Effects of modulation ratio on the microstructure,mechanical and tribological properties of WB2/Cr multilayer films deposited by magnetron sputtering

WB₂/Cr multilayer films with different modulation ratios (λ = 1, 3, 5, 7, 12, and 20) were deposited by a combination of direct-current and pulse direct-current magnetron sputtering, and the number of bilayers was fixed at ten. The effect of the modulation ratio on the microstructure, mechanical and tribological properties of the multilayer films was investigated in detail. X-ray diffraction demonstrates that a preferred orientation of WB₂ (101) and Cr (110) exists, and WB₂ (101) dominates the film's growth with increasing of modulation ratio. The TEM results show that the multilayer films consist of nanograins dispersed in an amorphous matrix in WB₂ layers and polycrystalline grains in Cr layers. The hardness increases with the increasing modulation ratio, and the maximum hardness (31.1 GPa) is obtained at λ = 20. The indentation toughness presents an opposite changing trend, and the maximum indentation toughness (1.264 MPa m^1/2) is obtained in S1 at λ = 1 which conforms to the rule of mixture due to the relatively thick bilayer thickness (Λ = 160–192 nm). The wear mechanism is investigated, and the results suggest that the multilayer film with λ = 7 possesses the best wear resistance (2.06 × 10^?7 mm³/Nm), benefiting from the balance of hardness and indentation toughness.     

Mechanical properties of a-C:H multilayer films

Multilayered amorphous hydrogenated carbon (a-C:H) films consisting of alternating sublayers with different mechanical properties have been deposited by an electron cyclotron resonance microwave-plasma chemical vapor deposition (ECR MP-CVD) system and modulating substrate bias voltage. The mechanical properties of the multilayer films were determined using nanoindentation and nanoscratch experiments with reference to single a-C:H layers of which the multilayer structure were composed. In nanoindentation tests, the relationship between the film hardness and indentation depth has been obtained over an indentation depth range of 20–500 nm. Since the films tend to fracture under high load in nanoindentation tests, their critical fracture loads were determined. The critical loads for fracturing the multilayered a-C:H films were higher than those of single a-C:H layers. The nanoscratch tests also showed that the multilayered a-C:H films required a higher critical load for scratching fracture. This study implies that the mechanical properties of a-C:H film can be improved by engineering suitable multilayer structures.     

Ceramic TiC/a:C protective nanocomposite coatings: Structure and composition versus mechanical properties and tribology

The relationship between the structure, elemental composition, mechanical and tribological properties of TiC/amorphous carbon (TiC/a:C) nanocomposite thin films was investigated. TiC/a:C thin film of different compositions were sputtered by DC magnetron sputtering at room temperature. In order to prepare the thin films with various morphology only the sputtering power of Ti source was modified besides constant power of C source. The elemental composition of the deposited films and structural investigations confirmed the inverse changes of the a:C and titanium carbide (TiC) phases. The thickness of the amorphous carbon matrix decreased from 10 nm to 1–2 nm simultaneously with the increasing Ti content from 6 at% to 47 at%. The highest hardness (H) of ~26 GPa and modulus of elasticity (E) of ~220 GPa with friction coefficient of 0.268 was observed in case of the film prepared at ~38 at% Ti content which consisted of 4–10 nm width TiC columns separated by 2–3 nm thin a:C layers. The H3/E2 ratio was ~0.4 GPa that predicts high resistance to plastic deformation of the TiC based nanocomposites beside excellent wear-resistant properties (H/E=0.12).     

Study on the diamond-like carbon multilayer films for tribological application

In this paper, DLC multilayer films consisting of alternating layers of soft and hard carbon films were deposited on Si wafer by a plasma CVD deposition system. Different DLC multilayer films were prepared by varying the sub-layer thickness (from 1000 to 25 nm) and the ratio of hard to soft sub-layer (H/S) thickness (from 1:1 to 4:1). By using a ball-on-disk tribo-tester, the friction and wear properties of the DLC multilayer films were measured in vacuum, O₂ and dry-air environments respectively. By comparing with single-layer DLC film, the change of the multilayer structure has little influence on friction coefficient of the multilayer films. However, the wear rate of the DLC multilayer films is restricted effectively by constructed the multilayer structure in the film. The wear rate of the multilayer films is lower than that of the single film in reactive (O₂ and dry-air) environments. An DLC multilayer film with excellent wear resistance, approximately in the level of 10⁻⁸ mm³/Nm in different environments (dry-air, O₂ and vacuum), is obtained as the DLC multilayer film at a certain sub-layer thickness and ratio.     

