Effect of transition layer on the performance of hydroxyapatite/titanium nitride coating developed on Ti-6Al-4V alloy by magnetron sputtering

A gradient transition multilayer hydroxyapatite/titanium nitride (HA/TiN) coating was prepared on the Ti-6Al-4V alloy by magnetron sputtering. The composition, surface topography, microstructure, adhesion strength and electrochemical properties of the as-deposited coatings were characterized by SEM/EDS, AFM, XRD, FT-IR and electrochemical workstation. The experimental results showed that the single TiN coating deposited at a partial pressure of nitrogen (N₂) of 0.08?Pa had the best internal stress and tribological performance, and its volume loss was only 0.89% of that of Ti-6Al-4V alloy. The introduction of the TiN transition layer greatly improved the wear resistance of the Ti-6Al-4V alloy, and the adhesion strength of the HA layer to the substrate increased from 6.50?±?0.5?N to 11.70?±?1.2?N, an increase of 56%. The HA/TiN coating surface consisted of uniform hemispherical particles with dense structure and invisible defects (micro-cracks and pores). For the HA surface layer, the crystal structure and active hydroxyl (-OH) group was restored after heat treatment. Potentiodynamic polarization experiments indicated that the HA/TiN coating achieved the lowest corrosion current density and the most positive corrosion potential compared to the single TiN layer and Ti-6Al-4V alloy. In summary, it can be conclude that the gradient transition layer can well improve the mechanical properties and electrochemical behavior of the titanium alloy, and largely ensuring the stability of the surface bioactive coating.     

Microstructural and optical properties of Ta-doped ZnO films prepared by radio frequency magnetron sputtering

Ta-doped ZnO films with different doping levels (0–5.02 at%) were prepared by radio frequency magnetron sputtering. The effects of the doping amount on the microstructure and the optical properties of the films were investigated. The grain size and surface roughness first significantly decrease and then slowly increase with the increase of Ta doping concentration. Both the grain size and the root mean square (RMS) roughness reach their minimum values at the doping content of 3.32 at%. X-ray Diffraction (XRD) patterns confirmed that the prepared Ta-doped ZnO films are polycrystalline with hexagonal wurtzite structure and a preferred orientation along the (002) plane. X-ray photoelectron spectroscopy (XPS) analysis reveals that Ta exists in the ZnO film in the Ta⁵⁺ and Ta⁴⁺ states. The average optical transmission values of the Ta-doped ZnO films are higher than those of the un-doped ZnO film in the visible region. The band gap energy extracted from the absorption edge of transmission spectra becomes large and the near band edge (NBE) emission energy obtained from PL spectra blueshifts to high energy when the Ta doping content grows from 0 at% to 5.02 at%, which can be explained by the Burstein–Moss shift.     

Structural evaluation,preliminary in vitro stability and electrochemical behavior of apatite coatings on Ti6Al4V substrates

Medical-grade alloys, such as Ti-6Al-4V, have been used for fixation of fractured bone and for the total replacement of defective bone. Their bioactivity could be improved by applying a bone-like apatite layer onto their surfaces. This, in turn, enhances their integration with the surrounding tissues upon implantation. In addition, the presence of a bioactive bone-like coating minimizes the likelihood of corrosion. Various methods are known for the formation of apatite coating onto Ti-6Al-4V, among which sputtering has shown its promise as a simple direct method. In the current work, a sputtering technique was used to develop a 300 nm-thick bone-like apatite layer onto Ti-6Al-4V. Structural composition, integrity and morphology of the as-coated and thermally treated coatings were investigated. Coated substrates were further evaluated after soaking them in a simulated body fluid (SBF) for up to 14 days. Results showed the formation of an amorphous apatite layer onto the alloy, that was further shown to partially crystallize upon heat treatment. As a result of SBF treatment, the apatite layer was found to remodel through a dissolution-precipitation mechanism due to its amorphous and non-stoichiometric nature, forming a smooth layer with better homogeneity and decreased surface roughness. Electrochemical analysis of the coated alloys showed the enhanced corrosion protection of the alloy surfaces by coating them with apatite. In addition, pre-grinding of the alloy surfaces before the formation of the coating was also found to improve the corrosion inhibition of the alloy surfaces in aqueous media.     

