Real indentation hardness of nano-polycrystalline cBN synthesized by direct conversion sintering under HPHT

The hardness characteristic of nano-polycrystalline cBN synthesized by direct conversion sintering was thoroughly investigated using Vickers and Knoop indenters. It was found that nano-polycrystals consisting of smaller cBN grains increase the elastic recovery of indentations during unloading of the indenters and the diagonal of Vickers indentations and the minor diagonal of Knoop indentations significantly decrease in length. Thus, if a Vickers indenter is used, the apparent hardness value increases, making it impossible to perform an accurate evaluation, e.g. incorrect Vickers hardness values in excess of 80 GPa were obtained from nano-polycrystalline cBN with a grain size of 50 nm or less. On the other hand, it was verified that a Knoop indenter ensures an accurate hardness evaluation even if the constituent grains are fine because its major diagonal length which is used for measurement is less susceptible to elastic recovery. In an accurate evaluation of the hardness of different types of nano-polycrystalline cBN using a Knoop indenter, the hardness of each type of cBN was around 45 GPa, and there was no clear Hall–Petch relationship between hardness and grain size without a slight bell-like correlation. These results suggest that reported hardness values higher than 80 GPa of similar nano-polycrystalline cBN evaluated using a Vickers indenter are incorrect values caused by elastic recovery occurring at the indentation.     

Hardness of polycrystalline SiO2 coesite

We measured elastic moduli and hardness of polycrystalline SiO₂ coesite. Translucent polycrystalline bulk coesite with a grain size of about 10 micrometers was fabricated at 8 GPa and 1600°C using a Kawai-type multianvil apparatus. The obtained bulk and shear moduli are 94(1) and 60.2(3) GPa, respectively. The resulting Vickers and Knoop hardness values are 10.9(7) and 9.6(4) GPa, respectively, at an indentation load of 4.9 N. Coesite is as hard as other fourfold coordinated silica materials such as quartz and densified silica glasses. The hardness values of coesite and the fourfold coordinated silica materials are about one-third of those of sixfold coordinated silica materials, stishovite, and seifertite, which are the hardest known oxides.     

Hardness and fracture toughness of moissanite

Disparities prevail among the reported hardness and fracture toughness values for hard and brittle materials. A better understanding of the physical nature of hardness and fracture toughness and a standardized technique for reliable measurements of these quantities is urgently needed. We strongly recommend the use of the measured hardness after the bend in the hardness versus load (H−F_Load) curve, when the hardness approaches its asymptotic value. The present work reports a systematic study of hardness and fracture toughness on moissanite (single crystal hexagonal silicon carbide, 6H-SiC) samples. The measurements were performed over a broad load range from 0.49 to 294 N with the direct indentation method. Asymptotic values of Knoop hardness of H_K = 19 GPa and Vickers hardness of H_V = 22 GPa were reached at a high load between 50 N and 100 N. A consistent fracture toughness of K_IC = 1.8 MPa·m^1/2 was obtained across the entire load range. Our study presents experimental results for the hardness and fracture toughness of moissanite in the asymptotic-hardness region, and it raises concern regarding the application of moissanite single crystals as anvil material under shear/fracture conditions.     

Synthesis of ultrafine nano-polycrystalline cubic boron nitride by direct transformation under ultrahigh pressure

Using a turbostratic pyrolytic boron nitride as a starting material, we synthesized a variety of ultrahard polycrystalline cubic boron nitride (PcBN) as a function of the heating duration changing from 1 to 60?min under a constant temperature and pressure conditions (1950?°C and 25?GPa) using a multi-anvil apparatus. When the heating duration was less than 13?min, ultrafine nano-polycrystalline cBN (U-NPcBN) with the mean grain size of <50?nm was produced. Among these U-NPcBNs those synthesized with 11–13?min were found to have a uniform texture composed purely of cBN (i.e. with no wurzite BN residue) and a Knoop hardness of >53?GPa, which is 20% higher than that of the hardest conventional binderless PcBN in practical use. Furthermore, the PcBNs synthesized with 18–20?min showed a unique nanocrystalline texture composed of relatively coarse grains dispersed in a fine grained matrix and even higher Knoop hardness (54.5–55.2?GPa).     

