MWCNT particles in a chitosan matrix with strong interfacial bonding was obtained. In the next stage, effects of pH and MWCNT content of the suspension on the corrosion behavior and deposition mechanism were studied. Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) curves revealed that increasing pH level of the suspension increases the corrosion protection properties of the deposited composite coating in simulated body fluid (SBF). Furthermore, Nyquist plots showed that increasing MWCNT content of the suspension resulted in higher amounts of R_p, but because of the capillary properties of MWCNTs and degradability of the chitosan matrix, corrosion protection level of the coatings containing HA–CH–MWCNT was lower than those of coatings containing solely HA–CH. Amperometric curves in different pH levels of the suspension revealed that the system is diffusion controlled at elevated pH values.     

Mechanosynthesis of hydroxyapatite–ferrite composite nanopowder

In the present work, an investigation of the mechanosynthesis of calcium hydroxyapatite (HA, Ca₁₀(PO₄)₆(OH)₂) from a mixture of calcium oxide (СаО) and ammonium hydrophosphate ((NH₄)₂HPO₄) and mechanotreatment of HA in a planetary mill with the use of steel drums and milling body has been performed. The obtained results have shown that the mechanosynthesis of crystalline nanodisperse HA proceeds through the stage of formation of an amorphous material. The temperature treatment of HA powders at 1000 °C has enabled us to establish the influence of the treatment time on the phase composition of the powders and establish the following sequence of phase transformations: Ca₁₀(PO₄)₆(OH)₂→β-Ca₃(PO₄)₂ (t_milling~2 h), β-Ca₃(PO₄)₂→α-Ca₃(PO₄)₂ (t_milling~5 h), β-,α-Ca₃(PO₄)₂→Ca₁₀(PO₄)₆(OH)₂ (t_milling~7 h).The mechanosynthesis and mechanotreatment of hydroxyapatite in steel drums with steel balls is accompanied by the contamination of hydroxyapatite by their wear debris (iron + manganese). A large part of oxidized iron forms superparamagnetic inclusions distributed in HA powder. A small part of Fe³⁺ and Mn²⁺ ions from the steel wear debris enters into the hydroxyapatite lattice, substituting Ca²⁺ ions. As a result, a nanocomposite powder consisting of hydroxyapatite, alloyed by Fe³⁺ and Mn²⁺ ions and ferrite inclusions forms. The phase composition of HA powders, the degree of their alloying by Fe³⁺ and Mn²⁺ ions, and the content of ferrite inclusions can be controlled by changing the time of mechanotreatment.     

Thermal stability of nanostructured 13 wt% Al2O3–8 wt% Y2O3–ZrO2 thermal barrier coatings

Nanostructured 13 wt% Al₂O₃–8 wt% Y₂O₃–ZrO₂ (13AlYSZ) coatings were developed by atmospheric plasma spraying (APS). The phase structure and the morphology of the 13AlYSZ coatings were characterized using X-ray diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscope (TEM). It was found that the as-sprayed coatings mainly consisted of tetragonal zirconia, with the Al element solid solution in ZrO₂. Heat treatment at 1100 °C increased the average grain size of the ZrO₂ phase from 61 to 120 nm and decreased the porosity from 23.8 to 18%. The addition of the nano-Al₂O₃ can effectively inhibit the grain growth of the zirconia phase. The mechanism on inhibiting the grain growth of nanostructured 8 wt% Y₂O₃–ZrO₂ thermal barrier coatings has been discussed in detail.     

Phase stability of plasma sprayed YAG–YSZ composite beads/coatings at high temperature

Beads and coatings of YAG–YSZ composite ceramic were prepared by plasma spray. YAG was applied as an additive in the hope of improving the phase stability and oxygen impermeability of YSZ. To achieve this aim, some basic research about crystallization behavior and chemical compatibility of the composite were carried out. Plasma sprayed YAG tended to form amorphous state. With the different content of YAG in the composite, crystallization of YAG and YSZ was delayed by each other to different extent due to the barrier effect of heavy atoms. The relative low melting point of YAG led to dense coatings without obvious splat structure and further distinctive vertical cracks during crystallization within the coatings. The cracks became less severe when YAG content was lower. With the addition of YAG, the development of monoclinic ZrO₂ was suppressed while Y-rich phases were promoted at higher temperature.     

