FTIR studies of tungsten carbide in bulk material and thin film samples

The use of Fourier transform infrared (FTIR) spectroscopy is proposed to characterize thin films of tungsten carbide (WC) coatings. For this reason, the IR reflection spectrum of a bulk sample was recorded and used as a reference. Three infrared bands were observed. They are located at 1067,1144, and 1220 cm⁻¹. They were assigned to hexagonal and cubic phases of WC. These assignments are supported by XRD measurements. These results were used to characterize different WC films deposited on stainless steel substrates.     

Influence of silicon content on the microstructure and hardness of CrN coatings deposited by reactive magnetron sputtering

CrN and CrSiN films were deposited on the stainless steel and silicon substrates by DC magnetron sputtering and their microstructural features were investigated by X-ray diffraction (XRD), scanning electron microscope (FE-SEM/EDS), and atomic force microscopy (AFM). The influence of Si content along with process parameters such as power on the microstructural characteristics of Cr–Si–N and CrN films were investigated and compared between each other. The power and increasing Si contents strongly influence the microstructural and hardness of the deposited films. XRD analysis of the coatings indicates a grain refinement with increase in Si content during deposition of coatings, which is tandem with AFM and SEM results. Also, the surface roughness and particle size are decreasing with addition of Si in the films. The hardness of CrN and CrSiN was measured by microhardness tester and found that introduction of Si content in the CrN system increases its hardness from 1839 Hv to 2570 Hv.     

Comparison of microstructure and mechanical properties of chromium nitride-based coatings deposited by high power impulse magnetron sputtering and by the combined steered cathodic arc/unbalanced magnetron technique

Sliding, abrasive, and impact wear tests were performed on chromium nitride (CrN)-based coatings deposited on mirror-polished M2 high speed steel substrates by the novel high power impulse magnetron sputtering (HIPIMS) utilising high peak cathode powers densities of 3000 W cm⁻². The coatings were compared to single layer CrN and multilayer superlattice CrN/NbN coatings deposited by the arc bond sputtering (ABS) technique designed to improve the coating substrate adhesion by a combined steered cathodic arc/unbalanced magnetron (UBM) sputtering process. The substrates were metal ion etched using non-reactive HIPIMS or steered cathodic arc at a substrate bias voltage of −1200 V. Subsequently a 2- to 3-μm thick CrN or CrN/NbN coating was deposited by reactive HIPIMS or UBM. No bias was used during the HIPIMS deposition, while the bias during UBM growth was in the range 75-100 V. The ion saturation current measured by a flat electrostatic probe reached values of 50 mA cm⁻² peak for HIPIMS and 1 mA cm⁻² continuous during UBM deposition. The microstructure of the HIPIMS coatings observed by transmission electron microscopy was fully dense in contrast to the voided columnar structure observed in conventional UBM sputtered CrN and CrN/NbN. The sliding wear coefficients of the HIPIMS CrN films of 2.3×10⁻¹⁶ m³ N⁻¹ m⁻¹ were lower by a factor of 4 and the roughness of the wear track was significantly reduced compared to the UBM-deposited CrN. The abrasive wear coefficient of the HIPIMS coating was 2.2×10⁻¹³ m³ N⁻¹ m⁻¹ representing an improvement by a factor of 3 over UBM deposited CrN and a wear resistance comparable to that of the superlattice CrN/NbN. The adhesion of the HIPIMS deposited CrN was comparable to state-of-the-art ABS technology.     

Structural comparison of GdF3 films grown on CaF2 (111) and SiO2 substrates

Wide bandgap metal fluorides are the materials of choice for optical coating applications at 193 nm. Low loss and environmentally stable optics requires a mitigating fluoride film structure on a nanometer scale. To understand the growth mechanism of fluoride materials, GdF(3) films grown on CaF(2) (111) and SiO(2) substrates were investigated. Film inhomogeneity and surface roughness were modeled by fitting ellipsometric data with an effective medium approximation, indicating a correlation between film inhomogeneity and surface roughness. The modeled surface roughness was compared with the atomic force microscope measurement. Film inhomogeneity was correlated to the cone-shaped columnar structure revealed by cross-sectional images from a scanning electron microscope. The film crystalline structure was determined by x-ray diffraction measurement, suggesting a different growth mechanism of GdF(3) films on crystalline and amorphous substrates.     

