CrAlYCN/CrCN nanoscale multilayer PVD coatings deposited by the combined High Power Impulse Magnetron Sputtering/Unbalanced Magnetron Sputtering (HIPIMS/UBM) technology

CrAlYCN/CrCN coating combining high hardness (H_p = 36 GPa) and low friction coefficient (µ = 0.42 against Al₂O₃) has been developed for machining of Si containing Al-alloys. The coating was deposited by the combined High Power Impulse Magnetron Sputtering/Unbalanced Magnetron sputtering, (HIPIMS/UBM) technology. Macroparticle free Cr⁺ ion flux was generated by HIPIMS discharge to sputter clean the substrates prior to the coating deposition. The use of HIPIMS for surface pre treatment resulted in excellent adhesion, scratch test adhesion critical load value of Lc = 55 N on HSS and Lc = 68 N due to the local epitaxial growth and extremely smooth coating surface, Ra = 0.012 μm due to the elimination of growth defects.The coating crystallised in fcc structure with a preferred {220} orientation. XTEM analysis revealed a nanoscale multilayer structure of the coating with carbon segregated at the column boundaries but also vertically to form a lateral phase at the interfaces between the individual nanolayers.Addition of C to CrAlYN/CrN increased the chemical inertness between cutting tool and workpiece material without deteriorating the oxidation resistance of the coating. Thermo gravimetric analysis showed that the temperature for the onset of rapid oxidation was as high as 940 °C.In dry milling of AlSi9Cu1 alloy, CrAlYCN/CrCN coated 8 mm diameter cemented carbide end mills outperformed non coated end mills by factor of 2.5 with effective hindered built up edge formation mechanism.     

CrN/NbN coatings deposited by HIPIMS: A preliminary study of erosion-corrosion performance

Nanoscale CrN/NbN multilayer PVD coatings have exhibited resistance to erosion-corrosion. However growth defects (under dense structures and droplets) in the coating produced by some deposition technologies reduce the ability to offer combined erosion-corrosion resistance. In this work a novel High Power Impulse Magnetron Sputtering (HIPIMS) technique has been utilised to pretreat substrates and deposit dense nanoscale CrN/NbN PVD coatings (HIPIMS-HIPIMS technique). This new technique, rich with metal ion plasma, deposits very dense structures and offers virtually defect free coatings (free of droplets as observed in cathodic arc technique and under-dense structures observed in standard dc sputtering). Plasma diagnostic studies revealed a high metal ion-to-gas ion ratio (Cr:Ar) of 3:1 for HIPIMS pretreatment conditions with the detection of 14% Cr²⁺ and 1% Cr³⁺ ions and J_s of 155 mAcm^− 2. For deposition conditions the metal ion-to-gas ratio was approximately 1:4 which is significantly higher compared to DC at 1:30. Characterisation results revealed a high adhesion of L_C 80 N, high hardness of 34 GPa and Young's modulus of 381 GPa. Low friction coefficient (0.46) and dry sliding wear coefficient, K_C (1.22 × 10^− 15 m³Nm^− 1) were recorded. The effect of deposition technique (droplet defect and intergranular void free coatings) on erosion-corrosion resistance of CrN/NbN coatings has been evaluated by subjecting the coatings to a slurry impingement (Na₂CO₃ + NaHCO₃ buffer solution with Al₂O₃ particles of size 500-700 µm) at 90° impact angle with a velocity of 4 ms^− 1. Experiments have been carried at − 1000 mV, + 300 mV and + 700 mV representing 3 different corrosion conditions.     

High rate deposition of thick CrN and Cr2N coatings using modulated pulse power (MPP) magnetron sputtering

