TiCN/TiNbCN multilayer coatings with enhanced mechanical properties

Enhancement of mechanical properties by using a TiCN/TiNbCN multilayered system with different bilayer periods (Λ) and bilayer numbers (n) via magnetron sputtering technique was studied in this work. The coatings were characterized in terms of structural, chemical, morphological and mechanical properties by X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and nanoindentation. Results of the X-ray analysis showed reflections associated to FCC (1 1 1) crystal structure for TiCN/TiNbCN films. AFM analysis revealed a reduction of grain size and roughness when the bilayer number is increased and the bilayer period is decreased. Finally, enhancement of mechanical properties was determined via nanoindentation measurements. The best behavior was obtained when the bilayer period (Λ) was 15 nm (n = 200), yielding the highest hardness (42 GPa) and elastic modulus (408 GPa). The values for the hardness and elastic modulus are 1.6 and 1.3 times greater than the coating with n = 1, respectively. The enhancement effects in multilayer coatings could be attributed to different mechanisms for layer formation with nanometric thickness due to the Hall-Petch effect; because this effect, originally used to explain the increase in hardness with decreasing grain size in bulk polycrystalline metals, has also been used to explain hardness enhancements in multilayers taking into account the thickness reduction at individual single layers that make the multilayered system. The Hall-Petch model based on dislocation motion within layers and across layer interfaces, has been successfully applied to multilayers to explain this hardness enhancement.     

Enhancement of surface mechanical properties by using TiN[BCN/BN]n/c-BN multilayer system

The aim of this work is to improve the mechanical properties of AISI 4140 steel substrates by using a TiN[BCN/BN]_n/c-BN multilayer system as a protective coating. TiN[BCN/BN]_n/c-BN multilayered coatings via reactive r.f. magnetron sputtering technique were grown, systematically varying the length period (Λ) and the number of bilayers (n) because one bilayer (n = 1) represents two different layers (t_BCN + t_BN), thus the total thickness of the coating and all other growth parameters were maintained constant. The coatings were characterized by Fourier transform infrared spectroscopy showing bands associated with h-BN bonds and c-BN stretching vibrations centered at 1400 cm⁻¹ and 1100 cm⁻¹, respectively. Coating composition and multilayer modulation were studied via secondary ion mass spectroscopy. Atomic force microscopy analysis revealed a reduction in grain size and roughness when the bilayer number (n) increased and the bilayer period decreased. Finally, enhancement of mechanical properties was determined via nanoindentation measurements. The best behavior was obtained when the bilayer period (Λ) was 80 nm (n = 25), yielding the relative highest hardness (∼30 GPa) and elastic modulus (230 GPa). The values for the hardness and elastic modulus are 1.5 and 1.7 times greater than the coating with n = 1, respectively. The enhancement effects in multilayered coatings could be attributed to different mechanisms for layer formation with nanometric thickness due to the Hall-Petch effect; because this effect, originally used to explain increased hardness with decreasing grain size in bulk polycrystalline metals, has also been used to explain hardness enhancements in multilayered coatings taking into account the thickness reduction at individual single layers that make up the multilayered system. The Hall-Petch model based on dislocation motion within layered and across layer interfaces has been successfully applied to multilayered coatings to explain this hardness enhancement.     

Bilayer period effect on corrosion-erosion resistance for [TiN/AlTiN]n multilayered growth on AISI 1045 steel

The aim of this work is to study the electrochemical behavior, under a corrosion-erosion condition, of [TiN/AlTiN]_n multilayer coatings with bilayers periods of 1, 6, 12 and 24, deposited by a magnetron sputtering technique on Si (1 0 0) and AISI 1045 steel substrates.The TiN and AlTiN structure for multilayer coatings were evaluated via X-ray diffraction (XRD) analysis. Silica particles were used as an abrasive in the corrosion-erosion test within a 0.5 M H₂SO₄ solution at an impact angle of 30° over the surface. The electrochemical characterization was carried out using a polarization resistance technique (Tafel), in order to observe changes in the corrosion rate as a function of the bilayers number (n) or bilayer period (Λ). Corrosion rate values of 359 mpy in uncoated steel substrate and 1.016×10⁻⁶ mpy for substrate coated with [TiN/AlTiN]₂₄ under impact angle of 30° were found. This behavior was related with the mass loss curve for all coatings and the surface damage was analyzed using SEM images. These results indicate that TiN/AlTiN multilayer coatings deposited on AISI 1045 steel provide a practical solution for applications in erosive-corrosive environments.     

