An analysis of macroparticle-related defects on CrCN and CrN coatings in dependence of the substrate bias voltage

Chromium nitride coatings with and without a carbon content being assigned as CrCN and CrN were prepared by cathodic arc evaporation. The effect of negative substrate bias voltages (10-300 V) on the microstructure, phase composition and morphology of the coating surface was studied. X-ray diffraction data show that almost all coatings crystallized in the cubic structure with (111) and (200) diffraction lines appearing only for low negative bias voltage and a (220) diffraction line being present for the coatings deposited at higher negative bias voltages. For CrN coatings obtained at −300 V a hexagonal structure was also observed. In case of CrCN coatings the (220) diffraction line shows much higher intensity than in case of CrN coatings and was significantly broadened. On the surface of the coatings a large number of macroparticles of different size was observed. An increase of bias voltage causes a reduction of the areal density of macroparticles and a decrease of the mean surface roughness Ra.     

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.     

脉冲偏压幅值对TiN／TiAlN多层薄膜微观结构和性能的影响

采用电弧离子镀的方法,通过改变脉冲偏压幅值在M2高速钢表面制备了TiN／TiAlN多层薄膜,研究了脉冲电压幅值TiN／TiAlN多层薄膜微观结构和性能的变化。随着脉冲偏压幅值的增加,薄膜表面的大颗粒数目明显减少。EDX结果表明,脉冲偏压幅值的增加还引起Al／Ti原子比的降低。TiN／TiAlN多层薄膜主要以（111）晶...     

负偏压对Be上磁控溅射离子镀Al膜结构影响的研究

以Be为基体，采用磁控溅射离子镀的在其上镀制Al膜，研究了负偏压对Al膜微结构的影响；研究表明，不加基体负偏压，Al膜在（111）面择优生长；随着基体负偏压升高Al膜在（111）面择优生长趋势减北，Al膜在（200）面生长趋势加强；当基体负偏压超过150V后，Al膜在（111）面择优生长的趋势又得到加强。晶粒在低负偏压时随负偏压增加而细化，当较高的负偏压引起基体温度升高时，此时晶粒又变大了。     

Deposition of TiN coatings on shape memory NiTi alloy by plasma immersion ion implantation and deposition

An investigation has been carried out to study the effect of pulse negative bias voltage on the morphology, microstructure, mechanical, adhesive and tribological properties of TiN coatings deposited on NiTi substrate by plasma immersion ion implantation and deposition. The surface morphologies were relatively smooth and uniform with lower root mean square values for the samples deposited at 15 kV and 20 kV negative bias voltages. X-ray diffraction results demonstrated that the pulse negative bias voltage can significantly change the microstructure of TiN coatings. The intensity of TiN(220) peak increased with the increase of negative bias voltage in the range of 5-20 kV. When the negative bias voltage increased to 30 kV, the preferred orientation was TiN(200). Nanoindentation test indicates that hardness and elastic modulus increased with the increase of the negative bias voltage (5 kV, 15 kV and 20 kV), and then dropped sharply at 30 kV. The adhesion between the TiN and NiTi alloy and tribological properties of TiN coated NiTi alloy depend strongly on the bias voltage parameter; the sample deposited at 20 kV possesses good adhesion strength and excellent tribological property.     

Oxidation resistance of TiN,CrN, TiAlN and CrAlN coatings deposited by lateral rotating cathode arc

