The structure and mechanical and tribological properties of TiBCN nanocomposite coatings

TiBCN nanocomposite coatings were deposited in a closed field unbalanced magnetron sputtering system using pulsed magnetron sputtering of a TiBC compound target with various Ar/N₂ mixtures. TiBCN coatings were characterized using X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, nanoindentation, Rockwell C indentation and ball-on-disk wear tests. The coatings with a nitrogen content of less than 8 at.% exhibited superhardness values in the range of 44–49 GPa, but also showed poor adhesion and low wear resistance. Improvements in the coating adhesion, H/E ratio and wear resistance were achieved together with a decrease in the coating hardness to 35–45 GPa as the N content in the coatings was increased from 8 to 15 at.%. The microstructure of the coatings changed from a nano-columnar to a nanocomposite structure in which 5–8 nm nanocrystalline Ti(B,C) and Ti(N,C) compounds were embedded in an amorphous matrix consisting of BN, free carbon and CN phases. With a further increase in the N content in the coatings to levels greater than 20 at.%, the inter-particle spacing of the nanocrystalline compounds increased significantly due to the formation of a large amount of the amorphous BN phase, which also led to low hardness and poor wear resistance of the TiBCN coatings.     

Effect of Ti content on the microstructure and mechanical properties of TiAlSiN nanocomposite coatings

TiAlSiN coatings has been proposed and studied because of their desirable properties in hardness and coating-substrate adhesion. Further improvement of their performance can be achieved by better understanding the effect of the concentration of each element on the microstructure and mechanical properties of the coatings. In this paper, the TiAlSiN coatings with different Ti content were deposited by reactive DC magnetron sputtering method. The microstructure and mechanical properties of the coatings were analyzed by energy dispersive spectroscopy, X-ray diffraction, transmission electron microscope, scanning electron microscope, nano-indentor and Rockwell indentation tester. The results reveal that TiAlSiN coatings consisted of amorphous phase and crystalline phase. With a Ti content of 63 at.%, as well as a Si content of 7 at.%, a super-hard TiAlSiN coating with a nanoindentation hardness of 66 GPa was achieved. What is more, in contrast to the well-described super-hard nanocomposite TiAlSiN coatings, another “nanocomposite” microstructure coating with a Ti content of 29 at.% in which the amorphous phase is wrapped in a crystalline phase was identified, with a comparatively low hardness value of 20 GPa. The highest adhesion strengths with a Rockwell indentation classes HF2 was achieved for a coating with a Ti content of 63 or 65 at.%.     

Mechanical and tribological properties of the High Target Utilization Sputtering W-C coatings on different substrates

The effects of three types of substrates (Si, bearing steel, and WC-Co) and acetylene addition (0–3.2 vol.% in Ar atmosphere) on the topography, structure, composition, nanohardness and tribological behavior of the High Target Utilization Sputtering W-C coatings were investigated. The results showed that the substrates affected mostly the coating topography, roughness and nanohardness whereas the composition, indentation moduli and coefficients of friction were influenced only by the increase of free carbon content from acetylene addition. Up to ~ 5 GPa difference in the hardness of the W-C coatings on Si substrates compared to that on steel was obtained. Simultaneously, methodological problems with the hardness measurements were identified on WC-Co substrate which has the hardness close to that of the coatings. The average values of the coefficient of friction were around 0.3 and slightly decreased at higher carbon contents but the influence of the substrates was small.     

Chromium carbide–CNT nanocomposites with enhanced mechanical properties

Chromium carbide is widely used as a tribological coating material in high-temperature applications requiring high wear resistance and hardness. Herein, an attempt has been made to further enhance the mechanical and wear properties of chromium carbide coatings by reinforcing carbon nanotubes (CNTs) as a potential replacement of soft binder matrix using plasma spraying. The microstructures of the sprayed CNT-reinforced Cr₃C₂ coatings were characterized using transmission electron microscopy and scanning electron microscopy. The mechanical properties were assessed using micro-Vickers hardness, nanoindentation and wear measurements. CNT reinforcement improved the hardness of the coating by 40% and decreased the wear rate of the coating by almost 45–50%. Cr₃C₂ reinforced with 2 wt.% CNT had an elastic modulus 304.5 ± 29.2 GPa, hardness of 1175 ± 60 VH_0.300 and a coefficient of friction of 0.654. It was concluded that the CNT reinforcement increased the wear resistance by forming intersplat bridges while the improvement in the hardness was attributed to the deformation resistance of CNTs under indentation.     