Anticorrosive behavior study by localized electrochemical techniques of sol–gel coatings loaded with smart nanocontainers

In the present work, sodium phosphomolybdate, an environmentally friendly corrosion inhibitor with good anticorrosive behavior when applied on steel substrates, has been loaded and encapsulated in mesoporous silica nanoparticles without and with a hollow core in order to produce different smart nanocontainers. These nanocontainers have been designed to allow controlled release of the inhibitor in response to an external stimulus, thereby achieving more efficient and more economical use of the active substance. Corrosion activity leads to local changes in pH, and this work considers such changes as a signal of great interest. The nanocontainers respond to a pH of 10 or higher by increasing the release rate of the encapsulated active material. The smart nanocontainers have been incorporated into hybrid organic–inorganic sol–gel coatings and applied on carbon steel substrates. Mechanical defects have been made in the organic coating, reaching through to the metallic substrate, in order to study anticorrosive behavior in the affected area. A characterization study has been carried out at the defects and in their surroundings by means of two different localized electrochemical techniques: Scanning Kelvin Probe and Localized Electrochemical Impedance Spectroscopy. The results have shown significant improvement in the anticorrosive behavior of sol–gel coatings when formulated with smart nanocontainers loaded with sodium phosphomolybdate compared to a reference sol–gel coating.     

Thermal stability of (0.15–0.35 wt%) rhodium on low-loaded ceria-supported rhodium catalysts

The thermal stability of rhodium on ceric oxides submitted to high-temperature reduction (773–1173 K) and aging in air at 1173 K was studied by high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy and benzene hydrogenation. Catalysts were prepared by anionic exchange of rhodium chloro complexes on both high (144 m² g^-1) and low specific surface area ceria (6 m² g^-1). In reducing conditions, both types of catalysts stabilized 5 nm metal rhodium particles. Calcination in air at 1173 K pointed out the interest of rhodium exchanged over a low surface precalcined ceria. In that case, all the metal remained at the surface of CeO₂ after calcination whereas 50% of the initial supported metal was buried into sintered ceria for the catalyst prepared from the high-surface CeO₂. This revised version was published online in July 2006 with corrections to the Cover Date.     

Development of polyorganosilazane–silicone marine coatings

The objective of the present work is the development and characterization of marine coatings based on polyorganosilazanes (PSZ). Two types of coatings containing silicone oils and biocidal compounds were investigated as anticorrosive and antifouling coatings. The flexibility, hydrophobicity and adhesion properties of the PSZ-based coatings on aluminum substrates were studied. Static immersions in natural seawater were investigated to evaluate the antifouling performances of these coatings. The corrosion properties were studied by salt spray tests. Results demonstrated that coatings based on silicone oils appeared to be the most efficient coatings in terms of antifouling and anticorrosive properties. Ten-month antifouling efficiency was revealed for biocide-free polydimethylsiloxane-based PSZ coatings in natural seawater static immersion. The adjunction of dicopper oxide as biocidal pigments was shown to decrease the stability in cans of the corresponding paints and therefore decreasing the flexibility of coatings. In addition, this pigment affected badly the anticorrosive properties of the coatings together with a short antifouling efficiency time. Thus, the silicone oil-based PSZ displayed remarkable advantages in addition to their dual antifouling and anticorrosive properties which are the absence of biocidal compounds released in marine environment and the absence of volatile solvent.     

Electrodeposition of Zn–SiC nanocomposite coatings

Zn–SiC composite coatings were obtained on mild steel substrate by electrodeposition technique with high-current efficiency. A slightly acidic chloride bath, containing SiC nanoparticles and gelatine as additive, was used. The electrodeposition was carried out under galvanostatic control with pulsed direct current; the effect of experimental parameters (temperature, average current density and particles concentration) on composition, morphology and structure of the deposit was studied. Coatings were characterized by means of scanning electron microscopy, energy dispersive X-ray analysis, X-ray diffractometry and Vickers microhardness measurements. Zn–SiC electrodeposits with the best characteristics were obtained by performing electrodepositions at 45 °C, with 20 g L^?1 SiC in the bath and with average current density in the range 100–150 mA cm^?2. Under these experimental conditions, homogeneous and compact coatings, with low-grain size and SiC content ranging from 1.7 to 2.1 wt%, were found to be electrodeposited. Microhardness measurements showed for these deposits an increase of about 50 % with respect to those without nanoparticles obtained in the same experimental conditions.     