Nanolayered multilayer coatings of CrN/CrAlN prepared by reactive DC magnetron sputtering

Single-phase CrN and CrAlN coatings were deposited on silicon and mild steel substrates using a reactive DC magnetron sputtering system. The structural characterization of the coatings was done using X-ray diffraction (XRD). The XRD data showed that both the CrN and CrAlN coatings exhibited B1 NaCl structure with a prominent reflection along (2 0 0) plane. The bonding structure of the coatings was characterized by X-ray photoelectron spectroscopy and the surface morphology of the coatings was studied using atomic force microscopy. Subsequently, nanolayered CrN/CrAlN multilayer coatings with a total thickness of approximately 1 μm were deposited on silicon substrates at different modulation wavelengths (Λ). The XRD data showed that all the multilayer coatings were textured along {2 0 0}. The CrN/CrAlN multilayer coatings exhibited a maximum nanoindentation hardness of 3125 kg/mm² at a modulation wavelength of 72 Å, whereas single layer CrN and CrAlN deposited under similar conditions exhibited hardness values of 2375 and 2800 kg/mm², respectively. Structural changes as a result of heating of the multilayer coatings in air (400-800 °C) were characterized using XRD and micro-Raman spectroscopy. The XRD data showed that the multilayer coatings were stable up to a temperature of 650 °C and peaks pertaining to Cr₂O₃ started appearing at 700 °C. These results were confirmed by micro-Raman spectroscopy. Nanoindentation measurements performed on the heat-treated coatings revealed that the multilayer coatings retained hardness as high as 2250 kg/mm² after annealing up to a temperature of 600 °C.     

Phase composition and tribological properties of Ti-Al coatings produced on pure Ti by laser cladding

Ti-Al coatings with ∼14.7, 18.1, 25.2 and 29.7 at.% Al contents were fabricated on pure Ti substrate by laser cladding. The laser cladding Ti-Al coatings were analyzed with X-ray diffraction (XRD), scanning electron microscope (SEM) and X-ray energy dispersive spectroscopy (EDS). It was found that with the increase of Al content, the diffraction peaks shifted gradually to higher 2θ values. The laser cladding Ti-Al coatings with 14.7 and 18.1 at.% Al were composed of α-Ti and α₂-Ti₃Al phases, while those with 25.2 and 29.7 at.% Al were composed of α₂-Ti₃Al phase. With the increase of Al content, the cross-sectional hardness increased, while the fracture toughness decreased. For the laser cladding Ti-Al coatings, when the Al content was ≤18.1 at.%, the wear mechanism was adhesive wear and abrasive wear; while when the Al content ≥25.2 at.%, the wear mechanism was adhesive wear, abrasive wear and microfracture. With the increase of Al content, the wear rate of laser cladding Ti-Al coatings decreased under 1 N normal load, while the wear rate firstly decreased and then increased under a normal load of 3 N. Due to its optimized combination of high hardness and high fracture toughness, the laser cladding Ti-Al coating with 18.1 at.% Al showed the best anti-wear properties at higher normal load.     

Microstructures and tribological properties of CrN/ZrN nanoscale multilayer coatings

Nanoscale multilayer CrN/ZrN coatings with bilayer thicknesses ranging from 11.7 to 66.7 nm were prepared by reactive magnetron sputtering techniques. The structure of the thin films was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). X-ray diffraction results showed that CrN individual layers presented a <1 1 1> preferred orientation in the multilayer coatings. The diffraction peaks of CrN shifted continuously to low diffraction angle with decreasing bilayer thickness. TEM observations showed that the multilayer did not form a superlattice structure instead of the coexistence of nanocrystalline CrN and ZrN layers. Columnar growth for all the coatings was observed by cross-sectional SEM. Nanoindentation tests showed that the multilayer coatings had almost a constant nanohardness of 29 GPa in spite of the variations of bilayer thickness. Pin-on-disk tests indicated that both the friction coefficients and wear rates increased when decreasing bilayer thickness. However, in comparison with the monolayer coating, the multilayer coatings exhibited excellent wear resistance.     

