Wear resistant composite coatings

In the search for wear resistant coatings, nanolaminated composite films composed of alternating metallic and ceramic layers, namely, Al/Al₂O₃ and Ti/TiN were produced using radio frequency magnetron sputtering. The metal layer thickness in the as-sputtered films of Al/Al₂O₃ ranged from 70 to 500 nm, and 150 to 450 nm in Ti/TiN. The non-metals (Al₂O₃ and TiN) layer thicknesses ranged from 10 to 40 nm and total film thicknesses of 10–15 µm. All coatings were characterized and tested for their tribological properties. Friction and wear tests were performed under non-lubricated sliding conditions using a pin-on-disc type tribometer. The coefficient of friction of the composite coatings tested, against a stainless steel pin, varied with the sliding distance. At the early stages of sliding the coefficient of friction rose to a peak, followed by a decrease to a steady-state value. Wear rates and coefficients of friction were related to the hardness and to the structure refinement of the coatings.     

Corrosion behavior of nanolayered TiN/NbN multilayer coatings prepared by reactive direct current magnetron sputtering process

TiN, NbN and TiN/NbN multilayer coatings were deposited on tool steel substrates using a reactive DC magnetron sputtering process. The coatings were characterized using X-ray diffraction, nanoindentation, atomic force microscopy, scanning electron microscopy (SEM) and energy-dispersive X-ray analysis. The corrosion behavior of TiN/NbN multilayer coatings was studied in 0.5 M HCl and 0.5 M NaCl solutions using potentiodynamic polarization and compared with single layered TiN and NbN coatings. Approximately 1.5 μm thick coatings of TiN, NbN and TiN/NbN multilayers showed good corrosion protection of the tool steel substrate and multilayer coatings performed better than single layered coatings. The corrosion behavior of the multilayers improved with total number of interfaces in the coatings. In order to conclusively demonstrate the positive effect of layering, corrosion behavior of 40-layer TiN/NbN multilayers was studied at lower coating thicknesses (32–200 nm) and compared with single layer TiN coatings of similar thicknesses. The polarization data and SEM studies of these coatings indicated that the corrosion behavior improved with coating thickness and multilayers showed better corrosion resistance as compared to the single layer coatings. Other studies such as intrinsic corrosion, effects of Ti interlayer and post-deposition annealing on the corrosion behavior of the multilayer coatings are also presented in this paper. The results of this study demonstrate that nanolayered multilayers can effectively improve the corrosion behavior of transition metal nitride hard coatings.     

Microstructure characterization of multilayered TiSiN/CrN thin films

Monolayered TiSiN and multilayered TiSiN/CrN coatings were synthesized by a cathodic arc deposition process. The chromium and Ti/Si (80/20 at.%) alloy targets were adopted as the cathode materials, altering the ratio of cathode current (I[TiSi]/I[Cr]) to obtain various multilayer periodic thicknesses of multilayered TiSiN/CrN coatings. X-ray diffraction and TEM analyses showed that all the deposited monolayered TiSiN and multilayered TiSiN/CrN films possessed the B1-NaCl structure. In this study, it was shown that the multilayer periods (Lambda) of the TiSiN/CrN deposited at I[TiSi]/I[Cr] cathode current ratios of 1.8, 1.0, and 0.55 were 8.3 nm, 6.2 nm, and 4.2 nm, respectively, with multilayer periodic thicknesses decreasing with smaller I[TiSi]/I[Cr] cathode current ratios. An amorphous phase was found at the boundaries of the TiN/CrN column grains. In addition, the multilayered TiSiN/CrN coatings displayed a lamellar structure that was well-defined and nonplanar between each TiN and CrN layer.     

Mechanical and tribological properties of nanocrystalline and nanolaminated surface coatings

The mechanical and tribological (friction/wear)properties were determined for nanocrystalline aluminum, as-sputtered Ti, Zr and Cu films, and nanolaminated Al-Al₂O₃, TiTiN, TiCu and TiZr composite films. The aluminum grain size varied between 15 and 10⁶ nm. The Al and Ti layer thicknesses in Al-Al₂O₃ and TiTiN composites ranged from 70 to 500 nm and from 150 to 450 nm, respectively. Within the grain size range of 15–100 nm, the hardness of the aluminum follows a Hall-Petch type relationship. The hardness of the TiTiN and Al-Al₂O₃ fllms also follows a Hall-Petch relationship with the Ti orAl layer thickness. The TiCu composites show a softening effect with decreasing Ti layer thickness. The coefficient of friction and wear rate for nanolaminated TiTiN and Al-Al₂O₃ composites are consistently reduced as the metal layer thickness is reduced. The micromechanisms responsible for the differences in mechanical and tribological properties are examined and the results compared with published literature.     

