Superhard and superelastic films of polymeric C60

The C₆₀ thin film deposited on steel substrate was transformed by high pressure–high temperature treatment to a superhard and superelastic material. The films were studied by Raman spectroscopy in situ at 20 GPa after heating at 300°C and ex situ after the quenching. The hardness and elastic properties of the high-pressure phases have been characterized with nanoindentation. The hardness of the films were determined to be 0.5±0.1 GPa and 61.9±9 GPa for unmodified C₆₀ and HPHT treated films, respectively. The hardness of the pressurized film is higher than for cubic BN but lower than hardness values reported for ultrahard fullerite samples prepared from powders. An interesting observation was that the HPHT treated film showed an extreme elastic response with an elastic recovery of approximately 90%.     

Mechanical properties of MWPECVD diamond coatings on Si substrate via nanoindentation

The mechanical properties of polycrystalline diamond coatings with thickness varying from 0.92 to 44.65 μm have been analysed. The tested samples have been grown on silicon substrates via microwave plasma enhanced chemical vapour deposition from highly diluted gas mixtures CH₄-H₂ (1% CH₄ in H₂). Reliable hardness and elastic modulus values have been assessed on lightly polished surface of polycrystalline diamond films.The effect of the coating thickness on mechanical, morphological and chemical-structural properties is presented and discussed. In particular, the hardness increases from a value of about 52 to 95 GPa and the elastic modulus from 438 to 768 GPa by varying the coating thickness from 0.92 to 4.85 μm, while the values closer to those of natural diamond (H = 103 GPa and E = 1200 GPa) are reached for thicker films (> 5 μm). Additionally, the different thickness of the diamond coatings permits to select the significance of results and to highlight when the soft silicon substrate may affect the measured mechanical data. Thus, the nanoindentation experiments were made within the range from 0.65% to 10% of the film thickness by varying the maximum load from 3 to 80 mN.     

Experimental investigation on the indentation hardness of precursor derived Si–B–C–N ceramics

The elasto-plastic response of the precursor derived Si–B–C–N ceramics upon contact loading was determined by depth sensing nanoindentation technique. The indentation response of as-thermolyzed Si–B–C–N ceramic was compared with the heat-treated counterpart. The as-thermolyzed ceramic was X-ray amorphous and the heat-treated ceramic was phase separated and crystallized. The hardness and reduced elastic modulus values of the as-thermolyzed ceramic were ～16 GPa and ～172 GPa, respectively. The reduction in hardness to ～9 GPa in the heat-treated ceramic was attributed to phase separation and crystallization of SiC and Si₃N₄. Furthermore, high elastic recovery with a plastic work ratio of ～0.3 was observed and ascribed to volume controlled deformation mechanism.     

纳米压痕技术对比研究DNAN和TNT晶体的微观力学性能

通过溶剂挥发法制备了DNAN和TNT晶体;利用纳米压痕技术研究了DNAN和TNT晶体的微观力学性能(硬度和弹性模量);通过原位扫描探针成像技术(SPM)研究了DNAN和TNT晶体的压痕形貌随时间的变化差异。结果表明,DNAN晶体的平均硬度和弹性模量分别为7.82GPa和0.22GPa,TNT晶体的平均硬度和弹性模量分别为12.19GPa和0.48GPa,表明TNT抵抗变形的能力优于DNAN;随着压痕深度由118nm增至856nm,DNAN的硬度从0.61GPa降至0.22GPa;随着压痕深度由27nm增至481nm,TNT的硬度从2.9GPa降至0.48GPa,表明DNAN和TNT均存在尺寸效应。随着时间由0增至50.4min,DNAN的压痕深度由-270.99nm减至-44.28nm,TNT的压痕深度由-415.12nm减至-369.21nm,表明DNAN晶体比TNT晶体具有更明显的慢回弹性,DNAN具有更强的冲击能量吸收能力。     

Mechanical properties of nanocrystalline diamond/amorphous carbon composite films prepared by microwave plasma chemical vapour deposition

Nanocrystalline diamond films (NCD) have been deposited by microwave plasma chemical vapour deposition from CH₄/N₂ mixtures with varying methane content. They consist of diamond nanocrystallites with sizes of 3–5 nm embedded in an amorphous matrix with grain boundary widths of 1–1.5 nm. The CH₄ content in the gas phase has almost no influence on the microscopic structure but a strong effect on the macroscopic structure and morphology. The mechanical and tribological properties of these films have been investigated by nanoindentation, nano tribo tests, and nano scratch tests. The hardness of a 4-μm-thick film deposited with 17% methane was about 40 GPa, the indentation modulus 387 GPa, and the elastic recovery 75%. Ball-on-disk tests against an Al₂O₃ ball revealed, after initially higher values, a friction coefficient of ≤0.1. Tribo tests and scratch tests proved a strong adhesion and a protective effect on silicon substrates. Finally, the correlations between the macroscopic structure of the films and their mechanical and tribological properties are discussed.     

