Multilayer coatings by chemical vapor deposition in a fluidized bed reactor at atmospheric pressure (AP/FBR-CVD): TiN/TaN and TiN/W

TiN/W and TiN/TaN multilayer coatings were deposited on stainless steel by Chemical Vapor Deposition in a Fluidized Bed Reactor at Atmospheric Pressure (AP/FBR-CVD). First, the conditions for the deposition of TiN single layers were investigated, both from the experiment and thermochemical estimations. TiN was deposited from TiCl₄ and NH₃ at temperatures in the range of 750-950 °C. In the synthesis of multilayers, the W- and Ta-based layers were obtained by reduction of tungsten chloride or tantalum chloride with H₂. During the deposition of the TiN layers on top of the Ta layers, Ta reacted with NH₃ to form a mixture of tantalum nitrides. Multilayer coatings were characterized by means of GD-OES, AES and XRD. Preliminary results of nanoindentation hardness and oxidation resistance are also presented. Our results show for the first time that AP/FBR-CVD can be tuned for the deposition of multilayered coatings with periodicities in the submicron range.     

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.     

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.     

TiN/SiNx submicronic multilayer coatings obtained by chemical vapor deposition in a fluidized bed reactor at atmospheric pressure (AP/FBR-CVD)

TiN/SiN_x multilayer coatings were deposited on stainless steel by Chemical Vapor Deposition in a Fluidized Bed Reactor at Atmospheric Pressure (AP/FBR-CVD) by reaction of TiCl₄ and SiCl₄ with NH₃ at 850 °C. Due to the immiscibility of crystalline TiN and amorphous SiN_x, interdiffusion between layers is avoided even at the high working temperature. The thickness of the individual layer was in the nanometer range. Coatings were characterized by means of SEM, TEM, GD-OES, SIMS, XRD and nanoindentation. A mechanism for the growth rate and diffusion of Ti and Si into the steel is discussed.     

Oxidation resistance improvement of arc-evaporated TiN hard coatings by silicon addition

Ti-Si-N coatings were deposited on M2 steel by arc evaporation using a Ti-Si composite target in an industrial reactor. The films structure before and after heat treatment at 700 °C was characterised by XRD. In addition, two types of quantitative experiments were performed in thermobalance: oxidation rate was deduced from isothermal thermogravimetric analyses at 800 °C, while the temperature of oxidation beginning (Tc) was measured in dynamic mode. Tc was then calculated by a mathematical approximation based on the non-linear least square. The results were compared to those obtained using TiN and SiN_x standards.Depending on the deposition conditions, ternary films have been deposited with an atomic ratio Si/Ti of 0.10 and 0.15. The hardness of the films was close to 40 GPa. Only the TiN phase was detected by XRD. The mean crystal size was estimated to be in the 6-8 nm range, which suggested the nanocomposite nature of the coatings. After air oxidation at 700 °C, it was found that this crystal size was not affected by the thermal treatment, indicating a good thermal stability of the structure. Moreover, incorporation of silicon into TiN-based coatings led to a drastic decrease of their oxidation rate, together with a shift of 200 °C of Tc. The high resistance of oxidation of Ti-Si-N films at elevated temperature is attributable to the network of refractory SiN_x, which acted as a diffusion barrier for oxygen and insulated TiN nanograins from the aggressive atmosphere.     