Ti/TiN multilayer thin films deposited by pulse biased arc ion plating

In this work, the effect of modulation period (Λ) on Ti/TiN multilayer films deposited on high-speed-steel (HSS) substrates using pulse biased arc ion plating is reported. The crystallography structures and cross-sectional morphology of Ti/TiN multilayer films were characterized by X-ray diffraction analysis (XRD) and scanning electron microscopy (SEM), respectively. Their mechanical properties were determined via nanoindentation measurements, while the film/substrate adhesion via the scratch test. It was found that the highest hardness value reached 43 GPa for the modulation period of 54 nm, while the film/substrate adhesion also reached the highest value of 83 N. Furthermore, the hardness enhancement mechanism in the multilayer films is discussed.     

The effects of Si3N4 interlayer on the thermal stability and hardness of Ti/TiNx (x = 0.5-1) nanolayered coatings

The polycrystalline Ti/TiN_x multilayer films were deposited by magnetron sputtering, and the as-deposited multilayer coatings were annealed at 500-800 °C for 2-4 h in vacuum. We investigated the effects of annealing temperature and annealing time on the microstructural, interfacial, and mechanical properties of the polycrystalline Ti/TiN_x multilayer films. It was found that the hardness increased with annealing temperature. This hardness enhancement was probably caused by the preferred crystalline orientation TiN(1 1 1). The X-ray reflectivity measurements showed that the layer structure of the coatings could be maintained after annealing at 500 °C and the addition of the Si₃N₄ interlayer to Ti/TiN_x multilayer could improve the thermal stability to 800 °C.     

Heterostructures design for Hf-Nitride/V-Nitride system

The multilayered films were grown via reactive r.f. magnetron sputtering technique by systematically varying the bilayer period (Λ) and the bilayer number (n), while maintaining constant the total coating thickness (~2.4 μm) on silicon(100) substrates. The multilayers were characterized through high-angle X-ray diffraction (HA-XRD), low-angle X-ray diffraction (LA-XRD), HfN and VN layers were analyzed via X-ray Photoelectron Spectroscopy (XPS) and electron and transmission microscopy (TEM). The HA-XRD results showed preferential growth in the face-centered cubic (111) crystal structure for HfN/VN multilayer systems with the (111)[100]_HfN//(200)[100]_VN epitaxial relation. The maximum coherent assembly was observed with presence of satellite peaks.     

Influence of bilayer periods on structural and mechanical properties of ZrC/ZrB2 superlattice coatings

ZrC/ZrB₂ multilayered coatings with bilayer periods ranging from 4.4 to 35.5 nm were synthesized by r.f. magnetron sputtering. X-ray diffraction, scanning electron microscopy and nanoindention were employed to investigate the microstructure and mechanical properties of the nanoscale multilayers. The results indicated that all coatings had the clear multilayered structure with mixed ZrB₂(0 0 1), ZrB₂(0 0 2) and ZrC(1 1 1) preferred orientations. The maximum hardness (41.7 GPa) was observed in the multilayer with 27.5-nm thick period, which is about 25% higher than the rule-of-mixture value of the monolithic ZrC and ZrB₂ coatings. It also exhibited the best adhesion. Its critical load was over 70 mN. While through insert ZrB₂ into ZrC layer periodically, higher residual stress built in ZrC layer can be released.     

Tribological properties of the Ti-Al-N thin films with different components fabricated by double-targeted co-sputtering

Ti-Al-N films with different chemical compositions were deposited on stainless steel by changing the relative substrate position to targets using double-targeted reactive magnetron sputtering technique in the same process. The tribological behavior of the Ti-Al-N films was investigated in the temperature ranging from room temperature to elevated temperature in air without any lubricant on UMT-3 multifunctional friction and wear tribometer. The structure of the as-deposited films and the worn surface after tribometer testing were identified using XRD, EDS and SEM. It was found that the chemical composition of the as-deposited films altered with substrate position from Ti_0.82Al_0.18N to Ti_0.12Al_0.88N. XRD results revealed that the sputtered films before heat treatment were amorphous, but different phases such as TiN, AlN and TiAlN were formed after heat treatment of 700 °C × 1 h. Friction and wear tests indicated the films with x = 0.57, 0.65 exhibited the best tribological performance during the Ti_1−xAl_xN films system because of its hard phase and the formation of transfer films.     

