Structural and mechanical properties of nano-crystal TiN coatings

The structural and mechanical properties of TiN coatings prepared by ion beam assisted deposition (IBAD) were studied. The coatings have a polycrystal structure with grain size of ≈10nm or less. The hardness of the coatings increases with increasing grain size of TiN crystallites. The coating with grain size of 10.3 nm even has a superhardness of 44.7 GPa. The relationship between the hardness and the grain size in the nano-crystalline coatings was discussed on the basis of grain-boundary triple junctions.

     

Nanostructured TiN coating prepared by reactive plasma spraying in atmosphere

In the present study, the nanostructured TiN coatings are obtained by means of reactive plasma spraying in the air. The XRD analysis shows the coating was mainly composed of TiN (max. 86.3%) and a small quantity of Ti₃O. Their microstructures were observed by SEM and TEM. The TEM pictures show the TiN coatings were composed of the nanoscaled grains (range from 70 to 90 nm), and the Scherrer equation analysis on the average grain size corresponded with that result. The effects on the average grain size also were studied by changing the spraying power and the spraying distance.     

Nanocomposite Ni–TiN coatings prepared by ultrasonic electrodeposition

Nanocomposite Ni–TiN coatings were prepared by ultrasonic electrodeposition and the effects of ultrasonication on the coatings were studied. X-ray diffraction analysis was utilized to detect the crystalline and amorphous characteristics of the composite coatings. The surface morphology and metallurgical structure were observed by scanning electron microscopy, high-resolution transmission electron microscopy and scanning probe microscopy. The results showed that ultrasonication had great effects on TiN nanoparticles in composite coatings. The moderate ultrasonication conduced to homogeneous dispersion of TiN particles in the coatings. Moreover, the TiN nanoparticles that entered and homogeneously dispersed in the composite coating led to an increase in the number of nuclei for nucleation of nickel grains and inhibition of grain growth. Therefore, the introduction of ultrasonication and TiN nanoparticles resulted in the formation of smaller nickel grains. The average grain diameter of TiN particles was ∼33 nm, while Ni grains measured approximately 53 nm.     

Microstructure and mechanical properties of reactive magnetron sputtered Ti-B-C-N nanocomposite coatings

Ti-B-C-N nanocomposite coatings with different C contents were deposited on Si (1 0 0) and high speed steel (W18Cr4V) substrates by closed-field unbalanced reactive magnetron sputtering in the mixture of argon, nitrogen and acetylene gases. These films were subsequently characterized ex situ in terms of their microstructures by X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM), their nanohardness/elastic modulus and facture toughness by nano-indention and Vickers indentation methods, and their surface morphology using atomic force microscopy (AFM). The results indicated that, in the studied composition range, the deposited Ti-B-C-N coatings exhibit nanocomposite based on TiN nanocrystallites. When the C₂H₂ flow rate is small, incorporation of small amount of C promoted crystallization of Ti-B-C-N nanocomposite coatings, which resulted in increase of nano-grain size and mechanical properties of coatings. A maximum grain size of about 8 nm was found at a C₂H₂ flux rate of 1 sccm. However, the hardness, elastic modulus and fracture toughness values were not consistent with the grain size. They got to their maximum of 35.7 GPa, 363.1 GPa and 2.46 MPa m^1/2, respectively, at a C₂H₂ flow rate of 2 sccm (corresponding to about 6 nm in nano-grain size). Further increase of C content dramatically decreased not only grain size but also the mechanical properties of coatings. The presently deposited Ti-B-C-N coatings had a smooth surface. The roughness value was consistent with that of grain size.     

TiN和Ti1-xSixNy薄膜的微观结构分析

使用x射线衍射(XRD)、x射线光电子谱(XPS)、高分辨透射电子显微镜(HRTEM)和原子力显微镜（AFM）多种观测手段分析了TiN薄膜和Ti_1-xSi_xN_y纳米复合薄膜的微观结构.实验分析证明Ti_1-xSi_xN_y薄膜是由直径为3—5nm的纳米晶TiN和非晶Si₃N₄相构成，并且Ti_1-xSi_{x关键词： 纳米复合薄膜 自由能 表面粗糙度 TiN 1-x}Si_xN_y')" href="#">Ti_1-xSi_xN_y     