As a variation of high power pulsed magnetron sputtering technique, modulated pulse power (MPP) magnetron sputtering can achieve a high deposition rate while at the same time achieving a high degree of ionization of the sputtered material with low ion energies. These advantages of the MPP technique can be utilized to obtain dense coatings with a small incorporation of the residual stress and defect density for the thick coating growth. In this study, the MPP technique has been utilized to reactively deposit thick Cr₂N and CrN coatings (up to 55 μm) on AISI 440C steel and cemented carbide substrates in a closed field unbalanced magnetron sputtering system. High deposition rates of 15 and 10 μm per hour have been measured for the Cr₂N and CrN coating depositions, respectively, using a 3 kW average target power (16.7 W/cm² average target power density), a 50 mm substrate to target distance and an Ar/N₂ gas flow ratio of 3:1 and 1:1. The CrN coatings showed a denser microstructure than the Cr₂N coatings, whereas the Cr₂N coatings exhibited a smaller grain size and surface roughness than those of the CrN coatings for the same coating thickness. The compressive residual stresses in the CrN and Cr₂N coatings increased as the coating thickness increased to 30 μm and 20 μm, respectively, but for thicker coatings, the stress gradually decreased as the coating thickness increased. The CrN coatings exhibited an increase in the scratch test critical load as the thickness was increased. Both CrN and Cr₂N coatings showed a decrease in the hardness and an increase in the sliding coefficient of friction as the coating thickness increased from 2.5 to 55 μm. However, the wear rate of the CrN coatings decreased significantly as the coating thickness was increased to 10 μm or higher. The 10-55 μm CrN coating exhibited low wear rates in the range of 3.5-5 × 10⁻⁷ mm³ N⁻¹ m⁻¹. To the contrary, the Cr₂N coating exhibited relatively low wear resistance in that high wear rates in the range of 3.5 to 7.5 × 10⁻⁶ mm³ N⁻¹ m⁻¹ were observed for different thicknesses.     

Mechanical and tribological properties of multilayered TiSiN/CrN coatings synthesized by a cathodic arc deposition process

The monolayered TiSiN and multilayered TiSiN/CrN were synthesized by cathodic arc evaporation. The Ti/Si (80/20 at.%) and chromium targets were used as the cathodic materials. With the different I_[TiSi]/I_[Cr] cathode current ratios of 1.8, 1.0, and 0.55, the multilayered TiSiN/CrN coatings possessed different multilayer periods (Λ) of 8.3 nm, 6.2 nm, and 4.2 nm. From XRD and TEM analyses, both the monolayered TiSiN and multilayered TiSiN/CrN revealed a typical columnar structure and B1-NaCl crystalline, no peaks of crystalline Si₃N₄ were detected. Among the multilayered TiSiN/CrN coatings, the multilayered coating with Λ = 8.3 nm possessed higher hardness of 37 ± 2 GPa, higher elastic modulus of 396 ± 20 GPa and the lower residual stress of − 1.60 GPa than the monolayered (Ti_0.39Si_0.07)N_0.54 coating(− 7.25 GPa). Due to the higher Cr/(Ti +Cr + Si) atomic ratio, the multilayered TiSiN/CrN with Λ = 5.5 nm possessed the lowest friction coefficient. But the lowest of wear rate was obtained by the multilayered TiSiN/CrN with Λ = 8.3 nm, because of higher H³/E^?2 ratio of 0.323 GPa. The monolayered TiSiN possessed the highest wear rate of 2.87 μm²/min. Therefore, the mechanical and tribological property can be improved by the design of multilayered coating.     

Microstructure control of CrNx films during high power impulse magnetron sputtering

The microstructure and composition of CrN_x (0 ≤ x≤ 1) films grown by reactive high power pulsed magnetron sputtering (HIPIMS or HPPMS) have been studied as a function of the process parameters: N₂-to-Ar discharge gas ratio, (f_N2/Ar), negative substrate bias (V_s), pulsing frequency, and energy per pulse. The film stoichiometry is found to be determined by the composition of the material flux incident upon the substrate during the active phase of the discharge with no nitrogen uptake between the high power pulses. Scanning electron microscopy investigations reveal that for 0 < f_N2/Ar < 0.15 and 150 V bias, a columnar film growth is suppressed in favor of nano-sized grain structure. The phenomenon is ascribed to the high flux of doubly charged Cr ions and appears to be a unique feature of HIPIMS. The microstructure of column-less films for 100 V ≤ V_s ≤ 150 V is dominated by the CrN and hexagonal β-Cr₂N phases and shows a high sensitivity to V_s. As the amplitude of V_s decreases to 40 V and self-biased condition, the film morphology evolves to a dense columnar structure. This is accompanied by an increase in the average surface roughness from 0.25 nm to 2.4 nm. CrN_x samples grown at f_N2/Ar ≥ 0.3 are columnar and show high compressive stress levels ranging from −7.1 GPa at f_N2/Ar = 0.3 to −9.6 GPa at f_N2/Ar = 1. The power-normalized deposition rate decreases with increasing pulse energy, independent of f_N2/Ar. This effect is found to be closely related to the increased ion content in the plasma as determined by optical emission spectroscopy. The HIPIMS deposition rate normalized to DC rate decreases linearly with increasing relative ion content in the plasma, independent of f_N2/Ar and pulsing frequency, in agreement with the so-called target-pathways model. Increasing frequency leads to a finer grain structure and a partial suppression of the columnar growth, which is attributed to the corresponding increase of the time-averaged mean energy of film-forming ions arriving at the substrate.     

