Reflectance and photoluminescence spectra of as grown and hydrogen and nitrogen incorporated tetrahedral amorphous carbon films deposited using an S bend filtered cathodic vacuum arc process

The study of reflectance and photoluminescence (PL) spectra of as grown and also hydrogen and nitrogen incorporated tetrahedral amorphous carbon (ta-C) films, deposited using an S bend filtered cathodic vacuum arc process is reported here. First the effect of negative substrate bias on the properties of as grown ta-C films and next the effect of varying hydrogen and nitrogen partial pressure at a high substrate bias of − 300 V on the properties of hydrogen and nitrogen incorporated ta-C (ta-C:H and ta-C:N) films are reported for the first time. The values of the optical band gap (E_g) evaluated using the reflectance spectra were found to decrease with the increase of the substrate bias in the as grown ta-C films. Hydrogen incorporation up to 1.9 × 10^− 2 Pa partial pressure in as grown ta-C films increased the values of E_g and beyond which the values of E_g decreased while the nitrogen incorporation up to 3.0 × 10^− 1 Pa partial pressure has no effect on the E_g values. The PL spectra indicated a strong peak at ∼2.66 eV in as grown ta-C films deposited at − 20 V substrate bias. This main peak was found to shift to higher energy with the increase of the substrate bias up to − 200 V and thereafter the PL peak shifted towards the lower energy. Other peak at 3.135 eV starts appearing and this is found to start shifting to higher energy for films deposited at higher substrate bias. The intensity of the main PL peak was enhanced at low temperature and several other peaks started appearing in place of the broad peak at ∼3.16 eV. The peak width and area of both the main peak were found to decrease with the increase of substrate bias in as grown ta-C films and with the increase of the hydrogen and nitrogen partial pressure used in depositing ta-C:H and ta-C:N films. The current models on the source of luminescence in amorphous carbon have been discussed.     

Combinatorial synthesis and sputter parameter optimization of chromium-doped yttrium aluminum garnet photoluminescent thin films

Chromium-doped Y₃Al₅O₁₂ or YAG thin films emitting at 688 nm due to the ⁴A₂-⁴E₂ transition were synthesized in a combinatorial fashion using reactive sputtering approach. Multilayer YAG and Cr thin films were sputter deposited with a gradient in the Cr thickness and subsequently annealed to diffuse the Cr dopant into the YAG matrix. The combinatorial thin film sputtering technique was used to rapidly determine that ∼ 0.69 at.% is the optimum chromium concentration for maximum photoluminescence (PL) intensity in YAG. This result was consistent with previous work in YAG:Cr powders. Design of experiments was conducted to determine the effects of various sputter parameters, namely, substrate bias, substrate temperature and oxygen flow rate on PL intensity and crystallinity of co-sputter deposited Cr-doped YAG thin films. The optimum sputtering condition consisted of high substrate bias and low oxygen flow rate and was independent of substrate temperature. The PL temperature dependent behavior of YAG:Cr film was also investigated. Thermal quenching was observed at ∼ 110 K where the total integrated PL emission intensity was found to rapidly decrease. A non-radiative activation energy of 25.2 meV was determined and is attributed to electron-phonon coupling.     

XPS study of carbon nitride films deposited by hot filament chemical vapor deposition using carbon filament

Amorphous carbon nitride, a-CN_x, thin films were deposited by hot filament CVD using a carbon filament with dc negative bias voltage on the substrate. The effects of the negative bias and the filament components on the binding structure of the films are investigated by XPS. The composition ratio of graphite to amorphous carbon in the filaments affects the bonding structure of carbon and nitrogen in the films, although the nitrogen content in the films is almost same as 0.1. The nitrogen content in the films changes from 0.1 to 0.3 as the negative bias changes from 0 to − 300 V.     

Substrate bias voltage influenced structural, electrical and optical properties of dc magnetron sputtered Ta2O5 films

Tantalum oxide (Ta₂O₅) films were formed on silicon (111) and quartz substrates by dc reactive magnetron sputtering of tantalum target in the presence of oxygen and argon gases mixture. The influence of substrate bias voltage on the chemical binding configuration, structural, electrical and optical properties was investigated. The unbiased films were amorphous in nature. As the substrate bias voltage increased to −50 V the films were transformed into polycrystalline. Further increase of substrate bias voltage to −200 V the crystallinity of the films increased. Electrical characteristics of Al/Ta₂O₅/Si structured films deposited at different substrate bias voltages in the range from 0 to −200 V were studied. The substrate bias voltage reduced the leakage current density and increased the dielectric constant. The optical transmittance of the films increased with the increase of substrate bias voltage. The unbiased films showed an optical band gap of 4.44 eV and the refractive index of 1.89. When the substrate bias voltage increased to −200 V the optical band gap and refractive index increased to 4.50 eV and 2.14, respectively due to the improvement in the crystallinity and packing density of the films. The crystallization due to the applied voltage was attributed to the interaction of the positive ions in plasma with the growing film.     

