Preparation and characterization of silicon-substituted hydroxyapatite coating by a biomimetic process on titanium substrate

A biomimetic method has been used to prepare silicon-substituted hydroxyapatite coatings on titanium substrates. The surface structures of the coatings were characterized by X-ray diffraction, X-ray photoelectron spectroscopy (XPS) and Fourier transformed infrared spectroscopy (FTIR). Si substituted hydroxyapatite (Si-HA) coatings with different Si contents were deposited successfully on the titanium substrate by immersing the pretreated titanium substrate into silicon containing supersaturated solutions (SSS) with different SiO₃²⁻ concentrations. The pretreatment of the Ti substrate in a mixed alkaline (NaOH + Ca(OH₂)) followed by a heat treatment produced a 3D porous surface structure with rutile and CaTiO₃ as main phases, which contributed mainly to the fast precipitation and deposition of Si-HA. FTIR results showed that Si in the Si-HA coating existed in the form of SiO₄⁴⁻ groups. The cross-section microstructure was observed by scanning electronic microscopy and the shear strength was tested. The coating was about 5-10 μm in thickness and no interval was observed at the interface between the coating and the substrate. Shear strength testing showed that Si-HA/Ti exhibited higher shear strength than HA/Ti due to the existence of the SiO₄⁴⁻ group in the coating.     

表面涂覆含氟羟基磷灰石和缺钙羟基磷灰石的镁合金体外降解行为(英文)

通过电化学沉积方法,在生物降解镁合金表面覆盖含氟羟基磷灰石(FHA)涂层和缺钙羟基磷灰石(CDHA)涂层。采用X射线衍射、傅立叶变换红外光谱、透射电子显微镜、扫描电子显微镜和能量色散X射线光谱研究涂层特性。结果表明:涂覆纳米FHA涂层的样品具有垂直于样品表面的纳米针状结构,比涂覆CDHA涂层样品的结构更致密和更均匀。纳米FHA涂层比纳米CDHA涂层具有更小的晶粒尺寸,分别为65 nm和95 nm。然而,CDHA涂层比FHA涂层更厚,厚度分别为19μm和15μm。通过极化、浸泡和析氢实验研究的腐蚀行为表明:纳米FHA涂层和纳米CDHA涂层显著降低腐蚀速率并引起钝化。纳米FHA和纳米CDHA涂层可以加速骨状磷灰石层的形成,相比未覆盖的镁合金可以显著减少溶出速率。纳米FHA涂层能对镁合金提供有效的防护并具有更高的腐蚀性能。因此,覆盖纳米FHA涂层的镁合金在整形外科领域具有良好的应用前景。     

The effect of substrate composition on the electrochemical and mechanical properties of PEO coatings on Mg alloys

Plasma electrolytic oxidation (PEO) is a unique surface treatment technology which is based on anodic oxidation forming ceramic oxide coatings on the surface of light alloys such as Mg, Al and Ti. In the present study, PEO coatings prepared on AZ91D, AZ31B, AM60B and AM50B Mg alloys have been investigated. Surface morphology and elemental composition of coatings were determined using scanning electron microscope (SEM) equipped with energy dispersive spectrometer (EDS). SEM results showed that the coating exhibited a porous top surface layer and a subsequent dense layer with micro-pores and shrinkage cracks. Phase analysis of coatings was carried out by X-ray diffraction (XRD). XRD analyses indicated that PEO coatings on AZ alloys had higher amount of Periclase (MgO) followed by the presence of Spinel (MgAl₂O₄) e.g. on the AZ91D alloy compared to that on AM series alloys. In order to examine the effect of substrate composition on adhesion strength of PEO coating scratch tests were carried out. Electrochemical corrosion tests were undertaken by means of potentiodynamic polarization technique in 3.5% NaCl solution at room temperature (20 ± 2 °C). Corrosion test results indicated that the corrosion rates of coated Mg alloys decreased by nearly two orders of magnitude as compared to bare Mg alloys. PEO coatings on AZ series alloys showed better corrosion resistance and higher adhesion properties than AM series alloys. In addition to the PEO processing parameters, such are mainly attributes of the compositional variations of the substrate alloys which are responsible for the formation, phase contents and structural properties of the PEO coatings.     

