Enhancement of mechanical and tribological properties in AISI D3 steel substrates by using a non-isostructural CrN/AlN multilayer coating

Enhancement of mechanical and tribological properties on AISI D3 steel surfaces coated with CrN/AlN multilayer systems deposited in various bilayer periods (Λ) via magnetron sputtering has been studied in this work exhaustively. The coatings were characterized in terms of structural, chemical, morphological, mechanical and tribological properties by X-ray diffraction (XRD), electron dispersive spectrograph, atomic force microscopy, scanning and transmission electron microscopy, nanoindentation, pin-on-disc and scratch tests. The failure mode mechanisms were observed via optical microscopy. Results from X-ray diffraction analysis revealed that the crystal structure of CrN/AlN multilayer coatings has a NaCl-type lattice structure and hexagonal structure (wurtzite-type) for CrN and AlN, respectively, i.e., made was non-isostructural multilayers. An enhancement of both hardness and elastic modulus up to 28 GPa and 280 GPa, respectively, was observed as the bilayer periods (Λ) in the coatings were decreased. The sample with a bilayer period (Λ) of 60 nm and bilayer number n  =  50 showed the lowest friction coefficient (∼0.18) and the highest critical load (43 N), corresponding to 2.2 and 1.6 times better than those values for the coating deposited with n = 1, respectively. The best behavior was obtained when the bilayer period (Λ) is 60 nm (n = 50), giving the highest hardness 28 GPa and elastic modulus of 280 GPa, the lowest friction coefficient (∼0.18) and the highest critical load of 43 N. These results indicate an enhancement of mechanical, tribological and adhesion properties, comparing to the CrN/AlN multilayer systems with 1 bilayer at 28%, 21%, 40%, and 30%, respectively. This enhancement in hardness and toughness for multilayer coatings could be attributed to the different mechanisms for layer formation with nanometric thickness such as the Hall–Petch effect and the number of interfaces that act as obstacles for the crack deflection and dissipation of crack energy.     

CrN/AlN superlattice coatings synthesized by pulsed closed field unbalanced magnetron sputtering with different CrN layer thicknesses

CrN/AlN superlattice coatings with different CrN layer thicknesses were prepared using a pulsed closed field unbalanced magnetron sputtering system. A decrease in the bilayer period from 12.4 to 3.0 nm and simultaneously an increase in the Al/(Cr + Al) ratio from 19.1 to 68.7 at.% were obtained in the CrN/AlN coatings when the Cr target power was decreased from 1200 to 200 W. The bilayer period and the structure of the coatings were characterized by means of low angle and high angle X-ray diffraction and transmission electron microscopy. The mechanical and tribological properties of the coatings were studied using the nanoindentation and ball-on-disc wear tests. It was found that CrN/AlN superlattice coatings synthesized in the current study exhibited a single phase face-centered cubic structure with well defined interfaces between CrN and AlN nanolayers. Decreases in the residual stress and the lattice parameter were identified with a decrease in the CrN layer thickness. The hardness of the coatings increased with a decrease in the bilayer period and the CrN layer thickness, and reached the highest value of 42 GPa at a bilayer period of 4.1 nm (CrN layer thickness of 1.5 nm, AlN layer thickness of 2.5 nm) and an Al/(Cr + Al) ratio of 59.3 at.% in the coatings. A low coefficient of friction of 0.35 and correspondingly low wear rate of 7 × 10^− 7 mm³N^− 1m^− 1 were also identified in this optimized CrN/AlN coating when sliding against a WC-6%Co ball.     

Modulation periods and ratios induced changes of microstructure and mechanical properties of AlN/ZrB2 multilayered coatings

AlN/ZrB₂ multilayered coatings were synthesized in a magnetron sputtering system. The extensive measurements were employed to investigate the influence of different nanoscale modulation periods and modulation ratios on microstructure and mechanical properties of the coatings. Analysis of X-ray diffraction, profiler and nanoindention indicated that multilayered coatings possessed much higher hardness and elastic modulus than monolithic AlN and ZrB₂ coatings. At the substrate negative bias of −80 V, maximum hardness (34.1 GPa) and elastic modulus (469.8 GPa) were obtained in the multilayer with Λ = 30 nm and t_AlN:t_ZrB2 = 1:3. This hardest multilayer showed a marked polycrystalline structure with the strong mixture of ZrB₂ (001), ZrB₂ (100), ZrB₂ (101), AlN (100) textures.     

