Influence of deposition temperature on the properties of hydroxyapatite obtained by electrochemical assisted deposition

Surface functionalization of pure titanium (cp-Ti) with hydroxyapatite (HAp) was successfully achieved by means of electrochemical deposition (ED) in a solution containing calcium nitrate and ammonium dihydrogen phosphate. The aim of this study is to evaluate the influence of the deposition temperature on the elemental and phase composition, chemical bonds, morphology, and in vitro electrochemical behaviour in biological simulated media (simulated body fluid - SBF). The roughness and wettability of the developed coatings are also investigated. By increasing the deposition temperature from 50 °C to 75 °C, the HAp coatings present a well-crystalized structure, denser and a nobler behaviour in terms of electrochemical behaviour in SBF at 37 °C. Also, by increasing the deposition temperature from 50 °C to 75 °C, the contact angle has decreased from 76.1° to 27.4°, exhibiting a highly hydrophilic surface. Taking into consideration all the obtained data, electrodeposition of HAp at 75 °C was found preferable when compared to 50 °C. The characteristics of the HAp coatings can be easily adjusted by optimizing the electrochemical deposition parameters and/or controlling specific features like pH, temperature, or ionic concentration of electrolyte, etc.     

Post-hydrothermal treatment of hydrothermal electrodeposited CaHPO4 on C/C composites in sodium silicate-containing solution at various temperatures

Direct deposition of hydroxyapatite (HA) coatings on carbon/carbon(C/C) composites through hydrothermal electrochemical deposition (HED) were limited by the poor bonding strength. To overcome this problem，in this work, CaHPO₄ (monetite) coating was firstly deposited on C/C using HED, and then converted into HA coating in a sodium silicate–containing solution by post-hydrothermal treatment. Effects of post-treatment temperatures on the chemical composition, structure, and bonding strength of the coatings were investigated. The results showed that obtained monetite showed a compact microstructure, and could react with the solution to produce a well-crystallized HA as well as amorphous silicate which contained some calcium and sodium ions. All the coatings were composed of rod-like crystals. The diameter of these crystals increased when the post-hydrothermal temperature was changed from 110?℃ to 140?℃, and then decreased at 155?℃. The Si contents and the adhesive strength of the HA coatings showed a similar temperature dependence to the crystal size of the HA. 140?℃ is determined to the optimal treatment temperature, at which the HA coating reached the highest critical load of 24.02?N, corresponding to the shear strength of 82.83?MPa. The bioactivity of the HA coating on C/C increased with the increasing post-treatment temperature.     

Phase, microstructure, and oxidation resistance of yttrium silicates coatings prepared by a hydrothermal electrophoretic deposition process for C/C composites

Oxidation-resistant yttrium silicates coatings for SiC precoated carbon/carbon composites were prepared by a novel hydrothermal electrophoretic deposition process. Sonochemical-synthesized yttrium silicates nanocrystallites, isopropanol, and iodine were respectively used as source materials, solvent, and charging agent during the deposition. Phase compositions, surface and cross-section microstructures of the as-prepared multilayer coatings were characterized by an X-ray diffractometer (XRD) and a scanning electron microscopy (SEM). The influence of deposition temperatures on the phase, microstructure, and oxidation resistance of the multilayer coated C/C composites was particularly investigated. Results show that the as-prepared outer coatings are composed of yttrium silicates crystallites with a main phase of Y₂Si₂O₇ and Y₂SiO₅. The thickness and density of the yttrium silicates coatings are improved with the increase of deposition temperature. Compared with SiC coating prepared by pack cementation, the multilayer coatings prepared by pack cementation with a later hydrothermal electrophoretic deposition process exhibit better antioxidation properties. The as-prepared multilayer coatings can effectively protect C/C composites from oxidation at 1773 K in air for 35 h with a weight loss of 0.32 × 10⁻³ g/cm².     

