Electrophoretic deposition of biomimetic zinc substituted hydroxyapatite coatings with chitosan and carbon nanotubes on titanium

In this study, a biomimetic method was used to prepare hydroxyapatite (HAP) and zinc substituted HAP (ZnHAP) nanoparticles, in which silk fibroin was used as template. The morphology of HAP is rod-like, while ZnHAP changes to wrinkled sheets. HAP and ZnHAP nanoparticles were used to coat titanium by EPD with additional chitosan and multiwalled carbon nanotubes. Phase composition, morphology and structure were studied using X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared and Raman spectroscopy. The results showed that the composite coatings containing HAP and ZnHAP had homogeneous morphology and good apatite formation ability. The ZnHAP composite coating possessed class 5B adhesive strength using tape test. Furthermore, the ZnHAP composite coating had better corrosion resistance compared to the HAP composite coatings.     

Influence of ionic substitution in improving the biological property of carbon nanotubes reinforced hydroxyapatite composite coating on titanium for orthopedic applications

The present work is aimed for the development of carbon nanotubes (CNTs) reinforced single mineral (Sr, Mg, Zn) as well as multi minerals (Sr+Mg+Zn) substituted hydroxyapatite composite (M-HAP) coatings on titanium (Ti). The effect of different mineral ions substitution and CNTs reinforcement in HAP composite coating is discussed in detail. Fourier Transform Infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM) equipped with energy dispersive X-ray analysis (EDX), and high resolution transmission electron microscopy (HRTEM) were used to characterize the structural and morphological behavior of the composite coatings. The corrosion resistance of the composite coatings in simulated body fluid (SBF) solution was evaluated by the potentiodynamic polarization and electrochemical impedance spectroscopic (EIS) studies. In addition, the biocompatibility of the composite coatings was evaluated by in vitro culture of human osteoblast MG63 cells on the composite coated Ti. All these results essentially suggest that CNTs/M-HAP composite coated Ti can be a potential candidate for orthopedic applications.     

Cerium-doped hydroxyapatite/collagen coatings on titanium for bone implants

The novelty of the present research consists in the possibility of obtaining cerium-doped hydroxyapatite/collagen coatings on the titanium support, to improve the performance of the bone implants. These coatings were deposited on the titanium surface by biomimetic method using a modified supersaturated calcification solution (SCS) additionally containing a cerium source and collagen. Prior to the deposition of the apatite layer, an alkali ÷ thermal oxidation pretreatment has been applied to ensure an increase in the bioactivity of the titanium surface. The coatings were examined by scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD) and Fourier transformed infrared (FTIR) spectroscopy. The EDX and XRD investigations of the coatings indicated that cerium was incorporated in the hydroxyapatite lattice. The collagen presence in the coatings was confirmed by FTIR analysis. The cerium-doped hydroxyapatite/collagen coatings showed good antibacterial efficacy against Escherichia coli and Staphylococcus aureus bacteria, being more effective against Escherichia coli. These coatings have a significant potential to be used in the dental and orthopedic implants, as the osseointegration depends on much more factors than simple formation of hydroxyapatite.     

Hydroxyapatite coating on selectively passivated and sensitively polymer-protected surgical grade stainless steel

Surgical grade stainless steel (316L SS) is a widely used implant material in orthopedic surgeries. However, the release of metallic ions evidenced from the 316L SS implants in vivo conditions is a big challenge. In order to minimize the release of metallic ions, coating the 316L SS implant with a biocompatible material like hydroxyapatite [HAP, Ca₁₀(PO₄)₆(OH)₂] is one of the suitable methods. In this paper, the hydroxyapatite coating on borate passivated through poly-ortho-phenylenediamine (PoPD)-coated 316L SS by a dip coating method has been reported. The coatings were characterized by electrochemical techniques such as potentiodynamic polarization, electrochemical impedance spectroscopy, and cyclic voltammetry. Surface characterization studies of the coatings such as X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM) were also carried out. The leach out characteristics of the coatings was determined at the impressed potential. The mechanical property of the coatings was evaluated by Vicker’s microhardness test. The Cr-rich passive film formed underneath the PoPD layer showed a higher protective efficiency. The ability to form apatite on the post-passivated PoPD-coated 316L SS specimen was examined by immersing it in the simulated body fluid. The enhanced corrosion resistivity of the HAP coating on the post-passivated PoPD-coated 316L SS was due to an effective barrier of PoPD followed by the passive film underneath the PoPD.     