Influence of Ni content on the structure and properties of Cr-Ni-N coatings prepared by direct current magnetron sputtering

Cr-Ni-N coatings were deposited on 304 stainless steel substrates using a conventional direct current magnetron reactive sputtering system in nitrogen-argon reactive gas mixtures. The influence of Ni content (0 ≦ x ≦ 20 at.%) on the coating composition, microstructure, and tribological properties was investigated by glow discharge optical spectroscopy, X-ray diffraction and transmission electron microscopy, scanning electron microscopy (SEM), nano-indentation, and pin-on-disk tests. The results showed that microstructure and properties of coatings changed due to the introduction of Ni. The ternary Cr-Ni-N coatings exhibited solid solution structures in spite of the different compositions. The addition of Ni strongly favoured preferred orientation growth of <200>. This preferred orientation resulted from the formed nano-columns being composed of grains with the same crystallographic orientation, as confirmed by SEM cross-sectional observations. The mechanical properties including the nano-hardness and reduced Young's modulus decreased with increasing Ni content. Pin-on-disk tests showed that low Ni content coatings presented higher abrasion resistance than high Ni content coatings.     

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

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

Comparison of microstructure and phase transformation for nanolayered CrN/AlN and TiN/AlN coatings at elevated temperatures in air environment

CrN/AlN and TiN/AlN multilayer coatings with modulation period of 4 nm and thickness ratio equal to 1.0 were manufactured by RF magnetron sputtering. Both films were annealed at temperatures of 800 °C in air for 1 h and then for an additional 9 h. Both coatings in as-deposited and after heat treatment were evaluated with a transmission electron microscope (TEM) equipped with EDS. After heat treatment at 800 °C for 1 h, a thick oxide layer around 260 nm was formed on the surface of the TiN/AlN coating. The oxide layer which formed on the coating was composed of three different regimes, including Al-enriched oxide with excess oxygen on the top surface, a crystalline Al-depleted TiO₂ layer 30-80 nm thick above the nitride coating and in between, mixed nano-crystalline Al₂O₃ and TiO₂ films. In comparison, only one oxide layer smaller than 50 nm in thickness was found in the annealed CrN/AlN coating. This amorphous or nanocrystalline oxide layer identified by EDS was a metal-deficient oxide, in which Al₂O₃ and Cr₂O₃ were mixed together forming a solid solution. As a result, the CrN/AlN coating exhibited superior stability compared to the TiN/AlN coating at elevated temperatures.     

Microstructure and mechanical properties of CrAlN/SiNx nanostructure multilayered coatings

Multilayered CrAlN and SiN_x films were deposited periodically by radio frequency reactive magnetron sputtering. In the CrAlN/SiN_x multilayered coatings, the thickness of CrAlN layer was fixed at 4 nm, while that of SiN_x layer was adjusted from 4 nm to 0.3 nm. The dependence of the SiN_x layer thickness on the preferred orientation, crystalline behavior and mechanical properties of multilayered coatings were discussed with the aid of XRD patterns and HRTEM. It was demonstrated that amorphous SiN_x layer transformed to a crystallized one when the thickness decreased from 4 nm to 0.3 nm. The crystalline SiN_x layer grew epitaxially, formed the coherent interface with the CrAlN layer, and the columnar structure was exhibited. The critical layer thickness for the transition from amorphous SiN_x to a crystallized one was found to be around 0.4 nm, and maximum hardness of 33 GPa was revealed.     