Friction and wear properties of TiN,TiAlN, AlTiN and CrAlN PVD nitride coatings

Four nitride coatings, TiN, TiAlN, AlTiN and CrAlN were deposited on YG6 (WC + 6 wt.% Co) cemented carbide by cathodic arc-evaporation technique. The friction and wear properties were investigated and compared using ball-on-disc method at high speed with SiC ball as a counter material. The tests were evaluated by scanning electron microscopy, X-ray diffractometer, energy dispersive X-ray, micro hardness tester and an optical profilometer. The results showed that TiN and TiAlN coatings presented lower friction coefficient and lower wear rate, and that high Al content AlTiN and CrAlN coatings didn't present better anti-wear properties in this test. Oxidation and abrasive wear were the main wear mechanism of TiN coating. In spite of the observation of micro-grooves and partial fractures, TiAlN possessed perfect tribological properties compared with the other coatings. High Al content increased the chemical reactivity and aroused severe adhesive wear of AlTiN coating. CrAlN coating presented better properties of anti-spalling and anti-adhesion, but abundant accumulated debris accelerated wear of the coating under this enclosed wear environment.     

Strengthening gold thin films with zirconia nanoparticles for MEMS electrical contacts

Thin gold films can be strengthened by the incorporation, during reactive sputtering, of nanosized dispersions of monoclinic zirconia. Micron-thick films containing ∼2 vol.% zirconia particles having a particle size of 1–3 nm are found to have an indentation hardness of 3.8 GPa after annealing for 60 h at 500 °C in air. Sputtered gold films of the same thickness and annealed under the same conditions had a hardness of 2.3 GPa. The nanoparticles of zirconia resist coarsening with no change in diameter between deposition and after 60 h at 500 °C. They also suppress grain growth of the gold grains. The electrical resistivity of the strengthened gold films was 4.5 μΩ cm, about 55% higher than gold films. The temperature coefficient of resistivity was unaffected.     

Microstructure evolution of Ti–Si–C–Ag nanocomposite coatings deposited by DC magnetron sputtering

Nanocomposite coatings consisting of Ag and TiC_x (x < 1) crystallites in a matrix of amorphous SiC were deposited by high-rate magnetron sputtering from Ti–Si–C–Ag compound targets. Different target compositions were used to achieve coatings with a Si content of ～13 at.%, while varying the C/Ti ratio and Ag content. Electron microscopy, helium ion microscopy, X-ray photoelectron spectroscopy and X-ray diffraction were employed to trace Ag segregation during deposition and possible decomposition of amorphous SiC. Eutectic interaction between Ag and Si is observed, and the Ag forms threading grains which coarsen with increased coating thickness. The coatings can be tailored for conductivity horizontally or vertically by controlling the shape and distribution of the Ag precipitates. Coatings were fabricated with hardness in the range 10–18 GPa and resistivity in the range 77–142 μΩ cm.     

Thermal and thermo-mechanical properties of Ti–Al–N and Cr–Al–N coatings

Metastable Ti–Al–N and Cr–Al–N coatings have been proven to be an effective wear protection due to their outstanding mechanical and thermal properties. Here, a comparative investigation of mechanical and thermal properties, for Ti–Al–N and Cr–Al–N coatings deposited by cathodic arc evaporation with the compositions (c-Ti_0.52Al_0.48N, c/w-Ti_0.34Al_0.66N and c-Cr_0.32Al_0.68N) widely used in industry, has been performed in detail. The hardness of Ti_0.52Al_0.48N and Ti_0.34Al_0.66N coatings during thermal annealing, after initially increasing to the maximum value of ~ 34.1 and 38.7 GPa with T_a up to 900 °C due to the precipitation of cubic Al-rich and Ti-rich domains, decreases with further elevated T_a, as the formation of w-AlN and coarsening of precipitated phases. A transformation to Cr₂N and finally Cr via N-loss in addition to w-AlN formation during annealing of the Cr_0.32Al_0.68N coating occurs, and thus results in a continuous decrease in hardness. Among our coatings, the mixed cubic-wurtzite Ti_0.34Al_0.66N coating exhibits the highest thermal hardness, but the worst oxidation resistance. The Cr_0.32Al_0.68N coating shows the best oxidation resistance due to the formation of dense protective α-Al₂O₃-rich and Cr₂O₃-rich layers, with only ~ 1.4 μm oxide scale thickness, after thermal exposure for 10 h at 1050 °C in ambient air, whereas Ti–Al–N coatings are already completely oxidized at 950 °C.     

