Thermal damage mechanisms of Si-coated diamond powder based polycrystalline diamond

The polycrystalline diamond (PCD) composites were synthesized from Si-coated diamond or diamond powder mixtures with Si. The characterizations of phase structures, morphologies and thermal stability of PCD were investigated by x-ray diffraction (XRD), scanning electron microscopy (SEM) and thermal gravimetric-differential scanning calorimetry (TG-DSC). The thermal damage mechanisms of PCD were studied under air condition up to 750 ℃ by thermal weight loss, XRD, SEM and wear tester. The results showed that the PCD was successfully synthesized by the Si-coated diamond with a homogeneous structure. The thermal stability and wear resistance of PCD with Si-coated diamond were better than those of PCD with uncoated diamond. It was determined that the chemical thermal damage mechanism with oxidation reaction dominated the damage of the PCD after high temperature annealing and the physical thermal damage mechanism also took effect on the exfoliation of binder and fine diamond grains from PCD.     

Antibacterial properties of polycrystalline diamond films

Electronic and mechanical properties, and their biocompatibility, make diamond-based materials promising biomedical applications. The cost required to produce high quality single crystalline diamond films is still a hurdle to prevent them from commercial applications, but the emergence of polycrystalline diamond (PCD) films grown by chemical vapour deposition (CVD) method has provided an affordable strategy. PCD films grown on silicon wafer have been used throughout and were fully characterised by SEM, XPS, Raman spectroscopy and FTIR. The samples contain nearly pure carbon, with impurities originated from the CVD growth and the silicon etching process. Raman spectroscopy revealed it contained tetrahedral amorphous carbon with small tensile stress. The sp² carbon content, comprised between 16.1 and 18.8%, is attributed to the diamond grain boundaries and iron-catalysed graphitisation. Antibacterial properties of PCD films were performed with two model bacteria, i.e. Escherichia coli (Gram-negative) and Staphylococcus aureus (Gram-positive) using direct contact and shaking flask methods. The samples showed strong bacteriostatic properties against S. aureus and E. coli with the direct contact method and no influence on planktonic bacterial growth. These results suggest that the bacteriostatic mechanism of PCD films is linked to their surface functional groups (carbon radicals and –NH₂ and –COOH groups) and that no diffusible molecules or components were involved.     

Electrochemical characteristics of boron doped polycrystalline diamond electrode sintered by high pressure and high temperature

The bulk B-doped polycrystalline diamond (PCD) electrode in this study was prepared by high-pressure, high-temperature (HPHT) technology. The PCD was sintered under HPHT conditions, using B-doped diamond powders and a metal catalyst as raw materials, then the metal solvent phase was dissolved by aqua regia. The morphology and composition of the PCD were investigated with a scanning electron microscope (SEM), X-ray diffraction (XRD), and energy dispersion spectrum (EDS). The results show that the sintered body possesses a polycrystalline structure with direct diamond–diamond bond and irregularly shaped pores of 1–10 μm distributed on the grain boundaries after the metal solvent phase was removed. The cyclic voltammogram and electrochemical impedance spectroscopy of this B-doped electrode have been investigated. The B-doped PCD electrode exhibits stable electrochemistry in a KCl support solution over a wide potential range. The quasi-reversible reaction occurs on the electrode for the [Fe(CN)₆]^3−/4− couples. The electrode process combines the diffusion-controlled mass transport plus the kinetic process. The electrochemical impedance spectroscopy (EIS) analysis shows the porous structure characteristic of the PCD electrode.     

Fractography of hardmetal dies used for the manufacture of polycrystalline diamond

Some WC/Co hardmetal dies used for the high-temperature, high-pressure fabrication of polycrystalline diamond have been subjected to fractographic investigation after service failure. In each die a number of flat plate-like fragments have been found showing an unusual fountain-like appearance to the fracture surface markings. Despite extensive probing, discrete fracture origins could not be found. Instead, from the evidence of the microcracking found in the die bore region and the recognised development of deformations during a campaign, it was concluded that microstructural damage was developed under the complex non-equitriaxial compression stresses which are developed during the duty cycles. When the propagation of this damage reached the axial tensile zone that exists in the cooler regions of the die, the plate-like, more-brittle failure pattern developed.     

