A simple chemical method for preparation of hydroxyapatite coatings on Ti6Al4V substrate

A novel, simple and economical chemical bath method for deposition of calcium hydroxyapatite coating has been developed. The coatings were prepared from EDTA solutions in alkaline media on Ti6Al4V substrates. The method is based on thermal dissociation of the Ca(EDTA)^2- complex at 65–95 °C. Two chemical baths with and without presence of Na⁺ and Cl^- were used for the deposition. The Rutherford back scattering study shows that the coating material from bath which contained sodium and chlorine ions have their presence in the coated material. The bath which has been prepared with potassium substituting sodium and nitrate substituting chlorine produced coatings with better stoichiometry, with Ca/P=1,67. The X-ray analysis revealed that the calcium hydroxyapatite coatings have preferred crystal orientation in the 002 direction. © 2001 Kluwer Academic Publishers     

In vitro dissolution and corrosion study of calcium phosphate coatings elaborated by pulsed electrodeposition current on Ti6Al4V substrate

Calcium-deficient hydroxyapatite (Ca-def-HAP) coatings on titanium alloy (Ti6Al4V) substrates are elaborated by pulsed electrodeposition. In vitro dissolution/precipitation process is investigated by immersion of the coated substrate into Dulbecco’s Modified Eagle Medium (DMEM) from 1 h to 28 days. Calcium and phosphorus concentrations evolution in the biological liquid are determined by Induced Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES) for each immersion time. Physical and chemical characterizations of the coating are performed by scanning electron microscopy (SEM) associated to Energy Dispersive X-ray Spectroscopy (EDXS) for X-ray microanalysis. Surface modifications are investigated by an original method based on the three-dimensional reconstruction of SEM images (3D-SEM). Moreover, corrosion measurements are carried out by potentiodynamic polarization experiments. The results show that the precipitation rate of the Ca-def HAP coating is more pronounced in comparison with that of stoichiometric hydroxyapatite (HAP) used as reference. The precipitated bone-like apatite coating is thick, homogenous and exhibits an improved link to the substrate. Consequently, the corrosion behaviour of the elaborated prosthetic material is improved.     

In situ synthesis of TiN/Ti3Al intermetallic matrix composite coatings on Ti6Al4V alloy

The aim of this paper was to develop an in situ method to synthesize the TiN reinforced Ti₃Al intermetallic matrix composite (IMC) coatings on Ti6Al4V alloy. The method was divided into two steps, namely depositing pure Al coating on Ti6Al4V substrate by using plasma spraying, and laser nitriding of Al coating in nitrogen atmosphere. The microstructure and mechanical properties of TiN/Ti₃Al IMC coatings synthesized at different laser scanning speeds (LSSs) in laser nitriding were investigated. Results showed that the crack- and pore-free IMC coatings can be made through the proposed method. However, the morphologies of TiN dendrites and mechanical properties of coatings were strongly dependent on LSS used in nitriding. With decreasing the LSS, the amount and density of TiN phase in the coating increased, leading to the increment of microhardness and elastic modulus and the decrement of fracture toughness of coating. When the LSS was extremely high (i.e., 600 mm/min), only a thin TiN/Ti₃Al layer with thickness around of 100 μm was formed near the coating surface.     

An interfacial study of sol-gel-derived magnesium apatite coatings on Ti6Al4V substrates

Magnesium apatite coatings on Ti6Al4V substrate were synthesized by the sol-gel dip-coating method. Magnesium was incorporated in the coating according to the formula (Ca_10−xMg_x)(PO₄)₆(OH)₂, where x = 0, 0.50, 1.00, 1.50 and 2.00. Approximately 2-μm-thick apatite coatings were derived after five cycles of dip-drawing-drying-firing process. A transitional region (R_t) was formed between substrate and coating during the firing process. Adhesion tests show that the adhesion strength between substrate and apatite coating is enhanced by the incorporation of magnesium in the coating. The quantity of magnesium incorporated appeared to correspond to the Mg-Ti-O chemical bonds formed in the transitional region, which contributed to the adhesion strength of the coatings.     

Recent trends towards improved plasma-sprayed advanced bioceramic coatings on Ti6Al4V implants

In this contribution several recent trends are being described towards engineering of bioceramic coatings applied by thermal spraying to titanium alloy substrates. (i) Optimization by statistical experimental design methodology of plasma spray parameters can be used to deposit coatings with low porosity, comparatively high adhesive strength and optimum crystallinity. (ii) Microstructural engineering of the hydroxyapatite powder by pre-spray annealing, i. e. sintering leads to a substantial decrease of the microporosity of the ceramic grains hence improving both adhesion strength and in vitro resorption resistance. (iii) Bond coats based on titania and titania / zirconia can be used to control the rate of heat transfer from the molten particles to the substrate and hence to improve the in vivo resorption resistance by suppressing the formation of amorphous calcium phosphate (ACP). (iv) Replacement of hydroxyapatite by specific compositions in the quaternary system CaO-TiO₂-ZrO₂-P₂O₅ is a potential way to generate coatings with high chemical stability for long-term performance.     

