Microstructure and superhardness effect of VC/TiC superlattice films

Vanadium carbide/titanium carbide （VC/TiC） superlattice films were synthesized by magnetron sputtering method. The effects of modulation period on the microstructure evolution and mechanical properties were investigated by EDXA, XRD, HRTEM and nano-indentation. The results reveal that the VC/TiC superlattice films form an epitaxial structure when their modulation period is less than a critical value, accompanied with a remarkable increase in hardness. Further increasing the modulation period, the hardness of superlattices decreases slowly to the rule-of-mixture value due to the destruction of epitaxial structures. The XRD results reveal that three-directional strains are generated in superlattices when the epitaxial structure is formed, which may change the modulus of constituent layers. This may explain the remarkable hardness enhancement of VC/TiC superlattices.

Synthesis and nitrogen content regulation of diamond in a high-pressure hydrogen-rich environment

The regulating nitrogen content of diamond in a hydrogen-rich high-temperature and high-pressure(HPHT) growth environment was systematically investigated in this work by developing three growth systems,namely, "FeNi+Ti", "FeNi+G_(3)N_(6)H_(6)",and "FeNi+Ti+C_(3)N_(6)H_(6)".Optical microscopy,infrared spectroscopy,and photoluminescence(PL)spectroscopy measurements were conducted to analyze the spectroscopic characteristics of diamonds grown in these three systems.From our analysis,it was demonstrated that the presence of hydrogen in the sp^(3) hybrid C-H does not directly affect the color of the diamond and facilitates the increase of the nitrogen-vacancy(NV) center concentration in a highnitrogen-content diamond.In addition,titanium plays an important role in nitrogen removal,while its impact on hydrogen doping within the diamond lattice is insignificant.Most importantly,by regulating the ratio of nitrogen impurities that coexist in the nitrogen and hydrogen HPHT environment,the production of hydrogenous Ⅱa-type diamond,hydrogenous Ib-type diamond,and hydrogenous high-nitrogen-type diamonds was achieved with a nitrogen content of less than 1 ppm to 1600 ppm.

Microstructure and mechanical properties of VAlN/Si_(3)N_(4) nano-multilayer coatings

VAlN coating is of particular interest for dry cutting applications owing to its low-friction and excellent abrasiveness.Nano-multilayer structure is designed to tailor the properties of VAlN coating.In this work,a series of VAlN/Si_(3)N_(4) nano-multilayer coatings with varied Si_(3)N_(4) layer thicknesses were prepared by reactive sputtering method.The microstructure and mechanical properties of the coatings were both investigated.It is revealed that Si_(3)N_(4) with a shallow thickness(~0.4 nm)was crystallized and grown coherently with VAlN,showing a remarkable increase in hardness compared to VAlN monolayer coating.The hardness of coherently VAlN/Si_(3)N_(4) nano-multilayer coatings reached to 48.7 GPa.With further increase of Si_(3)N_(4) layer thickness,the coherent growth of nano-multilayers was terminated,showing amorphous structure formed in nano-multilayers and the hardness was declined.On the other hand,when Si_(3)N_(4) layer thickness was 0.4 nm,the friction coefficient of VAlN/Si_(3)N_(4) nano-multilayer coating was almost equal to that of VAlN monolayer coating,which was attributed to the crystallization of Si_(3)N_(4) and the produced coherent interfaces between VAlN and Si_(3)N_(4) for the hardening effect of nano-multilayer coatings.Upon further increase of Si_(3)N_(4) layer thickness,pronounced improvement of friction coefficient in VAlN/Si_(3)N_(4) nano-multilayer coating was observed.