X-ray Photoelectron Spectroscopy Characterization of Ion-Beam Sputter-Deposited Calcium Phosphate Coatings

X-ray photoelectron spectroscopy (XPS) analysis of sputter-deposited calcium phosphate coatings on titanium substrates revealed four distinct zones. The ambient-exposed surface exhibited elevated concentrations of carbon because of atmospheric contamination. The bulk zone contained relatively constant concentrations of calcium, oxygen, phosphorus, and fluorine indicating the chemistry for calcium fluoride (CaF₂) and fluorapatite (Ca₅ (PO₄),F) formation. The transitional zone exhibited elevated titanium and oxygen photoelectron peaks suggesting the coexistence of calcium phosphate compounds within the titanium oxide. The substrate was shown to be identical to the passivated titanium surface prior to deposition.     

The effect of thermal annealing on Fe/TiO2 coatings deposited with the help of RF PECVD method. Part I. Chemical and phase composition

Results of the studies on chemical structure and phase composition of both non-annealed and thermally annealed iron doped TiO₂ coatings are presented. The coatings were synthesized with the help of radio frequency plasma enhanced chemical vapor deposition (RF PECVD) and characterized by iron content in the range of 0–4.76 at%. In these studies, an analysis of both elemental composition and chemical bonding was performed with the help of X-ray photoelectron spectroscopy (XPS). X-ray diffraction (XRD) was applied to determine phase composition and Fourier transform infrared spectroscopy (FTIR) was used as a supplementary source of information. The obtained elemental composition data show that, apart from titanium, oxygen and iron, traces of chlorine as well as substantial amounts of carbon are present in the coatings. While chlorine has originated from plasma decomposition of TiCl_4, used as a source of titanium, a presence of carbon is associated with a surface contamination resulting from photocatalytic reactions of TiO₂ with the adsorbed carbon dioxide. The results of XPS and FTIR indicate that thermal annealing not only modifies phase composition of these materials, but also affects chemical bonding. Finally, XRD analysis shows that iron content has an effect on the size of coherent diffraction domains present in the films.     

Influences of bias voltage on properties of TiAl-doped DLC coatings synthesized by cathodic arc evaporation

In this work, the combinations of TiAl-doped DLC (Diamond-like Carbon) and TiAlN/TiN double-layered films were designed to deposit on the tool steels using cathodic arc evaporation in a single process. The economic advantage in depositing the combined coating in one production scale PVD coating system is of practical importance. The TiAl-doped DLC as lubricant coatings were synthesized with TiAl-target arc sources to emit ion plasma to activate acetylene reactive gases. Scanning electron microscopy (SEM), Auger electron spectroscopy (AES), micro-Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) techniques were employed to analysis the microstructure properties of TiAl-doped DLC coatings. Vicker's and tribometer tester were used to measure the mechanical properties of TiAl-doped DLC coatings. The results show that the TiAl-doped DLC coatings retained lower friction coefficient at approximately 0.15 during the steady state sliding. The lubricity and wear resistance of TiAl-doped DLC coatings is then demonstrated to potentially be applied to the cutting tools with no lubricants.     

In situ synthesis,fabrication and Rietveld refinement of the hydroxyapatite/titania composite coatings on 316 L SS

The development of Hydroxyapatite (HAP)/Titania (TiO₂) composite coatings on metallic implants have received a great deal of attention during the recent years owing to their superior advantages in biomedical applications. The present study has focused on the in situ formation of HAP/TiO₂ composite powders through aqueous precipitation technique. Five different HAP/TiO₂ composite powders of varied HAP to TiO₂ ratios has been synthesized in the present study and the results were compared with the stoichiometric HAP, Rutile TiO₂ and Anatase TiO₂ which also have been synthesized by adapting a similar synthetic procedure. All the synthesized powders have been analyzed using X-ray diffraction (XRD) and X-ray fluorescence (XRF) techniques. Rietveld Refinement technique has been employed to generate quantitative information about the structural characteristics and phase content in all the powder samples. Further, the electrophoretic deposition (EPD) method has been employed to fabricate HAP/TiO₂ composite coatings on 316 L SS and the resultant coatings were analyzed for its quantitative structural characteristics. The results from the present investigation has confirmed that concentration of TiO₂ in the HAP/TiO₂ composites and heat treatment temperatures have played a major role in the degradation of HAP to β-Tricalcium phosphate and also in the conversion of Anatase to Rutile TiO₂ phase.     