氧化处理时间对Ti6Al4V微弧氧化陶瓷膜的影响

采用交流微弧氧化法于：Na：SiO3-KOH-(NaPO3)6溶液中在％6A14V表面形成了氧化物陶瓷膜．利用扫描电镜、电子探针及X射线衍射研究了陶瓷膜的组织形貌、元素的分布和相组成．研究表明：在恒定的微弧氧化电参数(U =500V，U-=100V和f=600Hz)下，随氧化时间延长，电流密度逐渐降低，膜层厚度不断增加；相对致密均匀的膜分为3层：过渡层、致密层与疏松层．膜层主要由TiO2(锐钛矿和金红石)相组成，延长处理时间，锐钛矿相及金红石相的相对含量发生变化，金红石相TiO2逐渐增多，而锐钛矿相TiO2减小．膜层相的形成过程可分为两个阶段。     

A comparative study of the impurity segregation from commercially pure Ti, Ti6Al4V and Ti3Al8V6Cr4Zr4Mo

The surface composition of commercially pure Ti, Ti6Al4V and Ti3Al8V6Cr4Zr4Mo during annealing at different constant temperatures was experimentally investigated. Auger electron spectroscopy was used to monitor the APPHs of the specified elements present on the surfaces. The surfaces of Ti and its alloys were contaminated by oxygen and carbon, and the contamination is attributed to the continual uptake of the background gases, even in the UHV chamber. It was found that mainly C and S segregated at 400 °C, and Cl at higher temperatures (500–630 °C) for commercially pure Ti. However, S was the main segregating species for all three samples. The segregation of Al was measured for the Ti6Al4V and Ti3Al8V6Cr4Zr4Mo samples at higher temperatures. The linear least-square fit method was employed to determine the contribution of pure Ti and TiC from the measured APPH's. The AES fitting confirmed the formation of TiC on the surface at temperatures 400–500 °C.     

Biocompatible and mechanical properties of low temperature deposited quaternary (Ti, Al, V) N coatings on Ti6Al4V titanium alloy substrates

A series of quaternary (Ti, Al, V) N coating layers were obtained by low temperature reactive plasma sputtering in differing deposition conditions to improve the wear resistance and the biocompatibility of a titanium surgical alloy, specifically Ti-6Al-4V. Characterization of the mechanical properties, structure and the chemical composition of the coating layer was explored by microhardness test, ball against flat wear test, scanning electron microscopy and X-ray diffraction. The biocompatibility of the optimum coating layer (as determined by mechanical performance) was examined by a modified MTT toxicity test and by monitoring cell growth assessed by quantitative stereological analysis. The experimental results are encouraging, indicating that this low temperature deposited, dense, quaternary (Ti, Al, V) N coating layer exhibits improved mechanical properties such as high hardness and excellent adhesion to a Ti alloy substrate and is highly biocompatible.     

Self-lubricating CrAlVN coatings for turning of Ti6Al4V: oxidation and wear behavior

The titanium alloy Ti6Al4V enables significant performance increases in various branches of industry. Nevertheless, it is difficult to machine, because of its material properties. Due to the low thermal conductivity of titanium, the heat generated while turning Ti6Al4V mainly flows into the tool leading to high temperature loads. In addition, the comparatively low Young's modulus and high yield strength contributes to high mechanical stresses during machining. Temperature active, self-lubricating physical vapor deposition hard coatings appear to be suitable for reducing friction and tool wear during turning of Ti6Al4V compared to the most commonly used uncoated carbide tools. The ability of the coating to form lubricating oxide phases at high temperatures is crucial for this purpose. This paper investigates the oxidation and diffusion behavior of vanadium doped chromium aluminium nitride (CrAlN) coatings after heat treatment at ϑ = 600 °C, ϑ = 700 °C und ϑ = 800 °C in atmosphere as well as the resulting coating properties. The wear behavior of certain coating variants while turning of Ti6Al4V is analyzed.     