Amorphous and amorphous-crystalline coatings of stainless steel with addition of refractory metals obtained by magnetron sputtering in vacuum

Amorphous and amorphous-crystalline stainless steel films were obtained with additions of Ti or W. The deposition rate was v = 6–630 nmmin⁻¹, the thickness h = 50 to 5000 nm and the substrate temperature T_s varied from 77 to 293 K. A magnetron compound target was used for sputtering and coatings were deposited on Al, steel, glass-ceramic and Corning glass substrates. Structural data for the coexistence of amorphous and amorphous-crystalline phases in stainless steel films are presented. A study was made of the structure sensitive properties: specific electrical resistivity and magnetic characteristics. Some data were obtained for films Fe + Ti and Fe + W, prepared by the same method. Properties affecting the practical application of such amorphous and amorphous-crystalline metal coatings were also studied.     

Atomic layer deposition of BN thin films

Boron nitride has for the first time been deposited from gaseous BBr₃ and NH₃ by means of atomic layer deposition. The deposition temperatures were 400 and 750 °C, and the total pressure was 10 torr. The BN films, deposited on silica substrates, showed a turbostratic structure with a c-axis of 0.70 nm at a deposition temperature of 750 °C as determined by X-ray diffraction. The films deposited at 400 °C were significantly less ordered. The film density was obtained by means of X-ray reflectivity, and it was found to be 1.65–1.70 and 1.90–1.95 g cm⁻³ for the films deposited at 400 and 750 °C, respectively. Furthermore, the films were, regardless of deposition temperature, fully transparent and very smooth. The surface roughness was 0.3–0.5 nm as measured by optical interferometry.     

Electrochemical evaluation of the reliability of plasma-polymerized methylcyclohexane films

Plasma-polymerized thin films are developed for electronic devices to satisfy the important requirement of a low dielectric constant in the interlayer dielectrics. Three types of methylcyclohexane coatings are deposited on copper as interlayer dielectrics by plasma-enhanced chemical vapor deposition at three different deposition temperatures. The coating performance is evaluated by electrochemical impedance spectroscopy and potentiodynamic polarization testing in a 3.5 wt.% NaCl solution. The coatings are also analyzed by surface analyses, including atomic force microscopy, Fourier transform infrared spectroscopy, and contact angle measurements. The electrochemical behavior of the coatings is improved by increasing the deposition temperature. The methylcyclohexane films on the copper substrate show high protective efficiency, charge transfer resistance and low porosity, which indicate that the coating performance increased with increasing deposition temperature. Atomic force microscopy, Fourier transform infrared spectroscopy and contact angle measurements confirm the enhanced formation of C-H, C-C, and CC stretching configurations, improved surface roughness and wettability with increasing deposition temperature.     

Vacuum-plasma-sprayed silicon coatings for biomedical application

Silicon coating was deposited on titanium alloy substrates by vacuum plasma spraying technology. The morphologies and phase composition of the coatings were analyzed by field-emission scanning electron microscopy and X-ray diffraction. The thermal expansion coefficient of silicon coating was measured to be about 3.70 × 10⁻⁶ K⁻¹. The bond strength of coating was approximately 20.6 MPa. The density, open porosity, roughness and Young's modulus of silicon coating were also measured. The as-sprayed silicon coating was treated by deionized water at 60 °C, 80 °C and 100 °C for a period of time and soaked in simulated body fluids to evaluate its bioactivity. The results showed that the water-treated coating could induce apatite to precipitate on its surface in simulated body fluid, indicating that the bioactivity of silicon coating was improved. The increase of temperature and duration of water treatment had a positive effect on the bioactivity of silicon coatings.     