Conditions of Attaining a Superhard State at a Critical Thickness of Nanolayers in Multiperiodic Vacuum-Arc Plasma Deposited Nitride Coatings

Possible mechanisms of the interfacial interaction in multiperiodic (bilayer) compositions at critical thicknesses (as small as below 10 nm) of conjugated phases have been studied for the first time using structure analysis, numerical simulations, and measurements of mechanical characteristics. For attaining a state of superhigh hardness (above 40 GPa), it is proposed to form coatings with variable layer thicknesses in the bilayer period Λ. Using this approach, 10-μm-thick coatings of the TiN/ZrN system with hardness above 44 GPa were obtained for a bilayer period of Λ ≈ 10 nm with a layer thickness ratio of 1.5/1.     

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.     

Evaluation of PVD nitride coatings, using impact, scratch and Rockwell-C adhesion tests

In this work the scratch test, the impact test and the Rockwell-C adhesion test were compared by investigating the adhesion properties of three types of sputtered physical vapour deposition coatings: TiN, CrN and Cr₂N. Each coating type was deposited on polished SAE 52100 steel, with different thicknesses in the nominal range of 2–20 μm, to evaluate the thickness influence on the test results. All the tests showed a ductile behaviour for the TiN coating with small delaminations and a brittle behaviour for the CrN and Cr₂N coatings with relatively large delaminations. An increase of the dimensions of the delaminations with increased coating thickness was detected for all layer types.

With the scratch test a significant increase in upper critical load with layer thickness was observed for all of the coatings. However, there was considerable variability especially for the Cr₂N coatings. The impact tests showed no coating failure for the TiN layer, and a decreasing impact crater volume with increasing layer thickness, whereas the CrN and Cr₂N layers failed after 10³ impacts and showed an increasing impact crater volume with increasing layer thickness.

The studies demonstrate the usefulness of using these test methods for differentiating between the behaviour of different coatings under various contact conditions.     

TiN/Ti多层膜韧性对摩擦学性能的影响

考察了TiN/Ti多层膜韧性对其摩擦学性能的影响.采用磁过滤阴极弧沉积的方法制备了具有不同Ti子层厚度的TiN/Ti多层膜.用透射电镜对其层状结构及子层厚度进行了观察和分析,分别用Rockwell硬度计和UMT摩擦磨损试验机,进行了压痕测试和摩擦磨损实验.结果表明,TiN/Ti多层膜中Ti子层的加人显著提高了多层膜的韧性,相对TiN单层薄膜,当载荷较大时,多层膜的耐磨性有明显的改善.结合实验结果,讨论了TiN/Ti多层膜韧性对其耐磨性的影响.     

Influence of multi-interfacial structure on mechanical and tribological properties of TiSiN/Ag multilayer coatings

The TiSiN/Ag multilayer coatings with bilayer periods of ~50, 65, 80, 115, 150, and 410 nm have been deposited on Ti6Al4 V alloy by arc ion plating. In order to improve the adhesion of the TiSiN/Ag multilayer coatings, TiN buffer layer was first deposited on titanium alloy. The multi-interfacial TiSiN/Ag layers possess alternating TiSiN and Ag layers. The TiSiN layers display a typical nanocrystalline/amorphous microstructure, with nanocrystalline TiN and amorphous Si₃N₄. TiN nanocrystallites embed in amorphous Si₃N₄ matrix exhibiting a fine-grained crystalline structure. The Ag layers exhibit ductile nanocrystalline metallic silver. The coatings appear to be a strong TiN (200)-preferred orientation for fiber texture growth. Moreover, the grain size of TiN decreases with the decrease of the bilayer periods. Evidence concluded from transmission electron microscopy revealed that multi-interfacial structures effectively limit continuous growth of single (200)-preferred orientation coarse columnar TiN crystals. The hardness of the coatings increases with the decreasing bilayer periods. Multi-interface can act as a lubricant, effectively hinder the cracks propagation and prevent aggressive seawater from permeating to substrate through the micro-pores to some extent, reducing the friction coefficient and wear rates. It was found that the TiSiN/Ag multilayer coating with a bilayer period of 50 nm shows an excellent wear resistance due to the fine grain size, high hardness, and silver-lubricated transfer films formed during wear tests.     

