Nanostructured Si,Mg, CO<Subscript>3</Subscript><Superscript>2−</Superscript> Substituted Hydroxyapatite Coatings Deposited by Liquid Precursor Plasma Spraying: Synthesis and Characterization

In this study, a novel liquid precursor plasma spraying (LPPS) process was used to deposit Si, Mg, CO₃ ²⁻ substituted hydroxyapatite (HA) coatings (alone and cosubstituted) onto Ti-6Al-4V substrates. Salts of silicon, magnesium, and carbonate elements were directly added into the HA liquid precursor for subsequent plasma spraying. The phase composition, structure, and morphology of all HA coatings were characterized by x-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Fourier transform infrared (FTIR) spectroscopy. The results indicated that the trace elements were successfully incorporated into the HA structure and nanostructured coatings were obtained for all doped HA formulations. The incorporation of trace elements into the HA structure reduced its crystallinity, especially when silicon, magnesium and carbonate ions entered simultaneously into the HA structure. FTIR spectra showed that the Si-HA and Mg-HA coatings had decreased intensities in both the O-H and P-O bands and that the CO₃ ²⁻-HA coating was mainly a B-type carbonate-substituted HA. The results showed that the LPPS process is an effective and simple method to synthesize trace element substituted biomimetic HA coatings with nanostructure.     

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.     

Adhesion of a chemically deposited monetite coating to a Ti substrate

Monetite is a promising biomaterial for restoring the function of the compromised skeletal structures due to its superior osteoconductive and resorption properties. However, its potential as a coating for orthopaedic implants in load bearing applications has not yet been investigated. The aim of this study was to prepare monetite coating on Ti substrate in mild conditions, which may allow incorporation of protein-based drugs during the coating deposition. Coatings were prepared using chemical deposition of monetite on Ti substrate in acidic conditions at 75 °C for 24 h. Coatings were characterised by scanning electron microscope (SEM), energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). Adhesion of the coatings to Ti substrate was measured using tensile tests. EDS confirmed the calcium phosphate nature of the coating and XRD and FTIR confirmed the monetite phase of the coatings. SEM revealed that the coatings were formed of densely packed plate-like monetite crystals, with the crystal size approximately 20 × 10 × 5 μm. Adhesion tests showed cohesive failure of the monetite coatings and the tensile strength of the coating was in the range of 15.43 ± 0.20 MPa. Mechanical tests showed that monetite coatings were stable and could be considered for use with Ti orthopaedic implants.     

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.     

低压沉积-微弧氧化制备钛金属HA-TiO2复合膜层

采用低压沉积-微弧氧化法,在钛金属表面直接制备了具有生物活性的HA-TiO2复合膜层,通过XRD和SEM分别分析了膜层的相结构和表面形貌,探讨了沉积参数对膜层中HA含量与表面形貌的影响.结果表明:低压沉积处理是微弧氧化法制备HA-TiO2复合膜层的必要条件;复合膜层主要由金红石型和锐钛矿型TiO2及HA组成,HA以白色...     

电泳沉积法制备HA/Ti0，复合涂层

羟基磷灰石是一种最有发展前途的生物材料之一.采用电泳沉积方法在钛合金基体上制备了HA/TiO2生物陶瓷涂层.将HA和TiO2粉体分散到正丁醇溶液中,再加入三乙醇胺,通过zeta电位确定了稳定的悬浮液中三乙醇胺和HA/TiO2的含量.研究了沉积电压和电泳时间对HA/TiO2涂层形貌和沉积量的影响.制得均匀致密涂层的适宜电压范围为250～350V.研究结果表明:由于电场强度随沉积时间改变,HA/TiO2沉积量随着沉积时间的增加表现出2段沉积速率不同的线性增长.     

Effects of Sr incorporation on surface structure and corrosion resistance of hydroxyapatite coated Mg-4Zn alloy for biomedical applications

Hydroxyapatite (HA) and strontium (Sr) incorporated HA coatings with different Sr contents were prepared on Mg-4Zn substrates by electrochemical deposition method. Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and electrochemical workstation were applied for the composition, phase constitution, morphology analyses and corrosion tests. The results reveal that the incorporation of Sr in coatings does not lead to dramatical change of functional groups and the crystal structure of the HA phase, but the crystal size and crystallinity decrease with increasing Sr content, which should be attributed to the lattice distortion and different occupancies of Sr and Ca ions. The 10SrHA@Mg-4Zn samples show the lowest corrosion current density and the highest corrosion potential, and also exhibit the lowest amount of hydrogen evolution among all coated samples.     

