Electron field emission from filtered arc deposited diamond-like carbon films using Au and Ti layers

In this work, tetrahedral diamond-like carbon (DLC) films are deposited on Si, Ti/Si and Au/Si substrates by a new plasma deposition technique — filtered arc deposition (FAD). Their electron field emission characteristics and fluorescent displays of the films are tested using a diode structure. It is shown that the substrate can markedly influence the emission behavior of DLC films. An emission current of 0.1 μA is detected at electric field E_DLC/Si=5.6 V/μm, E_DLC/Au/Si=14.3 V/μm, and E_DLC/Ti/Si=5.2 V/μm, respectively. At 14.3 V/μm, an emission current density J_DLC/Si=15.2 μA/cm², J_DLC/Au/Si=0.4 μA/cm², and J_DLC/Ti/Si=175 μA/cm² is achieved, respectively. It is believed that a thin TiC transition layer exists in the interface between the DLC film and Ti/Si substrate.     

Microstructure and corrosion properties of Ni-TiN nanocoatings prepared by jet pulse electrodeposition

Ni–TiN nanocoatings were successfully prefabricated by jet pulse electrodeposition. The effect of jet rate on cross-sectional composition, microstructure, microhardness, and corrosion properties of nanocoatings was examined by X-ray photoelectron spectroscopy, high-resolution transmission electron microscope, atomic force microscopy, microhardness tester and electrochemical workstation. Results illustrated that Ni–TiN nanocoatings deposited at jet rate of 3 m/s exhibited high concentration of Ni and Ti with average concentrations of Ni and Ti of 54.5 at% and 19.8 at%, respectively. Average diameters of Ni grains and TiN nanoparticles in Ni–TiN nanocoatings prepared at 3 m/s were 47.8 nm and 30.5 nm, respectively. Nanocoatings deposited at 1 m/s, 3 m/s and 5 m/s showed surface root-mean-square roughness value of 95.431, 30.091 and 58.454 nm, respectively, and presented maximum microhardness of 789.5, 876.2, and 849.9 HV, respectively. Ni–TiN nanocoating obtained at 3 m/s demonstrated minimum I_corr and E_corr values of 1.02 × 10⁻³ mA/cm² and − 0.551 V, respectively, signifying to offer the best corrosion resistance.     

Titania/hydroxyapatite bi-layer coating on Ti metal by electrophoretic deposition: Characterization and corrosion studies

Titania–hydroxyapatite (HAp) bi-layer coating on Ti metal substrate with improved adhesion strength is fabricated by a simple two step processes: electrodeposition of Ti sol and electrophoretic deposition of HAp powder, followed by heat treatment at 800 °C. At optimized process parameters, the bi-layer developed consists of dense, thin and crystalline titania interlayer with porous, thick and crystalline HAp top layer. The heat treatment of bi-layer coating allows elemental intermixing at the interface of TiO₂ and HAp, as determined by energy dispersive X-ray spectroscopy (EDX) and Raman spectra analysis. Compared to monolithic HAp coating, the TiO₂/HAp bi-layer coating shows significant enhancement in the adhesion strength (48 MPa) as well as corrosion resistance without compromising its biocompatibility. The steep increase in adhesion strength is believed to be due to mechanical interlocking and diffusion bonding at the interface. Presence of dense titania interlayer in the bi-layer coating reduces the corrosion current in Ringer's solution to a negligible value (～100 nA).     

Thickness-dependent phase evolution and bonding strength of SiC ceramics joints with active Ti interlayer

A robust solid state diffusion joining technique for SiC ceramics was designed with a thickness-controlled Ti interlayer formed by physical vapor deposition and joined by electric field-assisted sintering technology. The interface reaction and phase revolution process were investigated in terms of the equilibrium phase diagram and the concentration-dependent potential diagram of the Ti-Si-C ternary system. Interestingly, under the same joining conditions (fixed temperature and annealing duration), the thickness of the Ti interlayer determined the concentration and distribution of the Si and C reactants in the resulting joint layer, and the respective diffusion distance of Si and C into the Ti interlayer differentiated dramatically during the short joining process (only 5 min). In the case of a 100 nm Ti coating as an interlayer, the C concentration in the joint layer was saturated quickly, which benefited the formation of a TiC phase and subsequent Ti₃SiC₂ phase. The SiC ceramics were successfully joined at a low temperature of 1000 °C with a flexural strength of 168.2 MPa, which satisfies applications in corrosive environments. When the Ti thickness was increased to 1 μm, Si atoms diffused easily through the diluted Ti-C alloy (a dense TiC phase was not formed), and the Ti₅Si₃ brittle phase formed preferentially. These findings highlight the importance of the diffusion kinetics of the reactants on the final composition in the solid state reaction, particularly in the joining technique for covalent SiC ceramics.     