Synthesis and characterization of calcium phosphate coatings on Nitinol

In recent years, coating of metal orthopedic implants with bioactive layers to promote fixation with bones has become increasingly common. Calcium phosphate coatings on the Nitinol surface were formed using two low-temperature methods: sol–gel and electrochemically assisted deposition. The coatings formed were characterized using: X-ray diffraction analysis, field emission scanning electron microscopy, energy dispersive X-ray spectroscopy, and Fourier transform infrared spectroscopy. Cyclic voltammetry studies were carried out in the deposition solution to determine parameters for electrodeposition and to understand electrochemistry of deposition. The barrier properties and corrosion resistance of coatings were tested in the physiological Hanks’ solution using electrochemical impedance spectroscopy. The sol–gel deposited coating consisted of two phases, hydroxyapatite and tricalcium phosphate (TCP). Apatite coatings containing TCP offered the opportunity to create a grafting material with high bioactivity and bioresorbility. The electrodeposited coating consisted of Ca-deficient HAp which resembles to biological HAp.     

Structure and mechanical properties of hydroxyapatite coatings produced on titanium using plasma spraying with induction preheating

Coatings of hydroxyapatite (HAp) were prepared by plasma spraying with induction preheating of titanium substrate from 200 to 1000 °C. The combination of conventional plasma spraying and induction preheating ensured high mechanical properties of HAp coatings. The coatings produced in the temperature range 400–600 °C were characterized by homogeneous nanostructure of splats with an average grain size of 12–31 nm. According to the results of nanoindentation HAp coatings with high hardness 0.9–1.2 GPa and elastic modulus 7–16 GPa were formed on the titanium.     

Hydrothermal nucleation of hydroxyapatite on titanium surface

Titanium plates were submitted to nucleation and growth of hydroxyapatite (HAp) under hydrothermal conditions. A group of these plates were submitted to nucleation without any previous treatment and another group was treated with NaOH 1 M at 130°C inside an autoclave followed by heat-treatment at 600°C. The nucleation were performed by soaking all these titanium pieces, in a simulated body fluid (SBF) solution, containing calcium, phosphate and other ions, in order to promote the nucleation and growth of hydroxyapatite under hydrothermal conditions on the titanium surface. The results show that hydrothermal nucleation and growth of HAp occurs even on the non-treated titanium surface at 150°C. However, a better uniformity of the hydroxyapatite layer was observed on the pre-treated titanium surface, at 80°C, with the renewal of the SBF solution.     

Deposition temperature effect on sputtered hydroxyapatite coatings prepared on AZ31B alloy substrate

The corrosion of Mg alloys is a provocative topic and it is still a challenge to find a solution for the improvement of their degradation rate into solution found in human body (Simulated Body Fluid, SBF). The aim of the present paper is to coat AZ31B alloy by hydroxyapatite (HAp) as a possible solution in order to change its degradation behaviour for medical implants. Since the Mg alloy is sensible to temperature while the HAp properties depend on the deposition temperature, in this study, the effect of deposition temperature on the properties of the AZ31Balloy was evaluated. The HAp coatings were prepared using the RF magnetron sputtering technique, ranging the temperature from the room one to 400 °C. It was found that the grain size of the investigated Mg alloy increased more than 100% when the deposition temperature was increased. By increasing the temperature, the hardness level was reduced of about 15%. All HAp coatings revealed corrosion behaviour much better than the uncoated AZ31B alloy; in particular, the coating deposited at 200 °C exhibited the best corrosion behavior. Moreover, the best protection to the corrosive attack of SBF was found for the HAp coating deposited at 200 °C (97.3%), which was also characterized by the lowest porosity. To conclude, HAp coatings can be used to improve the properties of AZ31B alloys, but just up to 200 °C; beyond this temperature, the mechanical and the anticorrosion properties are lost.     