Mechanical properties of synthetic type IIa diamond crystal

The mechanical behavior of synthetic type IIa diamond has been investigated by the Knoop hardness measurement and observation of the cleavage surfaces. It was clarified that the Knoop hardness in (100)100 of synthetic diamonds increases with decreasing of the nitrogen impurities concentration, and that the synthetic type IIa diamond, having few nitrogen impurities, has the highest hardness of synthetic diamonds. In addition, it was found that the Knoop hardness in (100)110 of synthetic type IIa diamond is extremely high, and the anisotropy in the hardness of the diamond is different from those of natural diamond and synthetic type Ib diamond. The cleavage surfaces of the synthetic type IIa diamonds were very smooth and showed remarkably regular cleavage patterns. These results indicate that there are very few impurities and crystal defects in the synthetic type IIa diamond, and also suggest that the diamond has high resistance to plastic flow.     

Thermally activated deformation under Knoop indentations in super-hard directions of high-quality synthetic type-IIa diamond crystals

The deformation resistance at room temperature against a Knoop indentation in (001)<110> (the<110> direction on the (001) plane) of high-quality synthetic type-IIa diamond is known to be extremely high. The behavior of deformation in the hard direction activated thermally by heating was investigated, using super-hard Knoop indenters prepared from high-quality diamond crystals by taking the tip orientation to (001)<110>. Indentation tests in (001)<110> with a load of 4.9 N revealed that the formation of normal Knoop impressions arises suddenly at a threshold temperature of 200–240 °C, whereas no impressions are observed up to 200 °C. The hardness values derived from the impressions in (001)<110> formed above the threshold temperatures are as low as 50–60% those in (001)<100> at the same temperatures. The anisotropy in the Knoop hardness at such high temperatures is consistent with the nature of anisotropy predicted by an effective resolved shear stress model for a {111}<110> slip deformation.     

Modulus and hardness evaluation of polycrystalline superconductors by dynamic microindentation technique

In this study, depth-sensing Vickers indentation tests were conducted on polycrystalline superconductors under different peak load (0.49, 0.73, 0.98, and 1.22 N). The load (P)–penetration depth (h) curves were analyzed in order to evaluate the mechanical characteristics such as microhardness and elastic modulus. It was found that both of these characteristics exhibited significant peak load dependence which suggested a need for calculation of the load-independent hardness and modulus. The load independent hardness (0.88, 0.95, and 1.12 GPa) and modulus (1.98, 3.13, and 3.33 GPa) values were then calculated for YBCO, YBCO + 0.5% ZnO, and YBCO + 1% ZnO, respectively.     

Nano-mechano-electrochemistry of passive metal surfaces

In situ nanoindentation tests were performed to evaluate the mechanical properties of the iron (100) and (110) surfaces passivated potentiostatically for 1 h in pH 8.4 borate solution after or without immersion in 5×10⁻² M K₂Cr₂O₇ solution for 24 h. It was found from the measured load–depth curves at a maximum load of 400 μN that the hardness (3.2–3.3 GPa) of the passivated iron (110) surfaces was larger by 10% than that (2.9–3.1 GPa) of the passivated iron (100) surfaces. Moreover, the hardness of the passivated iron (100) and (110) surfaces increased slightly with increasing formation potential of passive film, which was ascribed to the presence of passive film. The dichromate treatment increased the hardness of the iron (100) and (110) surfaces to some extent. The loading discontinuity appeared frequently at a load of about 90 μN in the load–depth curves for the passivated iron (110) surfaces as compared with the passivated iron (100) surfaces. The loading discontinuity in the load–depth curves for the iron (110) surface, however, disappeared completely due to the dichromate treatment.     