Comparison of the wear particle size distribution of different a-C coatings deposited by vacuum arc

For biomedical application in the field of artificial hip joints diamond-like carbon (DLC) coatings have been widely studied due to their tribological properties. The wear particles as the main factor limiting the life expectancy of hip joints have attracted more and more interest, not only the number of them, but also the distribution of their size. In this study we have deposited DLC coatings on stainless steel (P2000) by a vacuum arc adjustable from anodic to cathodic operation mode, with the anode–cathode diameter ratio of d_a/d_c = 3/1 at a DC bias of − 250 V to − 1000 V. To improve the adhesion of the DLC coating on P2000, titanium as a metallic interlayer was deposited by cathodic vacuum arc evaporation. The internal structure of the coating was investigated by the visible Raman spectroscopy with the four-Gaussian curve fitting method. Comparing the results with the previous work (coatings deposited with d_a/d_c = 1/1), it was found that the anode–cathode diameter ratio has an effect on the structure (e.g. I_D/I_G) as well as the wear particle size distribution. It was shown that the maximum of the frequency distribution e.g. at − 1000 V bias can be shifted to below 1 μm with increasing d_a/d_c.     

Electrochemical investigation of chromium nanocarbide coated Ti–6Al–4V and Co–Cr–Mo alloy substrates

This study investigated the electrochemical behavior of chromium nano-carbide cermet coating applied on Ti–6Al–4V and Co–Cr–Mo alloys for potential application as wear and corrosion resistant bearing surfaces. The cermet coating consisted of a highly heterogeneous combination of carbides embedded in a metal matrix. The main factors studied were the effect of substrate (Ti–6Al–4V vs. Co–Cr–Mo), solution conditions (physiological vs. 1 M H₂O₂ of pH 2), time of immersion (1 vs. 24 h) and post coating treatments (passivation and gamma sterilization). The coatings were produced with high velocity oxygen fuel (HVOF) thermal spray technique at atmospheric conditions to a thickness of 250 μm then ground and polished to a finished thickness of 100 μm and gamma sterilized. Native Ti–6Al–4V and Co–Cr–Mo alloys were used as controls. The corrosion behavior was evaluated using potentiodynamic polarization, mechanical abrasion and electrochemical impedance spectroscopy under physiologically representative test solution conditions (phosphate buffered saline, pH 7.4, 37 °C) as well as harsh corrosion environments (pH ～ 2, 1 M H₂O₂, T = 65 °C). Severe environmental conditions were used to assess how susceptible coatings are to conditions that derive from possible crevice-like environments, and the presence of inflammatory species like H₂O₂. SEM analysis was performed on the coating surface and cross-section. The results show that the corrosion current values of the coatings (0.4–4 μA/cm²) were in a range similar to Co–Cr–Mo alloy. The heterogeneous microstructure of the coating influenced the corrosion performance. It was observed that the coating impedances for all groups decreased significantly in aggressive environments compared with neutral and also dropped over exposure time. The low frequency impedances of coatings were lower than controls. Among the coated samples, passivated nanocarbide coating on Co–Cr–Mo alloy displayed the least corrosion resistance. However, all the coated materials demonstrated higher corrosion resistance to mechanical abrasion compared to the native alloys.     

Effect of Ti particle size on mechanical and tribological properties of TiCN coatings prepared by reactive plasma spraying

Titanium carbonitride (TiCN) coatings were successfully fabricated by reactive plasma spraying (RPS) from agglomerated Ti-graphite feedstock. The effect of Ti particle size on the microstructure and phase composition of plasma sprayed TiCN coatings was investigated. The Vickers microhardness of coatings was measured by a Microhardness Test and the corresponding Weibull distribution were also analyzed. In addition, a pin-on-disk tribometer was employed to determine the trobological properties of coatings. Results show that all the coatings consist of TiC_xN_1−x (0 ≤ x ≤1) and minor Ti₂O phases, and the amount of Ti₂O increases with the increase of Ti particle size. The Weibull distribution of Vickers microhardness of all the coatings shows apparent scattering, while the coating sprayed with Ti particle size of 28 µm exhibits a relatively even distribution. Compared with the coating sprayed with Ti particle size of 14 µm or 48 µm, the coating sprayed with Ti particle size of 28 µm exhibits improved mechanical and tribological properties, which are attributed to the high microhardness and strong bonding strength.     