Deposition of hydroxyapatite coatings by axial plasma spraying: Influence of feedstock characteristics on coating microstructure,phase content and mechanical properties

Axial plasma spray is one of the thermal spray techniques to deposit multifunctional advanced coatings. The present work explores the use of this process to deposit thin, continuous, and adherent Ca₅ (PO₄)₃OH (hydroxyapatite, HAp) coatings and characterize its microstructure, phases, hardness and adhesion strength. Three different suspension-deposited HAp coatings were investigated and compared with powder-deposited HAp coating on a Ti6Al4V substrate. The effect of mean solute particle size and solid-loading in the suspension has been explored on the evolution of microstructure, phase content and mechanical properties of axial suspension plasma sprayed (ASPS) coatings. Phase-characterization has shown retention of hydroxyapatite phase and coating crystallinity in the deposited coatings, whereas the adhesion strength of the HAp coating decreased from ～40 MPa to ～13 MPa when bioglass was added to the feedstock material. The lower solid load content and lower mean solute particle size in the suspension were found to be beneficial in achieving porous, rougher, and well-adhering coatings. This work concludes that ASPS can potentially deposit thin HAp coatings (< 50 μm) with high adhesion strength.     

Dense Nanostructured Hydroxyapatite Coating on Titanium by Aerosol Deposition

In order to improve biocompatibility of Ti metal substrates, 1-μm-thick nanostructured hydroxyapatite (HAp) coatings were deposited on the substrates through aerosol deposition, which sprays HAp powder with an average particle size of 3.2 μm at room temperature in vacuum. The original HAp particles were fractured into nanoscale fragments to form highly dense coating during the deposition process. Density of the HAp coating was 98.5% theoretical density (TD). Transmission electron microscopy observation revealed that the as-deposited coating consisted of HAp crystallites with average grain size of 16.2 nm and amorphous phase. Tensile adhesion strength between the coating and the substrate was 30.5±1.2 MPa. Annealing up to 500°C in air increased crystallinity and grain size in the coating without any delamination or crack according to X-ray diffraction analysis and electron microscopy. MTS assay and alkaline phosphatase activity measurements with MC3T3-E1 preosteoblast cell revealed that the biocompatibility was greatly improved by postdeposition heat treatment at 400°C in air due to well-crystallized HAp with average grain size of 29.3 nm. However, further heat treatment at 500°C deteriorated biocompatibility due to rapid growth of HAp grains to average size of 99 nm. Cross section of the coating on a commercially available Ti dental implant revealed full coverage of the surface with HAp.     

Titania/hydroxyapatite bi-layer coating on Ti metal by electrophoretic deposition: Characterization and corrosion studies

Titania–hydroxyapatite (HAp) bi-layer coating on Ti metal substrate with improved adhesion strength is fabricated by a simple two step processes: electrodeposition of Ti sol and electrophoretic deposition of HAp powder, followed by heat treatment at 800 °C. At optimized process parameters, the bi-layer developed consists of dense, thin and crystalline titania interlayer with porous, thick and crystalline HAp top layer. The heat treatment of bi-layer coating allows elemental intermixing at the interface of TiO₂ and HAp, as determined by energy dispersive X-ray spectroscopy (EDX) and Raman spectra analysis. Compared to monolithic HAp coating, the TiO₂/HAp bi-layer coating shows significant enhancement in the adhesion strength (48 MPa) as well as corrosion resistance without compromising its biocompatibility. The steep increase in adhesion strength is believed to be due to mechanical interlocking and diffusion bonding at the interface. Presence of dense titania interlayer in the bi-layer coating reduces the corrosion current in Ringer's solution to a negligible value (～100 nA).     

Deposition and ablation resistance of HfC-based coatings prepared on SiC-coated C/C composites by supersonic atmospheric plasma spraying

In order to improve the ablation properties of C/C composites, HfC-based coatings with different mass ratios of SiC were deposited on the surface of SiC-coated carbon/carbon composites by supersonic atmospheric plasma spraying. The morphologies and microstructures of the HfC-based coatings were characterised. The ablation resistance test was carried out by oxyacetylene torch. The results show that the as-prepared coatings are multiphase coatings consisting of HfC, HfO₂, SiC and SiO₂. The structure of different coatings is dense. After ablation for 60?s, the ablation centre region of coating is smooth without obvious microcrack and pinhole, and no interlaminar crack can be observed at the cross-section. An Hf–Si–O compound oxide layer is generated on the surface of coating, which is beneficial for protecting the C/C composites from being ablated. Meanwhile, the further generated HfSiO₄ can play a pinning effect, which can prevent crack extension.     

