Nano-Ag-loaded hydroxyapatite coatings on titanium surfaces by electrochemical deposition

Hydroxyapatite (HA) coatings on titanium (Ti) substrates have attracted much attention owing to the combination of good mechanical properties of Ti and superior biocompatibility of HA. Incorporating silver (Ag) into HA coatings is an effective method to impart the coatings with antibacterial properties. However, the uniform distribution of Ag is still a challenge and Ag particles in the coatings are easy to agglomerate, which in turn affects the applications of the coatings. In this study, we employed pulsed electrochemical deposition to co-deposit HA and Ag simultaneously, which realized the uniform distribution of Ag particles in the coatings. This method was based on the use of a well-designed electrolyte containing Ag ions, calcium ions and l-cysteine, in which cysteine acted as the coordination agent to stabilize Ag ions. The antibacterial and cell culture tests were used to evaluate the antibacterial properties and biocompatibility of HA/Ag composite coatings, respectively. The results indicated the as-prepared coatings had good antibacterial properties and biocompatibility. However, an appropriate silver content should be chosen to balance the biocompatibility and antibacterial properties. Heat treatments promoted the adhesive strength and enhanced the biocompatibility without sacrificing the antibacterial properties of the HA/Ag coatings. In summary, this study provided an alternative method to prepare bioactive surfaces with bactericidal ability for biomedical devices.     

Controllable synthesis of hydroxyapatite nanocrystals via a dendrimer-assisted hydrothermal process

The morphology and size of hydroxyapatite Ca₁₀(PO₄)₆(OH)₂ (denoted HAP) can be controlled under hydrothermal treatment assisted with different dendrimers, such as carboxylic terminated poly(amidoamine) (PAMAM) and polyhydroxy terminated PAMAM. The structure and morphology were characterized by X-ray diffraction (XRD), infrared spectroscopy (IR) and transmission electron microscopy (TEM). IR spectra were also used to investigate the complexation of Ca²⁺ with PAMAM. The results revealed that the inner cores of the PAMAM dendrimers are hydrophilic and potentially open to calcium ions, since interior nitrogen moieties serve as complexation sites, especially in case of the polyhydroxy terminated PAMAM. And the reasonable mechanism of crystallization was proposed that it can be attributed to the localization of nucleation site: external or interior PAMAM. Additionally, the PAMAM dendrimer with carboxylic and polyhydroxy groups has an effective influence on the size and shape of hydroxyapatite (HAP) nanostructures. Different crystal morphology was accomplished by adsorption of different dendrimers onto specific faces of growing crystals, altering the relative growth rates of the different crystallographic faces and leading to different crystal habits.     

The process of electrochemical deposited hydroxyapatite coatings on biomedical titanium at room temperature

Calcium phosphate (CaP) ceramics, especially hydroxyapatite (HA), have received much attention and have been clinically applied in orthopaedics and dentistry due to their excellent biocompatibility. Among several methods for preparing HA coating, electrochemical deposition is a relatively new and possible process. However, documented electrochemical processes were conducted at elevated temperature. In this study, uniform HA coatings have been directly deposited on titanium at room temperature. X-ray diffractometry (XRD) results demonstrated that dicalcium phosphate dihydrate (CaHPO₄·2H₂O, DCPD) was the main component of the coating deposited at lower current densities (1 and 5 mA/cm²). HA structure was obtained at current density above 10 mA/cm² and remained stable after heat treatment at 100–600 °C for 1 h. Part of HA phase was transformed into β-TCP and became a biphasic calcium phosphate coating after annealing at 700 °C. Scratch tests showed that HA coating was not scraped off until a shear stress of 106.3 MPa. Coatings deposited at room temperature exhibited stronger adhesion than those at elevated temperature. HA coating revealed a dense inner layer and rough surface morphology which could fulfill the requisition of implant materials and be adequate to the attachment of bone tissue.     

Pulsed laser deposition of silicon-substituted hydroxyapatite coatings

Thin films of Si-substituted hydroxyapatite (Si-HA) were deposited on Si and Ti substrates by pulsed laser deposition (PLD), in the presence of a water vapour atmosphere. The PLD ablation targets were made with different mixtures of commercial carbonated HA and Si powder, in order to produce the Si-HA thin films. The physicochemical properties of the coatings and the incorporation of the Si into the HA structure was studied by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The Si atoms were successfully incorporated into the HA structure, and were found to be in the form of SiO₄⁴⁻ groups, principally displacing carbonate groups off the HA structure.     