Influence of hydrothermal temperature on hydroxyapatite coating transformed from monetite on HT-C/C composites by induction heating method

Hydrothermal post-treatment was used to convert monetite coating fabricated by induction heating method on H₂O₂ treated C/C (HT-C/C) composites to an adherent HA coating. The monetite coatings were hydrothermally treated for 4 h at 373 K, 403 K, 423 K, and 453 K in a 50 mL autoclave. After hydrothermal post-treatment, the structure, morphology and the chemical composition of these HA coatings were characterized with XRD, FTIR SEM and EDS. A scratch test was conducted to measure the strength of the adhesion of the coatings to the HT-C/C substrate. The results showed that the degree of crystallinity and the Ca/P ratio of the HA coatings increased with increasing hydrothermal temperature. The submicron-level morphology and adhesion of the HA coatings were highly affected by the hydrothermal temperature. From the results, it can be suggested that 423 K was the best hydrothermal treatment temperature for the HA coatings which were transformed from the monetite coatings produced by the induction heating method on HT-C/C composites.     

Electrophoretic deposition of titanium/silicon-substituted hydroxyapatite composite coating and its interaction with bovine serum albumin

Silicon-substituted hydroxyapatite (Ca10(PO4)6-x(SiO4)x(OH)2-x, Si-HA) composite coatings on a bioactive titanium substrate were prepared by electrophoretic deposition technique with the addition of triethanolamine (TEA) to enhance the ionization degree of Si-HA suspension. The surface structure was characterized by XRD, SEM, XRF, EDS and FTIR. The bond strength of the coating was investigated. The results show that the depositing thickness and the images of Si-HA coating can be changed with the variation of deposition time. The XRD spectra of Ti/Si-HA coatings show the characteristic diffraction peaks of HA, and the incorporation of silicon changes the lattice parameter of the crystal. The FTIR spectra shows that the most notable effect of silicon substitution is the decrease of intensities of -OH and PO43- groups with the silicon contents increasing. XRD and EDS element analyses present that the content of silicon in the coating increases with increasing silicon concentration in the suspension. The bioactive TiO2 coating formed may improve the bond strength of the coatings. The interaction of Ti/Si-HA coating with BSA is much greater than that of Ti/HA coating, suggesting that the incorporation of silicon in HA is significant to improve the bioactive performance of HA.     

Properties of the TiN coatings on previously Ti ion-implanted magnesium alloy substrate

To enhance the mechanical properties of TiN coating on magnesium alloy, metal vapor vacuum arc (MEVVA) ion implantation was performed to modify magnesium alloy substrate before TiN film deposition. Implantation energy was fixed at 45 keV and dose was at 9 × 10¹⁷ cm^− 2. TiN coatings were deposited by magnetically filtered vacuum-arc plasma source on unimplanted and implanted substrate. The microstructure composition distribution and phase structure were analyzed using scanning electron microscopy (SEM) and X-ray diffraction (XRD). The chemical states of some typical elements of the TiN coating were analyzed by means of X-ray photoelectron spectroscopy (XPS). The properties of corrosion resistance of TiN coatings were studied by CS300P electrochemical-corrosion workstation, and the mechanism of the corrosion resistance was also discussed.     

Alternative technique for hydroxyapatite coatings

Flame Assisted Chemical Vapor Deposition (FACVD), a novel technique that shows an enormous potential in porous oxides deposition, was employed for the first time aiming to obtain hydroxyapatite (HA) coatings on 316 L stainless steel metallic substrates. Calcium acetate and ammonium phosphate diluted in ethanol were employed as precursor salts. A Ca/P molar ratio of 1.66 was employed in precursor solution, which is equivalent to stoichiometric hydroxyapatite. A porous coating, formed by an open and interconnected network, was observed by scanning electronic microscopy (SEM) and associated with homogenous reactions. Thickness of hydroxyapatite coating was 412 ± 3 μm. X-ray diffraction (XRD) analysis indicated the presence of crystalline coatings, mainly constituted by hydroxyapatite phase and traces of tricalcium phosphate (β-TCP). Carbonate in the hydroxyapatite coatings was identified by Fourier transform-infrared (FTIR) spectroscopy.     