Microstructure and properties of the AlCrMoZrTi/(AlCrMoZrTi)N multilayer high-entropy nitride ceramics films deposited by reactive RF sputtering

The AlCrMoZrTi/(AlCrMoZrTi)N multilayer high-entropy nitride ceramic films (HENCFs) fabricated by reactive RF magnetron sputtering presented (200) preferentially oriented FCC crystal structures. With the increase in the modulation period, the nitrogen content and surface roughness of the multilayer films gradually increased, the template effect between the nanocrystalline and amorphous forms was weakened, and the multilayer interface structure decreased. The S4 film with a modulation period of 1500 nm had the highest hardness and modulus (16.6 and 225.7 GPa, respectively) and the highest H/E* and H³/E*² values. The results of friction experiments showed that the S1 film with the smallest modulation period had a stable friction coefficient and small wear rate on both Si and Cu substrates, and it exhibited the best friction and wear performance due to its low surface roughness, high toughness and compressive yield resistance, and dense multilayer structure. The friction mechanisms of the HECNFs on Si and Cu substrates were mainly adhesive wear, abrasive wear, and a small amount of oxidative wear.     

Mechanical performance of ITO/Ag/ITO multilayer films deposited on glass substrate by RF and DC magnetron sputtering

ITO/Ag/ITO multilayer thin films have been a potential substitute of the conventional single-layer transparent conducting film. Nevertheless, the mechanical stability under preparation and in-service conditions still limits their applications and developments. In this paper, the influences of different structural properties as well as layer structure on both surface morphological properties and mechanical properties of the ITO/Ag/ITO multilayer thin films in comparison with commercial single-layer ITO thin film were systematically investigated. The results demonstrate that, i) the tri-layer composite has large impacts on the preferential orientation, and exhibits the decreased values of surface roughness, net lattice distortion and residual stress; ii) the increased hardness (H) and decreased Young's modulus (E) for full annealed ITO/Ag/ITO multilayer films indicate that it is possible to tailor mechanical properties of the materials by manufacturing multilayer composite; iii) the ITO/Ag/ITO multilayer thin film exhibits remarkable improvements in wear resistance with the increase of annealing temperature, which is mainly attributed to the increased ratios of H/E and H³/E².     

Diamond-like carbon films in multilayered interference coatings for IR optical elements

In the majority of modern IR interference multilayer coatings (MLC), conventional film-forming materials (FFM) of fluoride and chalcogenide types are used. Such coatings are characterized by relatively low mechanical strength and stability against enhanced humidity and, therefore, require surface protection. Our present results support the view that mechanical strength of these MLCs can be improved by applying a diamond-like carbon (DLC) film as an external layer. Nanoindentation measurements show that the addition of a DLC film to ZnSe/BaF₂/Y₂O₃ IR antireflection MLC increases the combined hardness of the coatings from 0.5 to 3.6 GPa. The formation of an indent on the upper and subsequent layers of MLC has been studied by SEM and X-ray spectrum microanalysis. The resistance of DLC films applied onto MLC against light irradiation, organic solvents as well as against environmental factors was also studied. Atomic force microscopy (AFM) was used to study variations of the surface morphology of the initial MLC components before and after DLC film deposition.     

Vibratory response of diamond-like amorphous carbon cantilevers under different temperatures

Diamond-like amorphous carbon films were deposited using filtered cathodic vacuum arc (FCVA) with the plasma ion immersion implantation (PIII) system. A unique multilayer film, comprising of alternating high-sp³ content (90%), high-stress (9 GPa) films, low-sp³ content (50%), and low-stress films (<0.5 GPa), was fabricated. By alternating these layers, a 1.5-μm-thick film was subsequently deposited. Free-standing microcantilevers measuring 150×50 μm had been subsequently fabricated by using standard lithography and wet etching. The resonance frequency of the microcantilevers was measured by a vacuum laser vibrometer system to be 109.5 kHz. After gradual heating to 240 °C, the resonance frequency was observed to increase to a high of 111.5 kHz.     