Influence of strontium and niobium on the physical and biological performance of hydroxyapatite as a bioactive coating on implant materials

The coating of hydroxyapatite (HAP) on the surface of bio-inert metallic implants to augment their bioactivity is in use for the last two decades. Substitution of various materials in HAP further improves the functionality of these coatings. We demonstrate coating of Ti6Al4V alloy sheets with strontium and niobium reinforced HAP using microwave (MW) irradiation technique. Physical characterization revealed, uniform semicrystalline hydroxyapatite coating with enhanced surface roughness and microhardness. The increased surface roughness was accompanied by higher wettability and more protein adsorption. Electrochemical corrosion assessment showed a dramatic increase in corrosion potential and a noticeable decline in corrosion current density suggesting an enhanced anticorrosive behaviour. These implants also exhibited improved hemocompatibility and bacteriostatic properties. Cell viability and confocal microscopy studies of the coated samples showed enhanced cell attachment on the surface. We propose microwave irradiation as a fast and hassle-free alternative for one-pot synthesis and deposition of ionic substituted HAP on metallic implants.     

Microstructure,mechanical and tribological properties of TaCN composite films by reactive magnetron sputtering

In this paper, a series of TaCN composite films with different carbon content were deposited by the magnetron sputtering system and the microstructure, mechanical and tribological properties were investigated. The results showed that the deposited TaCN films exhibited a three-phase of face-centered cubic (fcc) Ta(C,N), hexagonal closed-packed (hcp) Ta(C,N) and amorphous CNx. With the increase of carbon content, the hardness of the TaCN films first increased and then decreased, after reaching a maximum of 33.1 GPa; the adhesion strength increased gradually; the coefficient of friction decreased monotonically and the wear property initially improved and then weakened at room temperature. The coefficient of friction of the TaCN film at 28.21 at.% carbon decreased first, then increased and then decreased again and its high-temperature wear rate first decreased slightly and then increased, as the temperature increased from room temperature (RT) to 600 °C. The TaCN film at 28.21 at.% carbon exhibited excellent an elevated-temperature tribological properties.     

阳极电压对钛合金微弧氧化膜性能的影响

摘要：在不同阳极电压下对Ti-6Al-4V合金进行了微弧氧化处理。考察了阳极电压对氧化膜生长速率、表面形貌、相组成及硬度的影响，并对其摩擦学性能进行了表征。研究结果表明，随着阳极电压的升高，氧化膜表面微孔数量减少，表面微孔孔径、粗糙度、氧化膜生长速率均增大，表面硬度先增大后减小。微弧氧化膜主要由Al3TiO5相和金红石TiO2相组成，随着阳极电压的升高，两者相对比例逐渐增大。阳极电压对微弧氧化膜与钢球的摩擦系数影响不大，但对磨损率影响较大，磨损率随阳极电压的升高先减小后增大，氧化膜均具有较好的耐磨性。     

Microstructure evolution and bonding mechanism of ZrO2 ceramic and Ti-6Al-4V alloy joints brazed by Bi2O3-B2O3-ZnO glass paste

Ceramics and metal joinings have been widely employed in aerospace, dental implants, and the electronic packaging industry for fabricating multifunctional components. In this study, the 35Bi₂O₃-50B₂O₃-15ZnO (mol.%) glass has been employed for joining the ZrO₂ ceramic and Ti-6Al-4V alloy. The effect of brazing temperature on the microstructure evolution, mechanical properties, and bonding mechanism of brazed joints has been analyzed. The microstructure of the ZrO₂/glass/Ti-6Al-4V joints and the content of Bi₄B₂O₉, Bi₂O₃ and Bi₂₄B₂O₃₉ precipitated crystals in glass were found to be dependent on the brazing temperature. The reaction product of Bi₄Ti₃O₁₂ was identified in the glass/Ti-6Al-4V interface because of the chemical reaction between the oxidized layer of Ti-6Al-4V alloy and glass. A maximum shear strength as high as 48.8 ± 5.2 MPa was obtained. Our work, thus, demonstrates that the 35Bi₂O₃-50B₂O₃-15ZnO glass is an effective bonding material for joining ZrO₂ ceramic and Ti-6Al-4V alloy under low temperature in an ambient atmosphere.     