Properties of electrodeposited silver–cobalt coatings

Silver–cobalt coatings were elecrodeposited from cyanide–pyrophosphate electrolytes with and without additives (diammonium oxalate monohydrate and 2-Butyne-1,4-diol). The deposition rate, the alloy composition, as well as some physicomechanical (internal stress, microhardness, plug-in forces, abrasion resistance) and electrical properties (contact resistance, magnetoresistance) of the obtained coatings, depending upon the applied current density or the cobalt content, respectively, were investigated. The increase in current density led to the increase in the Co content of the coatings and to a decrease in the grain size of both silver and cobalt phases. Granular structural type of deposits with a magnetoresistance of about 4% ratio was shown. The tensile stress observed in pure Ag deposits increased in the presence of Co and with an increase in its content in the alloy. The increase in the microhardness, abrasion resistance and electrical resistance of the Ag–Co coatings depended almost linearly on the Co content. The performed high speed electroplating showed significant increase in the deposition rate and smoothness of the coatings.     

Mechanical properties and thermal stability of ambient-cured thick polysiloxane coatings prepared by a sol–gel process of organoalkoxysilanes

Ambient-curable polysiloxane coatings were prepared by pre-hydrolysis/condensation of phenyltrimethoxysilane (PTMS) and dimethyldimethoxysilane (DMDMS) in the presence of ammonia solution and subsequently mixing with aminopropyltriethoxysilane (APS). The mechanical properties of coatings were thoroughly examined at both macro- and micro-level and the thermal stability of coatings was characterized by thermogravimetic analysis, both of which were correlated with coating composition and the hydrolysis/condensation degree of polysiloxane oligomer. It was found that pro-hydrolysis step is essential for fabrication of thick crack-free coatings (18–35 μm). Higher DMDMS molar ratio, more APS dosage and lower hydrolysis/condensation degree of polysiloxane oligomer favor enhancing the hardness. Excellent impact resistance (50 cm kg) of coatings was obtained at 5% and 10% APS dosage, despite of the type and structure of polysiloxane oligomer. Whatever, the best scratch resistance of coatings was attained using the polysiloxane oligomer, prepared at PTMS-to-DMDMS molar ratio of 2:8 and water-to-precursor molar ratio of 1:1, and 5% APS dosage. The polysiloxane coatings exhibit high thermal stability, however, which strongly depends on the coating composition.     

Effect of the polyester chemical structure on the stability of polyester–melamine coatings when exposed to accelerated weathering

The effect of the polyester chemical structure on the degradation of polyester/melamine coatings was studied. Four different polyesters were synthesized using different diacid monomers: (i) isophthalic acid (IPA) and mixtures of hexahydrophthalic anhydride (HHPA) with (ii) terephthalic acid (TA), (iii) phthalic anhydride (PAN) and (iv) 1,4 cyclohexanedicarboxylic acid (1,4-CHDA). Varnishes were prepared using melamine resin and submitted to accelerated degradation cycles. The process was monitored in terms of photooxidation index (POI), based on FTIR analysis, and in terms of changes in films’ hardness, level of gloss and surface morphology. The monomers which contributed the most to polymer degradation were the couple HHPA and 1,4-CHDA. The most important factor to degradation was the high number of hydrogen atoms attached to tertiary and secondary carbons in the polymer structure, due to their high sensitivity to abstraction, which favors the photooxidation reactions. The monomer IPA presented the lowest POI and the highest gloss retention.     

Thermal stability of MoSi2-TiB2-CrB2 composites at 900–1400°C

Slip casting procedure with subsequent firing in air is used to synthesize composites (100 ? x)MoSi₂?x MB₂, where M = Ti, Cr, (Ti, Cr) and x = 10, 20, and 30 mol % at 900–1400°C. The MoSi₂-CrB₂ and MoSi₂-(Ti, Cr)B₂ composites containing 20 and 30 mol % of borides are found to possess the highest protective properties. The optimum temperature range for sintering is 1100–1400°C.     

Selective photoepoxidation of propylene over hydroxyapatite–silica composites

Two types of hydroxyapatite (HAP)–silica composites were prepared from aqueous solutions of Ca(NO₃)₂ and (NH₄)₂HPO₄ in the presence of SiO₂ in a buffer (pH 7.5) and an alkaline condition. Photooxidation of propylene with oxygen was carried out over the composites at 303 K. The major product was propylene oxide which exceeded 80% among C3 oxygenated products. The conversion increased with an increase in HAP content, but the selectivity of propylene oxide decreased. This was caused by that propylene oxide was strongly adsorbed on HAP followed by consecutive photooxidation. The thin-layered HAP in the HAP–SiO₂ composite is more effective for photoepoxidation of propylene than the bulk HAP.