Structure and properties of selected (Cr–Al–N,TiC–C,Cr–B–N) nanostructured tribological coatings

The paper will present the state-of-art in the process, structure and properties of nanostructured multifunctional tribological coatings used in different industrial applications that require high hardness, toughness, wear resistance and thermal stability. The optimization of these coating systems by means of tailoring the structure (graded, superlattice and nanocomposite systems), composition optimization, and energetic ion bombardment from substrate bias voltage control to provide improved mechanical and tribological properties will be assessed for a range of coating systems, including nanocrystalline graded Cr_1−xAl_xN coatings, superlattice CrN/AlN coatings and nanocomposite Cr–B–N and TiC/a-C coatings. The results showed that the superlattice CrN/AlN coating exhibited a super hardness of 45 GPa when the bilayer period Λ was about 3.0 nm. Improved toughness and wear resistance have been achieved in the CrN/AlN multilayer and graded CrAlN coatings as compared to the homogeneous CrAlN coating. For the TiC/a-C coatings, increasing the substrate bias increased the hardness of TiC/a-C coatings up to 34 GPa (at −150 V) but also led to a decrease in the coating toughness and wear resistance. The TiC/a-C coating deposited at a −50 V bias voltage exhibited an optimized high hardness of 28 GPa, a low coefficient of friction of 0.19 and a wear rate of 2.37 × 10⁻⁷ mm³ N⁻¹ m⁻¹. The Cr–B–N coating system consists of nanocrystalline CrB₂ embedded in an amorphous BN phase when the N content is low. With an increase in the N content, a decrease in the CrB₂ phase and an increase in the amorphous BN phase were identified. The resulting structure changes led to both decreases in the hardness and wear resistance of Cr–B–N coatings.     

Composition and structure-property relationship of low friction, wear resistant TiN-MoSx composite coating deposited by pulsed closed-field unbalanced magnetron sputtering

Effect of MoS_x content has been studied in TiN-MoS_x composite coating deposited by closed-field unbalanced magnetron sputtering (CFUBMS) using separate MoS₂ and Ti target in N₂ gas environment. Pulsed dc power was applied for both the targets as well as for substrate biasing. Crystallographic orientation and structure of the coating was analysed by grazing incidence X-ray diffraction (GIXRD) technique. The surface morphology and coating fractograph were studied with field emission scanning electron microscopy (FESEM) whereas the composition of the coating was determined by energy dispersive spectroscopy (EDS) by X-ray. Scratch adhesion test, Vickers microhardness test and pin-on-disc test with cemented carbide (WC-6%Co) ball were carried out to investigate mechanical and tribological properties of the coating. Increase in MoS_x content (from 6.22 wt.% to 30.43 wt.%) was found to be associated with decrease in grain size (from 63 nm to 24 nm). Maximum hardness of 32 GPa was obtained for TiN- MoS_x composite coating. Film substrate adhesion was also observed to depend on MoS_x content of the composite coating. Significant improvement in tribological properties was observed. With optimal MoS_x content, it was possible to achieve low friction (µ = 0.02-0.04) and wear resistant (wear coefficient = 5.5 × 10^− 16 m³/Nm) composite solid lubricant coating.     