Coherent growth and superhardness effect of AlN/TiN nanomultilayers

The formation of metastable cubic AlN (c-AlN) and its effect on the mechanical properties of AlN/TiN nanomultilayers were studied. A series of AlN/TiN multilayers with different modulation periods were prepared by reactive magnetron sputtering. The microstructure and mechanical properties of multilayers were characterized with low-angle X-ray diffraction, transmission electron microscopy and a microhardness tester. The results show that AlN exists as a metastable cubic phase in multilayers at small modulation periods due to the “template effect” of TiN layer and forms superlattice with TiN through coherent epitaxial growth. Correspondingly, multilayers show the superhardness effect with the enhancement of hardness at small modulation periods. With the increase of modulation periods, AlN layer grows as c-AlN firstly and then its stable hexagonal structure (h-AlN) appears and grows on the already formed c-AlN. Correspondingly, the hardnesses of the multilayers decrease. The change of properties with the formation of c-AlN and the alternative strain field resulting from coherent growth of c-AlN and TiN are likely reasons for the superhardness effect of AlN/TiN multilayers.     

Combined Langmuir-Blodgett and sol-gel coatings

Optical properties and in-depth structure of double-layer coatings on glass substrates were investigated. One of the layers was prepared by dip coating either from silica or titania sol, the other layer was made from ca. 130 nm Stöber silica particles by the Langmuir-Blodgett (LB) technique. Two different types of combined coatings were prepared: (1) nanoparticulate LB films coated with sol-gel (SG) films and (2) nanoparticulate LB films drawn onto SG films.Scanning electron microscopy and optical methods, i.e. UV-vis spectroscopy and scanning angle reflectometry were applied for analyzing the structure and thickness of coatings. These measurements revealed that the precursor sols could not penetrate into the particulate LB film completely in case of coating type (1). For coating type (2) very little overlap between the SG and LB layers was found resulting in significant improvement of light transmittance of combined coatings compared to single SG films.To show some possible advantages of the combination of these techniques additional studies were carried out. Surface morphology of combined coatings (1) was studied by atomic force microscopy. Surfaces with different roughness were developed depending on the thickness of the sol-gel film (titania: ca. 70 nm; silica: ca. 210 nm). The adhesive peel off test revealed improved mechanical stability of combined coatings (2), in comparison to LB films which makes them good candidates for further applications.     

Adhesive and bending failure of thermal sprayed hydroxyapatite coatings: Effect of nanostructures at interface and crack propagation phenomenon during bending

Hydroxyapatite (HA) coatings have shown promising effects on rapid bone remodeling and suitable functional life in orthopedic and dental applications. However, the major problem encountered by the HA-coated implants is the failure of the coating due to its insufficient mechanical properties. The present study investigated the influence of the microstructure near to the coating/substrate interface on the adhesion of the coatings. In addition, the crack propagation behavior within the coatings was studied through 4-point bend test. Results showed that nanostructures (30-110 nm) within the HA coatings were achieved by high velocity oxy-fuel (HVOF) spraying. Comparison among HVOF HA coatings, which were deposited using different starting feedstock, suggests detrimental effect of the perpendicular-to-substrate nano-cuboids on adhesion of the coatings. The presence of the grains with hexagonal shape (<250 nm in length and <50 nm in diameter) triggered a deteriorated adhesion. Granular nanosized grains at the interface give rise to enhanced adhesion through improved mechanical interlocking. Formation mechanism of the nanosized grains was discussed in this paper. Furthermore, the 4-point bend test revealed consistent crack propagation path that the cracks actually grow within the coating with a direction parallel to the interface, and approximately several to 20 microns thick coatings were remained on the substrate. The critical strain energy release rate exhibited a value of ∼1.15 kJm⁻². During the crack propagation, kinking and trapping of the bending cracks were decided by the flaws within the coating, which were mainly located at splats’ interface. The interface between the first layer (with one splat thickness) and the second is believed to be the weakest zone in the nanostructured coating.     

Characterization of VPS-W coating layers on molybdenum after heat exposure

Tungsten (W) coating layers were successfully deposited using a vacuum plasma spraying (VPS) technique on a molybdenum (Mo) substrate. Tungsten powder with a median size of 10 μm was applied to prepare coatings via a plasma spray system. For the VPS process, argon and hydrogen were used as plasma-forming gases, and the coatings were deposited in 35 mbar vacuum pressure. A coating with a thickness of 300 μm was obtained, and some unmelted W powders were observed in the coating layer. This heat exposure experiment was performed in a sapphire crystal growing furnace at 2100 °C up to 110 h. After heat exposure, the VPS-W coating layers were soundly bonded with the Mo substrate due to the interdiffusion between W and Mo.     