Effect of synthesis temperature on hardness of carbon phases prepared from C60 and nanosized diamonds under pressure

Vicker’s hardness and Raman scattering spectra have been studied for carbon phases prepared from C₆₀ fullerene and nanosized diamonds at high temperatures and a pressure of 6 GPa. It was found that the hardness dependence on annealing temperature has a maximum near ∼1100 K for both fullerene and nanosized diamonds as initial materials. This temperature is only slightly higher than the temperature at which the C₆₀ cage collapses, and appears to correspond to the termination of intercluster bonding in the case of nanosized diamonds. The hardness maximum is interpreted as a result of competition between an increase in intercluster/intercage bonding and local instability for graphitic-like ordering.     

Load-dependence of Knoop hardness of Al2O3–TiC composites

Nine samples of Al₂O₃–30 wt.% TiC composites were prepared by hot-pressing the Al₂O₃ powder mixed with TiC particles. The average sizes of the TiC particles used for preparing the nine samples were different with each other. Knoop hardness measurements were conducted on these nine samples, respectively, in the indentation load range from 1.47 to 35.77 N. For each sample, the measured Knoop hardness decreases with the increasing indentation load. The classical Meyer's power law and an empirical equation proposed originally by Bückle were verified to be sufficiently suitable for describing the observed load-dependence of the measured hardness. Analysis based on Meyer's law can not provide any useful information about the cause of the observed ISE while true hardness values, which are load-independent, can be deduced from the Bückle's equation. It was found that the deduced true hardness increases with the average size of TiC particles existing in the sample.     

Comparison of instrumented Knoop and Vickers hardness measurements on various soft materials and hard ceramics

Vickers and Knoop hardness measurements performed on various ceramics (hard metals) and light alloy materials (soft metals) are compared. The results show that the Knoop hardness number is, in general, lower than the Vickers hardness number for the highest values of hardness, and this behaviour is reversed when the hardness values are low. This change in values, which occur at 8 GPa, has no real physical meaning and, therefore, it is difficult to interpret such behaviour in terms of the elasto-plastic deformation around the indent such as sinking-in, piling-up, and bulging of the indent faces, phenomena which take place during indentation or after the withdrawal of the indenter.Prior to interpreting the hardness difference, it is very important to consider the same area in the hardness calculations. That is why we have compared the available hardness data obtained from the literature and recalculated them by considering the projected and true areas of the contact. If the objective is to compare the two hardness numbers, it seems more suitable to consider the true area of contact, procedure which will provide a Vickers hardness number higher than the Knoop hardness number all over the range of the hardness values.     

Nanoindentation of WC–Co hardmetals

WC–Co cemented carbide has been investigated using instrumented indentation with maximum applied loads from 0.1 to 10 mN. The hardness and indentation modulus of individual phases and the influence of crystallographic orientation of WC on the hardness and indentation modulus have been studied. The hardness of the Co binder was approximately 10 GPa and that of WC grains up to 50 GPa with relatively large scatter under the indentation load of 1 mN. Investigation of the role of crystallographic orientation of WC grains on hardness at 10 mN load revealed average values of H_ITbasal = 40.4 GPa (E_ITbasal = 674 GPa) and H_ITprismatic = 32.8 GPa (E_Itprismatic = 542 GPa), respectively. The scatter in the measured values at low indentation loads is caused by the effects of surface and sub-surface characteristics (residual stress, damaged region) and at higher loads by “mix-phase” volume below the indenter.     

