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.     

Deposition of nano-scaled CrTiAlN multilayer coatings with different negative bias voltage on Mg alloy by unbalanced magnetron sputtering

In a magnetron sputtering system, the negative substrate bias voltage has been used as a basic process parameter to modify the deposition structure and properties of coatings. In this paper we report the effect of bias voltage ranging from −40 V to −90 V on nano-scaled CrN/TiN/CrN/AlN (CrTiAlN) multilayer coatings synthesized on a Mg alloy by a closed-field unbalanced magnetron sputtering ion plating system in a gas mixture of Ar + N₂. The technological temperature and atomic concentration in the multilayer coatings were controlled by adjusting the current density of different metal magnetron targets and the plasma optical emission monitor. The composition, crystallographic structure, deposition model and friction coefficient of multilayer coatings were characterized by X-ray photoelectron spectrometry (XPS), X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and ball-on-disc testing. The experimental results show that the deposition model and friction coefficient of nano-scaled CrTiAlN multilayer coatings were significantly affected by the negative bias voltage (V_b). The nitride species in multilayer coatings mainly involve CrN, AlN and TiN, and XRD analysis shows that the crystallographic structure was face-centered cubic. Under different bias voltage conditions, the multilayer coating composition shows a fluctuation, and the Al and Cr concentrations respond in the opposite sense to the bias voltage, attaining their greatest values at V_b = −70 V. The surface and cross-sectional morphology shows deposition model change from a columnar model into non-columnar model with the increase in negative bias voltage. The friction coefficient of the nano-scaled multilayer coatings at V_b = −55 V stabilize after 10 000 cycles.     

Inter-diffusion of carbon into niobium coatings deposited on graphite

The inter-diffusion of carbon (originating from a graphite substrate) into a niobium coating and the fabrication of its carbides by heat treatment in the temperature range of 1073-1773 K was studied. The thickness of the Nb₂C and NbC phases formed after heat treatment as well as the inter-diffusion coefficients for the formation of the carbide layers were also studied. It was found that the carbide layer growth displayed parabolic behavior patterns inherent in the growth rate constants (K) of Nb₂C and NbC layers.By assuming that the inter-diffusion coefficients are independent of concentration, it was possible to determine the inter-diffusion coefficients of carbon D^c into Nb₂C and NbC layers as a function of temperature.     

CrAlN coatings deposited by cathodic arc evaporation at different substrate bias

CrAlN is a good candidate as an alternative to conventional CrN coatings especially for high temperature oxidation-resistance applications. Different CrAlN coatings were deposited on hardened steel substrates by cathodic arc evaporation (CAE) from chromium-aluminum targets in a reactive nitrogen atmosphere at negative substrate bias between − 50 and − 400 V. The negative substrate bias has important effects on the deposition growth rate and crystalline structure. All our coatings presented hardness higher than conventional CrN coatings. The friction coefficient against alumina and tungsten carbide balls was around 0.6. The sliding wear coefficient of the CrAlN coatings was very low while an important wear was observed in the balls before a measurable wear were produced in the coatings. This effect was more pronounced as the negative substrate bias was increased.     

Nanostructure transition in Cr-C-N coatings deposited by pulsed closed field unbalanced magnetron sputtering