Study on tribological property of CrCN coating based on magnetron sputtering plating technique

The influence of carbon doping on tribological properties of CrCN coating was studied through preparation of coatings deposited on single crystal silicon and M2 high-speed steel (HSS) substrate using closed-field unbalanced magnetron sputtering ion plating technique. The friction coefficients were measured by pin-on-disc set-up and the wear traces of the coatings were observed by optical microscope. The microstructure and bond states of the coatings were characterized by atomic force microscope (AFM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results show that the friction coefficient of coating decreases from 0.75 to 0.38, the micro-hardness increases from 1930 HV to 2300 HV, and the specific wear ratio of the coatings decreases from 8.351 × 10⁻¹⁵ m³/Nm to 3.859 × 10⁻¹⁵ m³/Nm with the increasing of carbon target current (I_C) from 0 A to 1.5 A. The grain size and the roughness of the coatings both decrease with the increasing of carbon target current, at the same time the coatings transform from crystalline state to amorphous state.     

Nonlinear optical properties of thin iron films grown on MgO (100) by pulsed laser deposition

Thin films of iron were fabricated on MgO (100) substrates using pulsed laser deposition technique. The crystalline property and surface roughness of the films were investigated by X-ray diffraction and atomic force microscopy, respectively. It was found that the morphology of the Fe film deposited at room temperature was characteristic of continuous metal film. Increasing the deposition temperature caused the smooth Fe film to break up, and nanoscale Fe islands were formed. We performed the z-scan measurements to study the third-order optical nonlinearity of the continuous approximately 9-nm-thick iron film. The results show that the ultrathin iron film exhibits large nonlinear refractive coefficient, n₂=7.09×10⁻⁵ cm²/kW, and nonlinear absorption coefficient, β=−5.52×10⁻³ (cm/W), at the wavelength of 532 nm.     

The preparation and characterization of preferred (110) orientation aluminum nitride thin films on Si (100) substrates by pulsed laser deposition

The preferred (110) oriented aluminum nitride (AlN) thin films have been prepared by pulsed laser deposition on p-Si (100) substrates. The films were characterized with X-ray diffraction, Raman spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and atomic force microscope (AFM). The results indicate that the AlN thin films are well-crystallized when laser energy is higher than 300 mJ/puls. The AFM images show that the surface roughness of the deposited AlN thin films gradually increases with increasing laser energy, but the surface morphologies are still very smooth. The crystallinity and morphology of the thin films are found to be strongly dependent on the laser energy.     

The effect of exposure to biological fluids on the spallation resistance of diamond-like carbon coatings on metallic substrates

Diamond-like carbon (DLC) films have been deposited by RF plasma-assisted glow discharge CVD on AISI 304 stainless steel and Ti–6Al–4V substrates. A substrate plastic straining technique (to measure the strength and adhesion of the coating) and erosion testing (to measure its durability) have been used, before and after exposure to various fluids (distilled water, phosphate buffered saline solution (PBS) and bovine serum). The films on both substrates had excellent adhesion before exposure to the fluid, being slightly higher for those on Ti substrates. PBS solution affected the adhesion adversely, whereas distilled water and serum had no apparent effect. Fourier transform infrared (FTIR) and Raman spectroscopic studies revealed that there were no changes in the atomic structure of the coatings during exposure. X-ray photoelectron spectroscopy (XPS) measurements indicated that PBS tends to penetrate through perforations in the film and attack the thin transition layer of graded Si/C composition between the a: Si–H layer and the DLC coating. An increase in exposure temperature increased the population of defects in samples exposed to PBS. Coatings on Ti exhibited similar characteristics, but were considerably more resistant to damage. This may be due to a lower incidence of defects and perforations in these films.     