Numerical simulation and experimental verification of a novel double-layered split die for high-pressure apparatus used for synthesizing superhard materials

Based on the principles of massive support and lateral support, a novel double-layered split die(DLSD) for high-pressure apparatus was designed to achieve a higher pressure-bearing capacity and larger sample cavity. The stress distributions of the DLSDs with different numbers of divided blocks were investigated by the finite element method and compared with the stress distributions of the conventional belt-type die(BTD). The results show that the cylinders and first-layer supporting rings of the DLSDs have dramatically smaller stresses than those of the BTD. In addition, increasing the number of divided blocks from 4 to 10 gradually increases the stress of the cylinder but has minimal influence on the stress of the supporting rings. The pressure-bearing capacities of the DLSDs with different numbers of divided blocks, especially with fewer blocks, are all remarkably higher than the pressure-bearing capacity of the BTD. The contrast experiments were also carried out to verify the simulated results. It is concluded that the pressure-bearing capacities of the DLSDs with 4 and 8 divided blocks are 1.58 and 1.45 times greater than that of the BTD. This work is rewarding for the commercial synthesis of high-quality, large-sized superhard materials using a double-layered split high-pressure die.

Investigation of Element Profiles, Defects, Phase Composition and Physical and Mechanical Properties of Superhard Coatings Ti-Hf-Si-N

This paper investigates the microstructure, physical, chemical and mechanical of superhard nanocomposite of Ti-Hf-Si-N. The coatings were grown by C-PVD method. Profiles of elements and vacancy-type defects (S-parameter measurements of the Doppler broadening of the annihilation peak DBAP) in the studied coatings were investigated. Defined and calculated the elastic modulus E, hardness H, friction, adhesion. Wear rate was determined as a function of the bias potential supplied to the substrate and the pressure in the chamber. The developed coatings have hardness of 37.8 to 48 GPa, the friction coefficient of 0.48 to 0.15, the grain size of the solid solution from 3.9 to 10.8 nm (depending on deposition conditions). It was found that positrons are trapped by defects at the junction of three or more nanograins interfaces. In some cases, there was formed two phases in coatings: a solid solution (Ti, Hf)N with different volume content of Hf in a solid solution, and an amorphous phase α-Si3N4 (the layer between the nanograins).

Surperhard monoclinic BC6N allotropes:First-principles investigations

Via structural searching methodology and first-principles calculations, we predicted two new BC6N allotropes, a Ccentered monoclinic BC6N（Cm-BC6N） and a primitive-centered monoclinic BC6N（Pm-BC6N）.The lattice vibrations,elastic properties, ideal strength, theoretical hardness, and electronic structure of the predicted BC6N were investigated systematically.Our results reveal that Cm-BC6N is more favorable energetically than graphite-like g-BC6N above 20.6 GPa,which is lower than the transition pressures of r-BC6N, t-BC6N, and Pm-BC6N.Both Cm-BC6N and Pm-BC6N are indirect semiconductors with band gaps of 2.66 eV and 0.36 eV, respectively.Cm-BC6N exhibits the excellent ideal shear strength of 53.9 GPa in（011）■, much greater than that of Pm-BC6N（25.0 GPa in（010）[101] shear direction）, and Cm-BC6N shows a much lower anisotropy in shear strength than Pm-BC6N.The Vickers hardness of Cm-BC6N is estimated to be above 80 GPa, which is more outstanding than those of t-BC6N and r-BC6N.

Discovery of superhard materials via CALYPSO methodology

The study of superhard materials plays a critical role in modern industrial applications due to their widespread applications as cutting tools, abrasives, exploitation drills, and coatings. The search for new superhard materials with superior performance remains a hot topic and is mainly considered as two classes of materials:(i) the light-element compounds in the B-C-N-O(-Si) system with strong and short covalent bonds, and(ii) the transition-element light-element compounds with strong covalent bonds frameworks and high valence electron density. In this paper, we review the recent achievements in the prediction of superhard materials mostly using the advanced CALYPSO methodology. A number of novel, superhard crystals of light-element compounds and transition-metal borides, carbides, and nitrides have been theoretically identified and some of them account well for the experimentally mysterious phases. To design superhard materials via CALYPSO methodology is independent of any known structural and experimental data, resulting in many remarkable structures accelerating the development of new superhard materials.