Structure and mechanical properties of W incorporated diamond-like carbon films prepared by a hybrid ion beam deposition technique

W incorporated diamond-like carbon films were prepared on silicon(1 0 0) wafers using a hybrid deposition system composed of an end-Hall-type hydrocarbon ion gun and a tungsten DC magnetron sputter source. The W concentration in the films was controlled by changing the fraction of Ar in the Ar and C₆H₆ reaction gas. The chemical composition, atomic bond structure, and mechanical properties were investigated for W concentrations ranging from 0 to 8.6 at.%. When the W concentration was <2.8 at.%, the W atoms were dissolved in the amorphous carbon matrix without forming a WC_1−x phase. Amorphous and crystalline WC_1−x nano-particles appeared when the W concentration was >2.8 and >3.6 at.%, respectively. It was found that the hardness and elastic modulus were not sensitive to the W concentration in this concentration range. On the other hand, the residual compressive stress was strongly dependent on the chemical state of the incorporated W atoms. The change in mechanical properties is discussed in terms of the microstructural changes induced by W incorporation.     

Investigation into the effect of substrate material on microstructure and optical properties of thin films deposited via magnetron sputtering technique

This study aims at investigating the effect of the substrate material on growth mechanism and also microstructure of Ta₂O₅ thin films. For this purpose, atomic force microscopy, scanning electron microscopy, and interferometry analyses were implemented to reveal the influence of silicon wafer and amorphous BK7 glass substrates on the nucleation and growth mechanisms of Ta₂O₅ thin films deposited via the radio frequency magnetron sputtering technique. Results indicated that those films with finer morphologies had relatively higher nucleation densities. Compared with BK7 glass substrate, crystals formed on the silicon wafer were shown to be finer and had lower mean areas in more nucleation sites. Moreover, optical properties and morphological characteristics of the films on the silicon substrates had much more endurance after the annealing treatment. It was observed that shift in the transmission spectra of the deposited films after the treatment was insignificant, implying high packing density of the films. However, a 6-nm shift in the transmission spectra indicated low density and high porosity of the films. Finally, atomic force microscopy analysis along with the light scattering measurements confirmed the formation of a low-roughness film on the silicon wafer substrates.     

Microstructure and properties of Nb2O5/Mg gradient coating on AZ31 magnesium alloy by magnetron sputtering

A Nb₂O₅/Mg gradient coating was synthesized on AZ31 magnesium alloy through the magnetron sputtering technique. The microstructure and properties of the coating were investigated by SEM, AFM, EDS and XPS, scratch tester, nanoindenter, friction tester, and electrochemical workstation, with a Nb₂O₅ monolayer coating as a control. The results show that all the as-disposed films have an amorphous columnar structure, and can improve the mechanical, anti-wear and anti-corrosion properties of AZ31 magnesium alloy. The Nb₂O₅/Mg gradient coating shows a gradual change in chemical composition through its depth, decreasing the residual stress of the coating/substrate system, thus reducing the risk of film cracking, and increasing compactness of the coating. Compared with a Nb₂O₅ single-layer film of the same thickness, the gradient coating exhibits increased adhesion, H/E and H³/E² increased by about 16 times, 7.8% and 100% respectively, and a wear rate reduced by more than an order of magnitude. In addition, the gradient coating has better corrosion resistance, having a two orders of magnitude lower current density and one order of magnitude higher polarization resistance. This study provides a workable strategy for improving the performance of ceramic coatings on magnesium alloy, for medical applications.     

The influence of chloride and sulphate ions on the corrosion behavior of Ti and Ti-6Al-4V alloy in oxalic acid

The electrochemical behavior of pure Ti and Ti-6Al-4V alloy was investigated in oxalic acid solution using various electrochemical techniques, i.e. open circuit potential (OCP), potentiodynamic polarization, electrochemical impedance measurements (EIS) and surface examination via scanning electron microscope (SEM) technique. The influence of concentration and temperature on the electrochemical behavior of TI and its alloy were also studied. The results of polarization measurements showed that corrosion current density (i_corr) increases with increasing either temperature or oxalic acid concentration for both samples. Moreover, the value of i_corr for Ti was found to be lower than that for Ti-6Al-4 V alloy, where the corrosion resistance for titanium was always higher. The effect of additives as SO₄²⁻ and Cl⁻ ions was studied; results indicated that the oxide film resistance (R_ox) value decreases with increasing the concentration of SO₄²⁻ ion. However, for Cl⁻ ion, the value of R_ox decreases with increasing Cl⁻ ion concentration up to 1 mM before it starts to increase at higher concentrations. EIS and polarization results are in good agreement with each other. The obtained results were confirmed by surface examination.     