冠脉支架表面PLGA涂层制备及其血液相容性研究

采用静电喷涂沉积(electrospray deposition ESD)法在冠脉支架表面制备了PLGA涂层.采用OLYMPUS体式显微镜、原子力显微镜(AFM)观察了涂层宏观表面形貌及三维形貌;通过对涂层支架进行球囊扩张考察了PLGA涂层与支架的结合力;通过血小板粘附实验和动态凝血时间测定研究PLGA涂层的血液相容性.结果表明:ESD法在冠脉支架表面制备PLGA涂层,支架筋拐角处无明显的聚合物胶体缠绕、粘连且涂层表面光滑;PLGA涂层将316L不锈钢基体的微坑覆盖,基体Ra=16.174nm,PLGA涂层Ra=0.149nm,涂层表面粗糙度小;涂层支架撑开后在最大塑性变形位置无涂层撕裂、翘起等缺陷,涂层与支架有良好结合力;PLGA涂层血小板粘附量少,变形小,未引起血小板激活,动态凝血时间长,直到50min未产生凝血,PLGA涂层具有较好的血液相容性.     

Measurement of adhesion of thin evaporated films on glass substrates by means of the direct pull method

The so-called “direct pull method” is applied to the measurement of adhesion of vacuum-deposited thin film coatings on glass substrates. The results obtained by this method are influenced by errors in alignment of the experimental set-up and by non-uniformities of the cement films used to pull the coatings off the substrate. These effects are analysed. Results are presented for films of zinc sulphide, cryolite and silver deposited on BK7 glass substrates. The forces of adhesion on ion-bombarded substrates in these cases are found to be 430 kp/cm², 540 kp/cm² and 230 kp/cm² respectively.     

Electrophoretic deposition of hydroxyapatite‐shrimp crusts nanocomposite thin films for bone implant studies

Hydroxyapatite‐shrimp crusts nanocomposite thin films were deposited on titanium substrates by electrophoretic technique, under different preparation conditions, for bone implant applications. Fourier transform infrared spectrometer, atomic force microscope, X‐ray diffraction (XRD), optical microscope, and scanning electron microscope were employed to characterise the synthesised films. Vickers’ micro‐hardness measurements revealed a value of 502 HV for the hydroxyapatite films and 314.55 HV for the nanocomposite films. XRD results confirmed the polycrystalline nature of the hydroxyapatite and hydroxyapatite‐shrimp nanocomposite films. The in‐vitro bioactivity test of the synthesised films in simulated body fluid showed very low dissolution rate. Antibacterial activity of synthesised films was investigated against E. coli bacteria.Inspec keywords: electrophoretic coating techniques, thin films, nanocomposites, antibacterial activity, bone, prosthetics, nanomedicine, calcium compounds, bioceramics, nanofabrication, Fourier transform infrared spectra, atomic force microscopy, X‐ray diffraction, optical microscopy, scanning electron microscopy, Vickers hardness, microhardness, microorganisms, dissolvingOther keywords: Ti, Ca₁₀ (PO₄)₆ (OH)₂ , E. coli bacteria, antibacterial activity, dissolution rate, simulated body fluid, in‐vitro bioactivity test, polycrystalline nature, Vickers microhardness measurements, XRD, scanning electron microscopy, optical microscopy, X‐ray diffraction, atomic force microscopy, Fourier transform infrared spectrometer, bone implant applications, titanium substrates, hydroxyapatite‐shrimp crust nanocomposite thin films, electrophoretic deposition     

Ar + H2 plasma etching for improved adhesion of PVD coatings on steel substrates

Ar + H₂ plasma cleaning has been described for the surface modification of the steel substrates, which removes oxides and other contaminants from substrate surface effectively leading to a better adhesion of the physical vapor deposited (PVD) coatings. Approximately 1.1-1.3 μm thick TiAlN coatings were deposited on plasma treated (Ar and Ar + H₂) and untreated mild steel (MS) substrates. A mechanism has been put forward to explain the effect of plasma treatment on the substrate surface based upon the data obtained from X-ray photoelectron spectroscopy (XPS), field-emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM). The XPS measurements on untreated and Ar + H₂ plasma etched MS substrates indicated that the untreated substrate surface mainly consisted of Fe₃O₄, whereas, after etching the concentration of oxides decreased considerably. The FESEM and the AFM results showed changes in the surface morphology and an increase in the substrate roughness as a result of Ar + H₂ plasma etching. Removal of oxide/contaminants, formation of coarser surface and increased substrate surface roughness as a result of Ar + H₂ plasma etching facilitate good mechanical interlocking at the substrate surface, leading to a better adhesion of the deposited PVD coatings. The adhesion of TiAlN coating could be increased further by incorporating a very thin Ti interlayer.     