Ti、Ti6Al4V和Ti6Al7Nb对成骨细胞生物活性影响的研究

研究Ti、Ti6Al4V和Ti6Al7Nb 3种钛金属表面经喷砂酸蚀处理后的表面形貌、亲水性及对成骨细胞生物活性的影响。在Ti、Ti6Al4V和Ti6Al7Nb 3种钛金属表面进行Al2O3喷砂和盐酸、硫酸混合物酸蚀的表面改性处理(SLA),通过扫描电子显微镜(scanning electron microscope,SEM)观察样品的表面形貌,通过接触角测量仪在显微镜下测量接触角的大小;将SD大鼠成骨细胞以1×104cells/m L密度接种于Ti、Ti6Al4V和Ti6Al7Nb表面后通过MTT活性实验观察成骨细胞在样品表面的增殖,通过SEM观察细胞在样品表面生长的形态,通过碱性磷酸酶(AKP)活性实验,检测成骨细胞的分化能力。Ti、Ti6Al4V和Ti6Al7Nb在经过喷砂酸蚀处理后,表面均呈现出微米级多孔形貌,3种样品均为亲水性表面;细胞在SLA处理后的Ti、Ti6Al4V和Ti6Al7Nb表面增殖良好,细胞伸展显著;其中在Ti6Al7Nb表面细胞的增殖、黏附、分化能力最强。大颗粒喷砂酸蚀技术的表面处理方法能够促进Ti、Ti6Al4V和Ti6Al7Nb的生物活性;经SLA处理的Ti6Al7Nb比Ti和Ti6Al4V表现出更好的生物学活性,成骨细胞在其表面呈现出更好的增殖、黏附及分化能力。     

Improved thrombogenicity on oxygen etched Ti6Al4V surfaces

Thrombus formation on blood contacting biomaterials continues to be a key factor in initiating a critical mode of failure in implantable devices, requiring immediate attention. In the interest of evaluating a solution for one of the most widely used biomaterials, titanium and its alloys, this study focuses on the use of a novel surface oxidation treatment to improve the blood compatibility. This study examines the possibility of using oblique angle ion etching to produce a high quality oxide layer that enhances blood compatibility on medical grade titanium alloy Ti6Al4V. An X-ray photoelectron spectroscopy (XPS) analysis of these oxygen-rich surfaces confirmed the presence of TiO₂ peaks and also indicated increased surface oxidation as well as a reduction in surface defects. After 2 h of contact with whole human plasma, the oxygen etched substrates demonstrated a reduction in both platelet adhesion and activation as compared to bare titanium substrates. The whole blood clotting behavior was evaluated for up to 45 min, showing a significant decrease in clot formation on oxygen etched substrates. Finally, a bicinchoninic acid (BCA) total protein assay and XPS were used to evaluate the degree of key blood serum protein (fibrinogen, albumin, immunoglobulin G) adsorption on the substrates. The results showed similar protein levels for both the oxygen etched and control substrates. These results indicate that oblique angle oxygen etching may be a promising method to increase the thrombogenicity of Ti6Al4V.     

XRD and XPS characterization of superplastic TiO2 coatings prepared on Ti6Al4V surgical alloy by an electrochemical method

X-ray diffraction (XRD) and X-Ray photoelectron spectroscopy (XPS), in conjunction with argon ion etching, were used to characterize the microstructure and the chemical composition of alkoxy-derived TiO₂ coatings prepared on Ti6Al4V surgical alloy by an electrochemical method. The as-deposited oxide coatings prepared at room temperature (up to 40 m thick) were amorphous, but transformed into nanocrystalline anatase at 550°C. Using a micro-indentation technique, it was found that nanocrystalline anatase coatings were ductile, permitting significant plastic deformation at room temperature. The XPS data also revealed the presence of significant proportion of physisorbed (OH) and chemisorbed H₂O (i.e. Ti–OH) on the oxide surface, indicating that these coatings, similar to sol-gel-prepared titania, may serve as reactive substrates for heterogeneous nucleation of apatite under physiological conditions.     

Damage evolution in Ti6Al4V–Al3Ti metal-intermetallic laminate composites

The crack propagation and damage evolution in metal (Ti6Al4V)-intermetallic (Al₃Ti) laminate composites were investigated. The composites (volume fractions of Ti6Al4V: 14%, 20% and 35%) were tested under different loading directions (perpendicular and parallel directions to laminate plane), to different strains (1%, 2%, 3%) and at different strain rates (0.0001 and 800–2000 s⁻¹). Crack densities and distributions were measured. The crack density increases with increasing strain, but decreases (at a constant strain) with increasing volume fraction of Ti6Al4V. Differences in crack propagation and damage evolution in MIL composites under quasi-static (10⁻⁴ s⁻¹) and dynamic (800–2000 s⁻¹) deformation were observed. The fracture stress does not exhibit significant strain-rate sensitivity; this is indicative of the dominance of microcracking processes in determining strength. Generally, the crack density after dynamic deformation is higher than that after quasi-static deformation. This is attributed to the decreased time for crack interaction in high-strain rate deformation. The effect of crack density, as quantified by a damage parameter, on elastic modulus and stress–strain relation were calculated and compared with experimental results.     