High spatial resolution photoluminescence and Raman spectroscopic measurements of a natural polycrystalline diamond, carbonado

Photoluminescence and Raman spectra with high spatial resolution (< 1 μm) were observed on a natural polycrystalline diamond, carbonado. The studied sample is from Central African Republic (CAR) and was polished to optical grade. In addition to observation by optical microscopy, Scanning Near-field Optical Microscopy (SNOM) was applied for spectral and topographic analysis at high spatial resolution less than 300 nm. Mapping of the photoluminescence intensity of carbonado using SNOM indicated that the emission intensity was lower at the grain boundaries and the fringe of pores of carbonado revealed weakest intensity. Photoluminescence spectra of carbonado observed using optical microscopy and SNOM comprised three sharp bands at 504, 575 and 638 nm with their side bands and the color of photoluminescence changed according to its location. Raman spectra measured using optical microscopy revealed that the residual stress locally exists underneath the sample surface and the maximum stress value observed in this study was 0.72 GPa. Additionally, pressure dependence of the 575 nm band was measured using a diamond anvil cell up to 3.5 GPa. The 575 nm band shifted linearly to a lower wavelength with increasing pressure with a gradient of − 0.57 GPa/nm. This relationship was applied to estimations of the stress distribution of carbonados using SNOM. No significant changes in peak positions of photoluminescence spectra were detected on the surface of carbonados. This result suggests that carbonado is well sintered and that the residual stress of carbonado exists locally inside the crystal.     

Formation of low-resistance contact between titanium and lightly doped polycrystalline diamond using highly doped interlayer

A low-resistance ohmic contact between lightly doped polycrystalline diamond (poly-C) and metal was achieved for piezoresistive sensor applications using highly doped poly-C thin interlayer in the contact area for the first time for poly-C. Two Trimethylboron (TMB) doping concentrations were used during the growth of poly-C films using microwave plasma chemical vapor deposition (MPCVD), which yielded a 0.2 μm highly doped layer on top of 1.8 μm lightly doped layer. The resistivities of the highly and lightly doped poly-C layers are 0.022 and 151 Ω cm, respectively. The contacts were defined by partially etching the highly doped poly-C layer beyond the contact area. Kelvin bridges are fabricated to test the contact resistance. It is demonstrated that the contact resistivities are 0.0028 and 0.0083 Ω cm² for contacts with and without interlayer, respectively. This method reduced the contact resistance to one third of the original value and improved the performance of the piezoresistive sensor.     

Synthesis of alumina-bonded polycrystalline diamond by detonation

In this study, nanodiamond, aluminum isopropoxide, and hexogen (RDX) were used as starting materials to synthesize alumina-bonded polycrystalline diamond materials under high-temperature and high-pressure conditions generated by the detonation of the explosive. During detonation, the surface of the nanodiamond is coated with boron, silicon, and chromium through vacuum diffusion. Carbides of boron, silicon, and chromium referred as “bridges” are formed at the diamond/metal interface during the carbonization reaction. The "bridge" formed between diamond and nanoalumina considerably reduced the possibility of oxidation of nanodiamond as well as its graphitization during the detonation reaction. The phase, morphology, microstructure, and elemental composition of the detonation products were characterized by X-ray diffraction, scanning and transmission electron microscopy, and energy-dispersive X-ray spectroscopy. The results revealed that the explosion causes alumina and diamond to bond tightly to form alumina-bonded polycrystalline diamond composites. The thermal stabilities of the nanodiamond particles coated with boron, silicon, and chromium were found to be markedly higher, and the diamond phase remained intact even after heating at elevated temperatures. Thus, boron, silicon, and chromium reduced the wetting angle of diamond and alumina and improved the degree of bonding between them. Furthermore, boron facilitated the bonding between nanodiamond and alumina. In contrast, the bond was weaker in the case of silicon. Chromium also aided the bonding of the nanodiamond and alumina but introduced a large amount of oxygen into the composite.     