HOPG片电化学沉积羟基磷灰石初探

为探索羟基磷灰石(HA)在含碳基体上电化学沉积,采用了高定向裂解石墨(HOPG)片这一具有原子级平整表面的导电材料作为阴极材料,探索了电沉积时间、溶液pH值及溶液浓度对沉积层成分和形貌的影响,利用TEM、SEM、AFM、EDS及XRD等进行了表征分析,并初步探讨了羟基磷灰石电沉积机理。结果表明电解液初始pH值为5和钙离子浓度低于0.007mol/L时有利于促进HA的生长,并且可以形成单层片状结构,得到比较规整完善的多孔状单层HA涂层。而延长电沉积和陈化时间则有助于缺钙型HA垂直于基底表面生长,并促进钙磷比增加,形成缺钙性HA。研究将为电沉积羟基磷灰石的应用提供必要的理论和实验支持。     

Morphology and composition of hydroxyapatite coatings prepared by hydrothermal treatment on electrodeposited brushite coatings

Highly pure brushite CaHPO₄ · 2H₂O) coatings on porous Ti6Al4V substrates were prepared by electrodeposition from aqueous electrolytes. The influence of hydrothermal treatment parameters on brushite-to-hydroxyapatite conversion and the morphology and phase composition of hydroxyapatite (HAP) coatings was studied. It was found that the content, Ca/P atomic ratio, grain size and pore size of HAP in coatings increase with increasing hydrothermal treatment temperature, and that increasing the pH value can promote brushite-to-HAP conversion and reduce the grain size of HAP. Under optimal conditions, highly pure HAP coatings with needle-like crystals and non-stoichiometric form, which are similar to those of calcium phosphate in human bone, can be obtained. © 1999 Kluwer Academic Publishers     

电沉积法可控制备纳米羟基磷灰石涂层的研究

采用电化学沉积法在医用金属钛表面制备钙磷盐涂层,通过XRD、FT-IR和SEM表征,侧重探索电化学沉积技术在温和条件下制备结晶结构优良的纯羟基磷灰石涂层的可控性.通过控制电流密度和反应时间,即研究在恒电量条件下羟基磷灰石涂层的电化学沉积规律性,并获得电化学沉积制备纳米有序结构羟基磷灰石涂层的最佳实验条件,同时对纳米有序结构羟基磷灰石涂层的电化学沉积机理进行讨论.     

纳米羟基磷灰石粉体的水热合成

采用Ca(NO3)2·4H2O和(NH4)3PO4·3H2O作为反应前驱物,通过水热合成颗粒尺寸在100nm以下的短棒状或针状HA晶体.X射线衍射(XRD)、透射电镜(TEM)和红外光谱(FTIR)分析讨论水热温度、反应时间、表面活性剂和烧结与物相组成、晶粒尺寸和晶体形貌的关系.实验结果表明升高反应温度和延长反应时间有利于HA的生成;表面活性剂有助于改善粉体的分散性能;烧结能提高晶体的结晶程度,但粉体易团聚,当温度高于800℃时HA发生分解.     

工艺条件对低温燃烧/水热法合成纳米羟基磷灰石的影响

以Ca(NO3)2·4H2O、(NH4)2HPO4和柠檬酸为原料,浓硝酸为溶剂,NH4NO3为助燃剂,采用低温燃烧/水热法能够快速合成羟基磷灰石纳米粉体.通过对不同工艺条件下得到的试样进行XRD、SEM等分析,研究了柠檬酸和NH4NO3的加入量对燃烧反应的影响,以及水热处理的温度和时间对水热反应的影响.研究结果表明,选择合理的工艺条件能够快速合成高纯度的羟基磷灰石纳米粉体.     

Synthesis and properties of bio-waste-based hydroxyapatite via hydrothermal process

In this study, a facile hydrothermal method is applied to produce hydroxyapatite (HA) particles using egg shells as calcium precursors and fruit waste extracts (banana peel) as biomolecular templates at 150 °C for a reaction time period of 12 hours (h) and 24 hours. The sintering of the green samples of hydroxyapatite were conducted at 1250 °C in air for 2 h. The results showed that pectin extracted from banana peel extracts assisted in regulating crystal growth to obtain homogeneous hydroxyapatite powder, with higher purity observed for 24 h hydrothermal reaction time. Fourier-transform infrared spectroscopy (FTIR) spectra revealed the presences of phosphate (PO₄³⁻) and hydroxyl (OH⁻) groups in the powders. A relative density of 89.6 % was achieved for sintered hydroxyapatite compacts produced via hydrothermal method for 24 h. The sintered body was characterized by having high Vickers hardness of 5.35 GPa and good fracture toughness of 1.23 MPa√m, suitable for biomedical application.     