Influence of ZnO buffer layer on AZO film properties by radio frequency magnetron sputtering

Transparent conductive films of Al-doped zinc oxide (AZO) were deposited on glass substrates under various ZnO buffer layer deposition conditions (radio frequency (r.f.) power, sputtering pressure, thickness, and annealing) using r.f. magnetron sputtering at room temperature. This work investigates the influence of ZnO buffer layer on structural, electrical, and optical properties of AZO films. The use of grey-based Taguchi method to determine the ZnO buffer layer deposition processing parameters by considering multiple performance characteristics has been reported. Findings show that the ZnO buffer layer improves the optoelectronic performances of AZO films. The AZO films deposited on the 150-nm thick ZnO buffer layer exhibit a very smooth surface with excellent optical properties. Highly c-axis-orientated AZO/ZnO/glass films were grown. Under the optimized ZnO buffer layer deposition conditions, the AZO films show lowest electrical resistivity of 6.75 × 10⁻⁴ Ω cm, about 85% optical transmittance in the visible region, and the best surface roughness of R_a = 0.933 nm.     

A study of the oxidation behavior of CrN and CrZrN ceramic thin films prepared in a magnetron sputtering system

CrN and CrZrN ceramic thin films were produced by a planar type reactive sputtering system on glass and stainless steel substrates. We investigated oxidation resistance of CrN and CrZrN ceramic thin films with different Zr contents. The structure of the films at different thermal-annealing temperatures was investigated by X-ray diffraction (XRD), atomic force microscopy (AFM) and scanning electron microscopy (SEM). The mechanical properties of the films at different thermal-annealing temperatures were measured by nano-indentation. The results of this study showed that the addition of few amount of Zr (0.4 at%), can improve thermal stability of CrZrN ceramic thin film and increase the oxidation temperature of the film from 600 °C to 800 °C. The relatively good oxidation resistance (800 °C) and high hardness of the film with the lowest Zr content, indicates that this film is a good candidate for high temperature applications.     

Development of hydroxyapatite coatings on laser textured 316 LSS and Ti-6Al-4V and its electrochemical behavior in SBF solution for orthopedic applications

The current work focused on the development of hydroxyapatite (HAP) coating on laser textured metallic implants using electrophoretic deposition. HAP was synthesized by sol-gel technique and its phase purity and surface morphology were confirmed by FT-IR, XRD and SEM analysis. 316 L SS and Ti-6Al-4V metal implants were polished and the surface was modified using Nd-YAG laser operating at a pulse interval of 10 ns at various overlapping rate of 0%, 25% and 50%. The laser treated surface was characterized for its surface roughness using surface profilometry and surface morphology. The surface roughness of the metallic implants was increased by increase in the overlapping rate. The prepared HAP powder was electrophoretically deposited on bare and laser textured Ti-6Al-4V and 316 L stainless steel followed by vacuum sintering at 300 °C for 2 h. Scratch analysis results showed an improvement in adhesion strength for the HAP coatings on laser treated specimens than untreated metal. Corrosion efficiency of the coated samples was studied in SBF solution using EIS and potentiodynamic polarization studies. The result from the corrosion experiments proved increased corrosion resistance property of laser textured coated samples when compared to bare alloy due to higher adhesion of HAP coating on the metal surface.     

过渡层结构对PVC/AIM复合材料性能的影响

采用种子乳液聚合法合成了具有不同过渡层结构的核壳丙烯酸酯类抗冲击改性剂(AIM),用于聚氯乙烯(PVC)树脂的增韧改性.使用动态激光粒度分析仪、差示扫描量热仪和动态黏弹谱仪等测试了AIM的粒子结构、尺寸和玻璃化转变温度,研究了PVC/AIM复合材料的力学性能与AIM的结构及用量的关系.AIM的过渡层结构对PVC/AIM复合体系的力学性能影响显著.以"递变进料"方式合成过渡层的AIM增韧效率最高,在m(PVC)/m(AIM)为100:7时,复合材料可实现韧性断裂,缺口冲击强度达1.121 kJ/m,是纯PVc的26倍;拉伸强度为49.9 MPa.     