Microstructure and tribological properties of diamond-like carbon and TiAlSiCN nanocomposite coatings

Diamond-like carbon (DLC) and TiAlSiCN nanocomposite coatings were synthesized by multi-plasma immersion ion implantation and deposition. The DLC content in the composite coating was controlled by the flow ratio of N₂ to C₂H₂ during the deposition process. The microstructure and tribological properties of the as-deposited coatings were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), nanoindentation and ball-on-disk friction tests. The TEM results show that all the DLC-TiAlSiCN coatings had a two phase composite structure of the TiCN nanocrystals embedded in an amorphous matrix consisting of a-Si₃N₄, a-SiC, a-CN and DLC. TEM observations also reveal that the spacing between the adjacent nanocrystals increases with DLC content. In addition, the DLC-TiAlSiCN nanocomposite coating with a small crystalline spacing of about 0.6 nm shows a higher hardness up to 50 GPa and a larger friction coefficient. An increase in the DLC content of the coating benefits its friction coefficient while its hardness decreases. The friction coefficient reduces to 0.14 when the DLC content is about 31%.     

Flame Spray Deposition of Titanium Alloy-Bioactive Glass Composite Coatings

Powders of titanium alloy (Ti-6Al-4V) and bioactive glass (45S5) were deposited by flame spraying to fabricate composite porous coatings for potential use in bone fixation implants. Bioactive glass and titanium alloy powder were blended and deposited in various weight fractions under two sets of spray conditions, which produced different levels of porosity. Coatings were characterized with cross-sectional optical microscopy, x-ray diffraction (XRD), scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FTIR). Immersion testing in simulated body fluid (SBF) was conducted for 0, 1, 7, and 14 days. Hydroxyapatite (HA) was found on the bioactive glass-alloy composite coatings after 7 days of immersion; no HA was observed after 14 days on the pure titanium alloy control coating. The HA formation on the alloy-bioactive glass composite coating suggests that the addition of bioactive glass to the blend may greatly increase the bioactivity of the coating through enhanced surface mineralization.     

Surface characterization of plasma sprayed pure and reinforced hydroxyapatite coating on Ti6Al4V alloy

Hydroxyapatite coatings suffer from poor mechanical properties like fretting fatigue, toughness and abrasive wear resistance. These properties can be enhanced by incorporation of secondary ceramic and metallic reinforcements in HA. An attempt has been made to deposit HA and HA reinforced with 10 wt.% (80Al₂O₃-20TiO₂) by plasma spray process on Ti6Al4V substrate. These coatings have been characterized using SEM/EDAX, XRD and FTIR spectroscopy. Corrosion studies have been done in SBF solution. Bio compatibility study is not included in this work. Reinforcement has enhanced the tensile strength. There is marginal improvement in microhardness and surface roughness with reinforcement. Both pure and reinforced coatings show superior resistance against corrosion in simulated body fluid.     

SiC nanowire-toughened SiC-MoSi2-CrSi2 oxidation protective coating for carbon/carbon composites

To prevent carbon/carbon (C/C) composites from oxidation, a dense SiC nanowire-toughened SiC-MoSi₂-CrSi₂ multiphase coating was prepared by the two-step technique composed of chemical vapor deposition (CVD) and pack cementation. The coatings were characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD). SiC nanowires could decrease the dimension of cracks and improve the oxidation and thermal shock resistance of SiC-MoSi₂-CrSi₂ multiphase coating. Oxidation test shows that, after introducing SiC nanowires, the weight loss of the coated sample can be reduced from 1.06% to 0.64% after oxidation at 1773 K for 155 h and decreased from 6.92% to 3.42% after thermal cycling between 1773 K and room temperature for 30 times.     