Mineralized collagen coatings formed by electrochemical deposition

Understanding and controlling the process of electrochemical deposition (ECD) of a mineralized collagen coating on metallic orthopedic implants is important for engineering highly bioactive coatings. In this work, the influence of different ECD parameters was investigated. The results showed that the mineralization degree of the coatings increased with deposition time, voltage potential and H₂O₂ addition, while chitosan addition led to weakening of mineralization, heavy mineralization resulted in a porous coating morphology. Furthermore, two typical coatings, dense and porous, were analyzed to investigate their microstructure and evaluated for their cytocompatibility; the dense coating showed better osteoblast adhesion and proliferation. Based on our understanding of how the different coating parameters influenced the coating, we proposed an ECD process in which the pH gradient near the cathode and the collagen isoelectric point were suggested to play crucial roles in controlling the mineralization and morphology of the coatings. The proposed ECD process may offer a guide for controlled deposition of a desired bioactive coating.     

Aerosol deposition of silicon-substituted hydroxyapatite coatings for biomedical applications

Silicon-substituted hydroxyapatite (Si-HA) coatings on commercially pure titanium (Ti) were prepared by aerosol deposition using Si-HA powders. Si-HA powders with the chemical formula Ca₁₀(PO₄)_6 − x(SiO₄)_x(OH)_2 − x, having silicon contents up to x = 0.5 (1.4 wt.%), were synthesized by solid-state reaction of Ca₂P₂O₇, CaCO₃, and SiO₂. The Si-HA powders were characterized by X-ray diffraction (XRD), X-ray fluorescence spectrometry, and Fourier transform infrared spectroscopy. The corresponding coatings were also analyzed by XRD, scanning electron microscopy, and electron probe microanalyzer. The results revealed that a single-phase Si-HA was obtained without any secondary phases such as α- or β-tricalcium phosphate for both the powders and the coatings. The Si-HA coating was about 5 µm thick, had a dense microstructure with no cracks or pores, and showed a high adhesion strength ranging from 28.4 to 32.1 MPa. In addition, the proliferation and alkaline phosphatase activity of MC3T3-E1 preosteoblast cells grown on the Si-HA coatings were significantly higher than those on the bare Ti and pure HA coating. These results revealed the stimulatory effects induced by silicon substitution on the cellular response to the HA coating.     

Effect of suspension stability on electrophoretic deposition of hydroxyapatite coatings

In order to prepare densely packed hydroxyapatite (HAp) coating onto titanium substrate through electrophoretic deposition (EPD), it is highly desirable to produce stable HAp suspension. In this study, nano-HAp particles prepared by hydrothermal method were employed for EPD. The stability of HAp suspensions in various primary aliphatic alcohols (C1–C4) has been studied by measurement of sedimentation tests and electricity conductivity. Furthermore, to make a stable suspension, a dispersant [triethanolamine (TEA)] was added. Maximum stability is observed for the suspension containing n-butanol as the dispersion medium and TEA as the dispersant. The HAp coating deposited in this suspension was observed to be a crack-free and densely packed coating through scanning electron microscopy examination. The shear strength and nano-indention tests have confirmed the good adhesion between the coating and the substrate.     

Thin hydroxyapatite layers formed on porous titanium using electrochemical and hydrothermal reaction

In our previous study, it was found that hydroxyapatite (HA) microcrystals were precipitated by hydrothermal treatment on an anodic titanium oxide film containing calcium and phosphorus (AOFCP) with an equivalent Ca/P ratio to HA, which was formed on a titanium metal anode in an aqueous electrolytic solution of dissolved calcium acetate and -glycerophosphate. In this study, the formation mechanism of the AOFCP has been clarified. Spark discharges, which occur on titanium surface with a large amount of heat generation, cause crystallization of the TiO₂ matrix of the AOFCP and incorporation of calcium and phosphorus into the matrix from these electrolytes simultaneously. The calcium and phosphorus in the matrix seem to exist as ions rather than as calcium phosphate. Also, thin HA layers consisting of the many precipitated microcrystals can be uniformly formed even on titanium with complex shapes or surface geometries such as the mesh, roughened surfaces and bead-coated porous coating by the present method.     