A correlation between the microstructure and optical properties of hydrogenated amorphous carbon films prepared by RF magnetron sputtering

Comparative and systematic studies of the effect of the radiofrequency (RF) bias on the microstructure and the optical properties of hydrogenated amorphous carbon (a-C:H) have been carried out on films deposited by RF magnetron sputtering under different RF power varying from 10 to 250 W applied to the graphite target, leading to a negative bias voltage at the target in the range of −60 to −600 V.A combination of infrared (IR) absorption experiments, which give information about the local microstructure (i.e. C–C and C–H bonding), and optical transmission measurements in the UV-visible and near IR, from which we determined the optical gap E₀₄ and the refractive index n, are applied to fully characterize the samples in their as-deposited state. The results show first that the films deposited at low RF power (i.e. low negative bias) exhibit a more open microstructure (polymeric character) with a lower density than those deposited at high RF power (i.e. high negative bias). They also indicate that the total bonded H content as well as the sp³/sp² ratio of carbon atoms bonded to H decrease with increasing RF power leading to the formation of higher proportions of C-sp² sites. The same tendency is observed for the optical gap E₀₄. On the contrary, the refractive index increases with increasing RF power, suggesting the densification of the films in going to a higher RF power.     

Gallium oxide films deposition by RF magnetron sputtering; a detailed analysis on the effects of deposition pressure and sputtering power and annealing

In this study, gallium oxide (Ga₂O₃) thin films were deposited on sapphire and n-Si substrates using Ga₂O₃ target by radio frequency magnetron sputtering (RFMS) at substrate temperature of 300 °C at variable RF power and deposition pressure. The effects of deposition pressure and growth power on crystalline structure, morphology, transmittance, refractive index and band gap energy were investigated in detail. X-ray diffraction results showed that amorphous phase was observed in all the as-deposited thin films except for the thin films grown at low growth pressure. All the films showed conversion to poly-crystal β-Ga₂O₃ phase after annealing process. When the deposition pressure increased from 7.5 mTorr to 12.20 mTorr, change in the 2D growth mode to 3D columnar growth mode was observed from the SEM images. Annealing clearly showed formation of larger grains for all the thin films. Lower transmission values were observed as the growth pressure increases. Annealing caused to obtain similar transmittance values for the thin films grown at different pressures. It was found that a red shift observed in the absorption edges and the energy band gap values decrease with increasing growth pressure. For as-deposited and annealing films, increasing sputtering power resulted in the increase refractive index.     

Enhancement of the Ti-6Al-4V alloy corrosion resistance by applying CrN/CrAlN multilayer coating via Arc-PVD method

In this study, the Ti-6Al-4V substrate was coated by CrN-CrN/TiN-TiN and CrN/CrAlN multilayer coatings using the cathodic arc physical vapor deposition (Arc-PVD) method. The results of potentiodynamic polarization (PDP) have shown the lowest and highest corrosion current density belong to the double-layer (0.16 µA/Cm²) and TiN (0.51 µA/Cm²) samples, indicating the higher corrosion resistance of the double-layer coating. The field emission electron microscope (FESEM), X-ray diffraction pattern (XRD), open circuit potential (OCP), PDP, and electrochemical impedance spectroscopy (EIS) analysis were employed in order to characterize the coatings and evaluate their corrosion behavior. Finally, applying the double-layer coating resulted in the significant improvement of the protective behavior of the Ti-6Al-4V alloy, as compared to the sample coated with TiN in corrosive environments.     

Tunable structural transition and multiferroic properties of the composite thin films through the structural transition of magnetic layer

The Bi_0.9Er_0.1Fe_0.96Mn_0.02Co_0.02O₃/Co_1-xMn_xFe₂O₄ (BEFMCO/CM_xFO) thin films have been deposited by sol-gel method. Structural distortion is observed in the BEFMCO with the appearance of trigonal-R-3m: H in the CM_xFO. The enhanced multiferroic properties, well electrically writable and ferroelectric switching properties are obtained in BEFMCO/CM_xFO thin films. The investigation indicates that the structural transformation of the CM_xFO influences the structure and multiferroic properties of BEFMCO and the interfacial effects between BEFMCO and CM_xFO layers. This transformation and Mn-doping cause the change of carriers, which solves the problem that the magnetic layer exacerbates the ferroelectric properties. It promotes to form the weak local electric field, which causes the weak interface effect, and brings out the weak resistive switching in the BEFMCO/CM_xFO thin films. Therefore, it is believed that the BEFMCO/CM_xFO films can offer a potentially tunable structural transformation of composite films for practical applications.