Corrosion resistance of multilayer coatings of nanolayered Cr/Ni electrodeposited from Cr(III)-Ni(II) bath

In this study the corrosion resistance of chromium and nickel single layers and multilayer coatings of nanolayered Cr/Ni, electrodeposited from Cr(III)-Ni(II) baths on low carbon steel substrates, has been studied. The coatings were electrodeposited from a bath using pulse current and modulated agitation. The total thickness of single layer and multilayer coatings was fixed at 5 μm and multilayer coatings with different modulation wavelengths and Cr to Ni thickness ratio were electrodeposited. Corrosion behavior of coatings was then studied by using potentiodynamic polarization test and electrochemical impedance spectroscopy in 0.1 M H₂SO₄. The results showed that Cr and Ni single layers had low corrosion resistance due to the presence of surface cracks and pores, respectively. On the other hand, optimized 20 nm Cr/50 nm Ni multilayer deposition significantly improved corrosion resistance.     

Longitudinal conductivity of LaF3/SrF2 multilayer heterostructures

LaF₃/SrF₂ multilayer heterostructures with thicknesses of individual layers in the range 5–100 nm have been grown on MgO(100) substrates using molecular beam epitaxy. The longitudinal conductivity of the films has been measured using impedance spectroscopy in the frequency range 10^?1–10⁶ Hz and a temperature range 300–570 K. The ionic DC conductivities have been determined from Nyquist impedance diagrams and activation energies from the Arrhenius–Frenkel equation. An increase of the DC conductivity has been observed to accompany decreased layer thickness for various thicknesses as small as 25 nm. The greatest conductivity has been shown for a multilayer heterostructure having thicknesses of 25 nm per layer. The structure has a conductivity two orders of magnitude greater than pure LaF₃ bulk material. The increasing conductivity can be understood as a redistribution of charge carriers through the interface due to differing chemical potentials of the materials, by strong lattice-constant mismatch, and/or by formation of a solid La_1-xSr_xF_3-x solution at the interface during the growth process.     

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...     

纳米多层膜中的非晶晶化与超硬效应

通过对TiN/SiC、TiN/TiB₂和TiN/SiO₂纳米多层膜微结构和力学性能的研究, 展示了通常溅射沉积态为非晶的SiC、TiB2和SiO₂薄膜, 在立方结构的TiN晶体层模板作用下的晶化现象, 以及多层膜由此产生的生长结构和力学性能的变化. 结果表明: SiC在层厚0.6nm时晶化为立方结构后,可以反过来促进TiN/SiC多层膜中TiN层的晶体完整性; TiB₂在层厚2.9nm时晶化为六方结构, 并与TiN形成{111} _TiN//{0001} _TiB2, <100> _TiN//<11-20> _TiB2 的共格关系; SiO₂在层厚0.9nm 时晶化为立方结构的赝晶. 多层膜中SiC、TiB₂和SiO₂晶化后都与TiN形成共格外延的生长结构, 并相应产生了硬度升高的超硬效应. 随着SiC、TiB₂和SiO₂层厚的增加, 它们又转变为非晶态, 多层膜的共格外延生长受到破坏, 其硬度亦明显降低.     

Structure,Composition, and Properties of Arc PVD Mo–Si–Al–Ti–Ni–N Coatings

Using an arc physical vapor deposition process, we have produced nanostructured Mo–Si–Al–Ti–Ni–N coatings with a multilayer architecture formed by Mo₂N, AlN–Si₃N₄, and TiN–Ni and a crystallite size on the order of 6–10 nm. We have studied the physicomechanical properties of the coatings and their functional characteristics: wear resistance, adhesion to their substrates, and heat resistance. According to high-temperature (550°C) wear testing and air oxidation (600°C) results, the coatings studied here are wearand heat-resistant under appropriate temperature conditions. Their properties are compared to those of Mo–Si–Al–N coatings.     

SiO2层晶化对TiN/SiO2纳米多层膜结构和性能的影响

采用多靶磁控溅射法制备了一系列具有不同SiO2调制层厚的TiN/SiO2纳米多层膜.利用X射线衍射、X射线能量色散谱、扫描电子显微镜、高分辨电子显微镜和微力学探针表征和研究了多层膜的生长结构和力学性能.结果表明,具有适当厚度(0.45～0.9 nm)的SiO2调制层,在溅射条件下通常为非晶态,在TiN层的模板作用下晶化并与TiN层共格外延生长,形成具有强烈(111)织构的超晶格柱状晶多层膜;与此相应,纳米多层膜产生了硬度和弹性模量异常增高的超硬效应(最高硬度达45 GPa).随着SiO2层厚度的继续增加,SiO2层转变为非晶态,阻断了多层膜的共格外延生长,使纳米多层膜形成非晶SiO2层和纳米晶TiN层的多层结构,多层膜的硬度和弹性模量逐渐下降.     