Influence of Si-N interlayer on the microstructure and magnetic properties of γ′-Fe4N films

The (γ′-Fe₄N/Si-N)_n (n: number of layers) multilayer films and γ′-Fe₄N single layer film synthesized on Si (1 0 0) substrates by direct current magnetron sputtering were annealed at different temperatures. The structures and magnetic properties of as-deposited films and films annealed at different temperatures were characterized using X-ray diffraction, scanning electron microscopy and vibrating sample magnetometer. The results showed that the insertion of Si-N layer had a significant influence on the structures and magnetic properties of γ′-Fe₄N film. Without the addition of Si-N lamination, the iron nitride γ′-Fe₄N tended to transform to α-Fe when annealed at the temperatures over 300 °C. However, the phase transition from γ′-Fe₄N to ?-Fe₃N occurred at annealing temperature of 300 °C for the multilayer films. Furthermore, with increasing annealing temperature up to 400 °C or above, ?-Fe₃N transformed back into γ′-Fe₄N. The magnetic investigations indicated that coercivity of magnetic phase γ′-Fe₄N for as-deposited films decreased from 152 Oe (for single layer) to 57.23 Oe with increasing n up to 30. For the annealed multilayer films, the coercivity values decreased with increasing annealing temperature, except that the film annealed at 300 °C due to the appearance of phase ?-Fe₃N.     

Ultra-hard ceramic coatings fabricated through microarc oxidation on aluminium alloy

Ultra-hard ceramic coatings with microhardness of 2535 Hv have been synthesized on the Al alloy substrate by microarc oxidation (MAO) technique. The effects of anodic current density (j_a) and the ratio of cathodic to anodic current density (j_c/j_a) on the mechanical and corrosion resistance properties of MAO coatings have been studied by microhardness and pitting corrosion tests, respectively. In addition, the phase composition and microstructure of the coatings were analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The results show that the coatings prepared at high anodic current density consist mainly of α-Al₂O₃, while those fabricated at low anodic current density are almost composed of γ-Al₂O₃. Microhardness test shows that the coatings have high microhardness, and the highest one is found in the coating formed at j_a = 15 A/dm² and j_c/j_a = 0.7. Pitting corrosion test shows that the structure of coatings is strongly influenced by the varying j_c/j_a.     

Mechanical, tribological, and electrochemical behavior of Cr1−xAlxN coatings deposited by r.f. reactive magnetron co-sputtering method

Chromium aluminum nitride (Cr_1−xAl_xN) coatings were deposited onto AISI H13 steel and silicon substrates by r.f. reactive magnetron co-sputtering in (Ar/N₂) gas mixture from chromium and aluminum targets. Properties of deposited Cr_1−xAl_xN coatings such as compositional, structural, morphological, electrochemical, mechanical and tribological, were investigated as functions of aluminum content. X-ray diffraction patterns of Cr_1−xAl_xN coatings with different atomic concentrations of aluminum (0.51 < x < 0.69) showed the presence and evolution of (1 1 1), (2 0 0), and (1 0 2) crystallographic orientations associated to the Cr_1−xAl_xN cubic and w-AlN phases, respectively. The rate of corrosion of the steel coated with Cr_1−xAl_xN varied with the applied power; however, always being clearly lower when compared to the uncoated substrate. The behavior of the protective effect of the Cr_1−xAl_xN coatings is based on the substitution of Cr for Al, when the power applied to the aluminum target increases. The mechanical properties were also sensitive to the power applied, leading to a maximum in hardness and a reduced elastic modulus of 30 and 303 GPa at 350 W and a monotonic decrease to 11 and 212 GPa at 450 W, respectively. Finally, the friction coefficient measured by pin-on disk revealed values between 0.45 and 0.70 in humid atmosphere.     

Comparative study of titanium carbide and nitride coatings grown by cathodic vacuum arc technique

Titanium nitride (TiN), titanium carbide (TiC) thin films and TiC/TiN bilayers have been deposited on AISI 304 stainless steel substrates by plasma assisted physical vapor deposition technique—reactive pulsed vacuum arc method. The coatings were characterized in terms of crystalline structure, microstructure and chemical nature by X-ray diffraction and X-ray photoelectron spectroscopy, respectively. Tribological behavior was investigated using ball on disc technique. The average coefficient of friction was measured, showing lower values for the TiN/TiC bilayer. Dynamic wear curves were performed for each coating, observing a better wear resistance for TiN/TiC bilayers, compared to TiN and TiC monolayers. On the other hand, the TiCN formation in the TiN/TiC bilayer was observed, being attributed to the interdiffusion between TiN and TiC at the interface. Moreover, the substrate temperature influence was analysing observing a good behavior at T_S = 115 °C.     