Effect of substrate temperature on corrosion performance of nitrogen doped amorphous carbon thin films in NaCl solution

Nitrogen doped amorphous carbon (a-C:N) thin films were deposited on p-Si substrates by DC magnetron sputtering at varying substrate temperature from room temperature (RT) to 300 °C. The bonding structure, surface morphology and adhesion strength of the a-C:N films were investigated by using X-ray photoelectron spectroscopy (XPS), micro-Raman spectroscopy, atomic force microscopy (AFM) and micro-scratch testing. The corrosion behavior of the a-C:N films was evaluated by potentiodynamic polarization test in a 0.6 M NaCl solution. The results indicated that the corrosion resistance of the films depended on the sp³-bonded cross-link structure that was significantly affected by the substrate temperature.     

Localized corrosion behavior of 316L stainless steel in the presence of sulfate-reducing and iron-oxidizing bacteria

Localized corrosion behavior of 316L stainless steel was investigated in the presence of sulfate-reducing bacteria (SRB) and iron-oxidizing bacteria (IOB) isolated from cooling water system using polarization measurement, scanning electron microscopy (SEM) examinations and energy dispersive spectrum (EDS) analysis. The results show the corrosion potential (E_corr) and breakdown potential (E_b) of SS decreased in turn with the presence of IOB, SRB and SRB + IOB, indicating decreased relative resistance to localized corrosion. E_corr in the sterile medium remained virtually unchanged with exposure time, indicating that localized attack did not occur. However, micrometer-scale pitting was observed on the SS surface in the presence of bacteria. The presence of SRB demonstrated higher corrosion rates than IOB. The combination of SRB and IOB yielded the highest corrosion rate. The presence and metabolic activities of bacteria on SS surface produce environments that can alter rates of partial reactions in corrosion processes and shift corrosion mechanisms. The most severe microbiologically induced corrosion takes place in aquatic solution where physiological groups of aerobic and anaerobic microorganisms interact.     

Ion beam deposition of α-Ta films by nitrogen addition and improvement of diffusion barrier property

Ta thin films were deposited on Si (100) substrates by an ion beam deposition method at various substrate bias voltages under Ar + N₂ atmosphere with different pressure ratios of Ar and N₂. The effects of nitrogen pressure in the plasma gas and the substrate bias voltage on the surface morphology, crystalline microstructure, electrical resistivity and diffusion barrier property were investigated. It was found that the fraction of a metastable β-phase in the Ta film deposited at the substrate bias voltage of − 50 V films decreased by adding nitrogen gas, while the α-Ta phase became dominant. As a result, the Ta films deposited at the substrate bias voltage of − 50 V under Ar (9 Pa) + N₂ (3 Pa) atmosphere showed a dominant α-phase with good surface morphology, low resistivity, and superior thermal stability as a diffusion barrier.     

Anticorrosion behavior of ultrafine-grained Al-26?wt% Si alloy fabricated by ECAP

Ultrafine-grained (UFG) Al-26 wt% Si alloy was obtained through multipass equal-channel angular pressing (EACP) procedure and subsequently tested in 3.5 wt% NaCl solution for the evaluation of electrochemical corrosion. The results show that the ECAPed alloy with increased number of pressing passes obtain lower mass-loss ratios, nobler E _corr and E _pit, lower I _corr values, and higher anode polarization. The improved corrosion resistance of the ECAPed alloy results from the homogeneous UFG structure with the breakage of brittle large primary silicon crystals, which contributes to a higher pitting resistance. The oxidation product with improved adhesion force and protection efficacy can be formed with greater ease on UFG alloys. It implies that grain refinement through severe-plastic-deformation can enhance anticorrosion behavior of hypereutectic Al–Si alloys, besides the well-known strengthening and toughening effects.     