Cr-C-N coatings with different compositions, i.e. (C + N)/Cr atomic ratios (x) of 0.81-2.77, were deposited using pulsed closed field unbalanced magnetron sputtering by varying the chromium and graphite target powers, the pulse configuration and the ratio of the nitrogen flow rate to the total gas flow rate. Three kinds of nanostructures were identified in the Cr-C-N coatings dependent on the x values: a nano-columnar structure of hexagonal closed-packed (hcp) Cr₂(C,N) and face-centered cubic (fcc) Cr(C,N) at x = 0.81 and 1.03 respectively, a nanocomposite structure consisting of nanocrystalline Cr(C,N) embedded in an amorphous C(N) matrix at x = 1.26 and 1.78, and a Cr-containing amorphous C(N) structure at x = 2.77. A maximum hardness of 31.0 GPa and a high H/E ratio of 1.0 have been achieved in the nc-Cr(C,N)/a-C(N) nanocomposite structure at x = 1.26, whereas the coating with a Cr-containing amorphous C(N) structure had a minimum hardness of 10.9 GPa and a low H/E ratio of 0.08 at x = 2.77. The incorporation of carbon into the Cr-N coatings led to a phase transition from hcp-Cr₂(C,N) to fcc-Cr(C,N) by the dissolution into the nanocrystallites, and promoted the amorphization of Cr-C-N coatings with the precipitation of amorphous C(N). It was found that a high x value over 1.0 in the Cr-C-N coatings is the composition threshold to the nanostructure transition.     

Effect of bias voltage on microstructure, mechanical and wear properties of Al-Si-N coatings deposited by cathodic arc evaporation

Al-Si-N coatings were deposited on tungsten carbide (WC-Co) and silicon wafer substrates using Cr and AlSi (12 at.% Si) alloy targets using a dual cathode source with short straight-duct filter in the cathode arc evaporation system. Al-Si-N coatings were synthesized under a constant flow of nitrogen, using various substrate bias voltages at a fixed AlSi cathode power. To enhance adhesive strength, the Cr/(Cr_xAl_ySi_z)N graduated layer between the top coating and the substrate was deposited as a buffer interlayer. The effects of bias voltage on the microstructure, mechanical and wear properties of the Al-Si-N films were investigated. Experimental results reveal that the Al-Si-N coatings exhibited a nanocomposite structure of nano-crystalline h-AlN, amorphous Si₃N₄ and a small amount of free Si and oxides. It was also observed that the deposition rate of as-deposited films gradually decreased from about 25.1 to 18.8 nm/min when the substrate bias was changed from − 30 to − 150 V. The XRD results revealed that h-AlN preferred orientation changed from (002) to (100) as the bias voltage increased. The maximum hardness of approximately 35 GPa was obtained at the bias voltage of −90 V. Moreover, the grain size was inversely proportional to the hardness of the film. Wear test results reveal that the Al-Si-N film had a lower coefficient of friction, between 0.5 and 0.7, than that 0.7 of the AlN film.     

The influence of low-energy ion bombardment on the microstructure development and mechanical properties of TiBx coatings

The influence of the deposition parameters on the growth, structure and mechanical properties of the TiB_x coatings is studied. The TiB_x coatings represent a nanocomposite system, in which random or oriented TiB₂ nanocrystallites are embedded in an amorphous matrix as is revealed by cross-sectional transmission electron microscopy. We show that low-energy ion bombardment (E_i ) of growing TiB_x coating, influences the preferred orientation of TiB₂ crystallites. The increase of ion current density (i_s) by means of negative substrate bias voltage (U_s) leads to change from random to the (0001) preferred crystal orientation whereby the electrical biasing promotes crystal growth in the coating and the (0001) texture appears gradually during the film growth. Together with the (0001) preferred orientation selection the composition B/Ti ratio was changed from 2.9 (floating potential, E_i = 8 eV) to 2.4 (E_i = 94 eV). The highest amount of oriented (0001) crystallites and highest hardness H = 53 GPa exhibit TiB_x coatings deposited at E_i = 94 eV and i_s = 2.69 mA.cm⁻².     

Effect of ion bombardment on the optical properties of LDPE/EPDM polymer blends

Ion bombardment is a suitable tool to improve the physical properties of polymers. In the present study, the effect of ion bombardment on the optical properties of low density polyethylene (LDPE)/Ethylene propylene diene monomer (EPDM) blend (LDPE/EPDM) was studied. Polymer samples was bombarded with 130 keV He and 320 keV Ar ions at fluencies levels ranging from 1 × 10¹³ to 2 × 10¹⁶ ions/cm². The untreated and ion beam bombarded samples were investigated using ultraviolet-visible (UV-Vis) spectrophotometry. The optical band gap (E_g), was decreased from ∼2.9 eV for the pristine sample down to 1.7 eV for the samples bombarded with He and Ar ions at the highest fluences. Change in the optical gap indicates the presence of a gradual phase transition for the polymer blends. Activation energy has been investigated as a function of the ion fluences. With increasing ion fluence, a decrease in both the energy gap and the activation energy was observed. The number of carbon atoms (N) in a formed cluster is determined according to the modified Tauc's equation.     