Microstructure and physical properties of PVD TiN/（Ti, Al）N multilayer coatings

Magnetron sputtered （Ti, Al） N monolayer and TiN/（Ti, Al） N multilayer coatings grown on cemented carbide substrates were studied by using energy dispersive X-ray spectroscopy （EDX）, scanning electron microscopy （SEM）, nanoindentation, Rockwell A indentation test, strength measurements and cutting tests. The results show that the （Ti, Al）N monolayer and TiN/（Ti, Al）N multilayer coatings perform good affinity to substrate, and the TiN/（Ti, Al）N multilayer coating exhibits higher hardness, higher toughness and better cutting performance compared with the （Ti, Al）N monolayer coating. Moreover, the strength measurement indicates that the physical vapour deposition （PVD） coating has no effect on the substrate strength.     

Structure and Properties Characterization of Ceramic Coatings Produced on Steel Using a Combined Technique

STEEL is the most widely used material in engineering,but unfortunately,steel exhibits poor wear resistanceand obvious contact corrosion.For decades,researchersprepared coatings on steel to improve its properties;ceramic is one of these coatings.To obtain ceramiccoatings on steel,many researchers use techniques suchas plasma spraying,laser cladding,etc.,but some ofthem are too expensive,some of them have a deep heataffected zone in the substrate,and some of them cannot bond well with the subs…     

Evaluation of vanadium carbide coatings on AISI H13 obtained by thermo-reactive deposition/diffusion technique

Vanadium carbide coatings on AISI H13 steel were prepared by thermo-reactive deposition/diffusion process (TRD) in molten salt bath for 1 to 6 h at 920 °C and 1000 °C, respectively. The obtained coatings were characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectrometry (EDX) and X-ray diffraction analysis (XRD). Equiaxed grains were observed throughout the coatings. The grain size gradually increased from the coating/substrate interface to the top surface. The coatings were composed of ordered state V₆C₅ phase and disordered state VC_x (x = 0.83-0.88) phases and had a preferential orientation of (111) and (200) planes. The values of nano-indentation hardness and elastic modulus of the coating are 28.1 ± 0.7 GPa and 421 ± 14 GPa, respectively. The growth of the vanadium carbide coating by the TRD process followed a parabolic kinetics with an activation energy of 199.3 kJ/mol. The variation of the coating thickness on the AISI H13 steel with treating time and temperature can be determined.     

机械镀Zn-RE复合镀层的结构

以机械镀方法制备了Zn-RE复合镀层,采用SEM观察了镀层的结构,采用XRF、XPS分析了镀层表面的化学组成和镀层的表面化学状态,采用XRD分析了镀层的物相组成。结果表明,Zn-RE复合机械镀层主要由锌粉颗粒组成,稀土有利于镀层中的锌粉颗粒发生变形。镀层中主要含有Zn、Sn、Fe、La、Ce元素,其中La、Ce含量很低;Zn、Sn、Fe以单质态存在,La以La2O3存在。镀层表面主要由Zn、Sn、La、O组成,Zn以单质态存在,Sn以单质态和氧化态共存,La以La2O3存在。Zn-RE复合镀层形层过程中所添加混合稀土中的La未发生化学位态的变化。     