Hydroxyapatite formation by solvothermal treatment of α-tricalcium phosphate with water-ethanol solution

We investigated hydroxyapatite (HAp) formation from alpha-tricalcium phosphate (α-TCP) under solvothermal conditions using water-ethanol solution. The rate of HAp formation decreased with increasing ethanol fraction in the solution. Needle-like HAp was formed with a small amount of beta-tricalcium phosphate after solvothermal treatment for 3 h in solutions with water/ethanol volume ratios of 5/15 and 10/10. In the solution with water/ethanol volume ratio of 5/15, needle-like HAp formed with a small amount of dicalcium phosphate anhydrous (DCPA) at 12 h, and the amount of DCPA increased with increasing treatment period. The aspect ratio of the HAp crystals that formed increased with increasing ethanol fraction in the solution. The fraction of ethanol in the solution during the solvothermal processing affects not only the rate of transformation of α-TCP into HAp, but also the morphology of the HAp that is formed.     

峰值电流密度对脉冲电沉积Ni-Co-CNTs复合镀层机械性能的影响

研究了峰值电流密度对脉冲电沉积Ni-Co-CNTs复合镀层机械性能的影响。结果表明:当峰值电流密度升高时,镀层表面变得粗糙;随着峰值电流密度的增加,镀层中碳的质量分数先增加后下降,当峰值电流密度为80 A/dm~2时,镀层中碳的质量分数达到最大值;镀层的显微硬度和抗拉强度均在峰值电流密度为100 A/dm~2附近时达到其最大值,且高于直流电沉积时所得镀层的显微硬度值和抗拉强度值。说明采用脉冲电沉积工艺可以提高镀层的机械性能。     

Development and characterization of silver and zinc doped bioceramic layer on metallic implant materials for orthopedic application

A successful electrodeposition method for preparing silver and zinc modified bioactive calcium phosphate layers onto surgical grade titanium alloy material (Ti6Al4V) was developed. The coatings were deposited on the Ti6Al4V surface by pulse current at 70 °C from an electrolyte containing adequate amounts of calcium nitrate, ammonium dihydrogen phosphate, zinc nitrate and silver nitrate. The corrosion resistivity of the bioceramic coatings was assessed in conventional Ringer׳s solution in a three electrode open cell by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques. The results revealed the pure bioactive calcium phosphate (CaP) coated implant materials to possess the highest resistivity to corrosion, while the silver and zinc doped CaP layer showed at least one order of magnitude lower corrosion resistance. These modified CaP coatings can be further considered as antimicrobial coatings with enhanced biocompatibility. The morphology and structure of the coatings were characterized by Scanning electron microscopy (SEM), Energy-dispersive X-ray Spectroscopy (EDX) and X-ray diffraction (XRD) that confirmed the pulse current deposited CaP layer to consist of a mixture of different calcium phosphate phases such as hydroxyapatite (HAp), monetite (dicalcium phosphate, CaHPO₄) as well as other Ca-containing components, portlandite (Ca(OH)₂) and parascholzite (CaZn₂(PO₄)₂(H₂O)₂).     

New Processing Technique for Hydroxyapatite Ceramics by the Hydrothermal Hot-Pressing Method

A new processing technique for preparing hyroxyapatite (HAp) ceramics has been developed using the hydrothermal hot-pressing (HHP) method. Powder mixed dibasic calcium phosphate dihydrate and calcium hydroxide mixed with a Ca/P ratio of 1.67 was treated at 150°C and 40 MPa. The HHP method with the selection of the powder enabled the HAp to be solidified at the low temperature. The resulting HAp ceramics had a tensile strength of approximately 10 MPa. Furthermore, the HAp ceramics possessed a lamellar microstructure and high porosity.     

In-field reparation of the damaged coatings for C/C composites

Protective coatings are critical to the successful application of the carbon/carbon (C/C) composites in the thermal protection systems of space vehicles. The damages of such coatings during installation and operation would threaten the safety of flight. In this contribution, an in-field technology based on a multilayer structure was developed to repair the damaged coatings of C/C composites. The multilayer structure contains a silicon buffer inner layer, a mullite heat-resistant middle layer and a borosilicate glass outer layer. The oxidation tests in air at 1300 °C and 1500 °C indicated that the weight loss of the repaired samples was greatly reduced compared with that of the damaged ones. The plasma wind tunnel tests for both repaired and damaged coatings further demonstrated that the multilayer structure could effectively protect the damaged composites from ablation in oxidation environments.     