Performance evaluation of TiAlCrYN nanocomposite coatings deposited using four-cathode reactive unbalanced pulsed direct current magnetron sputtering system

Approximately 1.5-2.5 μm thick nanocomposite coatings of TiAlCrYN were deposited using a four-cathode reactive unbalanced pulsed direct current magnetron sputtering system from the sputtering of Ti, Al, Cr, and Y targets in Ar + N₂ plasma. The TiAlCrYN nanocomposite coatings were deposited on various substrates such as high speed steel (HSS) drill bits, mild steel and silicon. TiAlCrYN coatings with almost similar mechanical properties but with different Ti, Al, Cr and Y contents were prepared to study their thermal stability and machining performance. The structural and mechanical properties of the coatings were characterized using X-ray diffraction and nanoindentation technique, respectively. The elemental composition, bonding structure, surface morphology and cross-sectional data were studied using energy-dispersive X-ray analysis, X-ray photoelectron spectroscopy and field-emission scanning electron microscopy, respectively. Nanoscratch tests were performed to determine the adhesive strength of the coatings. The corrosion behavior of TiAlCrYN nanocomposite coatings on mild steel substrate was studied using potentiodynamic polarization in a 3.5% NaCl solution. Micro-Raman spectroscopy was used to characterize the structural changes as a result of heating of the nanocomposite coatings in air (600-1000 °C). TiAlCrYN coatings prepared at 17 at.% Ti, 13 at.% Al, 21 at.% Cr and 1 at.% Y exhibited thermal stability as high as 900 °C in air (denoted as Sample 3). For the performance evaluation, the TiAlCrYN coated HSS drill bits were tested under accelerated machining conditions. With a drill speed of 800 rpm and a feed rate of 0.08 mm/rev the TiAlCrYN coated HSS drill bits (Sample 3) averaged 657 holes, while drilling a 12 mm thick 304 stainless steel plate under dry conditions, before failure. Whereas, the uncoated drill bits failed after drilling 50 holes under the same machining conditions. Results indicated that for the HSS drill bits coated with TiAlCrYN, the tool life increased by a factor of more than 12.     

Ion bombardment-induced enhancement of the properties of indium tin oxide films prepared by plasma-assisted reactive magnetron sputtering

Research on tin doped indium oxide (ITO) has for many years been stimulated by the need to simultaneously optimize the electrical, optical and mechanical properties, and by new challenges related to the deposition of transparent conducting oxides on flexible plastic substrates. In the present work, we investigate the growth and optical, electrical, and mechanical (hardness, elastic modulus and stress) properties of ITO films deposited by plasma assisted reactive magnetron sputtering (PARMS) from an indium-tin alloy target. PARMS achieves an effective control of bombardment by reactive species (e.g., O₂⁺, O⁺) on the surface of the growing film by varying the bias voltage, V_B, induced by a radiofrequency power applied to the substrate. Stress-free films possessing high transparency (> 80% — film on glass) and low resistivity (4 × 10^− 4 Ω cm) can be deposited by PARMS under conditions of intense ion bombardment (≤ 600 eV).     