Thermal stability of superhard Ti-B-N coatings

Ternary transition-metal boron nitride Ti-B-N offers outstanding hardness and thermal stability, which are increasingly required for wear resistant applications, as the protective coatings are subjected to high temperature, causing thermal fatigue. Ti-B-N coatings with chemical compositions close to the quasibinary TiN-TiB₂ tie line and boron contents below ∼ 18 at.% contain a crystalline supersaturated NaCl structure phase, where B substitutes for N. Annealing above the deposition temperature causes precipitation of TiB₂, which influence dislocation mobility and hence the hardness of TiB_0.40N_0.83 remains at a very high level of ∼ 43 GPa with annealing temperature T_a up to 900 °C. Growth of Ti-B-N coatings with B contents above ∼ 18 at.% results in the formation of nm sized TiN and TiB₂ crystallites embedded in a high volume fraction of disordered boundary layer. The compaction of this disordered phase during annealing results in a hardness increase of TiB_0.80N_0.83 coatings from the as-deposited value of ∼ 37 GPa to ∼ 42 GPa at T_a = 800 °C. Excess B during growth of TiB_2.4 coatings causes the formation of bundles of ∼ 5 nm wide TiB₂ subcolumns encapsulated in a B-rich tissue phase. This nanocolumnar structure is thermally stable up to temperatures of ∼ 900 °C, and consequently the hardness remains at the very high level of ~ 48 GPa, as nucleation and growth of dislocations is inhibited by the nm sized columns. Furthermore, the high cohesive strength of the B-rich tissue phase prevents grain boundary sliding.     

Mechanical properties and oxidation resistance of chemically vapor deposited TiSiN nanocomposite coating with thermodynamically designed compositions

TiSiN coating with nanocrystallite surrounded by amorphous phase has attracted a broad interest because of its high hardness and excellent oxidation resistance desired for cutting tools. In the present work, TiSiN coatings were designed and prepared from a gaseous mixture of TiCl₄, SiCl₄, NH₃ and H₂ by low pressure chemical vapor deposition (CVD) process under the guidance of calculated CVD phase diagrams. The calculated compositions and phases in the deposited coatings agree well with the experimental ones. The deposited TiSiN coatings consist of nano-crystalline TiN and amorphous Si₃N₄ (a-Si₃N₄). A maximum hardness of about 2800 HV_0.02 was obtained, corresponding to a minimum crystallite size of 17.7 nm and a-Si₃N₄ volume fraction of 13.3% for TiSiN coating deposited at 1123 K under 3.0 kPa. After oxidation at 973 K for 1 h, TiSiN coating kept intact while TiN was completely oxidized. TiSiN nanocomposite coating formed by Si incorporation to TiN displayed superior hardness and oxidation resistance in comparison with those of TiN. The correlation of TiSiN coating hardness with volume fraction of a-Si₃N₄ and TiN grain size was discussed. The present work demonstrates a novel strategy of thermodynamic calculations and key experiments to deposit CVD TiSiN coatings highly efficiently, which is equally valid for the design of other CVD hard coatings.     

Hard and superhard TiAlBN coatings deposited by twin electron-beam evaporation

Superhard nanostructured coatings, prepared by plasma-assisted chemical vapour deposition (PACVD) and physical vapour deposition (PAPVD) techniques, such as vacuum arc evaporation and magnetron sputtering, are receiving increasing attention due to their potential applications for wear protection. In this study nanocomposite (TiAl)B_xN_y (0.09 ≤ x ≤ 1.35; 1.07 ≤ y ≤ 2.30) coatings, consisting of nanocrystalline (Ti,Al)N and amorphous BN, were deposited onto Si (100), AISI 316 stainless steel and AISI M2 tool steel substrates by co-evaporation of Ti and hot isostatically pressed (HIPped) Ti-Al-B-N material from a thermionically enhanced twin crucible electron-beam (EB) evaporation source in an Ar plasma at 450 °C. The coating stoichiometry, relative phase composition, nanostructure and mechanical properties were determined using X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD), in combination with nanoindentation measurements. Aluminium (∼ 10 at.% in coatings) was found to substitute for titanium in the cubic TiN based structure. (Ti,Al)B_0.14N_1.12 and (Ti,Al)B_0.45N_1.37 coatings with average (Ti,Al)N grain sizes of 5-6 nm and either ∼ 70, or ∼ 90, mol% (Ti,Al)N showed hardness and elastic modulus values of ∼ 40 and ∼ 340 GPa, respectively. (Ti,Al)B_0.14N_1.12 coatings retained their ‘as-deposited’ mechanical properties for more than 90 months at room temperature in air, comparing results gathered from eight different nanoindentation systems. During vacuum annealing, all coatings examined exhibited structural stability to temperatures in excess of 900 °C, and revealed a moderate, but significant, increase in hardness. For (Ti,Al)B_0.14N_1.12 coatings the hardness increased from ∼ 40 to ∼ 45 GPa.     