Enhanced biosorption of bisphenol A from wastewater using hydroxyapatite elaborated from fish scales and camel bone meal: A RSM@BBD optimization approach

In this work, camel bone biowaste and fish scales were used as a source for the production of hydroxyappatite. Hydroxyapatite (HAP) was extracted from fish scales (FS) and camel bone meal (CBM) using the alkaline heat treatment method. The HAP prepared was analyzed by different characterization techniques such as X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), Fourier Transformation Infrared spectroscopy (FTIR), Energy Dispersive X-ray spectroscopy (EDS) and Brunauer-Emmett-Teller (BET) analysis. The HAP developed from FS and CBM biomaterials was used as a highly effective green adsorbent to eliminate bisphenol A (BPA) from water. The pseudo-second-order and Langmuir models were well fitted with the kinetic and adsorption isotherm data, with a maximum adsorption capacity of 74.128 and 89.828 mg/g, respectively for FS and CBM. The BPA adsorption on FS and CBM were optimized by the surface response methodology and the Box Behnken Design (RSM@BBD). The optimal factors were obtained to be for FS (% Removal = 83.51%), an adsorbent dose of 1.375 g/L, C_i of 5 mg/L and contact temp 115.6 min and for CBM (% Removal = 79.38%) were an adsorbent dose of 1.1 g/L, C_i of 6.99 mg/L and contact temp 106.3 min.     

Hydroxyapatite Coating on Titanium Substrate by the Sol-Gel Process

Hydroxyapatite coatings on titanium were attempted by a sol-gel process combined with conventional heat treatment and with UV irradiation at ambient temperature after dipping/ withdrawing a substrate into/from the sol. X-ray diffraction data showed that a coating film prepared by heat treatment was amorphous and crystallized in Ca₅(PO₄)₃(OH) at a temperature of 773–973 K. The infrared spectra for coating films that have been prepared by heat treatment at a temperature of 573–873 K were in fair agreement with those for a coating film prepared by UV irradiation. After ethylene oxide sterilization, the cytotoxicity of coating film decreased with increasing irradiation time in UV irradiation, whereas it decreased with increasing temperature in conventional heat treatment. In comparisons between ethylene oxide sterilization and autoclave sterilization, the coating film sterilized by autoclave had much lower cytotoxicity than that sterilized by ethylene oxide. Furthermore, an animal test in the transfemoral drill hole on a rat for 4 weeks was examined using an implant prepared by heat treatment and autoclave sterilization. The sol-gel-coated titanium had slightly higher bone apposition than uncoated titanium as a control material.     

Investigation of surface pre-treatments for the structural bonding of titanium

This paper evaluates wet-chemical pre-treatments (alkaline etching, anodising) and a plasma treatment for structural bonding of titanium (Ti₆Al₄V). The main objective of this study is the comparison of the applicability of the plasma pre-treatment to wet-chemical treatments on titanium for structural bonding. In this context, an atmospheric pressure plasma device was used to deposit thin functional films from hexamethyldisiloxane (HMDSO) precursor on titanium.X-ray photoelectron spectroscopy (XPS) was employed to assess the chemical composition of the surface after different pre-treatments on the titanium substrate, while the morphology and the film thickness were investigated with scanning electron microscopy (SEM). The adhesion properties on titanium were evaluated by means of a wedge test in hot/wet conditions. After bonding tests the fracture surface and the failure loci were analysed.Using a long arc plasma generator and HMDSO precursor almost stoichiometric SiO₂ coatings were obtained on the titanium substrate. These coatings exhibit good long-term durability and bond strength compared to an alkaline etching in the wedge test. The investigated anodising process leads to oxide layers revealing a highly porous nanostructure. In contrast to the alkaline etching, the plasma derived coatings and the oxide layer produced by the anodising process exhibit a higher micro, respectively nano roughness, and hence a better long-term durability.     