Effect of properties of MWPECVD polycrystalline diamond films on photoemissive response

Diamond is an extremely interesting material for photoemission applications, due to the negative electron affinity of its surface, which can be obtained after suitable treatments. In the present work two sets of polycrystalline diamond films, characterized by different thicknesses and deposition conditions, are analyzed. In particular, in the examined films the relationship among the grain size, the amount of non-diamond carbon (sp²) located at the grain boundaries and their efficiency as photocathodes has been found and carefully investigated. The photoemission yield in the UV range is evaluated for all the samples, before and after hydrogenation, and after air exposure. The crucial parameter for the photocathode performances has been found not to be the film thickness, but the properties of polycrystalline diamond films, tunable with the plasma modulation and the methane percentage in the gas mixture.     

Application of Raman spectroscopy to determine stress in polycrystalline diamond tools as a function of tool geometry and temperature

Polycrystalline diamond (PCD) tools commonly consist of a PCD layer sintered onto a cobalt-tungsten carbide (Co-WC) substrate. These tools are used in diverse applications and both the magnitude and distribution of the stresses in the PCD layer affect tool behavior. These stresses in sample drill-bits were investigated by means of micro-Raman spectroscopy in which the properties of the diamond Raman peak reveal both the nature of the stress present (compressive or tensile) and its magnitude. It was found that the surface preparation techniques influenced the average stress present in the PCD surface layer which was in compression in all cases investigated. The largest stresses were encountered in the roughly lapped sample (1.4 GPa) with the stress values decreasing for fine lapping (0.8 GPa) and polishing (0.1 GPa). Small areas with low tensile stresses were found in some polished samples. Measurements of stress as a function of temperature for roughly lapped sample drill-bits indicated a linear trend of decreasing stress values with increasing temperature, although the stress remained compressive. Cyclic annealing of a sample drill-bit to 600 °C shows that the tool properties are retained after 5 cycles, while similar cycling to 800 °C resulting in a permanent degradation of the tool properties.     

The novel and facile electrolysis method for removing the cobalt binder phase from large diameter polycrystalline diamond compacts

The thermal stability, wear resistance and impact toughness of polycrystalline diamond compact (PDC) are the primary determining variables in determining the performance. The cobalt binder contributes significantly to the PDC's thermal stability and wear resistance. To increase the thermal stability of the PDC, this paper used electrolysis to remove the cobalt binder from the polycrystalline diamond (PCD) layer of the PDC with a diameter of 62 mm. The optimal process parameters for cobalt removal via electrolysis were determined by examining the electrolyte concentration, the electrolytic voltage, and the electrolytic time. The cobalt removal impact was evaluated using a scanning electron microscope (SEM), an energy dispersive spectrometer (EDS), an X-ray diffraction (XRD), and thermogravimetric analysis-differential thermal analysis (TG-DTA). In addition, the abrasion ratio of the PDC samples were tested. The experimental results indicated that the optimal electrolysis parameters for cobalt removal were obtained when the concentration of cobalt sulphate was 4 g/100 mL, the electrolysis voltage was 2.5 V, and the electrolysis time was 10 h; in this case, the cobalt removal rate from the PCD layer exceeded 80%, and the cobalt removal depth was 372 μm. TG-DTA analysis revealed that the thermal stability of PDC was significantly enhanced as a result of the initial graphitization temperature of the cobalt removal sample being increased from 1071 °C to 1113 °C, but the abrasion ratio rose by more than 20%. It was discovered that electrolysis may efficiently remove the cobalt binder phase from the PCD layer, therefore improving the thermal stability and wear resistance of PDC.     

The influence of microstructure on the mechanical properties of polycrystalline diamond: a literature review*