Crystallization of amorphous AlN and superhardness effect in VC/AlN nanomultilayers

VC/AlN nanomultilayers with various AlN layer thicknesses have been prepared by multi-target magnetron sputtering. Microstructure evolution and mechanical properties of the multilayers have been investigated. Under the “template effect” of cubic VC, as-deposited amorphous AlN has been crystallized to cubic structure with AlN layer thickness < 1 nm, correspondingly the multilayers exhibit coherent growth and obtain significantly enhanced hardness with the maximum of 40.1 GPa. A further increase of AlN layer thickness causes the formation of amorphous AlN, which blocks the coherent growth of the multilayers, resulting in a rapid decline of hardness.     

Effect of heat treatment on mechanical properties and microstructure of CrN/AlN multilayer coatings

Polycrystalline CrN/AlN multilayer coatings were deposited by RF magnetron sputtering on silicon (001) substrates. The bilayer periods of CrN/AlN were controlled from 4 nm to 20 nm by the use of shutters, which were adjusted by a programmable logic control (PLC). To evaluate the thermal stability, the films were annealed at 500 °C, 600 °C, 700 °C, 800 °C, and 850 °C, for 1 h in both vacuum and air environments. The phase transformation during thermal evolution was studied by X-ray diffraction (XRD). The microstructure of CrN/AlN multilayer coatings as-deposited and after annealing was observed by transmission electron microscopy (TEM). The hardness of as-deposited CrN/AlN coating with a period of 4 nm was 28.2 GPa, which was 60% higher than that predicted by the rule of mixtures. The hardness of CrN/AlN multilayer coatings annealed at 850 °C in vacuum remained similar to the as-deposited state, and the nano-layered structure still persisted. The thermal stability of CrN/AlN coatings was better than that of CrN coating. The hardness degradation ratio of CrN/AlN coating with modulation period of 4 nm was only 8.1% at 700 °C, which was superior to that of a simple CrN coating.     

Highly c-axis oriented AlN layers grown on c-plane sapphire substrates by radio-frequency sputter epitaxy at 1080 °C

Aluminum nitride (AlN) single-crystalline layers were grown on c-plane sapphire substrates by radio-frequency magnetron sputter epitaxy using N₂/Ar mixture ambient gas and 5-N grade Al target. The crystalline structures of the AlN layers depending on substrate temperature and N₂ composition ratio in ambient gas, were predominantly studied. The crystalline quality of the AlN layer was improved by elevating substrate temperature, and the full-widths at half-maximum (FWHMs) of X-ray rocking curves (XRC) for both symmetric and asymmetric planes of AlN layers grown at N₂ composition ratio of around 25%, became low. The FWHMs of XRC for (0002) diffraction of the AlN layers grown at 1080 °C, were less than 20 arcsec. The surface root-mean-square roughness of such highly c-axis oriented AlN layer was determined by atomic force microscopy, and was increased from 0.6 nm to 1.3 nm when AlN layer thickness was varied from 0.15 to 0.7 μm.     

High temperature oxidation behavior of CrN/AlN superlattice films

The oxidation behavior of CrN/AlN superlattice films with different bilayer periods (Λ), Al/(Cr + Al) ratios, and crystal structures of the AlN layer was investigated. The films were deposited using a pulsed dc closed field unbalanced magnetron sputtering system. The oxidation tests were carried out in the ambient air at elevated temperatures from 700 to 1100 °C for 1 h. The changes in the crystal phase, microstructure and hardness of the films after the oxidation tests were characterized using X-ray diffraction, scanning electron microscopy and nanoindentation, respectively. When both CrN and AlN layers were in the NaCl cubic structure, the film with Λ = 3.8 nm and an Al/(Cr + Al) ratio of 0.6 exhibited a superior oxidation resistance than the film with Λ = 12.4 nm and an Al/(Cr + Al) ratio of 0.19. The film with Λ = 3.8 nm maintained the nanolayered structure with an oxidation temperature up to 1000 °C by the protection of a thin and dense X-ray amorphous oxide layer. In contrast, when the AlN layers were in the Wurzite hexagonal structure, the film with Λ = 22.5 nm and an Al/(Cr + Al) ratio of 0.67 exhibited poor oxidation resistance. The film lost the superlattice structure at 800 °C and was completely oxidized at 1000 °C due to the formation of a porous crystalline oxide layer on the surface.     