悬浮液等离子喷涂制备氟代羟基磷灰石生物涂层

主要以氟代羟基磷灰石(FHA)悬浮液为原料,采用悬浮液等离子喷涂技术,在钛基体表面制备了FHA涂层。通过XRD,SEM,FT-IR以及XPS等测试手段,对不同喷涂功率制备的FHA涂层进行表征,并测试其性能。结果表明,粉体及制备的涂层主要晶相为HA,但是粉体进入等离子火焰形成涂层的过程中发生分解,生成α-磷酸钙(α-TCP),β-磷酸钙(β-TCP),以及磷酸四钙(TTCP)等分解产物。XPS结果证明F离子成功取代了OH基团进入HA晶格中,导致FHA涂层的抗溶解性明显提高。电化学实验结果表明,随着喷涂功率的增加,涂层的抗腐蚀性能提高。     

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.     

Hydroxyapatite coatings for biomedical applications deposited by different thermal spray techniques

Thermally sprayed hydroxyapatite (HAp) coatings are widely used for various biomedical applications due to the fact that HAp is a bioactive, osteoconductive material capable of forming a direct and firm biological fixation with surrounding bone tissue.Bioceramic coatings based on nanoscale HAp suspension and microscale HAp powder were thermally sprayed on Ti plates by high-velocity suspension flame spraying (HVSFS) technique and atmospheric plasma spraying (APS) as well as high velocity oxy fuel spraying (HVOF) technique. HVSFS is a novel thermal spray process developed at IMTCCC, for direct processing of submicron and nano-sized particles dispersed in a liquid feedstock.The deposited coatings were mechanically characterized including surface roughness, micro hardness and coating porosity. The bond strength of the layer composites were analyzed by the pull-off method and compared for the different spray techniques. Phase content and crystallinity of the coatings were evaluated using X-ray diffraction (XRD). The coating composite specimen and initial feedstock were further analysed by scanning electron microscope (SEM) and rheology analysis.     

CaCO3和CaHPO4·2H2O粉末配比对激光熔覆原位合成羟基磷灰石涂层的影响

使用碳酸钙(CaCO3)和二水磷酸氢钙(DCPD,CaHPO4·2H2O)混合粉末在纯钛表面利用激光熔覆的法制备羟基磷灰石HA,Ca5(PO4)3(OH)涂层,研究CaCO3和DCPD的质量比对涂层相组成和微观组织的影响。研究发现,CaCO3和DCPD之间的反应不仅在涂层中生成结晶度较高的HA,同时还生成了一定量的磷酸四钙(TTCP,Ca4P2O9),α-磷酸钙(α-TCP,α-Ca3(PO4)2),β-磷酸钙(β-TCP,β-Ca3(PO4)2)和焦磷酸钙(Ca2P2O7),且各相的含量与混合粉末的钙磷原子比有较大关系。HA只有在混合粉末的钙磷原子比大于1.54的情况下才能生成,其含量随钙磷原子比的升高而缓慢增加;当混合粉末的钙磷原子比达到2.0时,涂层中的HA的含量达到25%(质量分数),同时涂层中还存在大量的TTCP,因此制备的涂层需要进行一定的后续热处理以增加其中HA的含量。由于制备过程中粉末之间的反应会生成大量的气体,因此制备的涂层均为多孔结构,其中用钙磷原子比为2.0的混合粉末制备的涂层中,孔隙的尺寸在100~300μm之间。粉末钙磷原子比还能影响涂层的结合强度、孔隙率和裂纹数量。随钙磷原子比的升...     