Structure and mechanical properties of oxygen doped diamond-like carbon thin films

In this study, structure and mechanical properties of doped diamond-like carbon (DLC) films with oxygen were investigated. A mixture of methane (CH₄), argon (Ar) and oxygen (O₂) was used as feeding gas, and the RF-PECVD technique was used as a deposition method. The thin films were characterized by X-ray photoelectron spectroscopy (XPS), Raman spectroscopy (RS), attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) and a combination of elastic recoil detection analysis and Rutherford backscattering (ERDA-RBS). Nano-indentation tests were performed to measure hardness. Also, the residual stress of the films was calculated by Stoney equation. The XPS and ERDA-RBS results indicated that by increasing the oxygen in the feeding gas up to 5.6 vol.%, the incorporation of oxygen into the films' structure was increased. The ratio of sp² to sp³ sites was changed by the variation of oxygen content in the film structure. The sp²/sp³ ratios are 0.43 and 1.04 for un-doped and doped DLC films with 5.6 vol.% oxygen in the feeding gas, respectively. The Raman spectroscopy (RS) results showed that by increasing the oxygen content in doped DLC films, the amount of sp² CC aromatic bonds was raised and the hydrogen content reduced in the structure. The attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) confirmed the decrease of hydrogen content and the increase the ratio of CC aromatic to olefinic bonds. Hardness and residual stress of the films were raised by increasing the oxygen content within the films' structure. The maximum hardness (19.6 GPa) and residual stress (0.29 GPa) were obtained for doped DLC films, which had the maximum content of oxygen in structure, while the minimum hardness (7.1 GPa) and residual stress (0.16 GPa) were obtained for un-doped DLC films. The increase of sp³ CC bonds between clusters and the decrease of the hydrogen content, with a simultaneous increase of oxygen in the films' structure is the reason for increase of hardness and residual stress.     

The effect of annealing on mechanical and tribological properties of diamond-like carbon multilayer films

The diamond-like carbon (DLC) multilayer films have been deposited by plasma CVD deposition onSi wafer substrate. The deposited films have then been post-annealed in vacuum at 250 °C for 2 h. Changes in internal stress, hardness, critical load, friction coefficient and wear have been investigated toassess the influence of annealing on mechanical and tribological properties of DLC multilayer films. At the same time, DLC single layerfilms are also deposited and annealed in the same method for a comparison.The results show that there is 28–33% decrease in internal stress and 10–13% decrease in hardness of theDLC single layer films after the anneal treatment. However, for the DLC multilayer films, there is 41–43% decreasein internal stress and less than 2% decrease in hardness. In addition, the annealed DLC multilayer filmhas the same friction and wear properties as that un-annealed film. This result indicates that the anneal treatment isan effective method for the DLC multilayer films to reduce the internal stress and to increase the critical load.The by-effect of the annealing, decrease of hardness and wear resistance of the multilayer film, can be restrictedby the multilayer structure.     

DLC–ceramic multilayers for automotive applications

The present work explores the deposition of hard, wear resistant multilayer coatings, by magnetron sputtering onto Aluminium (Al) alloy substrates that are used in the automotive industry. Multilayer coatings have been manufactured to increase surface hardness and wear resistance for a commercial powder metallurgy Al alloys (Al 2618). The multilayer coating consisted of 25 bi-layers of Titanium Diboride (TiB₂) and diamond-like carbon (DLC). These DLC/TiB₂ coatings were fabricated, maintaining a constant composition wavelength (sum of two layers [λ] = 200 nm) for an array of ceramic fractions ranging from 75% to 95% by volume. The effect of the DLC content on the structure and performance (hardness and adhesion) of the films was investigated. The bi-layer thickness influences the failure patterns resulting from the scratch testing. This study has found hardness values of 27.8 GPa, with a critical load of 20 N and a friction coefficient of 0.47. As a result of these findings the multilayer with 10% of DLC was found to be a better compromise between high hardness (23.8 GPa) and high adhesion (critical load higher than 20 N) and with no signs of cracking during friction testing, proving to be a solution to be employed in components located in the upper valve train area of high performance vehicles.     

Study of the mechanical properties of tetrahedral amorphous carbon films by nanoindentation and nanowear measurements

Nanoindentation and nanowear measurements, along with the associated analysis suitable for the mechanical characterization of tetrahedral amorphous carbon (ta-C) films are discussed in this paper. Films of approximately 100-nm thick were deposited on silicon substrates at room temperature in a filtered cathodic vacuum arc evaporation system with an improved S-bend filter that yields films with high values of mass density (3.2 g/cm³) and sp³ content (84–88%) when operating in a broad bias voltage range (−20 V to −350 V). Nanoindentation measurements were carried out on the films with a Berkovich diamond indenter applying loads in the 100 μN–2 mN range, leading to maximum penetration depths between 10 and 60 nm. In this measurement range, the ta-C thin-films present a basically elastic behavior with high hardness (45 GPa) and high Young's modulus (340 GPa) values. Due to the low thickness of the films and the shallow penetration depths involved in the measurement, the substrate influence must be taken into account and the area function of the indenter should be accurately calibrated for determination of both hardness and Young's modulus. Moreover, nanowear measurements were performed on the films with a sharp diamond tip using multiple scans over an area of 3 μm², producing a progressive wear crater with well-defined depth which shows an increasing linear dependence with the number of scans. The wear resistance at nanometric scale is found to be a function of the film hardness.     