Influence of the N2 partial pressure on the mechanical properties and tribological behavior of zirconium nitride deposited by reactive magnetron sputtering

Zirconium nitride was deposited by reactive unbalanced magnetron sputtering at different N₂ partial pressures, on an AISI 316L stainless steel substrate. The mechanical properties of the coatings were evaluated by means of nanoindentation tests employing a Berkovich indenter and loads which varied between 120-9000 µN. The sliding wear behavior of the substrate-coating systems was studied under a normal load of 2 N using a ball-on-disc tribometer, with an AISI 52100 ball (6 mm diameter) as counterpart. It has been found that N₂ partial pressure has a significant effect both on the hardness and corresponding Young's modulus of the coatings. As the N₂ partial pressure increases from 1 × 10^− 4 Torr to 10 × 10^− 4 Torr, the hardness and Young's modulus of the coatings decrease from 26 to 20 GPa and 360 to 280 GPa, respectively. The nanoindentation tests revealed the presence of a third oxide layer (10 nm thick, approximately) on the surface of the coating. Scanning electron microscopy (SEM) analysis performed on the worn triboelements indicated that both abrasive and adhesive wear mechanisms could take place in addition to the substrate plastic deformation. The deposition conditions and coating mechanical integrity determine the predominant wear mechanism.     

Phase segregation and its effect on the adhesion of Cr-Al-N coatings on K38G alloy prepared by magnetron sputtering method

Cr_1 − xAl_xN (0 < x < 1) coatings were fabricated by a reactive magnetron sputtering method on a K38G alloy. The composition and microstructure of the coatings were investigated. Phase segregation of cubic AlN was considered in Cr_0.65Al_0.35N using X-ray diffraction analyses. This segregation of cubic AlN from CrAlN matrix might be induced by the high micro-stress. The critical failure load determined by scratch tests of the coating with c-AlN segregation was highest among all the coatings studied in the present work, which indicated that the coating has the best adhesion.     

Precise control of multilayered structures of Nb-O-N thin films by the use of reactive gas pulsing process in DC magnetron sputtering

Multilayered niobium oxynitride films were deposited onto (100) Si using DC magnetron sputtering with a reactive gas pulsing process. The argon and nitrogen flows were kept constant during sputtering of a pure niobium target and the oxygen flow was pulsed during deposition. Pulse durations of T = 10, 40 and 100 s and duty cycles α = t_ON / T of 0.3, 0.6 and 0.9 were chosen (t_ON = injection time of high oxygen flow). A mounting triangle was used as the pulse shape for the oxygen injection.During thin film deposition the cathode voltage, U_cath, the O₂ and N₂ partial pressures, p(O₂) and p(N₂), were recorded. A delay of both parameters (U_cath, p(O₂)) was observed after each pulse, for the return to the values during t_OFF = T − t_ON (off-time of oxygen injection with high flow).High resolution scanning electron microscopy revealed a multilayered structure for coatings deposited with T = 40 and 100 s. Transmission electron microscopy was used to verify that also the coatings with T = 10 s possess a multilayered structure with a period of λ = 10 nm. Despite this low period small crystallites (< 7 nm) were present in these layers. The indentation hardness and the Youngs modulus were in the range of 8.3-16.5 GPa and 154-180 GPa, respectively.     

The effect of oxygen content on the temperature dependent tribological behavior of Cr-O-N coatings

CrN, Cr-O-N and Cr-O coatings with different oxygen contents were produced with reactive cathodic arc physical vapor deposition on high speed steel substrates. The temperature dependent friction and wear behaviours of these coatings were investigated within the temperature range of 25-100 °C. The results of the study showed that it is possible to produce CrN coatings with temperature independent, low coefficient of friction (CoF) and wear behavior by introducing oxygen into them. The amount of oxygen in the coating played a critical role on the tribological behavior. Only, in the coatings produced with oxygen content higher than 46%, a temperature independent wear behavior was observed. The structure and chemistry of the coatings and wear tracks were investigated with XRD and micro Raman spectroscopy. The coatings, with an oxygen content higher than 46%, consisted of Cr₂O₃ and other compounds that are giving broad Raman shifts between 675-834 cm^− 1. With the presence of compounds giving Raman shifts at 675-834 cm^− 1, in the film and/or in the wear track, it became possible to achieve films with temperature independent, low CoF and wear behavior.     

