Wear resistance of nano- and micro-crystalline diamond coatings onto WC-Co with Cr/CrN interlayers

Cr/CrN bi-layers have been used recently to promote the growth of high quality Hot Filament Chemical Vapour Deposition (HFCVD) diamond coatings onto Co-cemented tungsten carbide (WC-6 wt.%Co) substrates. In the present investigation, the influence of the crystalline size of the diamond coatings on their wear endurance is looked into.Nano- (NDC) and micro-crystalline Diamond Coatings (MDC) were deposited by HFCVD onto untreated and Fluidized Bed (FB) treated Cr/CrN interlayers. NDCs, characterized by a cauliflower-like morphology, showed improved wear resistance. However, the superimposition of NDCs onto Cr/CrN interlayers micro-corrugated by FB treatment was found to be the most promising choice, leading to the formation of highly adherent and wear resistant coatings.     

Fluidized bed micro-machining and HFCVD of diamond films onto Co-cemented tungsten carbide (WC-Co) hardmetal slabs

The effect of fluidized bed (FB) treatment upon hot filament chemical vapor deposition (HFCVD) of polycrystalline diamond films onto WC-Co hardmetal substrates was investigated. Several scenarios to make the substrates ready for HFCVD were, comparatively, evaluated and the resulting diamond films were examined in terms of their morphology and adhesion. The diamond grain density was measured by scanning electron microscopy. The adhesion of continuous diamond film to substrate was evaluated by the reciprocal of the slope of crack radius-indentation load functions. Surface binder dissolution followed by FB treatment (PF pretreatment) allowed very high diamond nucleation density and smaller grain size. The adhesion of films grown on PF pretreated substrates was found to be very close to that of films deposited on hardmetal slabs pretreated by Murakami's reagent followed by Co etching with Caro's acid and seeded with diamond suspension in an ultrasonic vessel (MPS pretreatment). However, diamond coatings on MPS pretreated samples exhibited a rougher surface morphology as a result of both lower diamond nucleation density and larger substrate surface roughening by Murakami's etching. Based upon experimental findings, our newly developed PF pretreatment was found to be a very promising technique in substrates conditioning as well as in promoting adherent, uniform and smooth diamond coatings onto hardmetal tools and wear parts.     

The convection heat transfer coefficient in a Circulating Fluidized Bed (CFB)

Circulating Fluidized Beds are increasingly used in gas–solid and gas–catalytic reactions. A recent development involves their use in physical gas–solid processes such as drying, VOC adsorption or solar energy capture and storage. The heat transfer from the wall of the CFB to the flowing gas–solid suspension is the major design parameter, and was studied for different powders at different operating conditions as determined by the gas velocity and solids circulation flux. Measured values of the heat transfer coefficients are discussed, and compared with empirical predictions of Molodtsof–Muzyka, and Gorliz–Grace. Whereas Gorliz–Grace predicts heat transfer coefficients correctly within a narrow range of operating conditions only, the Molodtsof–Muzyka approach can be simplified into a linear relationship.     

Adhesion of diamond coatings on cemented carbides

Precise quantification of the adhesion of diamond coatings on cemented carbide (WC-Co) inserts is important for industrial applications. Adhesion is strongly influenced by the surface roughness, surface reactivity, catalytic effect of Co during diamond chemical vapour deposition (CVD) and by stresses developed in the film and at the bonding interface.

In this work we investigated the adhesion of diamond coatings on WC-Co by using Rockwell-C indentation. Various surface modifications were studied: Co leaching; replacement of Co by Cu; WC-Co decarburization and deposition of Ti intermediate layer prior to diamond CVD. Turning tests with diamond coated inserts for machining of Al alloy were carried out.     

Low friction CrN/TiN multilayer coatings prepared by a hybrid high power impulse magnetron sputtering/DC magnetron sputtering deposition technique

High power impulse magnetron sputtering (HIPIMS) has gained increasing scientific and industrial attention as it allows high plasma densities without the drawback of droplet formation. Recently, we showed that by a combination of HIPIMS with dc magnetron sputtering the properties of the coatings are comparable to those prepared solely with HIPIMS, but with the advantage of increased deposition rate.Here, we show that for CrN_HIPIMS/TiN_DCMS multilayered coatings the friction coefficient µ decreases from 0.7 to 0.35 (with an almost constant hardness H around 25 GPa, and modulus of indentation around 375 GPa) when decreasing the bilayer period λ from 7.8 to 6.4 nm, while keeping the CrN_HIPIMS layer thickness constant at 3.2 nm. A further reduction of the friction coefficient at room temperature dry-sliding testing to ∼ 0.25 or 0.05 is obtained when an additional HIPIMS cathode equipped with a Cr or Ti target material, respectively, is added to the process. Contact angle measurements of distilled water drops on as deposited film surfaces were carried out to investigate their wettability. The measurements show, that with increasing contact angle from 70° to 90°, for the individual coatings prepared, also their friction coefficient increases from ∼ 0.05 to ∼ 0.8. The depositions of all coatings were achieved with two- and threefold substrate rotation, which meet the industrial requirements of uniform deposition on complex shaped specimens.     