Characterization studies of pulse magnetron sputtered hard ceramic titanium diboride coatings alloyed with silicon

The composition, structure and mechanical properties of pulsed-DC unbalanced magnetron sputtered Ti–Si–B thin films—hard coatings with the potential for excellent thermal stability and oxidation resistance—are investigated and reported in this paper. Fully dense, hard (19–37 GPa) Ti–Si–B coatings were deposited at substrate bias voltages (V_s) ranging from floating potential to −150 V which resulted in substrate temperatures of ∼90–135 °C. We found that variation of substrate biasing conditions critically affected film composition, structure and resultant mechanical properties. For instance, concentration of Si in films decreased from 18.4 at.% to 3.8 at.% as V_s was increased from floating potential to −150 V; composition profile analysis of the near-surface region of films (0–10 nm) revealed them to be rich in Si with significant differences among specimens produced at different substrate bias conditions. Variation of substrate biasing conditions provided coating structures that ranged from completely amorphous at floating substrate potential to nanocrystalline at V_s = −50 to −100 V and crystalline nanocolumnar at V_s = −150 V. We found that each of the structures obtained exhibited different specific values of hardness and elastic modulus, which is also in a good agreement with results reported for other coatings possessing similar micro- and nano-structures. Film structure was analyzed in detail by conventional and analytical transmission electron microscopy. Coatings that exhibited the highest values of hardness (37 GPa) were found to possess features such as crystalline nanocolumnar grains a few nanometres in diameter and disordered intergranular regions of different chemical composition, thus qualifying as nanocomposite films. Results of this work allowed relationships to be drawn between deposition parameters and Ti–Si–B coating composition, structure and mechanical properties. Qualitatively similar relationships are also expected for other biased plasma-assisted physical vapour deposited transition-metal-based ceramic coatings alloyed with Si (e.g. Ti–Si–N, Cr–Si–N, Cr–Al–Si–N).     

Improved properties of Ti-Al-N coating by multilayer structure

Multinary Ti-Al-N coatings are used for various applications where hard, wear and oxidation resistant materials are needed. Here, we prepare TiAlN/TiN nano-multilayer coatings with modulation period of ~ 20 nm in order to further improve the properties of Ti-Al-N coating. Annealing of both coatings up to 700 °C results in an increase in hardness due to the precipitation of cubic Al-rich domains by spinodal decomposition. Multilayer structure results in an increase in adhesion with substrates from ~ 72 N for Ti-Al-N single layer coating to 98 N for TiAlN/TiN nano-multilayer coating. Additionally, the interfaces of TiAlN/TiN nano-multilayer coating retard the outward diffusion of metal atoms (Al and Ti) and inward diffusion of O while exposing coatings in air atmosphere with elevated temperature, and thus improve its oxidation resistance. An improved machining performance regardless of continuous cutting and milling is obtained by TiAlN/TiN nano-multilayer coated inserts, which can be attributed to the combined effects of higher adhesion with substrates and better oxidation resistance.     

Structural and mechanical properties of corundum and cubic (AlxCr1−x)2+yO3−y coatings grown by reactive cathodic arc evaporation in as-deposited and annealed states

Coatings of (Al_xCr_1?x)_2+yO_3?y with 0.51 ? x ? 0.84 and 0.1 ? y ? 0.5 were deposited on hard cemented carbide substrates in an industrial cathodic arc evaporation system from powder-metallurgy-prepared Cr/Al targets in pure O₂ and O₂ + N₂ atmospheres. The substrate temperature and bias in all the deposition runs were 575 °C and ?120 V, respectively. The composition of the coatings measured by energy dispersive X-ray spectroscopy and elastic recoil detection analysis differed from that of the facing targets by up to 11%. Microstructure analyses performed by symmetrical X-ray diffraction and transmission electron microscopy showed that corundum, cubic or mixed-phase coatings formed, depending on the Cr/Al ratio of the coatings and O₂ flow per active target during deposition. The corundum phase was promoted by high Cr content and high O₂ flow per target, while the cubic phase was observed mostly for high Al content and low O₂ flow per active target. In-situ annealing of the cubic coatings resulted in phase transformation from cubic to corundum, completed in the temperature range of 900–1100 °C, while corundum coatings retained their structure in the same range of annealing temperatures. Nanoindentation hardness of the coatings with Cr/Al ratio <0.4 was 26–28 GPa, regardless of the structure. Increasing the Cr content of the coatings resulted in increased hardness of 28–30 GPa for corundum coatings. Wear resistance testing in a turning operation showed that coatings of Al–Cr–O have improved resistance to crater wear at the cost of flank wear compared with TiAlN coatings.     