Morphology,Composition, and Bioactivity of Strontium-Doped Brushite Coatings Deposited on Titanium Implants via Electrochemical Deposition

Surface modification techniques have been applied to generate titanium implant surfaces that promote osseointegration for use in dental applications. In this study, strontium-doped brushite coatings were deposited on titanium by electrochemical deposition. The phase composition of the coating was investigated by energy dispersive X-ray spectroscopy and X-ray diffraction. The surface morphologies of the coatings were studied through scanning electron microscopy, and the cytocompatibility and bioactivity of the strontium-doped brushite coatings were evaluated using cultured osteoblasts. Osteoblast proliferation was enhanced by the addition of strontium, suggesting a possible mechanism by which strontium incorporation in brushite coatings increased bone formation surrounding the implants. Cell growth was also strongly influenced by the composition of the deposited coatings, with a 10% Sr-doped brushite coating inducing the greatest amount of bone formation among the tested materials.     

X-ray Photoemission and Energy Dispersive Spectroscopy of Hydroxyapatite-Coated Titanium

The purpose of this study was to determine the chemical composition changes of hydroxyapatite (HA) coated titanium using surface analysis (X-ray photoemission) and bulk analysis (energy dispersive spectroscopy). The specimens examined were controls and specimens aged 30 min and 3 h at room temperature in distilled water and 0.2 M sodium phosphate buffer (pH 7.2). Each X-ray photoemission cycle consisted of three scans followed by argon sputtering for 10 min for usually 20 cycles, corresponding to a sampling depth of ∼1500 Å. The energy dispersive spectroscopy analysis was on a 110 by 90 μm area for 500 s. The X-ray photoemission results indicated the oxidation effect of water on the titanium (as TiO₂) and the effect of the buffer to increase the surface concentration of phosphorus. No differences in the chemical composition were observed by energy dispersive spectroscopy analysis.     

Degradation of boron nitride interfacial coatings fabricated by chemical vapor infiltration on SiC fibers under ambient air/room temperature conditions

Hexagonal boron nitride (h-BN) interfacial coatings were deposited on SiC fibers by chemical vapor infiltration (CVI) and their degradation behavior under ambient air/room temperature conditions was studied with time. Degradation of the interfacial coatings with time was investigated by characterizing the morphology and microstructure of these materials with scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and transmission electron microscopy (TEM). Thermogravimetry coupled with differential thermal analysis (TG-DTA) and X-ray photoelectron spectroscopy (XPS) was used to analyze the chemical reactions and phase transitions taking place in the BN coatings. The results showed that the as-deposited BN interfacial coatings fabricated by CVI were compact and well bonded to the SiC fibers. BN coatings remained relatively stable under ambient air/room temperature conditions for 50?h, while severe degradation was observed after 500?h of exposure. The degradation of BN interfacial coatings was mainly caused by two factors, namely, reaction with atmospheric air to produce boric oxide and amorphization of the hexagonal structure. The degradation observed under ambient air/room temperature might be due to incomplete crystallinity of BN interfacial coatings. Presence of water vapor may accelerate degradation of the coatings. The results of this degradation test can be used as a reference for the storage of BN coatings fabricated by CVI.     

在改性模拟体液中电沉积羟基磷灰石涂层

Hydroxyapatite coatings were directly prepared on anodized titanium by electro-deposition method in a modified simulated body fluid. The configuration, structure and bioactivity of the coating were investigated with scanning electron microscopy (SEM), X-ray diffraction analyzer (XRD) and Fourier transform infrared spectroscopy (FTIR) techniques. The results demonstrated that pure and homogeneous hydroxyapatite coating can be obtained without any post-treatment. The prepared coating showed good bioactivity in simulated body fluid (SBF). The time required for a fully covered dense hydroxyapatite coatings was 4 days immersion in SBF.     

An electrochemical study of the behaviour of ear piercing studs immersed in a culture medium

Two commercial studs, of gold-coated stainless steel and copper–zinc alloy, respectively, and a laboratory-made titanium stud were chosen for corrosion studies. Corrosion behaviour in a culture medium (CM) was studied using electrochemical impedance spectroscopy and polarization measurements, as a function of immersion time. The elements that leached out into the CM electrolyte were analysed by instrumental neutron activation analysis. Scanning electron microscopy and energy dispersive X-ray techniques were utilized in the analysis of the stud surfaces before and after their immersion in a CM solution. The cytotoxicity of the tested studs was also determined. The titanium stud showed the best combination of properties, high corrosion resistance and low cytotoxicity, while the gold-coated stainless steel stud occupied an intermediate position.     