TiN/Si3N4纳米多层膜的生长结构与超硬效应

采用磁控溅射方法制备了一系列不同Si3N4和TiN层厚的TiN/Si3N4纳米多层膜,采用X射线衍射、高分辨电子显微分析和微力学探针表征了薄膜的微结构和力学性能,研究了Si3N4和TiN层厚对多层膜生长结构和力学性能的影响.结果表明:当Si3N4层厚小于0.7 nm时,原为非晶的Si3N4在TiN的模板作用下晶化并与之形成共格外延生长的柱状晶,使TiN/Si3N4多层膜产生硬度和弹性模量异常升高的超硬效应.最高硬度和弹性模量分别为34.0 GPa和353.5 GPa.当其厚度大于1.3 nm时,Si3N4呈现非晶态,阻断了TiN的外延生长,多层膜的力学性能明显降低.此外,TiN层厚的增加也会对TiN/Si3N4多层膜的生长结构和力学性能造成影响,随着TiN层厚的增加,多层膜的硬度和弹性模量缓慢下降.     

Influence of TiN-nanolayered insertions on microstructure and mechanical properties of TiSiN nanocomposite film

TiN nanolayers with different thicknesses were inserted in TiSiN nanocomposite film by magnetron-sputtering technique. The influences of TiN insertion nanolayers with different thicknesses on microstructure and mechanical properties of TiSiN film were investigated X-ray diffraction, high-resolution transmission electron microscopy, scanning electron microscopy, and nanoindentation techniques. When the TiN insertion layer thickness is <0.5 nm, TiN nanolayers can coordinate the misorientations between TiN nanocrystallites in adjacent TiSiN layers, leading to the transformation from the nanocomposite structure with TiN nanocrystallites encapsulated by SiN _x interfacial phase into columnar crystal structure, and disappearance of the strengthening effect from the nanocomposite structure. When the TiN insertion layer thickness increases to 1.0 nm, the film is strengthened with the epitaxial growth structures between TiSiN and TiN layers. As the TiN insertion layers further thicken, the hardness and elastic modulus evidently decrease, which can be attributed to the breakage of epitaxial growth structures between TiSiN and TiN layers.     

Deformation behavior of Au/Ti multilayers under indentation

Au/Ti multilayers with individual layer thicknesses of 25 nm and 250 nm were deformed by indentation with a Vickers indenter. The deformation behavior changes from delamination-controlled for the multilayer with an individual layer thickness of 250 nm to shear banding for the multilayer with an individual layer thickness of 25 nm. The length-scale effect on delamination resistance is discussed and it is found that the delamination resistance of the Au/Ti interfaces increases with decreasing layer thickness.     

Influence of bilayer period on the characteristics of nanometre-scale ZrN/TiAIN multilayers

In the last decade, considerable research effort was directed to the deposition of multilayer films with layer thicknesses in the nanometer range (superlattice coatings), in order to increase the performance of various cutting tools and machine parts. The goal of the present work was to investigate the main microstructural, mechanical and wear resistance characteristics of a superlattice coating, consisting of alternate multilayer ZrN/TiAIN films, with various bilayer periods (5 / 20 nm). The coatings were deposited by the cathodic arc method on Si, plain carbon steel and high speed steel substrates to be used as wear resistance surfaces. The multilayer structures were prepared by using shutters placed in front of each cathode (Zr and Ti+Al). The characteristics of multilayer structures (elemental and phase composition, texture, Vickers microhardness, thickness, adhesion, and wear resistance) were determined by using various techniques (AES, XPS, XRD, microhardness measurements, scratch, and tribological tests). A comparison with the properties of ZrN and TiAIN single-layer coatings was carried out.     

Electrical and mechanical properties of nano-structured TiN coatings deposited by vacuum cold spray

Titanium nitride (TiN) coatings were fabricated by vacuum cold spray (VCS) process at room temperature with nano-sized starting powder (about 20 nm in size). The microstructure of the powder and coating was examined by scanning electron microscope and X-ray diffraction. The porosity and pore distribution of the VCS TiN coatings were measured by the N₂ adsorption-desorption method. The microhardness and fracture toughness of the coatings were evaluated by using the micro-indentation technique. The sheet resistance and electrical resistivity of the coatings were characterized by the four-point probe method. The results show that the sheet resistance of coatings is significantly reduced from 13565 to 127 Ω with increasing the coating thickness. A minimum electrical resistivity of 1.8 × 10⁻³ Ω m is achieved. The VCS TiN coatings with high porosity ranging from 58.3 to 67.6% exhibit low hardness of 279-490 HV and relatively good fracture toughness of about 3.12 MPa m^1/2.