In this paper, four kinds of hard coatings, TiN, CrN, TiAlN and CrAlN (with Al/Ti or Al/Cr atomic ratio around 1:1), were deposited on stainless steel substrates by a lateral rotating cathode arc technique. The as-deposited coatings were annealed in ambient atmosphere at different temperatures (500–1000 °C) for 1 h. The evolution of chemical composition, microstructure, and microhardness of these coatings after annealing at different temperatures was systematically analyzed by energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD) and nanoindentation experiments. The oxidation behaviour and its influence on overall hardness of these four coatings were compared. It was found that the ternary TiAlN and CrAlN coatings have better oxidation resistance than their binary counterparts, TiN and CrN coatings. The Cr-based coatings (CrN and CrAlN) exhibited evidently better oxidation resistance than the Ti-based coatings (TiN and TiAlN). TiN coating started to oxidize at 500 °C. After annealing at 700 °C no N could be detected by EDX, indicating that the coating was almost fully oxidized. After annealed at 800 °C, the coating completely delaminated from the substrate. TiAlN started to oxidize at 600 °C. It was nearly fully oxidized (with little residual nitrogen detected in the coating by EDX) and partially delaminated at 1000 °C. Both CrN and CrAlN started to oxidize at 700 °C. CrN was almost fully oxidized (with little residual nitrogen detected in the coating by EDX) and partially delaminated at 900 °C. The oxidation rate of the CrAlN coating is quite slow. After annealing at 1000 °C, only about 19 at.% oxygen was detected and the coating showed no delamination. The Ti-based (TiN and TiAlN) coatings were not able to retain their hardness at higher temperatures (≥ 700 °C). On the other hand, the hardness of CrAlN was stable at a high level between 33 and 35 GPa up to an annealing temperature of 800 °C and still kept at a comparative high value of 18.7 GPa even after annealed at 1000 °C, indicating a very promising applicability of this coating for high speed dry machining and other applications under high temperature environments.     

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.     

Correlation between thermal properties and aluminum fractions in CrAlN layers deposited by PVD technique

The CrAlN coatings are a good alternative to conventional CrN coatings especially for high temperature oxidation-resistance applications. Different CrAlN coatings were deposited on silicon (100) by PVD (Physical vapor deposition) technique from two targets (chromium and aluminum) in a reactive nitrogen atmosphere at aluminum applied negative voltage (−300, −500, −700 and −900 V). The composition, structural, mechanical and thermal properties of the as-deposited coatings were systematically characterized by energy dispersive analysis of X-rays, X-ray diffraction, nanoindentation, and the “Mirage effect” experiments.The X-ray diffraction (XRD) data show that in general CrAlN coatings were crystallized in the cubic NaCl B1 structure, with the (1 1 1) and (2 0 0) diffraction peaks observed. Two-dimensional surface morphologies of CrAlN coatings were investigated by atomic force microscope (AFM). The results show that with increasing aluminum proportion the coatings became more compact and denser and their increased correspondingly, showing a maximum hardness of about 36 GPa (30 at% of Al) which is higher than that of CrN. Moreover, the results in this work demonstrate that the variation of aluminum fraction alter the resulting columnar grain morphology and porosity of the coatings. However, the thermal properties are greatly affected by these morphological alterations. The correlation between aluminum fraction in CrAlN coatings and its thermal properties revealed that the conductivity and the diffusivity are influenced primarily by size and shape distribution of the pores and secondarily by a decrease of the stitch parameter dimension.     

Vacuum arc deposition of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–ZrO<Subscript>2</Subscript> coatings: arc behavior and coating characteristics

Al₂O₃–ZrO₂ coatings were deposited using a vacuum arc deposition system equipped with two co-planar cathodes. The plasma was injected into a cylindrical magnetic duct through annular anode apertures toward a substrate or an electrostatic ion current probe positioned on the duct axis, in vacuum and in a low-pressure oxygen or argon + oxygen background. Ion current and arc voltage measurements and visual observation of the cathode spots were used to find stable arcing conditions, using a straight plasma duct configuration. The cathode spot operation and transport of the plasma beam in the duct were studied as a function of arc current (I _arc = 25–200 A) and oxygen or oxygen + argon pressures (P = 0.1–1.5 Pa). Coatings were fabricated by exposing Si or WC–Co substrates simultaneously to Al and Zr plasmas using a 1/8 torus filter configuration in O₂ + Ar pressures. The coating composition, structure, microhardness, adhesion, and wear behavior were studied as functions of the deposition parameters. Favorable conditions for stable arcing were obtained with I _arc = 75 and 100 A for Al and Zr plasmas, respectively. The ion current decreased, and the arc voltage increased with the oxygen pressure. Behavior of the ion current and arc voltage suggested that cathode poisoning started at P = 0.5 Pa. Deposition rates were 0.3-0.6 μm/min, depending on the substrate position. All coatings were “Zr rich”, i.e., the Zr:Al ratio was in the range of 1.2–5.6 depending on the substrate position and deposition conditions. The coatings with higher ZrO₂ concentration were harder and had better resistance to wear. The coating’s hardness reached a maximum of ~22–24 GPa at a deposition temperature of 500 °C or a negative bias voltage of 75–100 V.     