Mechanical properties of DLC films prepared in acetylene and methane plasmas using electron cyclotron resonance microwave plasma chemical vapor deposition

Diamond-like carbon (DLC) films were deposited on silicon using methane and acetylene plasma induced by electron cyclotron resonance microwave plasma chemical vapor deposition (ECR-MPCVD). The mechanical properties of DLC films were characterized by micro-Raman system, atomic force microscope, tribometer, nano-indenter used for both hardness and nano-scratch test measurements. The mechanical properties of both DLC films, prepared in methane and acetylene plasmas, respectively, strongly depended on the kinetic energy of impinging particles. The deposition at −120 V substrate bias gave rise to DLC films with the best mechanical properties for both methane and acetylene plasmas. The hardness measurements with variable indentation depth showed the characteristic changes in hardness values implying elastic deformations of supporting substrates. The maximum hardness value of DLC^M films was 20 GPa while that of DLC^A films was 28 GPa. However, the hardness dropped when DLC films were prepared at substrate biases more negative than −120 V due to the thermal graphitization. The improvement in DLC properties usually provided the films with smaller hydrogen content and higher density of sp³ bondings. These parameters were engineered through controlling the deposition parameters. Particularly, the bombardment of growing DLC films by energetic ions showed to be extremely important to yield films with lower internal stress.     

Crystallization of SiC and its effects on microstructure,hardness and toughness in TaC/SiC multilayer films

A series of TaC/SiC multilayer films with different SiC thicknesses (t_SiC) have been prepared by magnetron sputtering and their microstructure, hardness and toughness investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM), atomic force microscopy (AFM), scanning electron microscopy (SEM) and nanoindentation. Results show that SiC crystallized and grew coherently with TaC layers at low t_SiC (≤ 0.8 nm), resulting from the template effect of TaC layers. Maximum hardness and toughness of 46.06 GPa and 4.21 MPa m^1/2 were achieved at t_SiC = 0.8 nm with good coherent interface. With further increasing of t_SiC, SiC layers partially transformed to an amorphous structure and gradually lost their coherent interface, leading to a rapid drop in hardness and toughness. The crystallization of SiC layers and the coherent growth are required to achieve superhardness and high toughness in the TaC/SiC multilayers.     

Microstructure and mechanical properties of pulsed laser deposited boron nitride films

Boron nitride films were prepared by pulsed laser ablation from a boron nitride target using a KrF-excimer laser, where the growing films were deposited in nitrogen atmosphere or bombarded by a nitrogen/argon ion beam. Films deposited without or at weak ion bombardment (such films will be called l-BN in this paper) are hexagonal with amorphous to turbostratic microstructure (l-BN) and show high adhesive strength to silicon and stainless steel substrates. By using them as intermediate layers, the adhesion of pure cubic boron nitride films (c-BN) can significantly be improved. l-BN films and l-BN/h-BN/c-BN layer systems have been investigated by in-situ ellipsometry, infrared spectroscopy and cross-section and plan-view high-resolution transmission electron microscopy, including diffraction. The mechanical properties, i.e. stress and hardness, of these films and layer systems are presented. l-BN films deposited at higher laser energy densities have compressive stresses as high as 11.5 GPa. Films deposited at lower laser energy densities have stresses in the range of 4.7 to 1.3 GPa and a Vickers hardness in the range of 18.6 to 7.5 GPa depending on substrate temperature and ion bombardment. The compressive stresses of 400 nm thick adherent c-BN films were estimated to be 4.5 GPa.     

Microstructure,mechanical, tribological,and oxidizing properties of AlCrSiN/AlCrVN/AlCrNbN multilayer coatings with different modulated thicknesses

Multilayer structure design is one of the most promising methods for improving the comprehensive performance of AlCrN-based hard coatings applied to cutting tools. In this study, four types of AlCrSiN/AlCrVN/AlCrNbN multilayer coatings, with different modulated thicknesses, were deposited to investigate their microstructure, mechanical, tribological, and oxidizing properties. All multilayer coatings exhibited grain growth along the crystallographic plane of (200) with a NaCl-type face-centered cubic (FCC) structure. The results show that, as the modulation thickness decreases from ～35 nm to ～10 nm, (1) the grain refinement effect is increasingly evident; (2) all multilayer coatings show a hardness of >30 GPa and an elastic modulus of >300 GPa. Both the ability to resist elastic strain to failure and the plastic deformation of multilayer coatings increase. In addition, their resistance to cracking reduces; (3) the wear rates of these multilayer coatings reduce successively from 1.78 × 10^?16 m³ N^?1 m^?1 to 7.7 × 10^?17 m³ N^?1 m^?1. This is attributed to an increase in self-lubricating VO_x and a decrease in adhesives from the counterparts; (4) the best high-temperature oxidation resistance was obtained for the multilayer coating with a modulated thickness of ～15 nm.     