磁场诱导对AZ91D镁合金表面仿生矿化法制备羟基磷灰石涂层性能的影响

在无磁场及强度均为0.4 T的平行磁场和垂直磁场诱导下,采用仿生矿化法在AZ91D镁合金表面制备羟基磷灰石(HAP)涂层。采用扫描电镜、X射线衍射仪和测厚仪分析了HAP涂层的表面形貌、物相成分、晶体取向和厚度。结果表明,在垂直磁场条件下制备的HAP涂层最均匀、致密,晶体为a、b轴取向。     

Iron doped thin TiO2 films synthesized with the RF PECVD method

Iron doped titanium dioxide coatings were synthesized with the help of RF plasma enhanced CVD technique. As a source of titanium, titanium chloride (IV) TiCl₄ was used while iron pentacarbonyl (0) Fe(CO)₅ served as iron supply. The coatings were diagnosed using Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM). Their elemental and chemical composition was studied with the help of X-ray energy dispersive spectroscopy (EDS) and Fourier transform infrared (FTIR) spectroscopy, respectively. For the determination of their optical properties, variable angle spectroscopic ellipsometry (VASE) and ultraviolet-visible (UV-Vis) spectroscopy techniques were used. Iron content in the range of 0.07–11.5 at% was found in the films. Apart from oxygen, titanium and iron, a presence of trace amounts of chlorine, very likely originating from the titanium precursor, was recorded. FTIR studies showed that iron was built-in in the structure of TiO₂ matrix. Surface roughness, assessed using SEM and AFM techniques, increases with an increasing content of this element. VASE measurements revealed an increase of the coatings refractive index with a growing iron concentration, with the extinction coefficient remaining low and independent of that parameter. Trace amounts of iron resulted in a lowering of an absorption threshold of the films as well as their optical gap, but the tendency was reversed for high concentrations of that element.     

羧酸改性钛白粉促进光固化研究

采用油酸对商用二氧化钛进行表面改性,通过 X-射线光电子能谱仪（ XPS）、红外光谱（FT-IR）和 X射线粉末衍射分析（ XRD）对改性后的 TiO₂粒子进行了结构表征,并借助热重分析测定了改性剂的含量。采用光差示扫描量热法（ photo-DSC）研究了无机膜保护型 TiO₂、去包膜型 TiO₂、油酸改性 TiO₂和三甲基苯甲酰二苯基氧化膦（ TPO）对丙烯酸酯光聚合动力学的影响。结果表明：油酸改性的 TiO₂与无机膜保护的 TiO₂和去包膜的 TiO₂相比,能在空气中引发丙烯酸酯的光聚合,并能增强以 TPO为光引发剂的丙烯酸酯的光聚合,从而在相同固化效果下,可减少小分子光引发剂的添加,降低残留。本研究为后续紫外光（UV）固化白色涂料、油墨固化不完善等问题提供了解决途径。     

Morphology,structure and photowettability of TiO2 coatings doped with copper and fluorine

The work reports synthesis, structure and properties of doubly doped titanium dioxide coatings activated by ultraviolet and visible light. Copper within a concentration range of 0.4–3.4 at% and fluorine within a concentration range of 1.7–9.4 at% were introduced as dopants. The coatings were prepared with the help of radiofrequency plasma enhanced chemical vapor deposition technique with a single precursor compound providing both dopants and titanium (IV) chloride being a source of titanium. Elemental composition and chemical bonding analyses of the coatings were carried out with the help of X-ray photoelectron spectroscopy. The results indicate that both admixtures are chemically bound to the TiO₂ matrix – a notion confirmed by Fourier transform infrared spectroscopy. Phase composition studies, performed with a low angle X-ray diffraction method, revealed a presence of a threshold concentration of the dopants affecting the coatings crystallinity. Surface morphology and its topography were studied with the help of scanning electron microscopy and atomic force microscopy. Several coatings exhibited a superhydrophilic effect upon relatively short time of illumination.