Structural and mechanical stability upon annealing of arc-deposited Ti-Zr-N coatings

Ti-Zr-N coatings were formed by the method of vacuum arc deposition using combined Ti and Zr plasma flows in a N₂ atmosphere at different ratios of arc currents of Ti and Zr cathodes. After deposition, obtained samples were annealed in vacuum at the temperature of 850 °C. The element and phase composition, residual stresses and nanohardness were studied by Auger-Electron Spectroscopy, X-ray diffraction (XRD) and nanoindentation, respectively.XRD analysis reveals the formation of ternary Ti-Zr-N nitride coatings with the structure of solid solutions. It is shown that Ti-Zr-N coatings possess high hardness in comparison with TiN and ZrN binary nitrides. An increase in hardness is observed with increasing Zr content. However, it is established that after annealing coatings keep better stability of hardness with decrease of Zr content. The intrinsic stress in the as-deposited coatings is found to be largely compressive (− 4 GPa) and almost independent of Zr content, but much higher than in ZrN and TiN binary nitrides (− 2 GPa). After annealing, a significant stress relaxation is observed in all coatings due to relief of growth-induced point defects. Stress analysis on as-grown and annealed samples enabled us to determine the stress-free lattice parameter a₀. This latter is expanded by ∼ 0.4-0.7% as compared to Vegard's law.The thermal stability of Ti-Zr-N coatings will be discussed in terms of evolution and interdependence between structure, composition and hardness after annealing.     

Thermal barrier coating systems — analysis of nanoindentation curves

Mechanical properties (Young's modulus E, hardness H, degree of plasticity) of all three components of thermal barrier coatings systems, prepared by electron beam physical vapour deposition (EB PVD), have been investigated by nanoindentation. The power-law exponents n and m, describing the shapes of the loading and unloading nanoindentation curves, increase with peak load for the yttrium-stabilized zirconia top coat (TC), containing 4 mol% Y₂O₃, and the NiCoCrAlY bond coat (BC). The variations of m are correlated to the degree of plasticity. Decrease of the hardness with increasing peak load, generally known as indentation size effect (ISE), is observed only for the TC and the BC. The ISE in the TC is explained using a new empirical equation based on the concept of elastic recovery. The average Young's moduli of the Ni-based superalloy substrate, the BC and the TC are 189 ± 11 GPa, 166 ± 7 GPa, and 126 ± 25 GPa, respectively. The corresponding average hardness values are 3.3 ± 0.3 GPa, 5.5 ± 0.2 GPa, and 6.2 ± 1.7 GPa, respectively. The mechanical properties of the TC show complex behaviour upon annealing at 1000°°C in air, which can be explained by changes in the porosity and the residual stresses.     

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.     

Mechanical properties and oxidation resistance of CrAlN/BN nanocomposite coatings prepared by reactive dc and rf cosputtering

CrAlN/BN nanocomposite coatings were deposited through reactive cosputtering, i.e., pulsed dc and rf sputtering, of CrAl and h-BN targets, respectively. X-ray diffraction (XRD) and selected area electron-diffraction (SAED) analysis indicated that the CrAlN/BN coating consists of very fine grains of B1 structured CrAlN phase. With an increasing BN volume fraction of over 8 vol.%, the nanocrystalline nature of the grains is revealed through a dispersion of fine grains in the CrAlN/BN coating. A cross-sectional observation using a transmission electron microscope (TEM) clarified that the coating demonstrating the highest level of hardness has a fiber-like structure consisting of grains that are ~ 20 nm in width and ~ 50 nm in length. X-ray photoelectron spectroscopy (XPS) analysis revealed that the coating consists mainly of CrAlN and h-BN phase. The indentation hardness (H_IT) and effective Young's modulus (E*) of the coatings increased with the BN phase ratio, reaching a maximum value of ~ 46 and ~ 440 GPa at ~ 7 vol.% of BN phase; it then decreased moderately to ~ 40 and ~ 350 GPa at 18 vol.% of BN, respectively. Furthermore, CrAlN/BN coatings showed superior oxidation resistance compared with CrAlN coatings. After annealing at 800 °C in air for 1 h, the indentation hardness of CrAlN coatings decreased to 50% of the as-deposited hardness; in contrast, the hardness of CrAlN/BN nanocomposite coatings either stayed the same or increased, attaining a value of about 46 GPa. After annealing at 900 °C for 1 h, the hardness of all the coatings decreased to about 40%.     