Effect of graphene reinforcement on hybrid bioceramic coating deposited on the produced porous Ti64 alloys

Porous-Ti64 alloys (P-Ti64), produced at various porosities by hot-pressing technique with the help of Mg spacer, were coated by hybrid-Graphene Oxide (rGO) reinforced-hydroxyapatite (HAp), using the sol–gel method. The synthesized rGO powder was used in reinforcing HAp by the Modified Hummers method having 30 µm particle size and nano (nm) scale layer thickness. Hybrid coatings were executed on Ti64 substrates in four different groups as single-HAp, HAp reinforced with 0.5 wt%, 1.0 wt% and 1.5 wt% rGO for three different porosities (41, 52, and 64%) were characterized by FT-IR, Raman, XRD and SEM. The average 21 µm coating film thicknesses were obtained and desirably, the only superficial pores of the substrates were closed by coating material rather than the inner connected open pores. It was also shown that 0.5 wt% and 1.0 wt% rGO reinforcements into HAp prevented crack formation on the Ti64 surfaces, whereas 1.5 wt% rGo reinforcement and single-HAp coatings caused. The highest adhesion strength values were achieved at low porosities (41–52%) and of 0.5–1.0 wt% rGO reinforcements through the adhesion tests.

     

炭/炭复合材料抗氧化研究现状

总结了炭/炭复合材料抗氧化研究现状,重点介绍了抗氧化涂层的制备方法,包括包埋浸渍法、化学气相沉积(CVD)、溶胶-凝胶法(Sol-Gel)和水热电沉积法以及近几年针对抗氧化涂层开裂问题各国学者的最新研究成果。提出了炭/炭复合材料抗氧化研究今后努力的方向。     

CNT-PyC-SiC/SiC double-layer oxidation-protection coating on C/C composite

CNT-PyC-SiC/SiC double-layer coatings were prepared by growth of CNTs on C/C followed by pyrolytic carbon deposition and SiC deposition. The microstructure and the oxidation behavior of the coatings were investigated. With increasing PyC amount in the coating, the coating showed fewer cracks and a higher oxidation resistance and thermal shock resistance. CNT-PyC played a role in improving the bonding strength between C/C and coatings, alleviating stress in SiC coating and decreasing the cracks.     

Polypyrrole coatings for corrosion protection of Al alloy2024: influence of electrodeposition methods,solvents, and ZnO nanoparticle concentrations

Since ZnO nanoparticles increase the electrical conductivity of the polypyrrole (PPy) coatings, an investigation was carried out to evaluate the effect of ZnO nanoparticles loading on the corrosion protection performance of PPy coatings on AA2024 Al alloy in 3.5% NaCl solution. At first, some measurements were carried out to find the best experimental conditions containing the electrodeposition method, electrosynthesis solvent composition, and ZnO nanoparticles’ concentration for preparing the optimum PPy coating on Al alloy2024. Three different methods of electrodeposition, namely: cyclic voltammetry, galvanostatic, and potentiostatic techniques were analyzed. The anti-corrosion performance of the PPy coatings was evaluated by electrochemical impedance spectroscopy and Tafel polarization methods. The PPy prepared by potentiostatic method exhibited the best performance against corrosion of Al alloy2024 in 3.5% NaCl solution. Then, different mixtures of H₂O/ethanol were tested as electrosynthesis solvents for preparation of PPy coatings on the alloy by optimized electrodeposition mode (i.e., potentiostatic). In evaluation of the prepared coatings, the pure water was introduced as the optimum solvent in electrodeposition of PPy. The investigation of different ZnO nanoparticles’ concentrations proved that the PPy coating containing 0.025% ZnO nanoparticles was the optimum coating against the corrosion of Al alloy in NaCl solution. Finally, the long-term evaluation of the corrosion protection performance of the coatings revealed that the optimum coating provided suitable protection against corrosion up to 14 days after immersion.