Investigation of novel superhard materials by multi-cycling nanoindentation

Depth sensing nanoindentation is applied to characterize the mechanical properties of new superhard materials such as cubic c-BC_x. Special load–time functions are developed to test the material by repeated loading and unloading processes. These intelligent load functions are applied in multi-cycling indents at the same place on the sample surface. Besides being time-efficient, the data collection method also does not suffer from lateral inhomogeneities of the sample. The hardness of the single phase cubic c-BC_x sample was found to be 78 GPa and its indentation modulus is between 900 and 1000 GPa. Hysteresis loops are observed in the superhard material, which are attributed to the generation of nano-cracks.     

Mechanical properties of cubic BC2N, a new superhard phase

A new superhard phase, cubic BC₂N, has very recently been synthesized by direct conversion of graphite-like BN–C solid solutions at 25 GPa and 2100 K. The hardness, Young's modulus, fracture toughness and structure of this phase have been examined using micro- and nanoindentation and transmission electron microscopy. The hardness and elastic modulus values (E, G) of the c-BC₂N are intermediate between diamond and cubic boron nitride, which makes this new phase the hardest known solid after diamond.     

Nanoindentation with spherical tips of single crystals of YBCO textured by the Bridgman technique: Determination of indentation stress–strain curves

The mechanical properties of superconductor ceramics are of interest in the manufacture of superconducting devices. The current trend is to produce smaller devices (using, e.g., thin films), and the correct characterization of small volumes of material is critical. Nanoindentation is used to assess mechanical parameters, and several studies determine hardness and Young's modulus by sharp indentation. However, studies on the elasto-plastic transition with spherical indentation are scare. Here we used, spherical diamond tip indenter experiments to explore the elasto-plastic transition and to measure the yield strength of the orthorhombic phase of YBa₂Cu₃O_7?δ (YBCO or Y-123) at room temperature. The study was carried out for a range of monodomains on the (1 0 1)-plane for Bridgman samples. Inspection of the load–unload curves for penetration depths lower than 200 nm allows for observation of the elasto-plastic transitions. Focused ion beam (FIB) trenches showed no cracking due to the indentation, although oxygenation cracks were apparent. The mean pressure for the onset of elasto-plastic deformation is 3.5 GPa, and the elastic modulus, E, calculated using the Hertzian equations is 123.5 ± 3.4 GPa.     

Nanoscale elastic-plastic deformation and mechanical properties of 3C-SiC thin film using nanoindentation

The elastic-plastic deformation of 3C-SiC thin film was investigated by a nanoindenter equipped with the Berkovich tip. Transition from pure elastic to elastic-plastic deformation was evidenced at an approximate load of 0.35 mN, when loading the sample at several peak loads ranging from 0.5 to 5 mN. The indentation size effect observed in 3C-SiC and was analyzed by Nix-Gao model. In purely elastic region, the Oliver- Pharr hardness values were 44 ± 2 GPa. In contrast, indentation size effects were evidenced in 3C-SiC specimen and the average value of Oliver-Pharr hardness in the indentation size effect region was 36 ± 2 GPa. Furthermore, depth independent or intrinsic hardness extracted from Nix-Gao was estimated as H_o = 26 ± 1 GPa which was also validated by proportional specimen resistance model, ie, H₁ = 28 ± 1 and H₂ = 28.5 ± 0.1 GPa. Besides, energy principle was utilized to extract Sakai Hardness as 104 GPa, which is combined elastic and elastic-plastic response. Moreover, based on energy principle, another property, ie, work of indentation was also determined to be 20 nJ/μm³. Similarly, elastic modulus had almost depicted stabilized value of 325 ± 8 GPa in pure elastic and elastic-plastic regions. In addition, plastic zone size was also estimated in elastic-plastic region using Johnson cavity model at pop-in and higher loads. Based on the first pop-in load at 0.35 mN, the distributions of shear and principal stresses were evaluated on various slip planes to elaborate the deformation behavior. Increase in loading rate from 100 to 400 μN/s increased critical pop-in load from 0.35 to 0.64 mN. This increase in critical pop-in load with increasing loading rate and values of maximum contact pressure indicates that no phase assisted transformation will occur at pop-in load. Based on theoretically calculated maximum tensile and cleavage strengths, it was affirmed that the elastic-plastic deformation occurred due to pop-in formation rather than tensile stresses. Moreover, it was also concluded on basis of Hertzian contact theory and Schmidt law that the highest possibility of slippage in 3C-SiC was along the {111} glide plane.     