Extremely high pitting resistance of NiTi shape memory alloy thin film in simulated body fluids

In this paper the corrosion behavior of NiTi thin films fabricated by sputtering from Ni and Ti targets has been studied by cyclic potentiodynamic polarization tests in Hank's and Ringer's solution at 310 K. For comparison, bulk NiTi Shape Memory Alloy (SMA) has also been studied to elucidate the different corrosion behavior of bulk and thin film material. The electrochemical experiments reveal that thin film NiTi SMA has comparable corrosion current density (i_corr), much higher pitting corrosion potentials and wider passive range than the bulk NiTi. We show that NiTi SMA vapour deposited thin films are less susceptible to pitting corrosion than the bulk.     

Improved adhesion of ultra-hard carbon films on cobalt–chromium orthopaedic implant alloy

While interfacial graphite formation and subsequent poor film adhesion is commonly reported for chemical vapor deposited hard carbon films on cobalt-based materials, we find the presence of O₂ in the feedgas mixture to be useful in achieving adhesion on a CoCrMo alloy. Nucleation studies of surface structure before formation of fully coalesced hard carbon films reveal that O₂ feedgas helps mask the catalytic effect of cobalt with carbon through early formation of chromium oxides and carbides. The chromium oxides, in particular, act as a diffusion barrier to cobalt, minimizing its migration to the surface where it would otherwise interact deleteriously with carbon to form graphite. When O₂ is not used, graphitic soot forms and films delaminate readily upon cooling to room temperature. Continuous 1 μm-thick nanostructured carbon films grown with O₂ remain adhered with measured hardness of 60 GPa and show stable, non-catastrophic circumferential micro-cracks near the edges of indent craters made using Rockwell indentation.     

Structure, mechanical and tribological properties of diamond-like carbon films on aluminum alloy by arc ion plating

The low hardness and poor tribological performance of aluminum alloys restrict their engineering applications. However, protective hard films deposited on aluminum alloys are believed to be effective for overcoming their poor wear properties. In this paper, diamond-like carbon (DLC) films as hard protective film were deposited on 2024 aluminum alloy by arc ion plating. The dependence of the chemical state and microstructure of the films on substrate bias voltage was analyzed by X-ray photoelectron spectroscopy and Raman spectroscopy. The mechanical and tribological properties of the DLC films deposited on aluminum alloy were investigated by nanoindentation and ball-on-disk tribotester, respectively. The results show that the deposited DLC films were very well-adhered to the aluminum alloy substrate, with no cracks or delamination being observed. A maximum sp³ content of about 37% was obtained at −100 V substrate bias, resulting in a hardness of 30 GPa and elastic modulus of 280 GPa. Thus, the surface hardness and wear resistance of 2024 aluminum alloy can be significantly improved by applying a protective DLC film coating. The DLC-coated aluminum alloy showed a stable and relatively low friction coefficient, as well as narrower and shallower wear tracks in comparison with the uncoated aluminum alloy.     

Corrosion study of single crystal Ni–Mn–Ga alloy and Tb<Subscript>0.27</Subscript>Dy<Subscript>0.73</Subscript>Fe<Subscript>1.95</Subscript> alloy for the design of new medical microdevices

Once placed in a magnetic field, smart magnetic materials (SMM) change their shape, which could be use for the development of smaller minimally invasive surgery devices activated by magnetic field. However, the potential degradation and release of cytotoxic ions by SMM corrosion has to be determined. This paper evaluates the corrosion resistance of two SMM: a single crystal Ni–Mn–Ga alloy and Tb_0.27Dy_0.73Fe_1.95 alloy. Ni–Mn–Ga alloy displayed a corrosion potential (E _corr) of −0.58 V/SCE and a corrosion current density (i _corr) of 0.43 μA/cm². During the corrosion assay, Ni–Mn–Ga sample surface was partially protected; local pits were formed on 20% of the surface and nickel ions were mainly found in the electrolyte. Tb_0.27Dy_0.73Fe_1.95 alloy exhibited poor corrosion properties such as E _corr of −0.87 V/SCE and i _corr of 5.90 μA/cm². During the corrosion test, this alloy was continuously degraded, its surface was impaired by pits and cracks extensively and a high amount of iron ions was measured in the electrolyte. These alloys exhibited low corrosion parameters and a selective degradation in the electrolyte. They could only be used for medical applications if they are coated with high strain biocompatible materials or embedded in composites to prevent direct contact with physiological fluids.     