Deposition of nano-scaled CrTiAlN multilayer coatings with different negative bias voltage on Mg alloy by unbalanced magnetron sputtering

In a magnetron sputtering system, the negative substrate bias voltage has been used as a basic process parameter to modify the deposition structure and properties of coatings. In this paper we report the effect of bias voltage ranging from −40 V to −90 V on nano-scaled CrN/TiN/CrN/AlN (CrTiAlN) multilayer coatings synthesized on a Mg alloy by a closed-field unbalanced magnetron sputtering ion plating system in a gas mixture of Ar + N₂. The technological temperature and atomic concentration in the multilayer coatings were controlled by adjusting the current density of different metal magnetron targets and the plasma optical emission monitor. The composition, crystallographic structure, deposition model and friction coefficient of multilayer coatings were characterized by X-ray photoelectron spectrometry (XPS), X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and ball-on-disc testing. The experimental results show that the deposition model and friction coefficient of nano-scaled CrTiAlN multilayer coatings were significantly affected by the negative bias voltage (V_b). The nitride species in multilayer coatings mainly involve CrN, AlN and TiN, and XRD analysis shows that the crystallographic structure was face-centered cubic. Under different bias voltage conditions, the multilayer coating composition shows a fluctuation, and the Al and Cr concentrations respond in the opposite sense to the bias voltage, attaining their greatest values at V_b = −70 V. The surface and cross-sectional morphology shows deposition model change from a columnar model into non-columnar model with the increase in negative bias voltage. The friction coefficient of the nano-scaled multilayer coatings at V_b = −55 V stabilize after 10 000 cycles.     

Ion beam deposition of α-Ta films by nitrogen addition and improvement of diffusion barrier property

Ta thin films were deposited on Si (100) substrates by an ion beam deposition method at various substrate bias voltages under Ar + N₂ atmosphere with different pressure ratios of Ar and N₂. The effects of nitrogen pressure in the plasma gas and the substrate bias voltage on the surface morphology, crystalline microstructure, electrical resistivity and diffusion barrier property were investigated. It was found that the fraction of a metastable β-phase in the Ta film deposited at the substrate bias voltage of − 50 V films decreased by adding nitrogen gas, while the α-Ta phase became dominant. As a result, the Ta films deposited at the substrate bias voltage of − 50 V under Ar (9 Pa) + N₂ (3 Pa) atmosphere showed a dominant α-phase with good surface morphology, low resistivity, and superior thermal stability as a diffusion barrier.     

CrAlN coatings deposited by cathodic arc evaporation at different substrate bias

CrAlN is a good candidate as an alternative to conventional CrN coatings especially for high temperature oxidation-resistance applications. Different CrAlN coatings were deposited on hardened steel substrates by cathodic arc evaporation (CAE) from chromium-aluminum targets in a reactive nitrogen atmosphere at negative substrate bias between − 50 and − 400 V. The negative substrate bias has important effects on the deposition growth rate and crystalline structure. All our coatings presented hardness higher than conventional CrN coatings. The friction coefficient against alumina and tungsten carbide balls was around 0.6. The sliding wear coefficient of the CrAlN coatings was very low while an important wear was observed in the balls before a measurable wear were produced in the coatings. This effect was more pronounced as the negative substrate bias was increased.     

Bias effect on microstructure and mechanical properties of magnetron sputtered nanocrystalline titanium carbide thin films

Nanocrystalline titanium carbide (TiC) thin films were prepared by magnetron sputtering deposition at 473 K. The effect of substrate bias on microstructure and mechanical properties was studied in details using X-ray photoelectron spectroscopy, X-ray diffraction, field emission scanning electron microscopy, indentation and scanning microscratch. The TiC films exhibit a (111) preferential orientation. Substrate bias decreases grain size and deposition rate of the TiC films. The TiC films have columnar structure which becomes finer at high substrate bias. Nanoindentation hardness, Young's modulus, and toughness of the films are increased as the substrate bias goes up. However, the adhesion peaks at substrate bias of − 100 V and drops when bias is increased further.     