ABSTRACT

Polycrystalline diamond (PCD) is an extremely high-performance cutting tool material used in the machining of rock, high-strength, non-ferrous metal alloys and carbon-fibre-reinforced composites. It is favoured for its exceptional hardness and wear resistance which results in at least an order of magnitude improvement in performance over previous technologies in almost all metrics. However, PCD suffers from unpredictable brittle fracture and degradation at high temperature during service which limits its capabilities in cutting applications. The literature on the link between its microstructure and its mechanical properties, including strength, toughness and flaw size distribution as measured by pseudo-static tests, is investigated. The conclusions of the seminal paper on this topic are re-examined in the light of modern ceramics research and an alternative explanation is put forth for the strength–grain size relationship published in this paper. All known literature values for strength and toughness vs. grain size and binder content are collated showing no overall trend in strength with binder content but moderate trends in all other combinations. The common claim of weak grain boundaries is brought into question in the light of the lack of any evidence of this fracture mode being evident in pseudo-static tests. The industrial literature on wear testing and failure modes of PCD in service and service-like tests is examined to bridge the gap between pseudo-static and dynamic, application-based experiments. Six main failure modes are recorded and summarised with intergranular fracture being the most conspicuously absent from the pseudo-static tests. It is suggested that the temperature generated by friction in dynamic tests causes the weakening of grain boundaries, resulting in a transition from transgranular to intergranular fracture and a call for further research in this area is made.     

有序排布结构对金刚石电镀磨盘磨削性能的影响研究

文章主要对有序排布金刚石电镀磨盘和全面电镀型磨盘的磨削性能进行比较,体现有序排布结构在高效磨削、节能降耗等方面的优势。结果表明:在磨削初期,玻璃磨削量相差不大,磨削60分钟后磨削量分别为35.30g和30.70g,有序排布结构能够有效提高磨盘的磨削效率;玻璃磨削表面粗糙度与磨盘表面结构关系不大,主要与金刚石的粒度有关;但有序排布结构能够提高加压压力,有效防止玻璃崩边。     

Electrochemical performance of polycrystalline CuO nanowires as anode material for Li ion batteries

CuO nanowires were prepared by wet-chemical method through the reaction of CuSO₄, KOH and ammonia in aqueous solution and subsequent aging process. The XRD, SEM, TEM, HRTEM, CV and galvanostatic method are used to characterize the structure, morphology and electrochemical performance of the as-prepared CuO nanowires. The CuO nanowires are polycrystalline microstructure, which facilitates the electrochemical storing Li. Therefore, the polycrystalline CuO nanowires exhibit a good electrochemical performance as Li ion batteries anode. The CuO nanowires showed a high reversible capacity of 720 mAh/g. The capacity keeps up 650 mAh/g over 100 cycles.     

Development of high resolution position sensitive UV detector based on highly oriented polycrystalline diamond

UV position-sensitive sensor using a polycrystalline highly-oriented diamond film with a sensitive area of 2 × 4.5 mm² developed, and a proof-of-concept study was conducted. The charge division method was employed to establish the position when the light hits the sensitive area. A fifth higher harmonic of a Nd:YAG laser with pulse width of 100 ps was used as a light source. The position resolution was 0.25 mm, and there was good position linearity throughout the sensitive area. Considering the possibility of light-spot broadening due to diffraction by the slit, the sensor may have a better resolution than that indicated by the result. But the electric-field strength of some parts of the crystal was insufficient, the response time was relatively slow, approximately 0.5 ms.     

Formation of high density stacking faults in polycrystalline 3C-SiC by vibration-assisted diamond cutting

Revealing the ductile deformation mechanisms of ultra-hard brittle cubic silicon carbide (3C-SiC), as well as their correlations with microstructure evolution, are crucial for facilitating the ductile machinability of the ceramic material. In the present work, we report the formation of highly oriented high density stacking faults accompanied with suppressed amorphization and cracking in polycrystalline 3C-SiC in ultrasonic elliptical vibration-assisted diamond cutting, which contributes to significantly enhanced ductile material removal of the ceramic material compared to ordinary cutting. Specifically, characterizations of Raman spectroscopy on machined surface and cross-sectional transmission electron microscopy on subsurface, as well as molecular dynamics simulations of the two kinds of cutting processes, are jointly performed to elucidate the mechanisms of phase transformation and microstructure evolution that govern the ductile material removal of polycrystalline 3C-SiC under the vibration assistance. In particular, the formation mechanisms of highly oriented high density stacking faults emitted from grain boundaries are revealed. Current findings provide insights into the ductile deformation behavior of hard brittle ceramics enhanced by field-assisted deformation process.     