Effects of phosphate on the chloride-induced corrosion behavior of reinforcing steel in mortars

The influence of phosphate as a corrosion inhibitor on the corrosion behavior of as-received and pre-rusted reinforcing steels in mortar specimens was investigated after 360 days exposure in 3.5% NaCl solution. This involved the use of electrochemical techniques for studying the steel surface reactions and microscopic observations of the steel–mortar interface. The electrochemical methods, including electrochemical impedance spectroscopy (EIS) and measurements of corrosion potential (E_corr) and linear polarization resistance (LPR), were employed to evaluate the corrosion tendency and general corrosion rate of steel. In addition, the pitting corrosion resistance of steel was also determined by cyclic polarization (CP) measurements. The results indicate that different from nitrite, which is generally accepted as an anodic inhibitor, phosphate may be a cathodic inhibitor according to its reduced corrosion rate and more negative E_corr at the same dosage as nitrite in mortar specimens. The study also reveals that the inhibiting efficiency of phosphate against general corrosion of both as-received and pre-rusted specimens is lower than 10%, which is inferior to nitrite in some respects. However, as indicated by cyclic polarization measurements, the presence of phosphate provides slightly higher pitting corrosion resistance in comparison to nitrite. Furthermore, it suggests that the corrosion inhibition mechanism of phosphate in mortars mainly depends on a dual effect occurring at the steel–mortar interface. Furthermore, it is confirmed that phosphate has little effect on the long-term mechanical properties of mortars.     

Dependence of the electrical and optical properties on the bias voltage for ZnO:Al films deposited by r.f. magnetron sputtering

Aluminum-doped zinc oxide (ZnO:Al) thin films were deposited on glass, polycarbonate (PC), and polyethylene terephthalate (PET) substrates by r.f. magnetron sputtering. The substrate dc bias voltage varied from 0 V to 50 V. Structural, electrical and optical properties of the films were investigated. The deposition rate of ZnO:Al films on glass substrate initially increased with the bias voltage, and then decreased with further increasing bias voltage. It was found that the best films on glass substrate with a low as 6.2 × 10^− 4 Ω cm and an average transmittance over 80% at the wavelength range of 500-900 nm can be obtained by applying the bias voltage of 30 V. The properties of the films deposited on polymer substrate, such as PC and PET, have a similar tendency, with slightly inferior values to those on glass substrate.     

In-situ hydrothermal crystallization Mg(OH)2 films on magnesium alloy AZ91 and their corrosion resistance properties

Mg(OH)₂ films have been fabricated on magnesium alloy AZ91 substrates by an in-situ hydrothermal method. AZ91 alloy substrates act as both the source of Mg²⁺ ion and the support for the Mg(OH)₂ film in synthetic process. The effect of pH value and hydrothermal treatment time on the morphologies and corrosion resisting properties of Mg(OH)₂ film is studied. The obtained Mg(OH)₂ films are uniform and compact. The adhesion between the films and the substrate is strong due to the in-situ growth process, which enhances their potential for practical applications. Potentiodynamic polarization measurements showed that the Mg(OH)₂ films obtained at pH 10, 3 h exhibits the highest increase in corrosion potential at −0.7097 V and lowest i_corr, which suggests that it is the best effective film in improving the corrosion resistance of AZ91in all obtained films.     

Effects of pH on the electrochemical behaviour of titanium alloys for implant applications

The electrochemical behaviour of two commercial titanium alloys Ti-6Al-4 V (ASTM F136) and Ti-13Nb-13Zr (ASTM F1713) was investigated in Ringer physiological solution at two pH values (5.5 and 7.0). The corrosion properties were examined by using electrochemical techniques: Potentiodynamic anodic polarization, cyclic polarization and electrochemical impedance spectroscopy (EIS). The electrochemical corrosion properties of both alloys at different conditions were measured in terms of corrosion potential (E _corr), corrosion current density (i _corr) and passivation current density (i _pass). Equivalent electrical circuits were used to modulate EIS data, in order to characterize alloys surface and better understanding the pH effect on the interface alloy/solution.     