Deposition and characterization of CrN/Si3N4 and CrAlN/Si3N4 nanocomposite coatings prepared using reactive DC unbalanced magnetron sputtering

Nanocomposite coatings of CrN/Si₃N₄ and CrAlN/Si₃N₄ with varying silicon contents were synthesized using a reactive direct current (DC) unbalanced magnetron sputtering system. The Cr and CrAl targets were sputtered using a DC power supply and the Si target was sputtered using an asymmetric bipolar-pulsed DC power supply, in Ar + N₂ plasma. The coatings were approximately 1.5 μm thick and were characterized using X-ray diffraction (XRD), nanoindentation, X-ray photoelectron spectroscopy and atomic force microscopy. Both the CrN/Si₃N₄ and CrAlN/Si₃N₄ nanocomposite coatings exhibited cubic B1 NaCl structure in the XRD data, at low silicon contents (< 9 at.%). A maximum hardness and elastic modulus of 29 and 305 GPa, respectively were obtained from the nanoindentation data for CrN/Si₃N₄ nanocomposite coatings, at a silicon content of 7.5 at.%. (cf., 24 and 285 GPa, respectively for CrN). The hardness and elastic modulus decreased significantly with further increase in silicon content. CrAlN/Si₃N₄ nanocomposite coatings exhibited a hardness and elastic modulus of 32 and 305 GPa, respectively at a silicon content of 7.5 at.% (cf., 31 and 298 GPa, respectively for CrAlN). The thermal stability of the coatings was studied by heating the coatings in air for 30 min in the temperature range of 400-900 °C. The microstructural changes as a result of heating were studied using micro-Raman spectroscopy. The Raman data of the heat-treated coatings in air indicated that CrN/Si₃N₄ and CrAlN/Si₃N₄ nanocomposite coatings, with a silicon content of approximately 7.5 at.% were thermally stable up to 700 and 900 °C, respectively.     

Enhanced sulphidation/oxidation resistance of Ti–45Al–8Nb alloy by multilayered coatings at 850°C for up to 675 h

The high temperature sulphidation/oxidation behaviour of three multilayered coatings CrAlYN/CrN etched by Y⁺, CrAlYN/CrN etched by Cr⁺ and CrAlYN/CrN etched CrAl⁺ and the uncoated γ-TiAl (Ti–45Al–8Nb (at-%) used as reference sample was studied at 850°C for 675 h. Sulphidation/oxidation test was performed in the environment of H₂/H₂S/H₂O, yielding pS₂?=?10^?1 Pa and pO₂?=?10^?18 Pa. Kinetic data obtained by discontinuous gravimetric method showed that the multilayered coatings effectively enhanced the sulphidation/oxidation resistance of γ-TiAl alloy. The corrosion resistance decreasing in order: CrAlYN/CrN etched by Y⁺>CrAlYN/CrN etched by CrAl⁺>CrAlYN/CrN etched by Cr⁺>γ-TiAl. Scale development studies using SEM, EDX and X-ray diffraction confirmed two regions of the coated materials: ‘affected,’ where coating cracked and developed non-protective TiO₂ scale, and ‘unaffected,’ where protective (Al,Cr)₂O₃ scale formed. The uncoated γ-TiAl material, after exposure, showed a typical multilayered structure consisting of layers of TiO₂ and Al₂O₃.     

Mechanical properties, deformation behaviors and interface adhesion of (AlCrTaTiZr)Nx multi-component coatings

In this study, (AlCrTaTiZr)N_x multi-component coatings with quinary metallic elements were developed as protective hard coatings for tribological application. The mechanical properties, creep behaviors, deformation mechanisms and interface adhesion of the (AlCrTaTiZr)N_x coatings with different N contents were characterized. With increasing the N₂-to-total (N₂ + Ar) flow ratio, R_N, during sputtering deposition, the (AlCrTaTiZr)N_x coatings transformed from an amorphous metallic phase to a nanocomposite and finally a crystalline nitride structure. The hardness of the coatings accordingly increased from 13 GPa to a high value of about 30 GPa, but the creep strain rate also increased from 1.3 × 10^− 4 to 7.3 × 10^− 4 1/s. The plastic deformation of the amorphous metallic coating deposited with R_N = 0% proceeded through the formation and extension of shear bands, whereas dislocation activities dominated the deformation behavior of the crystalline nitride coatings deposited with R_N = 10% and 30%. With increasing R_N, the interface adhesion energy between the coatings and the substrates was also enhanced from 6.1 to 22.9 J/m².     