Deposition,structure and hardness of Ti–Cu–N hard films prepared by pulse biased arc ion plating

In this work, Ti–Cu–N hard nanocomposite films were deposited on 304 stainless steel (SS) substrate by using pulse biased arc ion plating system with Ti–Cu alloy target. The effects of negative substrate pulse bias voltages on chemical composition, structure, morphology and mechanical properties were investigated. The composition and structure of these films was found to be dependent on the pulse bias, whereas the pulse biases put little influence on hardness of these films. The XPS spectra of Cu 2p showed that obtained peak values correspond to pure metallic Cu. Cu content in Ti–Cu–N nanocomposite films changed with pulse bias voltage. In addition, X-ray diffraction analysis showed that a pronounced TiN (111) texture is observed under low pulse bias voltage while it changed to TiN (220) orientation under high pulse bias voltage. Surface roughness of the Ti–Cu–N nanocomposite films achieved to the minimum value of 0.11 μm with the negative pulse bias voltage of −600 V. The average grain size of TiN was less than 17 nm. The mechanical properties of Ti–Cu–N hard films investigated by nanoindentation revealed that the hardness was about 22–24 GPa and the hardness enhancement was not obtained.     

Deposition,structure and hardness of Ti–Cu–N hard films prepared by pulse biased arc ion plating

In this work, Ti–Cu–N hard nanocomposite films were deposited on 304 stainless steel (SS) substrate by using pulse biased arc ion plating system with Ti–Cu alloy target. The effects of negative substrate pulse bias voltages on chemical composition, structure, morphology and mechanical properties were investigated. The composition and structure of these films was found to be dependent on the pulse bias, whereas the pulse biases put little influence on hardness of these films. The XPS spectra of Cu 2p showed that obtained peak values correspond to pure metallic Cu. Cu content in Ti–Cu–N nanocomposite films changed with pulse bias voltage. In addition, X-ray diffraction analysis showed that a pronounced TiN (111) texture is observed under low pulse bias voltage while it changed to TiN (220) orientation under high pulse bias voltage. Surface roughness of the Ti–Cu–N nanocomposite films achieved to the minimum value of 0.11 μm with the negative pulse bias voltage of ?600 V. The average grain size of TiN was less than 17 nm. The mechanical properties of Ti–Cu–N hard films investigated by nanoindentation revealed that the hardness was about 22–24 GPa and the hardness enhancement was not obtained.     

Nanoindentation and atomic force microscopy measurements on reactively sputtered TiN coatings

Titanium nitride (TiN) coatings were deposited by d.c. reactive magnetron sputtering process. The films were deposited on silicon (111) substrates at various process conditions, e.g. substrate bias voltage (V_B) and nitrogen partial pressure. Mechanical properties of the coatings were investigated by a nanoindentation technique. Force vs displacement curves generated during loading and unloading of a Berkovich diamond indenter were used to determine the hardness (H) and Young’s modulus (Y) of the films. Detailed investigations on the role of substrate bias and nitrogen partial pressure on the mechanical properties of the coatings are presented in this paper. Considerable improvement in the hardness was observed when negative bias voltage was increased from 100–250 V. Films deposited at |V _B| = 250 V exhibited hardness as high as 3300 kg/mm². This increase in hardness has been attributed to ion bombardment during the deposition. The ion bombardment considerably affects the microstructure of the coatings. Atomic force microscopy (AFM) of the coatings revealed fine-grained morphology for the films prepared at higher substrate bias voltage. The hardness of the coatings was found to increase with a decrease in nitrogen partial pressure.     

The phase and microstructure of CrAlN films deposited by pulsed dc magnetron sputtering with synchronous and asynchronous bipolar pulses

CrAlN films have been deposited from a Cr target and an Al target using pulsed dc magnetron sputtering. The Cr and Al targets were pulsed in asynchronous and synchronous pulsing modes at different pulsing frequencies and duty cycles. The ion energy distributions of the plasma were characterized by a Hiden mass spectrometer. The pulsed plasma contains a wide range of energetic ions. The ion energies depend on the pulsing parameters and the pulsing mode of the two targets. The ion energy and ion flux increased as the pulsing frequency was increased. The plasma exhibited higher ion energies and ion fluxes in the synchronous pulsing mode than those in the asynchronous pulsing mode for the same pulsing frequency and duty cycle. A decrease in the N content and an increase in the Al/(Cr + Al) ratio were observed as the pulsing frequency was increased in both pulsing modes. When the pulsing frequency was increased to 350 kHz, the films deposited in the asynchronous pulsing mode exhibited a NaCl cubic structure, whereas a mixture of the cubic and hexagonal phases was formed in the films deposited in the synchronous pulsing mode. The hardness of the films increased with an increase in the pulsing frequency in the asynchronous pulsing mode. In contrast, a decrease in the hardness was found in the synchronously deposited films as the pulsing frequency was increased due to the formation of hexagonal AlN phase and the stress relaxation in the films.     