Characterization of nanostructured Cr2Nx/Cu multilayers deposited by reactive DC magnetron sputtering

Nitride/metal nanostructured multilayers of Cr₂N_x/Cu were deposited by reactive DC magnetron sputtering with various bilayer periods (2.5-30 nm) and substrate temperatures (25-400 °C). All films had a total thickness of about 470 nm and the overall chemical composition of the chromium nitride layers was close to Cr₂N_0.8. The deposited films were characterized by Rutherford Backscattering (RBS), low-angle X-ray reflectivity (XRR), high-angle X-ray diffraction (XRD) and transmission electron microscopy (TEM). The hardness and elastic modulus were measured by nanoindentation. The films deposited at 25 °C had a well-defined multilayer structure and the chromium nitride layers were found to crystallize into N-deficient fcc CrN_0.4 with traces of hexagonal Cr₂N_0.8. The layers were strongly textured with fcc CrN_0.4[002] and Cu[002] oriented along the growth direction — the fcc CrN_0.4 and Cu grains growing with a cube-on-cube relationship. The measured hardness values were about 8 GPa, and showed no dependence on the bilayer period. Higher deposition temperatures caused the multilayer structure to degrade, and at 400 °C the films were better described as non-textured nanocomposites with the chromium nitride crystallized entirely into the equilibrium hexagonal Cr₂N_0.8 structure. Hardness values of the high-temperature films in the range of 4-8 GPa were measured. Multilayer films deposited at 25 °C were found to be thermally stable against post-deposition annealing at temperatures up to about 400 °C. Annealing at 500 °C caused severe structural changes — the fcc CrN_0.4 phase transformed into hexagonal Cr₂N_0.8 accompanied by degradation of the periodic multilayer structure. The hardness decreased from the originally 8 GPa to about 5 GPa upon annealing.     

Extremely hard,damage-tolerant ceramic coatings with functionally graded,periodically varying architecture

Functionally graded, multilayer coatings consisting of alternating TiN/TiSiN layers were synthesized in an attempt to overcome the innate brittleness of TiSiN nanocomposite coatings, whilst maintaining high hardness. These coatings exhibited key structural characteristics that are known to render many naturally occurring materials extremely hard and robust. Transmission electron microscopy revealed that shear sliding of columnar TiN grains played a vital role in controlling the inelastic deformation of these coatings, conferring a greater resistance to contact damage. Moreover, nanoindentation experiments showed that the multilayer coatings exhibited high hardness, attributed to the strong shear resistance offered by the hard TiSiN layers. A dependence of coating hardness upon indentation penetration depth (h_t) was found to be proportional to 1/√h_t, according to a mechanistically based model, from which the shear stress was determined. The energy dissipation during indentation was also quantified to show the critical role of the shear stress, regulated by the thickness of TiSiN layers, in resisting contact damage in the coatings. Finite-element models were constructed and the presence of transgranular cracks in the monolithic TiSiN coating was clarified based upon experimental observations. Furthermore, the simulations revealed that the transition of the dominant deformation mechanism from brittle transgranular cracking to intergranular shear sliding was controlled by the microstructural characteristics of the coatings. Enabled by the shear sliding, as well as periodic changes in elastic modulus, such a functionally graded multilayer structure was effective in lowering the magnitude and extent of stress concentrations, thereby extending the damage tolerance accessible to a ceramic coating.     