Topography and microstructure of Cu-Sn coatings deposited by magnetron sputtering

The topographical and microstructural features of Cu-Sn coatings deposited by magnetron sputtering using alloy target of Cu-7.8%Sn and Cu-74%Sn onto ferritic stainless steel substrates with a temperature gradient were investigated by means of optical and scanning electron microscopy.Depending on the substrate temperature the alloy film forms by a vapour → solid process or a vapour → liquid process with solidification after substrate cooling. In between a mixed mechanism of vapour → liquid → solid occurs during condensation in the temperature ranges 990–1170 K and 460–790 K for coatings deposited by sputtering of Cu-7.8%Sn and Cu-74%Sn targets respectively.The copper-rich condensate formed in the temperature range 370–1220 K consists of a single-phase α solid solution of tin in copper. Its lattice parameter decreases with increasing temperature mainly because of the decreasing tin content.The film obtained by sputtering a Cu-74%Sn target has a two-phase η′-Cu₆Sn₅ plus tin structure independently of the deposition temperature.     

Influence of substrate bias voltage on properties of Pt thin films deposited by non-mass separated ion beam deposition method

Pt thin films were deposited on Si substrates by applying a negative substrate bias voltage using a non-mass separated ion beam deposition method. The effect of the substrate bias voltage on the properties of the deposited films was investigated. In the case of Pt thin films deposited without the substrate bias voltage, a columnar structure and small grains were observed. The electrical resistivity of the deposited Pt films was very high (49.3 ± 0.65 µΩ cm). By increasing the substrate bias voltage, no clear columnar structure was observed. At the substrate bias voltage of − 75 V, the resistivity of the Pt film showed a minimum value of 16.9 ± 0.2 µΩ cm closed to the value of bulk (10.6 µΩ cm).     

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.     

Oxidation behavior of Ti-B-C-N coatings deposited by reactive magnetron sputtering

Quaternary Ti-B-C-N coatings with different carbon concentrations are deposited on high-speed steel substrates by reactive magnetron sputtering. The oxidation behavior between 300 and 800 °C under ambient conditions is studied by scanning electron microscopy, high-resolution transmission electron microscopy, Vickers micro-hardness, and X-ray diffraction. The Ti-B-C-N coatings with smaller carbon contents have better oxidation resistance and the oxidation process can be divided into two stages: low-speed oxidation below 700 °C and high-speed oxidation above 700 °C. An oxidation mechanism is proposed to explain the relationship between the reaction with oxygen and observed oxidation behavior.     

Relation between the plasma characteristics and physical properties of functional zinc oxide thin film prepared by radio frequency magnetron sputtering process

The ZnO thin film was deposited on a glass substrate by a RF reactive magnetron sputtering method. Results showed that plasma density, electron temperature, deposition rate and estimated ion bombardment energy increase with increasing applied RF power. Three distinct power regimes were observed, which are strongly correlated with plasma properties. In the low-power regime, the largest grain size was observed due to slow deposition rate. In the medium-power regime, the smallest grain size was found, which is attributed to insufficient time for the adatoms to migrate on substrate surface. In the high-power regime, relatively larger grain size was found due to very large ion bombardment energy which enhances the thermal migration of adatoms. Regardless of pure ZnO thin film or ZnO on glass, high transmittance (> 80%) in the visible region can be generally observed. However, the film thickness plays a more important role for controlling optical properties, especially in the UV region, than the applied RF power. In general, with properly coated ZnO thin film, we can obtain a glass substrate which is highly transparent in the visible region, is of good anti-UV characteristics, and is highly hydrophobic, which is highly suitable for applications in the glass industry.     

An analysis of macroparticle-related defects on CrCN and CrN coatings in dependence of the substrate bias voltage

Chromium nitride coatings with and without a carbon content being assigned as CrCN and CrN were prepared by cathodic arc evaporation. The effect of negative substrate bias voltages (10-300 V) on the microstructure, phase composition and morphology of the coating surface was studied. X-ray diffraction data show that almost all coatings crystallized in the cubic structure with (111) and (200) diffraction lines appearing only for low negative bias voltage and a (220) diffraction line being present for the coatings deposited at higher negative bias voltages. For CrN coatings obtained at −300 V a hexagonal structure was also observed. In case of CrCN coatings the (220) diffraction line shows much higher intensity than in case of CrN coatings and was significantly broadened. On the surface of the coatings a large number of macroparticles of different size was observed. An increase of bias voltage causes a reduction of the areal density of macroparticles and a decrease of the mean surface roughness Ra.     