TC4合金表面激光熔覆B4C及B4C＋Ti粉末涂层的微观组织

利用XRD，SEM和EDS分析手段对B4C和B4C＋10％Ti（质量分数，下同）激光熔覆层的微观组织进行了分析。结果表明，TC4合金表面B4C与B4C＋10％Ti激光熔覆层的组成相基本相同，均由TiC1-x，TiB，TiB2和Ti相组成，说明在TC4合金表面熔覆过程中有一部分Ti进入熔覆层并与B4C发生化学反应原位生成了TiB，TiB2和TiC1-x相。TiC1-x相以树枝状相形式存在，TiB2相以粗大须状相形式存在，TiB相以细小须状相形式存在。熔覆层与基底结合良好，没有发现裂纹与孔洞。基底热影响区呈淬火组织形貌，为典型的针状马氏体组织特征。与B4C激光熔覆层相比，B4C＋10％Ti激光熔覆层的组织细小，TiB相含量增多，TiB2相含量减少。     

镁牺牲阳极法制备羟基磷灰石涂层的电化学性能

羟基磷灰石(HA)作为一种最重要的生物材料被成功采用镁牺牲阳极法在Ti6Al4V合金表面合成,以提高该复合材料的电化学抗腐蚀性能。使用电子能谱(EDX)、电子探针(EPMA)、傅里叶红外变换图谱(FTIR)和X射线衍射(XRD)对HA涂层进行分析。结果表明,涂层主要由针状羟基磷灰石晶体组成,Ca/P比为1.4063。浸泡30 d后,HA涂层在汉克氏溶液中晶体变大,在林格氏溶液和台氏溶液中针状晶体分别转变为片状和柱状。通过测试在3 种模拟体液和人血中的开路电位、极化曲线和交流阻抗图谱表明,有HA涂层的Ti6Al4V合金比未涂层的Ti6Al4V合金具有更好的电化学性能     

甘油磷酸钙浓度对钛合金MAO涂层性能的影响

目的 提高医用钛合金的生物活性。方法 在含葡萄糖酸钙(Ca Glu₂)、葡萄糖酸镁(MgGlu₂)、植酸钠(Na₁₂Phy)和磷酸(H₃PO₄)的基本溶液中,分别添加8、10、12 g/L甘油磷酸钙(Ca-GP),采用MAO方法在Ti-6Al-4V表面制备3种涂层。使用SEM、EDS、XRD、XPS和AFM检测涂层表面形貌、化学成分、物相结构、元素存在状态和表面粗糙度,并测试涂层的接触角、结合强度以及体外生物活性。结果 经过MAO处理后,钛合金表面可成功生长出多孔陶瓷涂层,Ca-GP参与了MAO涂层形成。当Ca-GP的质量浓度为8 g/L时,涂层非常粗糙,Ca和Mg的原子数分数分别为7.56%和1.74%。随着Ca-GP浓度的增加,微孔均匀性变好,表面微裂纹减少,且钙磷原子比(Ca/P)显著提高。在含8、10 g/L的Ca-GP溶液中,制备的涂层以Ti、锐钛矿和金红石型Ti O2组成为主;在12g/L的Ca-GP溶液中生成的涂层,Ca/P原子比可达1.77,含有Ti P     

Electrophoretic deposition of hydroxyapatite coatings on titanium from dimethylformamide suspensions

Hydroxyapatite powders were prepared by a chemical precipitation method and electrophoretically deposited on pure Ti surgical substrates. The powders were suspended in dimethylformamide (DMF). The zeta potential, electromobility and the conductivity of the HA suspension was characterized at various pH values to identify the most stable dispersion conditions. The effect of applied voltage and deposition time on deposition rate, deposition thickness and coating morphology were studied. The coating morphology and composition were characterized by scanning electron microscopy (SEM). The crystalline phase of HA before and after electrophoretic deposition was examined using X- ray diffraction (XRD). Transition electron microscope (TEM) indicated that HA consisted of needle-shaped crystallites.     

Induction Plasma Sprayed Nano Hydroxyapatite Coatings on Titanium for Orthopaedic and Dental Implants

This paper reports preparation of a highly crystalline nano hydroxyapatite (HA) coating on commercially pure titanium (Cp-Ti) using inductively coupled radio frequency (RF) plasma spray and their in vitro and in vivo biological response. HA coatings were prepared on Ti using normal and supersonic plasma nozzles at different plate powers and working distances. X-ray diffraction (XRD) and Fourier transformed infrared spectroscopic (FTIR) analysis show that the normal plasma nozzle lead to increased phase decomposition, high amorphous calcium phosphate (ACP) phase formation, and severe dehydroxylation of HA. In contrast, coatings prepared using supersonic nozzle retained the crystallinity and phase purity of HA due to relatively short exposure time of HA particles in the plasma. In addition, these coatings exhibited a microstructure that varied from porous and glassy structure at the coating-substrate interface to dense HA at the top surface. The microstructural analysis showed that the coating was made of multigrain HA particles of ~200 nm in size, which consisted of recrystallized HA grains in the size range of 15- 20 nm. Apart from the type of nozzle, working distance was also found to have a strong influence on the HA phase decomposition, while plate power had little influence. Depending on the plasma processing conditions, a coating thickness between 300 and 400 μm was achieved where the adhesive bond strengths were found to be between 4.8 MPa to 24 MPa. The cytotoxicity of HA coatings was examined by culturing human fetal osteoblast cells (hFOB) on coated surfaces. In vivo studies, using the cortical defect model in rat femur, evaluated the histological response of the HA coatings prepared with supersonic nozzle. After 2 weeks of implantation, osteoid formation was evident on the HA coated implant surface, which could indicate early implant- tissue integration in vivo.     