Influence of Si content and growth condition on the microstructure and mechanical properties of Ti-Si-N nanocomposite films

Thin films of Ti-Si-N have been prepared by ion beam assisted deposition (IBAD) from two Ti and Si targets. The silicon concentration in the deposited coatings is varied between 0 and 23.7 at.%. The influence of Si content and growth conditions on the microstructure and mechanical properties were investigated using XPS, AFM, XRD and nanoindenter. These nanocomposite coatings exhibit improved mechanical properties in comparison with TiN deposited under the same condition. The hardness measured by nanoindentation reached 42 GPa in Ti-Si-N films containing 11.32 at.% of Si, whereas TiN films only had a value of about 18 GPa. AFM showed that the finest grain size of Ti-Si-N appeared to be 5 nm when Si content was 11.32 at.%. From XPS and XRD results, the microstructures of the high hardness samples were found to consist of nanocrystal TiN grains and amorphous Si₃N₄.     

Comparative investigation of Al- and Cr-doped TiSiCN coatings

The aim of this work was a comparative investigation of the structure and properties of Al- and Cr-doped TiSiCN coatings deposited by magnetron sputtering of composite TiAlSiCN and TiCrSiCN targets produced by self-propagating high-temperature synthesis method. Based on X-ray diffraction, scanning and transmission electron microscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy data, the Al- and Cr-doped TiSiCN coatings possessed nanocomposite structures (Ti,Al)(C,N)/a-(Si,C) and (Ti,Cr)(C,N)/a-SiC_xN_y/a-C with cubic crystallites embedded in an amorphous matrix. To evaluate the thermal stability and oxidation resistance, the coatings were annealed either in vacuum at 1000, 1100, 1200, and 1300 °C or in air at 1000 °C for 1 h. The results obtained show that the hardness of the Al-doped TiSiCN coatings increased from 41 to 46 GPa, reaching maximum at 1000 °C, and then slightly decreased to 38 GPa at 1300 °C. The Cr-doped TiSiCN coatings demonstrated high thermal stability up to 1100 °C with hardness above 34 GPa. Although both Al- and Cr-doped TiSiCN coatings possessed improved oxidation resistance up to 1000 °C, the TiAlSiCN coatings were more oxidation resistant than their TiCrSiCN counterparts. The TiCrSiCN coatings showed better tribological characteristics both at 25 and 700 °C and superior cutting performance compared with the TiAlSiCN coatings.     

Structure-property-performance relations of high-rate reactive arc-evaporated Ti-B-N nanocomposite coatings

This study demonstrates the successful synthesis of hard and wear resistant nanocomposite Ti-B-N coatings by high-rate reactive arc-evaporation from Ti/B compound targets in a commercial industrial-sized deposition chamber. Morphological investigations by profilometry and scanning electron microscopy indicate that the coatings exhibit a lower droplet density as compared to a TiN reference as well as a compositionally graded multilayer structure. These results will be related to the previously reported microstructural characterization, which revealed a highly stressed nanocrystalline TiBN solid solution formed at lower N₂ fractions and a stable TiN/(amorphous) BN dual-phase structure obtained at higher N₂ partial pressures. Emphasis is further laid on mechanical and tribological characterization. A maximum hardness of 34.5 GPa is detected for the TiBN solid solution decreasing to 24 GPa for the coatings containing approximately 30-40 vol.% amorphous BN. The maximum in hardness coincides with the minimum in wear, while the coefficient of friction is fairly constant at 0.7-0.8.     