Effect of addition of surface modified nanosilica into silica–zirconia hybrid sol–gel matrix

An organic–inorganic hybrid sol (MZ) comprising a methacrylate functionalized silane matrix (M) and zirconium-n-propoxide (Z) was prepared using sol–gel technique. Two methodologies were adopted to modify the hybrid sol for generating nanocomposite coatings viz., (a) addition of acrylic surface modified silica nanoparticles (N) of diameter ～20 nm to the sol to enhance their compatibility with the hybrid sol–gel matrix and (b) in-situ formation of a three dimensional silica network by addition of tetraethoxy silane (T) to the sol MZ. In the first methodology, the sols were prepared with six different weight ratios of the nanoparticles to the sol, i.e. 0, 0.01, 0.05, 0.1, 0.25 and 1 which were labelled as MZ+Nx where x=0, 1, 2, 3, 4 and 5 respectively. The prepared sols were dip coated on 100 mm×100 mm polycarbonate substrates followed by thermal curing at 130 °C. The coatings were characterized for their mechanical properties like pencil scratch hardness, scratch resistance using scratch tester, nanoindentation hardness, and abrasion resistance as well as visible light transmittance. FT-IR studies were also carried out on heat-treated gels derived from the sols. A maximum pencil scratch hardness of 3H was obtained for the MZ+T coatings and these coatings withstood a critical load of 4.3±0.7 N before failure during scratch test. The maximum nanoindentation hardness of 3.8±0.01 GPa was obtained for the MZ+N5 coatings. The abrasion resistance of MZ+T coatings was higher when compared to MZ+N0 and MZ+N5 coatings. The scratch and nanoindentation hardness were seen to be better for an in-situ formed –Si–O–Si– network in the hybrid sol when compared to those obtained from coatings generated by external addition of acrylic surface modified silica nanoparticles. The difference in properties was attributed to the level of interaction between the nanoparticles and hybrid sol–gel matrix.     

Titanium diboride–silicon carbide–boron carbide ceramics with super‐high hardness and strength

Triplex particulate composites composed of boride and carbide ceramics were found to have high strength, hardness, and fracture toughness values. Two compositions consisting of 70:15:15 and 1:1:1 volume ratios of TiB_2, SiC, and B₄C were produced from commercially available powders by hot‐pressing. The 70:15:15 ceramic exhibited a strength of ~1.3 GPa, while the 1:1:1 ceramic had a strength of ~0.9 GPa. These strengths are comparable to super‐strong Y₂O₃‐PSZ and β‐SiAlON based composites. The Vickers’ hardness values of these ceramics were ~32 GPa for indent loads of 9.8 N. Hardness increased as indentation load decreased. The 1:1:1 ceramic had a hardness of ~53 GPa at an indentation load of 0.49 N, higher than values reported for so‐called “super‐hard” ceramics, and comparable to c‐BN.     

Highly Dense Amorphous Si2BC3N Monoliths with Excellent Mechanical Properties Prepared by High Pressure Sintering

The fabrication of dense amorphous Si–B–C–N monoliths is a processing challenge given that it is hard to avoid crystallization at the sintering temperatures needed to attain full density up to 1900°C for conventional hot pressing and SPS methods. We report here successful densification of amorphous Si₂BC₃N monoliths achieved by heating at 1100°C and 5 GPa. The relationships between microstructure, types of chemical bonding, and mechanical properties were investigated. The strong amorphous 3‐D networks of Si–C, C–B, C‐N (sp³), N‐B (sp³), and C–B–N bonds provide high densities at high applied pressure and thus amorphous Si₂BC₃N monoliths show high hardness of 29.4 GPa and elastic modulus of 291 GPa. The amorphous structure is lost with crystallization of β‐SiC and BN(C) reducing contributions from Si–C, C‐N (sp³), and C–B–N bond networks thereby decreasing mechanical properties.     

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.     