Structural,mechanical and electrical-contact properties of nanocrystalline-NbC/amorphous-C coatings deposited by magnetron sputtering

Niobium-carbide nanocomposite coatings with a carbon content varying from 43 to 64 at.% were deposited by dual DC magnetron sputtering. X-ray diffraction, x-ray photoelectron spectroscopy and electron microscopy showed that all coatings consisted of nanometer sized NbC grains embedded in a matrix of amorphous carbon. Mechanical properties and electrical resistivity showed a strong dependency on the amount of amorphous carbon (a-C) and NbC grain size in the coating. The highest hardness (23 GPa), elastic modulus (295 GPa) and the lowest resistivity (260 μΩ cm) were measured for the coating with about 15% of a-C phase. Contact resistance measurements using a crossed cylinder set-up showed lowest contact resistance for the coating containing 33% a-C (140 μΩ at a contact force of 100 N), which is comparable to a Ag reference (45 μΩ at a contact force of 100 N). Comparison with TiC-based nanocomposites studied under similar conditions showed that the NbC system has less tendency to form a-C and that lowest contact resistance is obtained at comparable amounts of a-C phase in both material systems (33% for NbC compared to 35% for TiC). With these good electrical contact properties, the NbC nanocomposites can be considered as a potential material for electrical contact applications.     

Carbon-based coatings doped by copper: Tribological and mechanical behavior in olive oil lubrication

We deposited C-based films doped with Cu and tested their sliding properties in olive oil as environment-friendly lubricant, which can be used in many mechanical systems, particularly in agriculture engineering. The coatings were deposited in a four unbalanced magnetron sputtering device combining C and C/Cu targets; argon (hydrogen-free films) and Ar/CH₄ (hydrogenated films) atmospheres were used. Cu content of the films was in the range 5–14 at.%. The hardness of the films was almost constant whatever the Cu content was. On the other hand, hydrogen-free coatings were much harder (about 15 GPa) than hydrogenated ones (about 4 GPa). The coatings were oleophilic and their sliding properties were evaluated using ball-on-plate tests with 200,000 cycles. The non-hydrogenated coating with 6 at.% of copper showed the best tribological performance with negligible wear for all olive oil testing temperatures (i.e. up to 120 °C).     

Designing superhard,self-toughening CrAlN coatings through grain boundary engineering

One of the toughest challenges that hinders the application of ceramic coatings is their poor damage tolerance. Addressing this problem requires the development of novel micro- or nanostructures that would impart to these coatings both high hardness and high toughness. In this paper, CrAlN coatings, with varying Al contents up to 30 at.%, were engineered onto steel substrates using the magnetron sputtering technique. Whilst the addition of Al does not significantly alter the columnar microstructure, it does change the preferred grain orientation and increase the compressive residual stress. Moreover, the hardness, elastic strain to failure (H/E) and plastic deformation resistance (H³/E²) of the resultant CrAlN coating with the highest Al content were found to increase ～47, ～29 and ～140%, respectively, as compared to CrN. Evidence collected from transmission electron microscopy and X-ray photoelectron spectroscopy experiments shows that AlN, existing in an amorphous state at the columnar CrN grain boundaries, has a crucial role in providing the unusual combination of high hardness and exceptional damage resistance. The results provide a new pathway to developing durable ceramic coatings suitable for applications involving severe loading conditions.     

Microstructures and properties of Ni based composite coatings prepared by plasma spray welding with mixed powders

The Ni based composite coatings have been obtained by using the plasma spray welding process and mixed powders (NiCrBSi + NiCr-Cr₃C₂ + WC). Their microstructures and properties were studied. The results showed that the coatings consist mainly of γ-Ni, WC, Cr₂₃C₆, Cr₇C₃, Ni₃Si, Cr₅B₃, CrB and FeNi₃ phases, and the Ni₃Si, Cr₅B₃, CrB and FeNi₃ phases mainly segregated between the carbide grains. The carbide contents in the coatings increased with increasing the mass fractions of NiCr-Cr₃C₂ and WC powders in the mixed powders, which results in enhancing the coating hardness. The abrasive wear resistance of the coatings depends on their hardness. The higher the coating hardness, the stronger the wear resistance is. When the mixed powder (15wt%WC + 30 wt% NiCr-Cr₃C₂ + 55wt%NiCrBSi) was used, the composite coating has higher hardness and more excellent wear resistance, and the coating hardness and weight loss after wear tests are 991 HV and 8.6 mg, respectively.     