Electrophoretic deposition of bioactive glass/polymer composite coatings with and without HA nanoparticle inclusions for biomedical applications

Electrophoretic deposition (EPD) methods have been developed for the fabrication of composite bioactive glass–hydroxyapatite (HA)–chitosan and bioactive glass–HA–alginate composite coatings. Two different strategies have been utilized, which are based on the use of cationic chitosan and anionic alginate biopolymers. The mechanism of cathodic deposition of chitosan is based on the pH increase at the cathode surface, whereas the pH decrease at the anode surface enabled the deposition of alginate coatings. The use of chitosan and alginate enabled the electrosteric stabilization and deposition of bioactive glass and HA particles. Composite coatings were obtained on various conductive substrates and studied by thermogravimetric analysis (TGA), differential thermal analysis (DTA), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The composition of the coatings can be varied by variation of bioactive glass and HA concentrations in the suspensions. The proposed method offers the advantages of room temperature fabrication of bioactive composite coatings that are suitable for biomedical applications.     

电泳沉积法制备羟基磷灰石涂层

羟基磷灰石是一种最有发展前途的生物材料之一.采用电泳沉积方法分别在Ti6Al4V基体和电泳沉积的HA/TiO2复合涂层上制备了HA生物陶瓷涂层.将HA粉体分散到正丁醇溶液中,通过测量zeta电位确定了悬浮体系中三乙醇胺和HA的含量.研究发现:HA沉积量随沉积温度和沉积电压的增加而增加,随沉积时间延长呈线性增长.对沉积量与电泳沉积工艺参数的关系进行了理论探讨.SEM结果表明,采用二次电泳沉积在HA/TiO2涂层表面制备的HA涂层更加致密、平整.     

电沉积制备氧化石墨烯-羟基磷灰石复合涂层

采用电沉积方法在钛表面制备氧化石墨烯-羟基磷灰石(Graphene oxide/Hydroxyapatite,GO/HA)复合涂层,通过调整GO的浓度,研究GO对所得涂层晶体结构及生物学性能的影响。采用扫描电镜(SEM)、透射电镜(TEM)、X射线衍射(XRD)仪、傅里叶变换红外光谱(FTIR)、拉曼光谱分析所得涂层的表面形貌和物相构成,用SEM观察涂层表面MG63成骨样细胞生长情况。结果表明,电沉积法可在钛表面制备GO/HA复合涂层,且随GO浓度增加,HA结晶度增加。此外,复合涂层较单纯HA涂层更能促进成骨样细胞早期粘附。     

Cross-sectional analysis on microstructure of plasma-sprayed HA＋TiO2 composite coatings on titanium substrate

The cross-sectional analysis on hydroxyapatite (HA) coating and HA TiO2 composite coating was conducted by using electron probe microanalyser (EPMA). The results reveal that annealing at 650℃ leads to the cracking within the HA coating or along the coating/substrate interface. The ribbon-like regions in HA coating are verified to contain less PO4^4- groups resulted from the high temperature melting of HA particles in plasma flame. From the viewpoint of microstructural observation, it can be concluded that the addition of TiO2 into HA coating can effectively strengthen and toughen the whole coating system with a shift of the well-bonded interface from the THA (top HA) coating/HTBC (HA TiO2 bond coat) interface in the as-sprayed THBC (top HA-HTBC) coating to the HTBC/Ti substrate interface in the heat treated THBC coating. The THA coating bonds well to Ti substrate per-haps via its TiO2 hobnobbing with the Ti oxides formed on the Ti substrate.