Effects of High Pressure on BC3

High-pressure phases of BC3 are studied within the local density approximation under the density functional theory framework. When the pressure reaches 20 GPa, the layered BC3 that is a semiconductor at ambient pressure, becomes metallic. As the pressure increases, the material changes into a network structure at about 35 GPa. To understand the mechanism of phase transitions, band structure and density of states are discussed. With the increase of pressure, the width of bands broadens and the dispersion of bands enlarges. Additionally, the density of states of the network bears great resemblance to that of diamond. Formation of the sp3 bonding in the network is the main reason for the structural transformation at 35 GPa.

Superhard BC_2N:an Orthogonal Crystal Obtained by Transversely Compressing(3,0)-CNTs and(3,0)-BNNTs

By means of density functional theory calculations, an orthogonal boron-carbon-nitrogen compound called （3,0）- BC2N is predicted, which can be obtained by transversely compressing （3,03 carbon nanotubes （CNTs） and boron nitride nanotubes （BNNTs）. Its structural stability, elastic properties, mechanical properties and electronic structure are systematically investigated. The results show that （3,0）-BU2N is a superhard material with a direct bandgap. However, its similar structures, （3,0）-C and （3,0）-BN are indirect semiconductors. Strikingly, （3,0）-C is harder than diamond. We also simulate the x-ray diffraction of （3,0）-BC2N to support future experimental investigations. In addition, our study shows that the transition from （3,03 CNTS and BNNTs to （3,0）-BC2N is irreversible.

Reproducibility of deposition and industrial applications of stable superhard nanocomposites

After a brief introduction regarding the different approaches to superhard coatings we shall concentrate on the problem of the reproducibility of the deposition of superhard and thermally very stable nanocomposites according to the design principle published by Veprek and Reiprich in 1995. It will be shown that either the choice of inappropriate deposition conditions, in contradiction to our design principle, or impurities in the coatings are the reason for the lack of reproducibility of our earlier results by many other workers. We shall also briefly summarize the recent industrial applications.

Superhard Nanocomposite Coatings

The recent development in the field of nanocomposite coatings with good mechanical properties is critically reviewed in this paper. The design principle and materials selection for the nanocomposite coatings are introduced. Different methods for the preparation of superhard nanocomposite coatings are described with emphasis on the magnetron sputtering. Based on recent theoretical and experimental results regarding the appearance of superhardness in nanocomposite coating, lattice parameter changes, crystallite size, microstructure and morphology are reviewed in detail. Also emphasized are the mechanical properties (especially on hardness) and the ways by which the properties are derived.

SUPERPLASTIC DEFORMATION BEHAVIOR OF SUPERHARD Al ALLOY LC4

The superplasticity of high strength superhard A1 alloy LC4 was improved to a great extent by modified thermomechanical treatment.Its maximum elongation may be up to 2100% un- der deformation at initial strain rate of 8.33×10^(-4) S^(-1) at 510℃.Observations of the microstructure changes revealed that with the increase of the deformation,the grain grows and the alloy exhibits strain hardening.The excellent elongation of the alloy seems due to the in- crease of grain stability under deformation.

tP40 carbon: A novel superhard carbon allotrope

In this work, a novel carbon allotrope tP40 carbon with space group P4/mmm is proposed. The structural stability, mechanical properties, elastic anisotropy, and electronic properties of tP40 carbon are investigated systematically by using density functional theory (DFT). The calculated elastic constants and phonon dispersion spectra indicate that the tP40 phase is a metastable carbon phase with mechanical stability and dynamic stability. The B/G ratio indicates that tP40 carbon is brittle from 0 GPa to 60 GPa, while tP40 carbon is ductile from 70 GPa to 100 GPa. Additionally, the anisotropic factors and the directional dependence of the Poisson's ratio, shear modulus, and Young's modulus of tP40 carbon at different pressures are estimated and plotted, suggesting that the tP40 carbon is elastically anisotropic. The calculated hardness values of tP40 carbon are 44.0 GPa and 40.2 GPa obtained by using Lyakhov–Oganov's model and Chen's model, respectively, which means that the tP40 carbon can be considered as a superhard material. The electronic band gap within Heyd–Scuseria–Ernzerhof hybrid functional (HSE06) is 4.130 eV, and it is found that the tP40 carbon is an indirect and wider band gap semiconductor material.