Reduced-temperature processing and consolidation of ultra-refractory Ta4HfC5

TaC, HfC, and WC powders were subjected to high-energy milling and hot pressing to produce Ta₄HfC₅, a composite of Ta₄HfC₅ + 30 vol.% WC, and a composite of Ta₄HfC₅ + 50 vol.% WC. Sub-micron powders were examined after four different milling intervals prior to hot pressing. XRD was used to verify proper phase formation. SEM, relative density, and hardness measurements were used to examine the resulting phases. Hot pressed compacts of Ta₄HfC₅ showed densification as high as 98.6% along with Vickers hardness values of 21.4 GPa. Similarly, Ta₄HfC₅ + 30 vol.% WC exhibited 99% densification with a Vickers hardness of 22.5 GPa. These levels of densification were achieved at 1500 °C, which is lower than any previously reported sintering temperature for Ta₄HfC₅. Microhardness values measured in this study were higher than those previously reported for Ta₄HfC₅. The WC additions to Ta₄HfC₅ were found to improve densification and increase microhardness.     

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.     

Effect of graphene platelets on tribological properties of boron carbide ceramic composites

The friction and wear behaviour of hot pressed boron carbide/graphene platelets (GPLs) composites have been investigated using the ball-on-flat technique with SiC ball under dry sliding conditions at room temperature. The hardness and fracture toughness of the investigated materials varied from 18.21 GPa to 30.35 GPa and from 3.81 MPa·m^1/2 to 4.60 MPa·m^1/2, respectively. The coefficient of friction for composites were similar, however the wear rate significantly decreased ~ 77% in the case of B₄C + 6 wt.% GPLs when compared to reference material at a load of 5 N, and ~ 60% at a load of 50 N. Wear resistance increased with increasing GPLs content in regards to the present graphene platelets, which during the wear test pulled-out from the matrix, exfoliated and created a wear protecting graphene-silicon based tribofilm.     

Effect of Ni content on the compression properties and abrasive wear behavior of the (TiB2–TiCxNy)/Ni composites

The (TiB₂–TiC_xN_y)/Ni composites were fabricated by the method of combustion synthesis and hot press consolidation in a Ni–Ti–B₄C–BN system. The effect of Ni content on the microstructure, hardness, compression properties and abrasive wear behavior of the composites has been investigated. The results indicate that with the increase in Ni content from 30 wt.% to 60 wt.%, the average size of the ceramic particles TiB₂ and TiC_xN_y decreases from 5 μm to ≤ 1 μm, while the hardness and the abrasive wear resistance of the composites decrease. The composite with the Ni content of 30 wt.% Ni possesses the highest hardness (1560.8 Hv) and the best abrasive wear resistance. On another hand, with the increase in the Ni content, the compression strength increases firstly, and then decreases. The composite with 50 wt.% Ni possesses the highest compression strength (3.3 GPa). The hardness and fracture strain of the composite with 50 wt.% Ni are 1251.2 Hv and 3.9%, respectively.     

Depth profile analyses of nc-TiC/a-C:H coating prepared by balanced magnetron sputtering

Nanocrystalline titanium carbide embedded in an hydrogenated amorphous carbon matrix (nc-TiC/a-C:H) shows high hardness and Young's modulus together with low wear and low friction coefficient. In this paper, we report on the preparation of well adherent nc-TiC/a-C:H coatings ~ 5 μm thick on stainless steel substrates using a well balanced magnetic field configuration and only very low power RF bias on the substrate. Hardness and Young's modulus of these coatings are 43 GPa and 380 GPa, respectively. The mechanical properties – hardness and Young's modulus – measured from the coating's top reach the values obtained at optimized experiments where the unbalanced magnetic field configuration was used. A simple method of depth profiling suitable for evaluation of mechanical properties of several micrometers thick coatings is developed and employed. The paper reports on the depth profile analyses of the coating hardness, Young's modulus, composition and morphology.