Study of the delamination of diamond coatings under thermal stress

The influence of the thickness of CVD diamond coatings on the adhesion to a substrate, after cooling down from deposition temperature to room temperature, has been studied experimentally and theoretically. Diamond layers have been deposited at 850°C on W substrates by microwave plasma enhanced CVD. Cooling down of the substrate-diamond coating system to room temperature induces thermal stresses, due to different thermal expansion coefficients of coating and substrate. For thick diamond coatings a total and sudden delamination could be observed as a consequence of these stresses. On the contrary thin coatings, produced under identical circumstances, adhered well. These phenomena have been modelled and explained by the use of an energetic criterion for the delamination of a two-layer system under thermal stress. From the model a critical thickness of the coating can be calculated. Above this critical thickness, delamination will suddenly occur. The calculations also predict that for intermediate coating thicknesses delamination can easily be induced by external causes.     

Influence of bi-layer period thickness on the residual stress, mechanical and tribological properties of nanolayered TiAlN/CrN multi-layer coatings

TiAlN/CrN nanoscale multi-layered coatings have been deposited using cathodic arc evaporation system. The coatings were deposited using one Ti₅₀Al₅₀ alloy target and one Cr target with a fixed target power in all the processes, while the bi-layer thickness was varied by various rotation speeds of the substrate holder in order to produce different nanoscale multi-layered period thickness. The texture structure, residual stress, and nanoscale multi-layer period thickness of the coatings were determined by X-ray diffraction using both Bragg-Brentano and glancing angle parallel beam geometries. Hardness and adhesion strength of the coatings were measured by Nano-indentation and Rockwell-C indentation methods, respectively. It has been found that the structural and mechanical properties of the films correlate with nano-scaled bi-layer thickness and crystalline texture. The maximum hardness of nano-scaled TiAlN/CrN multi-layered coatings was approximately 36 GPa with highest residual stress of −6.2 GPa, for a bi-layer thickness ranging from 6 to 12 nm.     

Interfacial structure, residual stress and adhesion of diamond coatings deposited on titanium

The interfacial structures of diamond coatings deposited on pure titanium substrate were analyzed using scanning electron microscopy and grazing incidence X-ray diffraction. Results showed that beneath the diamond coating, there was one titanium carbide and hydride interlayer, followed by a heat-affected and carbon/hydrogen diffused Ti layer. Residual stress in the diamond coating and TiC interlayer under different process parameters were measured using Raman and X-ray diffraction (XRD) methods. Diamond coatings showed large compressive stress on the order of a few giga Pascal. XRD analysis also showed the presence of compressive stress in the TiC interlayer and tensile stress in the Ti substrate. With increasing deposition duration, or decreasing plasma power and concentration of CH₄ in gas mixture, the compressive residual stress in the diamond coating decreased. The large residual stress in the diamond coating resulted in poor adhesion of the coatings to substrate, but adhesion was also related to other factors, such as the thickness and nature of the TiC interlayer, etc. A graded interlayer design was proposed to lower the thermal stress, modify the interfacial structure and improve the adhesion strength.     

流化喷雾造粒法制取低糖速溶豆粉的研究（Ⅰ）──流化喷雾造粒机理的实验研究

本文在间歇式流化喷雾造粒床内，研究了豆粉流化造粒的颗粒生长机理和规律。考察了床层温度、过剩流化气速、料液的黏度和流率、品种尺寸、晶种量和晶种的类别等操作条件对颗粒生长速率的影响，寻找到较好的工艺操作条件。     

Annealing effects on microstructure and mechanical properties of chromium oxide coatings

Reactive radio frequency magnetron sputter-deposited chromium oxide coatings were annealed at different temperatures and times. The influence of annealing temperature on the microstructure, surface morphology and mechanical properties was examined by X-ray diffraction, nanoindentation, pin-on-disc wear and scratch tests, respectively. X-ray results show that the chromium oxide sputtered at room temperature in low oxygen flux is primarily amorphous. Annealing below 400 °C did not cause much change, while annealing at higher temperature of 500 °C caused a significant change in microstructure and mechanical properties. Hardness increased from 12.3 GPa to 26 GPa, and the wearability improved with higher annealing temperature due to the formation of crystalline Cr₂O₃ phase, which occurs at 470 °C. Annealing time had little effect on mechanical properties and microstructure, although coating surface roughness increased with a longer annealing time. Coating adhesion was improved by annealing, due to residual stress relief and possible interfacial interdiffusion.     