Dielectric properties and electromagnetic wave transmission performance of polycrystalline mullite fiberboard at 2.45 GHz

Refractory lining is an indispensable part of high temperature microwave heating equipment, and its wave transmission performance exerts an important impact on the mode and efficiency of microwave heating, while the complex dielectric constant (dielectric constant and dielectric loss) of the material is the decisive factor in determining the wave transmission performance of the material. In this work, we measured the complex dielectric constant of polycrystalline mullite fiber board (PMF) in the temperature range of 25–1000 °C, and the effect of temperature on dielectric constant and dielectric loss was analyzed; The wave-transmission properties of the material were calculated according to the theory of electromagnetic wave transmission line, and the effects of temperature, material thickness, polarization modes of electromagnetic wave and incident angle on the wave transmission performance were analyzed. The results reveal that the dielectric constant of PMF does not change much with the increase of temperature, which is about 1.6; The dielectric loss does not change much within 200 °C, but when the temperature is higher than 200 °C, the change presents approximately exponential increase with the rise of temperature. The wave transmission performance fluctuates with the increase of the thickness, and there are maximum value and minimum value, and the overall wave transmission performance decreases with the increase of the material thickness. In a transverse electric (TE) field, the overall wave transmission performance decreases with the increase of the incident angle, and better wave transmission performance can be obtained by priority selection of vertical incidence of electromagnetic wave. In a transverse magnetic (TM) field, with the increase in the incident angle, the wave transmission performance firstly climbs up then declines, and there is an optimal incident angle where total transmission can occur. Finally, this work selected the thickness corresponding to different temperature as the preferred thickness. This work is of important theoretical significance for understanding the mechanism of the dynamic change of the wave transmission performance of the thermal insulation materials in microwave heating, and provides important practical guidance for the design and optimization of microwave heating equipment.     

国内主要厂家金刚石锯片的胎体成分和性能研究(下)

采用扫描电子显微镜和能谱分析对国内主要厂家的金刚石锯片的胎体成分、微观形貌和烧结情况进行分析研究,并对实际切割效率进行对比.结果表明,目前国内金刚石锯片胎体主要以Cu、Fe为主,其含量约占胎体总量的70％左右;金刚石锯片刀头中的金刚石晶形完整,胎体烧结致密,且胎体与金刚石界面结合较紧密;不同的金刚石锯片根据胎体中主要金属含量的不同,适用于切割不同的岩石,且实际使用性能良好,寿命均在150～170m2之间.     

High pressure and high temperature treatment of chemical vapor deposited polycrystalline diamond: From opaque to transparent

The enhanced optical properties of chemical vapor deposited (CVD) diamond have been pursued in academia and industry for many applications. However, the barrier of CVD technology limits the application field of diamond. Herein, the performance of CVD polycrystalline diamond thick films was improved by high-pressure and high-temperature (HPHT) treatment. The microstructures of CVD polycrystalline diamond films before and after HPHT treatments were thoroughly examined using optical microscope, UV–visible and infrared absorption, Raman spectroscopy, scanning electron microscope (SEM) and transmission electron microscope (TEM). It is found that the transparency of the CVD samples at 10 GPa increases dramatically with processing temperatures, from the original opacity to almost full optical transparency. Through spectroscopic and microstructural analyses, the modification mechanism of CVD polycrystalline diamond under HPHT conditions is proposed. The results show that the HPHT treatment can significantly enhance the optical properties of the starting CVD polycrystalline diamond films.     

A comparative study on comb electrodes devices made of MWPECVD diamond films grown on p-doped and intrinsic silicon substrate

Diamond is considered as a very promising material for the development of devices for radiation detection. Unlike other conventional photoconductive detectors diamond-based devices should provide high discrimination between UV and visible radiation. In this work we present the electro-optical properties of devices based on randomly oriented diamond films, synthesized in a microwave plasma enhanced chemical vapor deposition reactor. A comparative study on devices with coplanar interdigitated Cr/Au electrodes (with different interelectrode pitches) made of films grown simultaneously on intrinsic and p-doped silicon (100) substrates has been performed. The chemical-structural, morphological, electrical and optical properties of ROD films have been studied. In particular, the optical response has been measured in air using a Xe flash lamp coupled with an optical quartz fiber and a properly tailored front-end electronics based on a charge sensitive amplifier. Experimental results gave indications on how the device performances are dependent on the two types of employed substrates.     

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.