负偏压对Be上磁控溅射离子镀Al膜结构影响的研究

以Be为基体，采用磁控溅射离子镀的在其上镀制Al膜，研究了负偏压对Al膜微结构的影响；研究表明，不加基体负偏压，Al膜在（111）面择优生长；随着基体负偏压升高Al膜在（111）面择优生长趋势减北，Al膜在（200）面生长趋势加强；当基体负偏压超过150V后，Al膜在（111）面择优生长的趋势又得到加强。晶粒在低负偏压时随负偏压增加而细化，当较高的负偏压引起基体温度升高时，此时晶粒又变大了。     

Deposition of TiAlN coatings using reactive bipolar-pulsed direct current unbalanced magnetron sputtering

We have deposited TiAlN coatings on high-speed steel (HSS) drill bits, silicon and mild steel substrates using a four-cathode reactive direct current (DC) unbalanced magnetron sputtering system. Asymmetric bipolar-pulsed DC generators have been used to deposit TiAlN coatings from the reactive sputtering of Ti and Al targets in N₂ + Ar plasma. Various treatments have been given to the substrates for improved adhesion of the TiAlN coatings. The process parameters have been optimized to achieve highly adherent good quality TiAlN coatings. These coatings have been characterized using X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray analysis, X-ray photoelectron spectroscopy, nanoindentation, atomic force microscopy, wear tester, potentiodynamic polarization techniques. The performance of the TiAlN coated HSS drill bits is evaluated by drilling a 13-mm thick 304 stainless steel plate, which is considered to be difficult to machine material. The performance evaluation tests have been carried out with and without coolant. The results show significant improvement in the performance of the TiAlN coated HSS drill bits. Furthermore, it has been shown that dry drilling of 304 stainless steel plate is possible with TiAlN coated HSS drill bits. Improvement in the performance of TiAlN coated tools has been attributed to excellent high temperature oxidation resistance and corrosion resistance of TiAlN coatings.     

Influence of the surface morphology and microstructure on the biological properties of Ti-Si-C-N-O coatings

Detailed structural, microstructural, biofilm formation and cytotoxicity studies were performed on Ti-Si-C-ON hard coatings prepared by DC reactive magnetron sputtering, in order to evaluate the relation among these properties. Compositional analysis showed the existence of two distinct regimens; regime I: high C/Si atomic ratio (C/Si ≥ 1.42) and intermediate N/Ti atomic ratio; regime II: low C/Si atomic ratio (C/Si ≤ 0.49) and low N/Ti atomic ratio. The structural analysis revealed that, in regime I, films crystallized in a B1-NaCl crystal structure typical of TiC_0.2N_0.8. In regime II, the decrease of C/Si and increase in silicon concentration led to the formation of Ti-Si-C-ON along with a reduction of grain size in the films. Atomic force microscopy observations showed that the surface morphology of these Ti-Si-C-ON films became smoother when the silicon content increased and the nitrogen content decreased, which is consistent with the formation of nanosized clusters. Concerning biological properties, it was observed that cytotoxicity could be related with the titanium concentration while biofilm formation ability was found to be related with the surface morphology of the films.     

Influence of process parameters on structure and optical properties of GeC thin films deposited by RF magnetron sputtering

Germanium carbide (Ge_1 − xC_x) films on silicon and quartz substrates have been prepared by the radio frequency (RF) reactive sputtering of a pure Ge target in a CH₄/Ar discharge. Their structural and optical properties have been investigated as functions of the substrate temperature (T_S) and the CH₄ percentage to the gas mixture. The optical band gap of the films lies within the range 0.96-1.65 eV, varying proportionally with the carbon content and in inverse proportionality with T_S.