Investigation in the interface roughness of DC-sputtered Mo/B4C multilayer mirrors with variable layer pairs for 7-nm soft X-ray polarizers

The surface and interface roughness of Mo/B₄C multilayer mirrors for 7-nm soft X-ray polarizer with variable layer pairs (N = 50, 70, 90 and 110), fabricated by DC sputtering technique is investigated by atomic force microscopy and X-ray scattering and reflecting. The experimental results present that the surface and interface roughness of Mo/B₄C multilayer mirrors increase layer by layer from its substrate as its Mo layer thickness greater than 2 nm, and the roughness grown tendency could be characterized by a quadratic function.     

Periodicity and orientation dependence of electrical properties of [(Pb0.90La0.10)Ti0.975O3/PbTiO3]n (n = 1-6) multilayer thin films

The [(Pb_0.90La_0.10)Ti_0.975O₃/PbTiO₃]_n (PLT/PT)_n (n = 1-6) multilayer thin films were deposited on the PbO_x(1 0 0)/Pt/Ti/SiO₂/Si substrates by RF magnetron sputtering method. The layer thickness of PbTiO₃ in one periodicity kept unchanged, and the layer thickness of (Pb_0.90La_0.10)Ti_0.975O₃ is varied. The electrical properties of the (PLT/PT)_n multilayer thin films were investigated as a function of the periodicity (n) and the orientation. The studied results show that the PbO_x buffer layer results in the (PLT/PT)_n films’ (1 0 0) orientation, and the (1 0 0)-oriented (PLT/PT)_n multilayer thin films with n = 2 exhibit better pyroelectric properties and ferroelectric behavior than those of (PLT/PT)_n films with other periodicities and orientations. The underlying physical mechanism for the enhanced electrical properties of (PLT/PT)_n multilayer thin films was carefully discussed in terms of the periodicities and orientations.     

The ferroelectric and ferromagnetic characterization of CoFe2O4/Pb(Mg1/3Nb2/3)O3-PbTiO3 multilayered thin films

The multiferroic (PMN-PT/CFO)_n (n = 1,2) multilayered thin films have been prepared on SiO₂/Si(1 0 0) substrate with LNO as buffer layer via a rf magnetron sputtering method. The structure and surface morphology of multilayered thin films were determined by X-ray diffraction (XRD) and atom force microscopy (AFM), respectively. The smooth, dense and crack-free surface shows the excellent crystal quality with root-mean-square (RMS) roughness only 2.9 nm, and average grain size of CFO thin films on the surface is about 44 nm. The influence of the thin films thickness size, periodicity n and crystallite orientation on their properties including ferroelectric, ferromagnetic properties in the (PMN-PT/CFO)_n multilayered thin films were investigated. For multilayered thin films with n = 1 and n = 2, the remanent polarization Pr are 17.9 μC/cm² and 9.9 μC/cm²; the coercivity H_c are 1044 Oe and 660 Oe, respectively. In addition, the relative mechanism are also discussed.     

Correlation between bioactivity and structural properties of titanium dioxide coatings grown by atomic layer deposition

TiO₂ coatings were grown on Ti and Si by Atomic Layer Deposition (ALD) from titanium ethoxide and water at 300 °C in a wide range of the reaction cycles number N = 100-2000. TiO₂ coatings were found to be amorphous at low value of N < 300 while the coatings grown at N ≥ 300 revealed anatase polycrystalline structure. The TiO₂ coatings bioactivity was evaluated by hydroxyapatite forming ability by the technique of soaking in Simulated Body Fluid (SBF). Correlation between bioactivity and structural properties of TiO₂ was determined. X-ray diffraction and scanning electron microscopy with electron probe microanalysis showed that amorphous TiO₂ coating did not induce the hydroxyapatite growth whereas anatase resulted in the hydroxyapatite forming on the samples surfaces which confirmed TiO₂ anatase bioactivity.     

Structural characterization of Ni and Ni/Ti ohmic contact on n-type 4H-SiC

In this study, we report on the structural characterization of Ni layer and Ni/Ti bilayer contacts on n-type 4H-SiC. The resulting Ni-silicides and the redistribution of carbon, after annealing at 950 °C, in the Ni/SiC and the Ni/Ti/SiC contacts are particularly studied by Rutherford Backscattering Spectrometry (RBS) at E_α = 3.2 MeV, nuclear reaction analysis (NRA) at E_d = 1 MeV, scanning electron microscopy (SEM) and Energy Dispersive X-ray Spectrometry (EDS) techniques.