Suppression of de-wetting of copper coatings on carbon substrates by metal (Cr, Mo, Ti) doped boron interlayers

Boron coatings doped with Cr, Ti or Mo were deposited on plane substrates of vitreous carbon (“Sigradur G”) by magnetron sputtering from a composite target. The amount of included metal was determined by Auger electron spectroscopy and found to be in the range of 1-4 at%. The metal content relative to boron was chosen to be in the range of 3 at% for all interlayers. Onto these interlayers a Cu film of 300 nm thickness was deposited by magnetron sputtering. After that the Cu coated samples were subjected to heat treatment of 800 °C for 30 min.The heat treated samples were investigated by scanning electron microscopy and time of flight secondary ion mass spectroscopy (TOF-SIMS). Different intensities of de-wetting of the Cu coatings could be observed. It was possible to quantify the de-wetting process by determining the area density of holes formed within the Cu coating after thermal treatment. Interlayers which lead to the lowest hole density will be considered as candidate materials for optimizing the thermal properties of the Cu/C interface in subsequent experiments.     

Local electrical properties of hydrogenated (001) and (111) surfaces of single crystalline diamond

The hydrogenation of Ib-type single crystalline diamond with grain size of several tens of micrometers, synthesized by high-pressure and high-temperature (HPHT) sintering, was carried out by hydrogen plasma treatment in a hot-filament chemical vapor deposition (HFCVD) system. After exposure to air, the surface conductivity of (001) and (111) facets of HPHT single crystalline diamond was measured. The influences of hydrogenation duration, temperature and gas pressure on the surface conductivity of (001) and (111) facets have been investigated. The measurement results show that the variation of hydrogenation conditions has a noticeable effect on the surface conductivity of single crystalline diamond, which is closely related to the formation of a chemical vapor deposition (CVD) regrowth layer on the facets induced by hydrogen plasma treatment process. In addition, (001) surface exhibits higher electrical conductivity than (111) surface, which is mainly attributed to less nitrogen concentration on the (001) surface than on the (111) surface.     

Manufacture of Slow-Release Matrix Granules by Wet Granulation with an Aqueous Dispersion of Quaternary Poly(meth)acrylates in the Fluidized Bed

ABSTRACT

Slow-release matrix granules were manufactured in the fluidized bed using an aqueous dispersion of quaternary poly(meth)acrylates (Eudragit® RS 30 D) as binder for granulation. A factorial design was carried out to investigate the influence of the following parameters, spraying rate, applied polymer amount, and inlet air temperature, on various granule properties. Prerequisites for a slow release of the model drug theophylline are high spraying rate, high amount of polymer, and low inlet air temperature. No considerable decrease of the drug release rate can be achieved without a subsequent curing of the dry granules. A clear correlation exists between the moisture content of the fluidized bed, indicated by the terminal moisture content (TMC), and the mean dissolution time for 80% of the drug (MDT₈₀).     

Electrodeposition of poly(o-anisidine) coatings onto copper

Abstract

Uniform and strongly adherent poly(o-anisidine) (POA) coatings have been successfully electrodeposited onto copper (Cu) substrates from the aqueous bath containing sodium oxalate and o-anisidine by using cyclic voltammetry (CV). CV, UV visible absorption spectroscopy, Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and X-ray diffraction (XRD) measurements were used to characterise these coatings, which indicates that the aqueous sodium oxalate solution is a suitable medium for the formation and deposition of POA onto Cu substrates. It is observed that the electrodeposition of POA coatings takes place after the passivation of the Cu substrate via formation of copper oxalate (CuC₂O₄.H₂O) layer, which is confirmed by XRD measurement. The optical absorption spectroscopy study reveals the formation of the mixed phase of pernigraniline base (PB) and emeraldine salt (ES) forms of POA. The surface morphology of the coating is uniform, compact and featureless as revealed by SEM imaging.     

Characterization of reactively sputtered c-axis orientation (Al, B)N films on diamond

In this research, we demonstrated the viability of oriented AlN layer that incorporated BN to enhance the texturing. Wurtzite (Al, B)N films were deposited on a diamond wafer (diamond film on Si wafer) by a co-sputtering technique. The preferred orientation structure is sensitive to sputtering control factors. The relationship between the microstructures and process conditions were examined with XRD, TEM and AFM analysis. The cross-section TEM images showed that amorphous and randomly aligned structures were produced in the initial sputtering period, but the higher c-axis orientation structure formed as the sputtering time increased. The thickness of the amorphous and randomly aligned layer decreased with increasing sputtering power, nitrogen concentration, substrate temperature and bias voltage. As the thickness of the amorphous and the randomly aligned layer decreased, an (Al,B)N film with higher film quality than AlN was observed.     