Microstructure and physical properties of arc ion plated TiAlN/Cu thin film

Multilayered TiAlN/Cu coatings were produced by using a cathodic vacuum arc (CVA) deposition system. Filter was incorporated to the system in order to get rid of oversized particles. The TiAlN layer gives a columnar structure. If the TiAlN deposit was interrupted periodically by adding copper to its composite, TiAlN/Cu nanomultilayer structure formed. Which can be clearly observed through high-resolution transmission electron microscopy (HRTEM), and the thickness of periodic nano-laminates of TiAlN in composite TiAlN/Cu coatings is approximately 7-8 nm. EDS analysis showed the copper content in TiAlN/Cu specimen is only about 4.5 at.%, yet it brings significant influence to the film composition, in which the titanium is suppressed while the aluminum is increased.By adding copper to TiAlN, the electron diffraction patterns were changed from spotty ring to continuous indicating the formation of nanocrystalline structure in TiAlN/Cu multilayered coating. The oxidation resistant temperature of TiAlN coating is examined at about 868.8 °C, and decreased to about 855.7 °C after adding copper in the coating. The nanoindentation measurement of TiAlN/Cu multilayered coated material shows a higher elastic modulus of about 361 GPa than that of TiAlN about 348 GPa, but a lower hardness of about 24 GPa than that of TiAlN about 30 GPa.     

The influence of the magnetic field configuration on plasma parameters and microstructure of niobium nitride films

Niobium nitride (NbN) coatings have a variety of interesting properties such as high chemical inertness, excellent mechanical properties, high electrical conductivity, high melting point, and a superconducting transition temperature around 16 K. We have investigated the effects of magnetic field configuration on the plasma characteristic (electron temperature, plasma density, the ion-to-metal flux ratio J_i/J_a and energy parameter E_p) and the microstructure of NbN films grown with a variable magnetron system. The coatings were deposited under identical deposition conditions but with varying the configuration of the magnetic field in the magnetron. The plasma characteristics were determined by planar and cylindrical Langmuir probes for the different magnetic field configurations. The film microstructure and composition were analyzed by X-ray diffraction, scanning electron microscopy and X-ray photoelectron spectroscopy, respectively. The film hardness and Young's Modulus were measured by Nanoindentation.The variation of the magnetic field with respect to the unbalance state showed that the field changed from a minimum of 3.6 to a maximum of 4.6 mT at the substrate position (5 cm away from target) while in the target center the corresponding values were 49.0 to 98.0 mT, respectively. The lower magnetic field at the target resulted in higher J_i/J_a ratios, plasma densities and potentials. These characteristics resulted in changes in the value of E_p and as this increased the preferred crystalline orientation changed from [200] to [111] and the hardness and Young Modulus increased to 40 GPa and 430 GPa, respectively.     

Effect of C2H2 gas flow rate on synthesis and characteristics of Ti–Si–C–N coating by cathodic arc plasma evaporation

The influences of C₂H₂ gas flow rate on the synthesis, microstructure, and mechanical properties of the Ti–Si–C–N films were investigated. Quaternary Ti–Si–C–N coatings were deposited on WC-Co substrates using Ti and TiSi (80:20 at.%) alloy target on a dual cathodic arc plasma evaporation system. The Ti–Si–C–N coatings were designed with Ti/TiN/TiSiN as an interlayer to enhance the adhesion strength between the top coating and substrate. The Ti–Si–C–N coatings were deposited under the mixture flow of N₂ and C₂H₂. Composition analysis showed that as the C₂H₂ gas flow increased, the Ti, Si and N contents decreased and the carbon content increased in the coatings. The results showed the maximum nanohardness of approximately 40 GPa with a friction coefficient of 0.7 was obtained at the carbon content of 28 at.% (C₂H₂ = 15 sccm). However, as the C₂H₂ gas flow rate increased from 15 to 40 sccm (carbon content from 25.2 to 56.3 at.%), both the hardness and friction coefficient reduced to 20 GPa and 0.3, respectively. Raman analysis indicated the microstructure of the deposited coating transformed from Ti–Si–C–N film to TiSi-containing diamond-like carbon films structure, which was strongly influenced by the C₂H₂ flow rate and is demarcated at a C₂H₂ flow of 20 sccm. The TiSi-containing diamond-like carbon films reveal low-friction and wear-resistant nature with an average friction coefficient between 0.3 and 0.4, lower than both TiSiN and Ti–Si–C–N films.