Ti-B-C-N纳米复合薄膜结构及力学性能研究

利用反应磁控溅射方法在单晶硅和高速钢(W18Cr4V)基片上制备出不同C含量Ti-B-C-N纳米复合薄膜. 使用X射线衍射和高分辨透射电子显微镜研究了Ti-B-C-N纳米复合薄膜的组织和微观结构,用纳米压痕仪测试了它们的硬度和弹性模量. 结果表明,利用往真空室通入C₂H₂气体的方法制备得到的Ti-B-C-N纳米复合薄膜中,在所研究成分范围内只发现TiN基的纳米晶. 当C₂H₂流量较小时,C元素的加入可以促进Ti-B-C 关键词： Ti-B-C-N薄膜 磁控溅射 微观结构 力学性能     

Peculiarities of structural phase and elastic stress states of superhard TiN-based nanocomposite coatings

A new concept of designing nanocomposite coatings is proposed. The concept consists in microstructural self-organization through simultaneous nucleation of islands of different mutually insoluble or slightly soluble phases at the stage of coating formation. Physical principles on which to select compositions of the coatings were developed and were experimentally verified on multicomponent nanocomposite coatings. With a Sprut magnetron arc plasma complex, superhard (H _μ > 40 GPa) multicomponent nanocomposite coatings of the system Ti-Al-Si-Cr-Ni-Cu-O-C-N were obtained. The peculiarities of structural phase and elastic stress states of the multicomponent coatings before and after annealing at a temperature of up to 1000 °C were studied by transmission electron microscopy, X-ray diffraction analysis, microhardness measurements and scratch tests. The study reveals a wide range of lattice bending-torsion (up to 200° μm^?1) of nanosized (less than 30 nm) coherent scattering regions in the two-level coating structure and of individual (up to 15 nm) TiN nanocrystals. Annealing of the coatings causes the two-level grain structure to relax with the formation of TiN-based nanocrystals of size less than 30–40 nm and with a decrease in lattice bending-torsion down to 40°–50° μm^?1. Comparative analysis of acoustic emission signals and tracks of the multicomponent and TiN coatings in scratch tests points to an increase in fracture ductility in the multicomponent coatings.     

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

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

Characterization of bilayer coatings of TiN/ZrN grown using pulsed arc PAPVD

Nitride coatings have been used to increase hardness and to improve the wear and corrosion resistance of structural materials. Coatings of TiN/ZrN were grown on stainless steel substrates using a physical vapour deposition system assisted by pulsed arc plasma (PAPVD). The coatings have been characterized by X-ray diffraction (XRD) in order to identify the present phases of the films, microstrain level generated, crystallite size and the variation of the lattice parameter. The results showed plane orientations (1 1 1) and (2 0 0) in both TiN and ZrN films. Morphology surface analysis of the samples were performed using a scanning probe microscope to characterize the grain size and roughness in the mode of the atomic force microscopy (AFM) hence it was observed that the root-mean-squared (rms) roughness for ZrN is smaller than for TiN. Besides elastic and friction properties of the films were characterized qualitatively, and then, they were compared with those of the substrates by using force modulation microscopy (FMM) and lateral force microscopy (LFM) modes. In addition, an elemental analysis of the samples was realized by means of energy dispersive spectroscopy (EDS). Both, XRD and AFM results are given as a function of the number of shots. Chemical states of the TiN and ZrN films were determined by X-ray photoelectron spectroscopy (XPS).     

Microstructure of TiN coatings synthesized by direct pulsed Nd:YAG laser nitriding of titanium: Development of grain size,microstrain, and grain orientation

Pure titanium was irradiated by pulsed Nd:YAG laser irradiation in nitrogen atmosphere. As a result, nitrogen uptake and diffusion occurred and a TiN layer was synthesized at the titanium surface. These TiN coatings were analyzed by X-ray diffraction and the diffraction patterns were investigated in detail, in order to obtain more information about the physical processes during the coating formation. The diffraction peaks were fitted by Pearson VII profiles and the grain size and the microstrain were determined by the analysis of line broadening and peak shifts, using the Williamson–Hall and the Warren–Averbach formalisms. Additional single-line analyses were performed by means of the method of Langford and Keijser to obtain information about the preferred grain orientation and the texture development. The maximum grain size was about 100 nm and a corresponding average lattice strain of 0.002 was found. A relation between the treatment parameters and the coating properties, such as grain size and microstrain, can be shown. Thus, it was possible to determine optimal scan parameters for material processing and to establish the physical limits of the coating properties. PACS 81.65.Lp; 81.15.Fg; 61.10.Nz; 68.55.Jk     