Fabrication and mechanical properties of single-wall carbon nanotubes and hyperbranched diazonium salt multilayers

Acidized single-wall carbon nanotubes (SWNTs) were fabricated into multilayers with a hyperbranched azobenzene-containing polymeric diazonium salt (PDAS) using the layer-by-layer adsorption technique. The fabrication process, multilayer thickness variation, multilayer surface morphology and the interaction between SWNTs and PDAS were monitored by UV-Vis absorption spectroscopy, optical ellipsometry, Atomic Force Microscopy, Scanning Electron Microscopy and Raman spectroscopy. Moreover, the nanomechanical properties of the multilayer films were measured by nanoindentation. All results show that SWNTs and PDAS can be fabricated into multilayers based on the cooperation of electrostatic absorption and chemical cross-linkage between SWNTs and PDAS. Further, this cooperation endows the SWNT/PDAS multilayer films with outstanding nanomechanical properties. The hardness and modulus are about 2.0GPa and 10.0GPa, respectively. Finally, the SWNT/PDAS multilayer film can be peeled off to be a free-standing film. __________ Translated from Acta Polymerica Sinica (China), 2007, (11): 1052–1056 [译自: 高分子学报]     

Mechanical Properties of Sputter-Deposited Titanium-Silicon-Carbon Films

The effect of SiC additions on the mechanical properties of TiC films was investigated. Ti-Si-C films with varying SiC content were deposited using dual-cathode radio-frequency magnetron sputtering. The nanoindentation hardness of these films increased with SiC content to a maximum of 20–22 GPa for films in the range of 15–30 at.% SiC. The elastic modulus was also measured, and the hardness to modulus ratio ( H / E ) increased with SiC content, indicating that hardness increases were due to microstructural effects. The residual stress was measured in several films, but was low in magnitude, indicating that hardness measurements were not influenced by residual stress. TEM examination of several films revealed that the SiC additions altered the film microstructure in a manner that could account for the observed hardness increases.     

Hardness of nanocomposite a-C:Si films deposited by magnetron sputtering

Hydrogen-free a-C:Si films with Si concentration from 3 to 70 at.% were prepared by magnetron co-sputtering of pure graphite and silicon at room temperature. Mechanical properties (hardness, intrinsic stress), film composition (EPMA and XPS) and film structure (electron diffraction, Raman spectra) were investigated in dependence on Si concentration, substrate bias and deposition temperature. The film hardness was maximal for ∼ 45 at.% of Si and deposition temperatures 600 and 800 °C. Reflection electron diffraction indicated an amorphous structure of all the films. Raman spectra showed that the films in the range of 35–70 at.% of Si always contain three bands corresponding to the Si, SiC and C clusters. Photoelectron spectra showed dependency of Si–C bond formation on preparation conditions. In the films close to the stoichiometric SiC composition, the surface and sub-surface carbon atoms exhibited dominantly sp³ bonds. Thus, the maximal hardness was observed in nanocomposite a-C:Si films with a small excess of carbon atoms.     

Nitrogenated carbon films deposited using filtered cathodic arc

Nitrogenated carbon films were deposited on various substrates using filtered cathodic arc. Non-uniformity of the film thickness was less than 5% over a 15 cm diameter area. Mechanical, optical (refraction index, extinction coefficient versus wavelength) and electrical properties were investigated as a function of nitrogen flow rate. Deposited coatings demonstrated high hardness of 40–65 GPa, Young's modulus 200–285 GPa, excellent elastic recovery, high critical pressure for scratch formation, and surface smoothness. While the hardness showed a relatively small decrease with nitrogen flow increase, the stress decrease was more significant (8–3.8 GPa). Extremely low wear rates were observed, even at high contact pressures, and no substantial debris was detected indicating that carbon is oxidized during wear. Clear correlation was found between transparency, electrical resistivity and stress of the films. Transparency and resistivity showed a significant rise with an increase of stress. An explanation of the film properties is based on the assumption that the basic characteristics of the deposited films were determined by the relative proportion of two three dimensional complementary type of bonds; the tetrahedral sp³ bonds leading to stiff networks, and the trigonal sp² arrangments close to fullerene-like, or nanotube-like, structures.