High-pressure synthesis of TaN compacts with high hardness and thermal stability

High-hardness TaN compacts with a diameter and height of 6 mm were synthesized through the phase transformation of CoSn-type into WC-type TaN under experimental conditions of high temperature and high pressure. The Vickers hardness of WC-type TaN compacts obtained at the pressure of 5 GPa and the temperature of 1873 K is found to be ~21.5 ± 1.5 GPa with a load of 3 Kg, which is comparable to that of the pure tungsten carbide compact (~20 GPa) and higher than those of ultrahigh temperature ceramics ZrB₂ and HfB₂ under the same load. The high hardness of WC-type TaN compacts presented in this work is attributed to the deviatoric strain and well-bonded nanograins. The synthesized WC-type TaN compacts also possess a high oxidation temperature (1072 K). These results suggest that the WC-type TaN with high hardness and high thermal stability holds great promise for industrial applications.     

Influence of negative bias voltage on microstructure and property of Al-Ti-N films deposited by multi-arc ion plating

In this study, we systematically investigated the effects of negative bias voltage on the composition, deposition efficiency, microstructure, and mechanical properties of multi-arc ion plated (MAIP) AlTiN films. The films were deposited on high-speed steel substrates by MAIP at various negative bias voltages. The results indicated that the Al content [Al/(Al+Ti) ratio] and the deposition efficiency were significantly altered by the application of negative bias voltages. X-ray photoelectron spectroscopy analysis showed that the AlTiN films were composed of Ti–N and Al–N bonds. The macroparticles (MPs) on the film surface decreased with increasing negative bias voltage. We also discussed the different types of MPs found on the films and their influence on the process of determining the hardness of the films. The microhardness of the films depends on the negative bias voltages. The films deposited at −250 V exhibited a maximum hardness of ~45 GPa. The adhesion and frictional tests revealed that the film deposited at −150 V demonstrated the highest cracking resistance, the best adhesion under a critical load of 78 N, highest adhesion strength, and the lowest and stablest coefficient of friction at 0.23.     

Nanoindentation and tribology of a (Hf-Ta-Zr-Nb-Ti)C high-entropy carbide

A (Hf-Ta-Zr-Nb-Ti)C high-entropy carbide was prepared by ball milling and a two-step Spark Plasma Sintering process, achieving a single-phase ceramic sample with a high relative density of 99.4 %. The wear resistance of the sample was measured by tribology and micro-scale mechanical behaviour was studied by nanoindentation on both the non-deformed and worn surfaces. Grains and the vicinity of grain boundaries exhibited high hardness values of 38.5 ± 0.5 GPa and 35.5 ± 1.0 GPa with similar Young’s moduli of 562 ± 11 GPa and 547 ± 16 GPa, respectively. The dominant wear mechanism was mechanical wear with limited grain pull-out and fracture, and with a localized and thin tribo-layer formation. The specific wear rate exhibited an increase with the increasing load from 2.53·10^?6 mm³/Nm at 5 N to 9.03·10^?6 mm³/Nm at 50 N. This was correlated to the decrease of nanohardness of the worn surfaces with increasing wear load, which is attributed to the increased number of microcracks.     

Mechanical properties of thermally sprayed porous alumina coating by Vickers and Knoop indentation

Depending on the thermal spraying conditions, coatings obtained can present different defects, like pores, cracks and/or unmelted particles, and different surface roughnesses, that can affect the determination of the hardness and elastic modulus. The present work investigates the mechanical properties, determined by means of Knoop and Vickers indentations, of a plasma as-sprayed alumina coating, obtained with a nano-agglomerated powder sprayed using a PTF4 torch, in order to highlight how the surface defects interfere into the indentation process. As a main result, Knoop indentation compared to Vickers one gives less dispersive results (15% and 33%, respectively), that are, in addition, more representative of the coating properties. The mean values obtained are 110 ± 40 GPa for the elastic modulus and 1.75 ± 0.42 GPa for the hardness. In addition, and for the two indenter types used, multicyclic indentation has been performed because it allows a more appropriate characterization of such heterogeneous coatings due to the representation of the mechanical properties as a function of the indentation load and/or the penetration depth, leading to more reliable results according to the depth-variability of the coating microstructure.