Corrosion behavior of surface-modified titanium in a simulated body fluid

We investigate the influence of micro-sandblasting and electrochemical passivation on properties such as corrosion rate and surface roughness, which are important to the biocompatibility of titanium (Ti), using surface analysis techniques and electrochemical measurements. Results of microscopy and surface profilometry experiments reveal roughened but uniform surface topography with an average surface roughness in the 0.87–1.06 μm range, depending on the alternating current passivation voltage applied to the micro-sandblasted samples. Open circuit potential versus time measurements in Hank’s Balanced Salt Solution (HBSS, a simulated body fluid) allow determination of the corrosion potential (E _corr) and reveal a shift of E _corr toward higher values upon passivation, thus pointing to increased corrosion stability. Corrosion rates in HBSS range between 0.049 and 0.288 μm year⁻¹ for micro-sandblasted and passivated Ti, as compared to that for the micro-sandblasted and non-passivated surface that is 0.785 μm year⁻¹. Results from this study demonstrate that micro-sandblasting coupled with electrochemical passivation provides a roughened surface with increased corrosion stability and a low corrosion rate in HBSS. Application of this technique to Ti in medical and dental applications may be expected to result in an improvement of biocompatibility.     

Bias effects on microstructure, mechanical properties and corrosion resistance of arc-evaporated CrTiAlN nanocomposite films on AISI 304 stainless steel

CrTiAlN films were deposited on AISI 304 stainless steel by cathodic arc evaporation under a systematic variation of the substrate bias voltage. The effects of substrate bias on the coating morphology and mechanical properties, such as structure, composition, adhesion, hardness and Young's modulus, were studied in details using field emission scanning electron microscopy, X-ray diffraction, electron probe microanalysis and indenter. Polarization test and immersion test were also carried out to evaluate the corrosion behavior of the various films. CrTiAlN films are nanocrystalline that exhibit a CrN/TiAlN multi-layered morphology. At the optimal value of substrate bias voltage (i.e., − 150 V), the CrTiAlN film showed an increased Cr content and improved properties, such as higher adhesion, higher hardness (38 ± 2 GPa), and greater Young's modulus (319 ± 16 GPa) vs. the films deposited at other substrate bias voltages. Moreover, the optimum film has better corrosion resistance in 3.5 wt.% NaCl and 20 vol.% HCl solutions.     

Hardness and residual stress in nanocrystalline ZrN films: Effect of bias voltage and heat treatment

The purpose of this study was to investigate the effects of both bias voltage and heat treatment on the composition, microstructure, and associated mechanical properties of the zirconium nitride (ZrN) thin films deposited on AISI 304 stainless steel substrates by a filtered cathodic arc ion-plating (FCA-IP) system. The depositions were carried out by varying negative substrate bias voltage, from −40 V_b to −80 V_b. The deposited film specimens were heat-treated at 800 °C for 1 h. X-ray diffraction (XRD) revealed that (a) texture coefficients of (1 1 1) plane increased with negative bias, and (b) the grain size was approximately less than 15 nm, i.e. nano-scale grain size. The hardness of the deposited ZrN films was correlated with point defects, (1 1 1) texture coefficient, and crystallinity characterized for the films. For the as-deposited films, it was found that the hardness increased with decreasing (1 1 1) full width of the peak at half maximum (FWHM) and increasing (1 1 1) texture coefficient, suggesting a better crystallinity and lower grain boundary mobility in the highly textured films. The decrease in film hardness after heat treatment may be attributed mainly to the reduction of point defects present in the films. Measurements performed for the intrinsic residual stress reported a significant 5.5 GPa release in the heat-treated films, due to recovery of point defects by heat treatment.     

Characterization of magnetron co-sputtered W-doped C-based films

In this paper, W-doped C-based coatings were deposited on steel and silicon substrates by RF magnetron sputtering, using W and C targets, varying the cathode power applied to the W target and the substrate bias. The chemical composition was varied by placing the substrates in a row facing the C and W targets. W content in the films increased from 1 to 2 at.% over the C target to ∼ 73 at.% over the W target. The coatings with W content lower than ∼ 12 at.% and ∼ 23 at.%, for biased and unbiased conditions, respectively, showed X-ray amorphous structures, although carbide nanocrystals must exist as shown by the detection of the WC_1−x phase in films with higher W content. C-rich films were very dense and developed a columnar morphology with increasing W content. An improvement in the hardness (from 10 GPa, up to 25 GPa) of the films was achieved either when negative substrate bias was used in the deposition, or when the WC_1−x phase was detected by X-ray diffraction. The adhesion of the coatings is very low with spontaneous spallation of those deposited with negative substrate bias higher than 45 V. Varieties in cathode power (90 W or 120 W) applied to the W target showed no observable influence on the characteristics of the films.