Morphological changes of electrodeposited Zn and Zn-Fe coatings during heating

The planar surface morphology of as-plated Zn crystals was found to be plate-like with a highly preferred orientation, whereas, the Zn-Fe coatings showed a nodular morphology. These nodules were clusters of many small polyhedral crystals. The surface morphology of Zn and Zn-Fe coatings did not change on heating up to a critical temperature. On heating above that temperature the surface started to smear. This critical temperature was found to increase with average Fe content in the coating. The cross-sectional view of as-plated Zn-Fe coatings showed a banded structure where the average grain size of each band was determined to be about 30 nm. As heat treatment progressed, the bands gradually disappeared. The pure Zn coating formed a layered structure with each layer corresponding to a different phase.     

TiN／AIN纳米多层膜的调制周期及力学性能研究

采用一种新型的离子束辅助非平衡反应磁控溅射设备制备了TiN／AlN纳米多层复合膜。采用XRD衍射、TEM、显微硬度计和干涉显微镜对TiN／AlN纳米多层膜的微结构和力学性能进行了表征。结果表明：TiN／AlN多层膜有良好的周期；调制结构影响薄膜的择优取向，薄膜整体表现出硬度增强的效果，硬度随调制周期的变化而变化并在调制周期为7、5nm时达到最大值。     

Microstructure and corrosion characteristics of CrN/NiP sputtering thin films

The CrN top layer and NiP interlayer were sequentially deposited to form a CrN/NiP composite coating through sputtering technique. The CrN/NiP coating systems deposited at 350 °C, 450 °C, and 550 °C, showed amorphous/nanocrystalline, nanocrystallize with precipitations, and fully crystallized microstructure respectively for the NiP interlayers. With the introduction of NiP interlayer, the coating assemblies exhibited superior corrosion characteristics than single CrN coatings. The amorphous NiP interlayer deposited at 350 °C revealed a lower corrosion current as compared to those with crystallized NiP layers owing to their structural defects in the alloy layer. With the combination of CrN and NiP layers the corrosion attach was retarded and a better corrosion resistance was found for the CrN/NiP composite coating.     

Increase of hardness and oxidation resistance of VN coating by nanoscale multilayered structurization with AlN

AlN/VN nanoscale multilayered coatings with various bilayer periods from 2.1 nm to 10.0 nm have been prepared by alternating deposition of AlN and VN. The maximum hardness, 45.4 GPa, was obtained for the AlN/VN nanoscale multilayered coating with bilayer period of 2.1 nm, which is an increase of 54% over the rule of mixture hardness value (29.5 GPa) of AlN and VN coatings. The mass gain of heat-treated AlN/VN nanoscale multilayered coating at temperatures from 600 °C to 700 °C in air was measured to be less than that of the VN single layered coating, which indicates that the oxidation resistance as well as hardness of the VN coating can be increased by nanoscale multilayered structurization with AlN.     

Synthesis of c-axis oriented AlN thin films on different substrates: A review

Highly c-axis oriented AlN thin films have been deposited by reactive sputtering on different substrates. The crystallographic properties of layered film structures consisting of a piezoelectric layer, aluminum nitride (AlN), synthesized on a variety of substrates, have been examined. Aluminum nitride thin films have been deposited by reactive pulsed-DC magnetron sputtering using an aluminum target in an Ar/N₂ gas mixture. The influence of the most critical deposition parameters on the AlN thin film crystallography has been investigated by means of X-ray diffraction (XRD) analysis of the rocking curve Full-Width at Half Maximum (FWHM) of the AlN-(0 0 0 2) peak. The relationship between the substrate, the synthesis parameters and the crystallographic orientation of the AlN thin films is discussed. A guide is provided showing how to optimize these conditions to obtain highly c-axis oriented AlN thin films on substrates of different nature.