Microstructures and bond strengths of the calcium phosphate coatings formed on titanium from different simulated body fluids

Calcium phosphate (Ca-P) coatings were deposited on Ti substrates by a biomimetic method from m-SBF and 10× SBF, respectively. Comparative study of microstructures and bond strengths of the Ca-P coatings deposited from those different SBFs was carried out. Effect of the surface roughness of the substrates on the bond strength of the Ca-P coatings was also studied. Scanning electron microscopy (SEM), X-ray diffractometry (XRD), Fourier transformed infrared spectroscopy (FTIR), inductive coupled plasma spectrometry (ICP) and thermogravimetry (TG) were used to characterize the Ca-P coatings. The bond strengths between the coatings and Ti substrates were measured using an adhesive strength test. Results indicated that the ionic concentrations of the SBFs and the surface roughness of the substrate had a significant influence on the formation, morphology and bond strength of the Ca-P precipitates. The induction period of time to deposit a complete Ca-P layer from the m-SBF is much longer, but the Ca-P coating is denser and has higher bond strength than that formed from the 10× SBF. The Ti with a surface roughness of R_a 0.64 µm and R_z 2.81 µm favoures the formation of a compact Ca-P coating from the m-SBF with the highest bond strength of approximately 15.5 MPa.     

An atomic force microscopy tip model for investigating the mechanical properties of materials at the nanoscale

Investigation of the mechanical properties of materials at the nanoscale is often performed by atomic force microscopy nanoindentation. However, substrates with large surface roughness and heterogeneity demand careful data analysis. This requirement is even more stringent when surface indentations with a typical depth of a few nanometers are produced to test material hardness. Accordingly, we developed a geometrical model of the nanoindenter, which was first validated by measurements on a reference gold sample. Then we used this technique to investigate the mechanical properties of a coating layer made of Balinit C, a commercially available alloy with superior anti-wear features deposited on steel. The reported results support the feasibility of reliable hardness measurements with truly nanosized indents.     

Brush electrodeposited CdS films on low temperature substrates

Cadmium sulphide films were deposited by the brush plating technique on titanium and conducting glass substrates using a current density of 80 mA cm^− 2. X-ray diffraction studies indicated the polycrystalline nature of the films with hexagonal structure. As the deposition temperature decreased, the peaks were broad indicating the formation of nanocrystallites. Optical absorption measurements yielded band gap values in the range of 2.39-3.10 eV as the deposition temperature decreases. XPS studies confirmed the formation of CdS. Atomic force microscope studies indicated the roughness of the films decreases with the decrease of deposition temperature. The as deposited films were photoactive.     

Pulsed plasma treatment of Ti-Al coatings produced by mechanical alloying method

By means of the mechanical alloying method (MA), Ti-Al coatings were deposited on Ti substrates. Then, as-synthesized coatings were treated by pulsed argon plasma with energy up to 185 J/cm². Irradiation of the Ti-Al MA-coating with pulsed argon plasma beams with energy density higher than 135 J/cm² resulted in melting of the near-surface layer that in turn initiated the liquid-phase reaction between Ti and Al to form the Al₃Ti compound. Melting led to smoothing of the coating structure. The coating microstructure and volume fraction of Al₃Ti phase was conditioned by plasma energy. The thickness of the modified layer was several microns. Phase composition of plasma-treated coatings depended on its element composition. The plasma treatment of the Ti-Al-Si-C and Ti-Al-W-C coatings with energy of 150 J/cm² led to formation of Ti₅Si₃ and TiC along with Al₃Ti compound.