Structural and mechanical properties of AlTiN/CrN coatings synthesized by a cathodic-arc deposition process

Monolayered AlTiN and Multilayered AlTiN/CrN coatings were synthesized by a cathodic-arc deposition process, using TiAl (with 50/50 and 33/67 at.%) and Cr elemental cathodes. The atomic ratio of Al/(Ti + Al) in the AlTiN coatings was reduced to 0.44 and 0.61, respectively, compared with the corresponding Ti₅₀Al₅₀ and Ti₃₃Al₆₇ cathode materials. The multilayered AlTiN/CrN films showed smaller crystallite size, larger lattice strain, higher hardness, higher residual stress, and better adhesion strength as well than the monolayered AlTi films. The multilayered Al_0.35Ti_0.22N_0.43/CrN coating exhibited the highest hardness of about 38 GPa and the highest H³/E*² ratio value of 0.188 GPa, indicating the best resistance to plastic deformation, among all the coatings studied.     

Mechanical and tribological properties of duplex treated TiN, nc-TiN/a-SiNx and nc-TiCN/a-SiCN coatings deposited on 410 low alloy stainless steel

The use of hard and superhard nanocomposite (nc) coatings with tailored functional properties is limited when applied to low alloy steel substrates due to their low load carrying capacity. Specifically in this work, in order to enhance the performance of martensitic SS410 substrates, we applied a duplex process which consisted of surface nitriding by radio-frequency plasma followed by the deposition of single layer (TiN, nc-TiN/a-SiN_x or nc-TiCN/a-SiCN) or multilayer (TiN/nc-TiN/a-SiN_x, TiN/nc-TiCN/a-SiCN) coating systems prepared by plasma enhanced chemical vapor deposition (PECVD). We show that plasma nitriding gives rise to a diffusion layer at the surface due to diffusion of nitrogen and formation of the α-Fe and ε-Fe₂N phases, respectively, leading to a surface hardness, H, of 11.7 GPa, compared to H = 5 GPa for the untreated steel. Among the TiN, nc-TiN/a-SiN_x and nc-TiCN/a-SiCN coatings, the latter one possesses the highest H value of 42 GPa and the highest H³/E_r² ratio of 0.83 GPa. Particularly, the TiN/nc-TiCN/a-SiCN multilayer coating system exhibits superior tribological properties compared to single layer TiN and multilayer TiN/nc-TiN/a-SiN_x coatings: this includes excellent adhesion, low friction (C_f = 0.17) and low wear rate (K = 1.6 × 10^− 7 mm³/N m). The latter one represents an improvement by a factor of 600 compared to the bare SS410 substrate. The significance of the relationship between the H/E and H³/E_r² ratios and the tribological performance of the nano-composite coatings is discussed.     

The structure and properties of chromium nitride coatings deposited using dc, pulsed dc and modulated pulse power magnetron sputtering

The time averaged ion energy distributions and ion fluxes of continuous dc magnetron sputtering (dcMS), middle frequency pulsed dc magnetron sputtering (PMS), and modulated pulse power (MPP) magnetron sputtering plasmas were compared during sputtering of a Cr target in an Ar/N₂ atmosphere in a closed field unbalanced magnetron sputtering system. The results showed that the dcMS plasma exhibited a low ion energy and ion flux; the PMS plasma generated a moderate ion flux of multiple high ion energy regions; while the MPP plasma exhibited a significantly increased number of target Cr⁺ and gas ions with a low ion energy as compared to the dcMS and PMS plasmas. Cubic CrN coatings were deposited using these three techniques with a floating substrate bias. The structure and properties of the coatings were characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, nanoindentation, microscratch and ball-on-disk wear tests. It was found that the deposition rate of the MPP CrN depositions was slightly lower than those of the dcMS depositions, but higher than in the PMS depositions at similar average target powers. The coatings deposited in the dcMS and PMS conditions without the aid of the substrate bias exhibited large columnar grains with clear grain boundaries. On the other hand, the interruption of the large columnar grain growth accompanied with the renucleation and growth of the grains was revealed in the MPP CrN coatings. The MPP CrN coatings exhibited a dense microstructure, fine grain size and smooth surface with high hardness (24.5 and 26 GPa), improved wear resistance (COF = 0.33 and 0.36) and adhesion, which are the results of the low ion energy and high ion flux bombardment from the MPP plasma.     