Structure and Properties of TiB_2 Thin Films Deposited at Low Temperatures Using RF Magnetron Sputtering

The TiB2 thin films were deposited on steel substrates using RF magnetron sputtering technique with the low normalized substrate temperature （0.1〈Ts/Tm〈0.2）. Microstructure of these films was obtained by field emission scanning electron microscope （FESEM） and the grazing incidence X-ray diffraction （GIXRD） characterization, while the composition of films was obtained using Auger emission spectroscopy （AES） analysis. It was found that the TiB2 thin films were overstoichiometric with the B/Ti ratio at 2.33 and the diffusion of Ti and B atoms on the substrate surface was greatly improved at 350 ℃. Moreover, a new dense structure, named ＂equiaxed＂ grain structure was observed by FESEM at this substrate temperature, Combined with FESEM and AES analysis, it was suggested that the ＂equiaxed＂ grain structure was located in Zone 2 at the normalized substrate temperature as low as 0.18.

Research on C_3N_4 Superhard Compound Thin Film and Its Application

By combination of DC reactive magnetron sputter i ng with multiple arcplating, the alternating C 3 N 4 /TiN compo und film is deposited onto HSS. The core level binding energy and the contents o f carbon and nitrogen are characterized by X\|ray photoelectron spectrum. X\|ray diffraction(XRD) shows that compound thin film contains hard crystalline phases of α \|C 3 N 4 and β \|C 3 N 4 . The Knoop microhardne ss in the load range of 50.5\|54.1 GPa is measured. According to acoustic emissi on scratch test, the critical load values for the coatings on HSS substrates are in the range of 40\|80 N. The metal coated with C 3 N 4 /TiN compound f ilms has a great improvement in the resistance against corrosion. Many tests sho w that such a coating has a very high wearability. Compared with the uncoated an d TiN coated tools, the C 3 N 4 /TiN coated tools have a much longer cut ting life.

A new family of sp3-hybridized carbon phases

A new family of superhard carbon allotropes C48（2i ＋ 1 ） is constructed by alternating even 4 and 8 membered rings. These new carbon allotropes are of a spatially antisymmetrical structure, compared with the symmetrical structures of bet- C4, Z-carbon, and P-carbon. Our calculations show that bulk moduli of C48（2i ＋ 1 ） are larger than that of c-BN and smaller than that of cubic-diamond. C48（2i ＋ 1 ） are transparent superhard materials possessing large Vicker hardness comparable to diamoud. This work can help us understand the structural phase transformations of cold-compression graphite and carbon nanotubes.

Low-temperature phase transformation from nanotube to sp^3 superhard carbon phase

Numerous new carbon allotropes have been uncovered by compressing carbon nanotubes based on our computational investigation. The volume compression calculations suggest that these new phases have a very high anti-compressibility with a large bulk modulus （B0）. The predicted B0 of new phases is larger than that of c-BN （373 GPa） and smaller than that of diamond （453 GPa）. All of the predicted structures are superhard transparent materials with a larger band gap and possess the covalent characteristics with sp3-hybridized electronic states. The simulated results will help us better understand the structural phase transition of cold-compressed carbon nanotubes.

First Principles Study on Mechanical Properties of Superhard α-Ga Boron

The mechanical properties and intrinsic hardness of the α-Ga boron phase （α-Ga-B） are studied by using the combination of first-principles calculations and a semiempirieal macroscopic hardness model. It is found that α- Ga-B is mechanically stable and possesses higher bulk/shear modulus as compared with γ-B28, a newly discovered high-pressure boron phase. The theoretical hardness of α-Ga-B is estimated to be 45 GPa, which is much higher than 38 GPa for γ-B28. The results strongly indicate that α-Ga-B is a potential superhard boron phase. To further obtain insight into the superhard nature of α-Ga-B, we simulate stress-strain curves under tensile and shear deformation. Meanwhile, the microscopic mechanism driving the tensile and shear deformation modes in α-Ga-B is discussed in detail.