High-velocity oxyfuel thermal spray coatings for biomedical applications

Plasma spraying is used to produce most commercially available bioceramic coatings for dental implants; however, these coatings still contain some inadequacies. Two types of coatings produced by the high- velocity oxyfuel (HVOF) combustion spray process using commercially available hydroxyapatite (HA) and fluorapatite (FA) powders sprayed onto titanium were characterized to determine whether this relatively new coating process can be applied to bioceramic coatings. Diffuse reflectance Fourier transform infrared (FTIR) spectroscopy, x- ray diffraction (XRD), and scanning electron microscopy (SEM) were used to characterize the composition, microstructure, and morphology of the coatings. The XRD and FTIR techniques revealed an apatitic structure for both HA and FA coatings. However, XRD patterns indicated some loss in crystallinity of the coatings due to the spraying process. Results from FTIR showed a loss in the intensity of the OH^∼ and F^∼ groups due to HVOF spraying; the phosphate groups, however, were still present. Analysis by SEM showed a coating morphology similar to that obtained with plasma spraying, with complete coverage of the titanium substrate. Interfacial SEM studies revealed an excellent coating-to-substrate apposition. These results indicate that with further optimization the HVOF thermal spray process may offer another method for producing bioceramic coatings.     

A study on microstructure and properties of calcium phosphate coatings processed using ion beam assisted deposition on heated substrates

In this study a set of thin Hydroxyapatite (HA) [Ca₁₀(PO₄)₆(OH)₂] coatings was deposited on heated silicon and titanium substrates using Ion Beam Assisted Deposition (IBAD). The effects of substrate temperature and processing parameters on the microstructural properties and composition of the coatings are being studied. Analytical techniques include transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM) with an energy dispersive X-ray spectroscopy (EDS), as well as scanning electron microscopy (SEM) with EDX, X-ray diffraction (XRD), and Fourier Transform Infrared Spectroscopy (FTIR). The current results indicate that as substrate temperature increases the Ca/P ratio of the coatings both on titanium and silicon substrates increases. The crystallinity of the coatings and the number of calcium phosphate compounds within the coating including HA also increases. STEM-EDS revealed an atomically diffused intermediate layer at the interface between the coating and substrate. XRD results along with TEM selected area diffraction (SAD) revealed that the coatings are composed of HA, other calcium phosphate, and calcium oxide compounds.     

Zirconium vacuum arc operation in a mixture of Ar and O2 gases: Ar effect on the arcing characteristics,deposition rate and coating properties

The effect of oxygen and argon partial pressures (P_O2, P_Ar) in a Zr vacuum arc on plasma ion current density J_p, arc voltage V_arc, deposition rate v_d, and selected coating properties was determined. A d.c. arc current of I_arc = 100 A was initiated between a Zr cathode and a grounded anode. Cathode spots produced a plasma jet, which entered a 1/8 torus macroparticle (MP) filter. The plasma was guided by a d.c. magnetic field through an aperture to a glass substrate or a flat disk probe, mounted on a rotatable holder. J_p was measured with the probe, negatively biased to V_b = − 60 V. Coating thickness was measured using a profilometer, and coating properties were investigated using optical microscopy, energy dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), nano-indentation and optical analysis.     

(Ti,Al)N单层和TiN/(Ti,Al)N复合涂层的切削性能研究

借助EDX、SEM、强度测试和切削实验研究了采用磁控溅射在硬质合金基体上沉积的(Ti,Al)N单层和TiN/(Ti,Al)N复合涂层的切削性能。研究表明,两种涂层均与基体结合紧密;TiN/(Ti,Al)N复合涂层则表现出更好的切削性能。     

Aluminium electroplated from ionic liquids as protective coating against steel corrosion

The protective action of thin layers of aluminium electroplated on a carbon steel (UNI Fe360B) has been studied. The coatings were obtained via electroreduction, at room temperature, from an ionic liquid constituted by 1-butyl-3-methyl-imidazolium heptachloroaluminate. Coatings of different thickness, ranging from 10 to 40 μm, were obtained. Their morphology and chemical composition were investigated using SEM microscopy coupled with EDX microanalysis and X-ray diffraction. Electrochemical tests (potentiodynamic polarization curves, open-circuit potential and electrochemical impedance spectroscopy) were performed in order to characterise the corrosion resistance of the coating in 3.5% NaCl aqueous solution. Visual investigation of the samples during long term of exposition to neutral salt spray gave an evaluation of their free corrosion properties. It was found that the aluminium layers deposited from ionic liquids significantly protect the substrate from the general corrosion and this action increases with the coating thickness.