Pulsed laser deposition of antifriction thin-film MoSex coatings at the different vacuum conditions

MoSe_x coatings were obtained by pulsed laser deposition in vacuum at the pressure of background Ar gas up to 10 Pa. The deposition temperature was 200 °С. The films were studied by means of X-ray diffraction, scanning and transmission electron spectroscopy, X-ray photoelectron spectroscopy, and Rutherford backscattering spectroscopy of helium ions. The tribological properties of thin-film coatings were investigated by pin-on-disk testing in air with 50% relative humidity. In addition, wear tracks were studied by micro-Raman spectroscopy. Chemical composition, structure, and tribological properties of the coatings were found to be sensitive to the presence of the inert gas. Thus, increasing the gas pressure from 10^− 4 to 10 Pa changes the chemical composition, so that the ratio of the atomic concentrations of Se and Mo (x = Se/Mo) increases from 1.5 to 2.4 in the principal deposition zone. The changing of the structure concerns the accumulation of distortions in the lattice of MoSe_x nano-crystals as increasing the distance between the basal planes and intensive formation of nano-sized inclusions of the amorphous phase and Mo nano-crystals in the volume of the coatings. At the optimal gas pressure (∼ 2 Pa), the composition of the coating was close to the stoichiometric one, and the layer adjacent to the substrate consisted of MoSe_x nano-crystals with the basal planes parallel to the substrate surface or oriented at small angles to the surface. The thickness of the oriented layer in such coatings was greater than the thickness of the similar layer in the coatings deposited in vacuum (10^− 4 Pa). The tribological properties of MoSe_x coatings deposited on substrates of stainless steel type 95 × 18 (18 at.% Cr) depend on the gas pressure. The friction coefficient in air decreases from 0.08 for deposition at the background pressure of 10^− 4 Pa to 0.04 for deposition at the optimal pressure. This change in the deposition conditions has only a marginal effect on the coating durability. Means to increase the durability are also considered.     

High power pulsed magnetron sputtering: A review on scientific and engineering state of the art

High power pulsed magnetron sputtering (HPPMS) is an emerging technology that has gained substantial interest among academics and industrials alike. HPPMS, also known as HIPIMS (high power impulse magnetron sputtering), is a physical vapor deposition technique in which the power is applied to the target in pulses of low duty cycle (< 10%) and frequency (< 10 kHz) leading to pulse target power densities of several kW cm^− 2. This mode of operation results in generation of ultra-dense plasmas with unique properties, such as a high degree of ionization of the sputtered atoms and an off-normal transport of ionized species, with respect to the target. These features make possible the deposition of dense and smooth coatings on complex-shaped substrates, and provide new and added parameters to control the deposition process, tailor the properties and optimize the performance of elemental and compound films.     

Microstructure and mechanical properties of W-C:H coatings deposited by pulsed reactive magnetron sputtering

Reported are results of microstructure, mechanical and tribological properties studies for thin, amorphous hydrogenated carbon based coatings with tungsten content from 4.7 at.% up to 10.3 at.%. Studied coatings have been deposited by pulsed, reactive magnetron sputtering on substrates under planetary rotation. Resulting coatings, characterized by transmission electron microscopy (TEM) also at high resolution (HREM), show multilayer structure consisting of sub-layers of W-C:H type, with alternately high and low tungsten concentration. Thickness and number of sub-layers depend on rotation speed of planetary substrate holder. An average tungsten concentration decreases with increasing partial pressure of reactive gas (C₂H₂) during deposition. More insight into the microstructure of coatings provided HREM analysis showing crystalline precipitations of about 1-2 nm in size as well as tungsten-rich and tungsten-poor W-C:H sub-layers. Raman spectra confirm presence of amorphous, hydrogenated carbon (a-C:H) phase in the coatings. Microhardness of studied coatings depends on tungsten content and increases from 10.7 GPa to 13.7 GPa, for 5.1 at.% and 10.3 at.% of tungsten content, respectively. The highest cracking resistance and best adhesion (L_c2 = 78 N and HF1) has been achieved for coatings containing 4.9 at.% of tungsten and a sub-layer thickness of 5 nm. Tribological processes occurring in the coating-coating contact zone are dominated by graphitization and oxidation of W-C:H coating. Very low friction coefficient (0.04) and low wear rate seems to be an effect gaseous micro-bearing by tribo-generated carbon oxides and methane as well as hydrogen released from the coating. In the W-C:H-steel contact zone a tribo-layer composed of iron and tungsten oxides mixed with graphite-like products is growing at the surface of steel counterpart. This tribo-layer becomes a barrier restricting direct contact of steel with the coating and thus preventing it from further intense wear.