Brittle nanomaterials: Hardness and superplasticity

The data on the hardness and superplasticity of nanomaterials based on brittle high-melting point compounds such as carbides, nitrides, borides, intermetallics, and oxides are analyzed. The nonmonotonic change in the hardness with a change in the nanolayer thickness in multilayer films and the grain size in bulk nanomaterials is discussed. The fracture of these materials has intercrystalline character. However, residual plastic deformation is observed in some cases, for example, in for nanocolumnar TiN coatings and SiC single-crystal nanowire. The nanostructured approach was very successful in the development of nanocomposites with high-strain-rate superplasticity (∼10⁻² s⁻¹, T = 1400°C). The poorly investigated problems are pointed.     

Studying the effects of the addition of TiN nanoparticles to Ni–P electroless coatings

The effects of the addition of nano TiN on the surface morphology, deposition rate, hardness and corrosion properties of Ni–P electroless coatings were studied. Heat treatment was conducted to compare the corrosion and hardness behavior of the coatings before and after heat treatment. It was observed that the incorporation of TiN particles into the coating has an adverse effect on the corrosion properties of the specimens. The hardness of the specimens increased dramatically by adding TiN. Furthermore, the hardness of the specimens increased after conducting the heat treatment. The corrosion and hardness behavior of the Ni–P system after heat treatment largely depended on the temperature of heat treatment. The heat treatment temperatures at which the desired corrosion and hardness properties were expected were determined.     

Structural and photoluminescent properties of TiN thin films

Structural and photoluminescent properties of TiN thin films deposited by dc reactive magnetron sputtering are studied. It is found that TiN thin films are polycrystalline with a grain size of ～15 nm and have a NaCl-type cubic crystal structure with a lattice constant of 0.42 nm. The TiN films under study exhibit photoluminescence in the spectral range h _ν ≈ 2.1–3.4 eV at 300 K.     

Structure and mechanical properties of titanium nitride/carbon nitride multilayers

The structure and mechanical properties of the multilayers consisting of 5-73 nm thick titanium nitride (TiN) and 4.6 nm thick carbon nitride (CN) have been investigated. It has been found that the CN layers are amorphous and the TiN layers thinner than 17 nm are amorphous. The TiN layers become crystallized as the thickness is increased to 30 nm or thicker. The hardness from the composite response of the multilayered films and their substrates determined using continuous stiff measurement is smaller than the film-only hardness (without substrate effects) calculated using Bhattacharya-Nix empirical equation. The hardness increases with raising the thickness of TiN layers. With the crystallization of the TiN layer, the multilayers become even harder than that calculated based on the rule of mixtures. However, no enhancement in hardness has been observed when the TiN layers are amorphous.     

Nanocomposite and nanostructured superhard Ti-Si-B-N coatings

Electron microscopy, x-ray diffraction analysis, and micro-and nanohardness measurements were used to investigate the interrelations between the fine structure and the variations in strength properties of nanostructured and nanocomposite Ti-Si-B-N coatings with high oxygen and carbon contents. It has been shown that under the conditions of low-temperature (T = 200°C) coating deposition, a two-level grain structure forms with {200} texture and grains 0.1–0.3 μm in size fragmented into subgrains 15–20 nm in size. As the silicon content is increased, textureless coatings with the crystal phase grain size less than 15 nm and high amorphous component or coatings of amorphous-crystalline structure are produced. At coating deposition temperatures of 400–450°C, a nanocomposite structure with a grain size d = 10–15 nm and no texture is observed. For all test compositions and conditions of coating production, a Ti _1−x Si _x N crystal phase with the lattice parameter a = (0.416–0.420) ± 0.001 nm has been detected. For optimum coating compositions and synthesis conditions, the hardness is over 40–50 GPa. It has been supposed that superhardness can be attained with multiphase grain-boundary interlayers of thickness more than 1 nm. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 10, pp. 13–23, October, 2007.     