Ti6Al4V等离子体浸没式离子注入

采用新型等离子体浸没式离子注入技术,对Ti6Al4V合金进行氮离子注入.对注入层的成分、组织和性能的分析表明,注入层中氮浓度的分布具有类高斯分布特征,在注入层中有TiN和非晶态相形成.注入层的显微硬度和摩擦性能得到了明显的改善.     

置氢Ti6Al4V合金的微观组织演变规律

为研究置氢Ti6Al4V合金的高温加工改性机理,从微观组织的角度对合金进行了对比分析.利用OM、SEM、XRD等研究了置氢对Ti6Al4V合金变形前后微观组织演变的影响.研究结果表明:氢的加入不仅使置氢Ti6Al4V合金中β相比例明显增大,而且改变了α相与β相之间的电势差,在氢含量为0.3%~0.5%两相颜色将发生互换,氢含量增加到0.50%以上时,合金中将出现面心立方结构的δ氢化物;随氢含量的增加,合金超塑拉伸变形后的组织由α+β两相等轴晶粒变为粗大的β晶粒,造成α与β界面的协调能力下降,并改变了合金的变形机制.     

Fabrication of nano-structured HA/CNT coatings on Ti6Al4V by electrophoretic deposition for biomedical applications

In order to improve the bone bioactivity and osteointegration of metallic implants, hydroxyapatite (HA) is often coated on their surface so that a real bond with the surrounding bone tissue can be formed. In the present study, cathodic electrophoretic deposition (EPD) has been attempted for depositing nanostructured HA coatings on titanium alloy Ti6Al4V followed by sintering at 800 degrees C. Nano-sized HA powder was used in the EPD process to produce dense coatings. Moreover, multiwalled carbon nanotubes (CNTs) were also used to reinforce the HA coating for enhancing its mechanical strength. The surface morphology, compositions and microstructure of the monolithic coating of HA and nanocomposite coatings of HA with different CNT contents (4 to 25%) on Ti6Al4V were investigated by scanning-electron microscopy, energy-dispersive X-ray spectroscopy and Xray diffractometry, respectively. Electrochemical corrosion behavior of the various coatings in Hanks' solution at 37 degrees C was investigated by means of open-circuit potential measurement and cyclic potentiodynamic polarization tests. Surface hardness, adhesion strength and bone bioactivity of the coatings were also studied. The HA and HA/CNT coatings had a thickness of about 10 microm, with corrosion resistance higher than that of the substrate and adhesion strength higher than that of plasma sprayed HA coating. The properties of the composite coatings were optimized by varying the CNT contents. The enhanced properties could be attributed to the use of nano-sized HA particles and CNTs. Compared with the monolithic HA coating, the CNT-reinforced HA coating markedly increased the coating hardness without deteriorating the corrosion resistance or adhesion strength.     

Photo-induced properties of anodic oxide films on Ti6Al4V

Photocatalytic activity and wettability of the anodic oxide layer on Ti6Al4V prepared by anodization in a sulfuric acid electrolyte are explored. The oxide is composed mainly of TiO₂ with V₂O₅, VO₂ and Al₂O₃. The crystal structure of the TiO₂ varies from anatase to rutile with the sulfuric acid concentration in the electrolyte. Anatase exhibits better photocatalytic activity compared with rutile, which is different from those on Ti and Ti-Nb-Sn alloy. Contact angles of the oxides decrease with ultraviolet light illumination, and hydrophilicity is observed in the rutile oxide. Both photocatalytic activity and hydrophilicity are inferior to the corresponding Ti and Ti-Nb-Sn alloy, which is explained by the presence of Al₂O₃ in the anodic oxide.     

Biomimetic coating of bisphosphonate incorporated CDHA on Ti6Al4V

Bi-functional coatings of carbonated calcium deficient hydroxyapatite (CDHA) on Ti alloys were developed by using a biomimetic coating process. The bi-functionality was achieved by loading alendonate sodium (AS), an approved bisphosphonate drug used for the treatment of osteoporosis, into the inner layers of CDHA coatings. Three possible methods of loading AS into CDHA coatings were systematically studied and compared. The results indicated that the co-precipitation method had greater benefits and can modify the release profile of AS by incorporating AS in the inner layers of the coatings. As a preliminary study, the influences of applied AS dosage to CDHA coatings were evaluated using XRD and SEM. In vitro tests indicated that the AS content on CDHA coatings played a significant role, and optimum AS content in local area is beneficial for osteoblast cells proliferation. It is expected that the CDHA–AS coatings via the co-precipitation approach have potential for bone tissue engineering applications.