Mechanical Properties of Sputter-Deposited Titanium-Silicon-Carbon Films

The effect of SiC additions on the mechanical properties of TiC films was investigated. Ti-Si-C films with varying SiC content were deposited using dual-cathode radio-frequency magnetron sputtering. The nanoindentation hardness of these films increased with SiC content to a maximum of 20–22 GPa for films in the range of 15–30 at.% SiC. The elastic modulus was also measured, and the hardness to modulus ratio ( H / E ) increased with SiC content, indicating that hardness increases were due to microstructural effects. The residual stress was measured in several films, but was low in magnitude, indicating that hardness measurements were not influenced by residual stress. TEM examination of several films revealed that the SiC additions altered the film microstructure in a manner that could account for the observed hardness increases.     

Nano-to-microscale ductile-to-brittle transitions for edge cracking suppression in single-diamond grinding of lithium metasilicate/disilicate glass-ceramics

To suppress grinding-induced edge cracks in dental lithium metasilicate/disilicate glass-ceramics (LMGC/LDGC), this paper established a contact stress model for single-diamond grinding (SDG) to relate their crack generation and ductile-to-brittle transition (DBT) thresholds with the mechanical properties, diamond tool profiles and process variables. Nanoindentation, friction test and SDG were conducted to unravel material responses and dynamic diamond grit-workpiece interactions to determine the DBT thresholds. The nanoindentation revealed significant indentation size effects (ISEs) on the hardness and elastic moduli of the ceramics. SDG clearly elucidated their DBT behaviors, wherein edge cracks initiated at diamond peripheries when the concurrent contact stresses reached the DBT thresholds. Accordingly, the indicated critical cutting depths for DBT may be changed from the nanoscale to the microscale by increasing the tool radius and reducing the machining speed. This research contributes to edge crack suppression for ductile machining of brittle materials at large removal rates.     

Multiple cohesive cracking during nanoindentation in a hard W-C coating/steel substrate system by FEM

Stress evolution and subsequent cohesive cracking in the hard and stiff W-C coating on steel substrate during nanoindentation have been investigated using finite element modelling (FEM) and eXtended FEM (XFEM). The FEM simulations showed that the maximum principal stresses in the studied system were tensile and always located in the coating. They evolved in several stages. At indentation depths below 15% of the relative indentation depth, the maximum principal tensile stresses of ∼3 GPa developed at the top surface of the coating along the indenter/coating interface. At relative depths range 15–60%, the maximum tensile stresses of ∼6–8 GPa concentrated under the indenter tip in the coating along the interface with the substrate. At relative depths exceeding 60%, the maximum stresses gradually increased up to 10 GPa and they were located in the sink-in zone outside the indent as well as below the indenter tip. The first and subsequent cohesive cracks developed when the maximum tensile stresses in the sink-in zone at the top surface of the coating (and at the coating/substrate interface under the indenter) repeatedly reached the ultimate tensile strength of the coating. The hardness profile as well as cohesive cracking is controlled by the deformation of the substrate defined by the ration of the yield stresses of the coating and substrate. Very good correlation between the experimentally obtained cracks and multiple cracks predicted by XFEM confirmed the ability of the applied modelling in the prediction of fracture behavior of the studied coating/substrate system.     