Synthesized silicon-substituted hydroxyapatite coating on titanium substrate by electrochemical deposition

Silicon-substituted hydroxyapaptite (Si-HA) coatings were prepared on titanium substrates by electrolytic deposition technique in electrolytes containing Ca²⁺, PO₄ ³⁻ and SiO₃ ²⁻ ions with various SiO₃ ²⁻/(PO₄ ³⁻ + SiO₃ ²⁻) molar ratios(η_si). The deposition was all conducted at a constant voltage of 3.0 V, with titanium substrate as cathode and platinum as anode, for 1 h at 85°C. The coatings thus prepared were characterized with inductively coupled plasma (ICP), X-ray diffraction (XRD), fourier transform infrared spectroscopy (FTIR), field-emission-type scanning electron microscope (FSEM). The results show that the silicon amount in the coatings increases linearly to about 0.48 wt% at first with increasing η_si between 0 and 0.03, then increases slowly to about 0.55 wt% between 0.03 and 0.10 and finally maintains almost at a level around 0.55 wt% between 0.10 and 0.30. The tree-like Si-HA crystals are observed in the coatings prepared in the electrolyte of η_si = 0.20. And the presence of silicon in electrolytes decreases the thickness of the coatings, with effect being more significant as η_si increased. Additionally, the substitution of Si causes some OH⁻ loss and changes the lattice parameters of hydroxyapatite (HA).     

Interfacial study of magnesium-containing fluoridated hydroxyapatite coatings

Magnesium-containing fluoridated hydroxyapatite (Mg_xFHA) coatings have been developed to improve the biological performances of fluoridated hydroxyapatite (FHA) coatings. The coatings are deposited on Ti6Al4V substrates via a sol-gel process. The interface between the coating and substrate is characterized by scanning electron microscopy, glow discharge optical emission spectroscopy and X-ray photoelectron spectroscopy for coating thickness, elemental distribution and chemical states. Pull-off test is used to evaluate the adhesion strength. The results show that the interdiffusion of elements happens at the coating/substrate interface. The incorporation of Mg ions into FHA coatings enhances the pull-off adhesion strength between the coating and the substrate, but no significant difference is observed with different Mg concentrations.     

Preparation of layered bioceramic hydroxyapatite/sodium titanate coatings on titanium substrates using a hybrid technique of alkali-heat treatment and electrochemical deposition

Bioceramic hydroxyapatite/sodium titanate coating on sandblasted titanium substrate was fabricated by a three-step process. At first, the sandblasted titanium substrate was coated with a flake-like sodium titanate layer by alkali-heat treatment. In the second step, the alkali-heat treated titanium substrate was hydrothermal treated at 180 °C for 4 h with calcium solutions. In the third step, the hydroxyapatite (HA) coating was deposited onto the hydrothermal treated layer via electrochemical deposition method. The surface topography and roughness of the coatings were determined by field emission scanning electron microscope (FESEM) and a mechanical contact profilometer, respectively. The surface compositions were evaluated by X-ray diffraction (XRD), energy-dispersive X-ray spectrum (EDS), and X-ray photoelectron spectroscopy (XPS). The EDS, XPS, and XRD analysis confirm the presence of element Ca, Ca²⁺, and CaTiO₃ on sodium titanate layer after hydrothermal treatment with Ca(NO₃)₂ solution, respectively. FESEM micrograph shows the rod/needle-shaped crystallites are highly densely packed on the calcium-ion-containing layer with an average size of ~50 nm in diameter. The results indicate that the sodium titanate layer containing Ca²⁺ ions possesses higher ability to induce HA formation compared with the pure sodium titanate layer. It is revealed that surface composition plays an important role in the electrochemical deposition of HA. The calcium-ion-containing layer probably makes the nucleation of HA easy and effectively promotes orientated growth of HA on flake-like sodium titanate surface. The sodium titanate layer possesses a lower corrosion current density and a higher corrosion potential than sandblasted-Ti substrate. The sodium titanate layer should act as a barrier to the release of metal ions from metallic substrate to physiological solutions and thus reducing the electrochemical reaction rate.     

Silver doped hydroxyapatite coatings by sacrificial anode deposition under magnetic field

Uniform distribution of silver (Ag) in the hydroxyapatite (HA) coated Ti surface has been a concern for which an attempt has been made to dope Ag in HA coating with and without magnetic field. Cathodic deposition technique was employed to coat Ag incorporated hydroxyapatite coating using a sacrificial silver anode method by using NdFeB bar magnets producing 12 Tesla magnetic field. While uniform deposition of Ag was observed in the coatings under magnetic field, dense coating was evident in the coating without magnetic field conditions. Uniformly distributed Ag incorporated HA in the present study has potential to fight microorganism while providing osseoconduction properties of the composite coating.