Fabrication of calcium ion sensitive diamond field effect transistors (FETs) based on immobilized calmodulin

We have developed calcium (Ca²⁺) ion sensitive solution-gate field effect transistors (SGFETs) on polycrystalline diamond by using partial amination and immobilization of calmodulin (CaM), a specific protein to calcium ions. The CaM is covalently immobilized on functionalized diamond surface, and the functionalized surface was analyzed by X-ray photoelectron spectroscopy, respectively. Also, the high performance of the CaM-immobilized diamond SGFET for detecting Ca²⁺ were studied with respect to high selectivity and sensitivity in various concentrations and pH.     

Fabrication of diamond microstructures for microelectromechanical systems (MEMS) by a surface micromachining process

Selective polycrystalline diamond thin film has been grown on a silicon dioxide/silicon substrate using high pressure microwave plasma-assisted chemical vapor deposition from a gas mixture of methane and hydrogen at a substrate temperature of 950°C. A simple process flow has been developed to fabricate diamond microstructures such as diamond beams and cantilever beams using surface micromachining and photolithography for the first time. Scanning electron and optical microscopy has been used to characterize the surface micromachined diamond microstructures.     

Electron energy loss spectroscopy of nano-scale CrAlYN/CrN-CrAlY(O)N/Cr(O)N multilayer coatings deposited by unbalanced magnetron sputtering

The nano-scale chemical distribution and microstructure of a nitride based wear and oxidation resistant coating prepared by unbalanced magnetron sputtering was investigated. The coating consisted of multilayers of CrAlYN/CrN with a partially oxidised CrAlY(O)N/Cr(O)N oxy-nitride surface layer. The multilayer period of both the nitride and oxy-nitride layers was 3.8 ± 0.2 nm. Nano-scale chemical analysis and imaging was performed using sub-nanometer resolution electron energy loss spectroscopic profiling in a spherical aberration corrected scanning transmission electron microscope. Experimentally determined fine edge structure in electron energy loss spectra were in good agreement with theoretically determined spectra, calculated using electron density functional theory. This analysis indicated the CrN layers to be near stoichiometric with a relative Cr/N ratio of 1.05 ± 0.1 while for the CrAlYN layers the best match between the direct chemical analysis and the simulated edges was (Cr_0.5Al_0.5)N. A diffuse interface, ∼ 1 nm wide was observed between the CrAlYN and CrN layers. For the outermost oxy-nitride layer, the chromium to nitrogen ratio remains approximately constant though out the layer, while the aluminium decreases as a function of increasing oxygen content.     

Growth and morphological studies of (100) textured diamond thin films by microwave plasma-enhanced chemical vapor deposition

Textured (100) diamond films have been successfully grown using the plasma-enhanced chemical vapor deposition technique and characterized by scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, and X-ray diffraction. The thickness of such a (100)-oriented diamond film can be as thin as 4 μm, and the just-emerged transitional layer is found to be only 1.5 μm, which is very thin compared with the computer simulation value of 700d₀, where d₀ is the average distance between the nuclei. A systematic study of various parameters in the carburization and bias steps on the growth of textured (100) diamond films and the subsequent change of surface morphology has been investigated. Experimental results show that these two pre-growth steps seem to ease the growth of textured (100) diamond films and they should be optimized for a set of growth conditions. It is suggested that varying these parameters in the pre-growth steps may cause a change of microstructure, alignment of nuclei, and defect states in the diamond-like layer, resulting in the morphological change of textured (100) diamond films.     

Superconductivity of p-type diamond (001) and (111) thin films: Ab initio calculations

The surface structure, electronic properties, lattice dynamics, and the electron-phonon coupling for p-doped diamond (001)-(2 × 1) and (111)-(2 × 1) thin films have been extensively investigated using ab initio methods within the virtual crystal approximation. The calculations of p-doped diamond thin films strongly favor dimer reconstruction of diamond surfaces. The physical origin of superconductivity of diamond (001)-(2 × 1), respectively, and (111)-(2 × 1) thin films which is higher than that of bulk diamond is systematically studied. It is showed that surface vibrational modes of diamond (001)-(2 × 1) surfaces give main contributions to superconducting transition temperature T_c, while T_c of diamond (111)-(2 × 1) surfaces is attributed to the combined action of surface and bulk vibrational modes. Therefore, at the highest concentration (13.98 × 10²¹ cm^− 3) T_c ≈ 56.5 K of diamond (111)-(2 × 1) surfaces is about twice as high as that of bulk and diamond (001)-(2 × 1) surfaces.