Mechanical characterization of ultra-thin fluorocarbon films deposited by R.F. magnetron sputtering

Fluorocarbon films were deposited on silicon substrate by R.F. magnetron sputtering using a polytetrafluoroethylene (PTFE) target. Structure of the deposited films was studied by X-ray photoelectron spectroscopy (XPS). Hardness, elastic modulus and scratch resistance were measured using a nanoindenter with scratch capability. -CF_x (x = 1, 2, 3) and C-C units were found in the deposited fluorocarbon films. The hardness and elastic modulus of the films are strongly dependent on the R.F. power and deposition pressure. The film hardness is in the range from 0.8 GPa to 1.3 GPa while the film elastic modulus is in the range from 8 GPa to 18 GPa. Harder films exhibit higher scratch resistance. Differences in nanoindentation behavior between the deposited fluorocarbon films, diamond-like carbon (DLC) films and PTFE were discussed. The fluorocarbon films should find more applications in the magnetic storage and micro/nanoelectromechanical systems.     

A molecular dynamics simulation of the mechanical characteristics of a C60-filled carbon nanotube under nanoindentation using various carbon nanotube tips

The mechanical characteristics of a single-walled carbon nanotube (SWCNT) filled with C₆₀ fullerene subject to nanoindentation is studied using molecular dynamics (MD) simulations. The effects of temperature, indentation velocity, adhesion, and tip sizes were evaluated. The simulated results clearly show that the exerted load, Young’s modulus, elastic energy, and plastic energy decrease significantly with increasing temperature and decreasing indentation velocity and tip size. C₆₀ fullerenes can effectively increase the mechanical strength of a SWCNT because they act as a “barrier” to resist the radial deformation, as well as an inner wall in a double-walled carbon nanotube. With the same indentation depth, the ratio of elastic energy to plastic energy for a material gradually increases with the increase in the radius of the tip. This indicates that the elastic recovery of a material is better when the tip has a larger radius.     

Shock-wave synthesis of diamonds from fullerenes C60−C100

Shock-wave synthesis of diamond from C₆₀–C₁₀₀-fullerene powder was first accomplished by using the explosive compaction technique with plane wave loading in the pressure range of 24–40 GPa. The compacts of various initial composition comprised diamond, FCC C₆₀-fullerite, graphite, and amorphous carbon. The largest diamonds of 0.1–1.0 m were obtained under shock loading of pellets consisting of copper powder with 5 wt. % fullerite at 24 and 38 GPa, and pellets consisting of copper powder with 10 wt. % fullerite at 40 GPa. The end product consists of diamond without intermediate diamondlike phases such as n-diamond and hexagonal diamond (lonsdaleite).Central Machine-Building Technology Research Institute, 109088 Moscow. Translated from Fizika Goreniya i Vzryva, Vol. 31, No. 2, pp. 131–138, March–April, 1995.     

Synthesis of ultrahard fullerite with a catalytic 3D polymerization reaction of C60

3D polymerization of C₆₀ realizes under conditions of large plastic deformation at pressure 6–7 GPa and room temperature in the presence of CS₂. The phase of 3D-polymerized C₆₀ is identical to ultrahard fullerite synthesized from pure C₆₀ at 18 GPa pressure: in both cases, the samples plough diamond during the rotation of the sample in a shear diamond anvil cell, bulk module is 585 GPa, and a sequence of phase transitions preceding to ultrahard phase is also the same in both cases (in the presence of CS₂, the phase transitions take place at lower pressures than in pure C₆₀). Raman and transmission microscope studies confirm the structure equivalence of samples of both types. The absence of sulfur in the structure of ultrahard fullerite synthesized in the presence of CS₂ proves the catalysis role of CS₂ in the 3D polymerization of C₆₀.     

Properties of nanocrystalline diamond thin films grown by MPCVD for biomedical implant purposes

Nanocrystalline diamond (NCD) thin films have been grown by microwave plasma chemical vapor deposition (MPCVD) and investigated to determine their suitability for biomedical applications. Growth conditions were chosen to produce very uniform films over the surface of curved temporomandibular joint implants. These parameters include methane flow rates exceeding 20% of the hydrogen gas flow rate, and chamber pressure and microwave power were maintained at 30 Torr and 0.73 kW, respectively, in a Wavemat 6 kW MPCVD device. Films (3 μm thick) that completely coated 2.54-cm-diameter Ti–6Al–4V disks under these conditions exhibit mean grain size of 30.4 nm as determined by XRD peak broadening, hardness of 80 GPa as determined by nanoindentation, RMS mean roughness of 15.3±5.3 nm as determined by stylus profilometry, and film adhesion toughness (Γ_C) of 158 J/m² as determined by a Rockwell indentation method. Similar deposition performed on small Ti–6Al–4V hemispheres produce films with smaller mean grain size of 21.1 nm and correspondingly lower hardness and roughness. Overall, these films exhibit properties well suited for use in biomedical applications.     