界面和择优取向对TiN/ZrN纳米多层膜硬度变化的影响

利用射频反应磁控溅射方法，制备了调制比约为4，调制周期不同的一系列TiN/ZrN纳米多层膜. 利用X射线衍射仪(XRD)、高分辨电子显微镜(HRTEM)和纳米压痕仪(Nanoindentation)对多层膜的调制结构、界面状态和力学性能进行了表征. 研究结果表明TiN/ZrN多层膜具有很好的调制结构，但是在TiN层和ZrN层之间存在一定厚度的界面混合层. 力学性能分析表明：当调制周期小于15 nm时，TiN/ZrN多层膜的硬度介于单一TiN和ZrN薄膜的硬度之间；当调制周期为15.24 nm时，硬度达到最大，但随着调制周期增加，多层膜的硬度基本上保持为常数. 分析了TiN/ZrN多层膜硬度变化的机制，认为界面厚度和择优取向是导致硬度变化的主要原因. 关键词： TiN/ZrN多层膜 界面宽度 择优取向 硬度变化     

TiN/SiO2纳米多层膜的晶体生长与超硬效应

高硬度的含氧化物纳米多层膜在工具涂层上具有重要的应用价值.研究了TiN/SiO2_{2纳米多 层膜的晶体生长特征和超硬效应.一系列具有不同SiO22和TiN调制层厚的纳米多 层膜采用多 靶磁控溅射法制备；采用x射线衍射、x射线能量色散谱、高分辨电子显微镜和微力学探针表 征了多层膜的微结构和力学性能.结果表明，虽然以单层膜形式存在的TiN和SiO22分别形成 纳米晶和非晶结构，它们组成多层膜时会因晶体生长的互促效应而呈现共格外延生长的结构 特 关键词： 2纳米多层膜')" href="#">TiN/SiO22纳米多层膜 外延生长 非晶晶化 超硬效应}     

Development of novel titanium nitride-based decorative coatings by calcium addition

Calcium was added into titanium nitride coatings deposited using a hybrid magnetron sputtering-arc evaporation process. The calcium content in the films was adjusted by the variation of the pulsed DC current applied to the Ca sputtering target. X-ray diffraction analyses suggested that the increase of the calcium content induced the partial substitution of titanium atoms by calcium ones in the TiN lattice and a refinement of the grain size. Optical reflectance investigations showed that the absorption band of TiN was shifted towards higher wavelengths and that (Ti,Ca)N coatings may be suitable for decorative applications. Finally, the decrease of the film reflectivity was interpreted as a consequence of a free electron concentration decrease as confirmed from electrical resistivity measurements.     

Characteristics of ZrC/ZrN and ZrC/TiN multilayers grown by pulsed laser deposition

ZrC/ZrN and ZrC/TiN multilayers were grown on (1 0 0) Si substrates at 300 °C by the pulsed laser deposition (PLD) technique using a KrF excimer laser. X-ray diffraction investigations showed that films were crystalline, the strain and grain size depending on the nature and pressure of the gas used during deposition. The elemental composition, analyzed by Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS), showed that films contained a low level of oxygen contamination. Simulations of the X-ray reflectivity (XRR) curves acquired from films indicated a smooth surface morphology, with roughness below 1 nm (rms) and densities very close to bulk values.Nanoindentation results showed that the ZrC/ZrN and ZrC/TiN multilayer samples exhibited hardness values between 30 and 33 GPa, slightly higher than the values of 28-30 GPa measured for pure ZrC, TiN and ZrN films.     

A transmission electron microscopy study of the deformation behavior underneath nanoindents in nanoscale Al–TiN multilayered composites

Nanoscale multilayered Al–TiN composites were deposited using the dc magnetron sputtering technique in two different layer thickness ratios, Al : TiN = 1 : 1 and Al : TiN = 9 : 1. The Al layer thickness varied from 2 nm to 450 nm. The hardness of the samples was tested by nanoindentation using a Berkovich tip. Cross-sectional transmission electron microscopy (TEM) was carried out on samples extracted with focused ion beam from below the nanoindents. The results of the hardness tests on the Al–TiN multilayers with two different thickness ratios are presented, together with observations from the cross-sectional TEM studies of the regions underneath the indents. These studies revealed remarkable strength in the multilayers, as well as some very interesting deformation behavior in the TiN layers at extremely small length scales, where the hard TiN layers undergo co-deformation with the Al layers.