Effect of ion cleaning pretreatment on interface microstructure, adhesive strength and tribological properties of GLC coatings on Al substrates

In this work, a series of ion cleaning procedures (bias and time) were performed on aluminum substrate surface prior to the deposition of graphite-like carbon (GLC) coatings. Special attention has been paid on the interface microstructure, coating/substrate bonding strength and tribological properties. It was found that ion cleaning critically influenced the adhesion and the wear resistance of GLC coatings. The optimization of ion cleaning pretreatment revealed that 400 V/30 min is the best ion cleaning conditions. HRTEM observations on the interfacial region showed that the oxide layer has been removed completely, a strong bonding diffusion interface formed. However, for the low energy ion cleaning (300 V/10 min), TEM observations on the interfacial region between the coating and the Al substrate showed that the oxide contamination still existed. The optimization of GLC layer thickness revealed that the GLC coating with 1 μm GLC layer exhibited the highest critical load and the lowest friction coefficient of 14.7 N and 0.065, respectively.     

A study of the nanostructure and hardness of electron beam evaporated TiAlBN Coatings

TiAlBN coatings have been deposited by electron beam (EB) evaporation from a single TiAlBN material source onto AISI 316 stainless steel substrates at a temperature of 450 °C and substrate bias of − 100 V. The stoichiometry and nanostructure have been studied by X-ray photoelectron spectroscopy, X-ray diffraction and transmission electron microscopy. The hardness and elastic modulus were determined by nanoindentation. Five coatings have been deposited, three from hot-pressed TiAlBN material and two from hot isostatically pressed (HIPped) material. The coatings deposited from the hot-pressed material exhibited a nanocomposite nc-(Ti,Al)N/a-BN/a-(Ti,Al)B₂ structure, the relative phase fraction being consistent with that predicted by the equilibrium Ti-B-N phase diagram. Nanoindentation hardness values were in the range of 22 to 32 GPa. Using the HIPped material, coating (Ti,Al)B_0.29N_0.46 was found to have a phase composition of 72-79 mol.% nc-(Ti,Al)(N,B)_1 − x+ 21-28 mol.% amorphous titanium boride and a hardness of 32 GPa. The second coating, (Ti,Al)B_0.66N_0.25, was X-ray amorphous with a nitride+boride multiphase composition and a hardness of 26 GPa. The nanostructure and structure-property relationships of all coatings are discussed in detail. Comparisons are made between the single-EB coatings deposited in this work and previously deposited twin-EB coatings. Twin-EB deposition gives rise to lower adatom mobilities, leading to (111) (Ti,Al)N preferential orientation, smaller grain sizes, less dense coatings and lower hardnesses.     

A study on the microstructure and property development of d.c. magnetron cosputtered ternary titanium aluminium nitride coatings Part III effect of substrate bias voltage and temperature

Advanced ternary (Ti,Al)N coatings were produced by reactive magnetron co-sputtering technique with separate titanium and aluminium targets at a 30° magnetron configuration under various substrate bias voltages and temperatures. The effect of substrate bias and temperature on the microstructure and property development of the coatings was investigated. It was found that an increase in substrate bias and/or substrate temperature imposed no major effect on the composition and phase formation of the (Ti,Al)N coatings, but had significant influence on the development of their microstructure and surface morphology. As the substrate bias and/or temperature increased, the coating structure was densified with development of fine grain size and reduced surface roughness, resulting in a substantial increase of the coating hardness. However as the substrate bias increased over 200 volts, excessive residual stress was built up, causing a fracture of the coatings. It is believed that the microstructure and property enhancement is attributed to an increased translational kinetic energy of the depositing atoms and a greater thermal energy provided to the substrate and the coating material with increasing substrate bias and/or temperature. The adatom mobility and the surface diffusion of atoms are enhanced to reduce the detrimental effects induced by the statistical roughening and self-shadowing of asputter deposition process. A densified zone T structure with low porosity and improved properties is produced.