Non-Hall-Petch hardness dependence in ultrafine fibrous MgAl2O4-MgO eutectic ceramics fabricated by the laser-heated floating zone (LFZ) method

MgAl₂O₄-MgO eutectic ceramics were fabricated by the laser-heated floating zone (LFZ) method with various growth rates to assess its possible beneficial effect on microstructural aspects and mechanical properties. It was determined that the growth rate optimizing the microstructure and mechanical properties is 750 mm/h; below this value, coarsening of the fibrous microstructure takes place with a degradation of these properties. In the extreme case of 50 mm/h growth rate, the presence of undesirable transverse cracks was unavoidable. Thanks to the high growth rate of 750 mm/h, ultra-fine fibrous microstructure MgAl₂O₄-MgO eutectic ceramics can thus be fabricated with greater hardness (15.5 GPa from Vickers indentation and 22 GPa from nanoindentation) and flexural strength (?345 MPa). It is reported that hardness scales with the interfiber spacing λ according to a law of the type lnλ/λ, contrary to the assumed Hall-Petch-like dependence. This proposed law can be explained in terms of dislocation hardening induced by the MgO fibers.     

Methods for studying the mechanical and tribological properties of hard and soft coatings with a nano-indenter

This study illustrates the capabilities of a nanoindentation/nanoscratch tester to assess mechanical and tribological properties of coating films. Properties such as hardness, elastic modulus, mar and scratch resistance, and critical force for cracking can be accurately measured. Operation of the Nano-Indenter is described in detail. A scanning probe microscope (SPM) is shown to be a valuable supplement to the Nano-Indenter. Well-characterized thermoset acrylic clearcoats and thermoplastic latex films were studied. For the first time, operating parameters are described for measurement of relatively soft coatings, such as films cast from a latex with a glass transition temperature (T_g) of 8°C. Thus, the method is made available for study of most types of coatings. The method can easily discriminate between coatings with different T_gs and crosslink densities. Once operating parameters are established, it takes about 10 minutes for an indentation test and 10 minutes for a scratch test with the Nano-Indenter, and with further automation this time could be reduced. Each indentation test accurately measures hardness and elastic modulus as a function of depth within the coating, and each scratch test provides additional insight into the material’s behavior. The method is sensitive to small changes in polymer composition and formulation, and results are highly reproducible. Presented at the 81st Annual Meeting of the Federation of Societies for Coatings Technology, November 12–14, 2003, in Philadelphia, PA.     

Influence of porosity on the mechanical properties of microporous β-TCP bioceramics by usual and instrumented Vickers microindentation

Beta-tricalcium phosphate [Ca₃(PO₄)₂, β-TCP] is a bioresorbable material showing an excellent biocompatibility. However, sintering of β-TCP is difficult and the material presents poor mechanical strength and a low resistance to crack-growth propagation. In this study, influence of the porosity on the hardness and the elastic modulus is studied by means of usual and instrumented microindentation tests. Nevertheless, indentation diagonals measurement by optical observations is not accurate due to the crack formation around the residual indent. That is why instrumented indentation test which allows deducing the hardness and the bulk modulus from the load-depth curve analysis is used as an alternative method. The corresponding hardness number can be calculated by using the maximum indentation depth (Martens Hardness) or the contact depth determined by Oliver and Pharr's method (Contact Hardness). But in order to give representative values when comparing classical and instrumented hardness measurements, Martens hardness is preferred because its value can be directly related to the value of the Vickers hardness number by simple geometrical considerations.In this work, bioceramics were produced by conventional sintering of β-TCP powders synthesized by aqueous precipitation. Different process conditions were chosen to obtain microporous ceramics with a porosity rate between 0 and 14% in volume. As main results, the elastic modulus is found decreasing between 166 GPa and 108 GPa and the hardness number from 4.4 GPa to 2.2 GPa when increasing the porosity rate. A model connecting mechanical properties to porosity rate and grain arrangement is validated for the elastic modulus whereas deviation is observed for the hardness number. However, we propose an original approach where the relative variation of the two mechanical properties can be expressed with a unique relation as a function of the porosity volume fraction.