Fabrication and high-temperature thermoelectric properties of Ti-doped Sr0.9La0.1TiO3 ceramics

Ti-doped Sr_0.9La_0.1TiO₃ ceramics with high density were successfully prepared in argon atmosphere by conventional solid state reaction. The influences of titanium doping content on the microstructure and thermoelectric properties were investigated. The results showed that titanium was oxidized during the calcination procedure. TiO₂ phase survived and coexisted with Sr_0.9La_0.1TiO₃ phase in the sintered ceramics. The Seebeck coefficients were increased from −163 to −259 μV/K as the temperature increased from 350 K to 1073 K. The thermal conductivity can be significantly reduced by doping Ti. Thermoelectric figure of merit (ZT) first decreased and then increased with increasing Ti doping content. Ceramics showed the best thermoelectric properties when Ti doping amount was 5 wt%, the maximum PF was 7.13 μW/K²/cm, and ZT value was 0.144 at 1073 K.     

Electron field emission properties on UNCD coated Si-nanowires

The electron field emission (EFE) properties of Si-nanowires (SiNW) were improved by coating a UNCD films on the SiNWs. The SiNWs were synthesized by an electroless metal deposition (EMD) process, whereas the UNCD films were deposited directly on bare SiNW templates using Ar-plasma based microwave plasma enhanced chemical vapor deposition (MPE–CVD) process. The electron field emission properties of thus made nano-emitters increase with MPE–CVD time interval for coating the UNCD films, attaining small turn-on field (E₀ = 6.4 V/μm) and large emission current density (J_e = 6.0 mA/cm² at 12.6 V/μm). This is presumably owing to the higher UNCD granulation density and better UNCD-to-Si electrical contact on SiNWs. The electron field emission behavior of these UNCD nanowires emitters is significantly better than the bare SiNW ((E₀)_SiNWs = 8.6 V/μm and (J_e)_SiNWs < 0.01 mA/cm² at the same applied field) and is comparable to those for carbon nanotubes.     

Microwave dielectric properties of the (BaxSr1−x)TiO3 thin films on alumina substrate

Barium strontium titanate, (Ba_xSr_1?x)TiO₃ (BST) thin films have been prepared on alumina substrate by sol–gel technique. The X-ray patterns analysis indicated that the thin films are perovskite and polycrystalline structure. The interdigital electrode with 140 nm thickness Au/Ti was fabricated on the film with the finger length of 80 μm, width of 10 μm and gaps of 5 μm. The temperature dependence of dielectric constant of the BST thin films in the range from ?50 °C to 50 °C was measured at 1 MHz. The dielectric properties of the BST thin films were measured by HP 8510C vector network analyzer from 50 MHz to 20 GHz.     

Casting and characterization of LiMgPO4 glass free LTCC tape for microwave applications

The LiMgPO₄ ceramic has been prepared through the solid state ceramic route. The powder has an average particle size of 1.1 μm and BET surface area of 2.7 m² g^?1. Good dispersion of LiMgPO₄ has been achieved in ethanol/xylene mixture with the addition of 2 wt.% fish oil. The tape casting slurry of LiMgPO₄ with typical pseudoplastic behavior has been prepared and cast into thin tapes of thickness 70 μm. LiMgPO₄ green tape shows a tensile strength of 0.22 MPa and average surface roughness of 0.25 μm. The green tape has an ?_r of 3.2 and tan δ of 0.0688 at 5 GHz. The thermo-laminated tape (4 layers) sintered at 950 °C/2 h shows good microwave dielectric properties: ?_r = 6.4 and tan δ = 0.0002. LiMgPO₄ has a coefficient of thermal expansion of 10.5 ppm/°C and thermal conductivity of 7.1 W m^?1 K^?1.     

TaB2–SiC–Si multiphase oxidation protective coating for SiC-coated carbon/carbon composites

To improve the oxidation resistance of the carbon/carbon (C/C) composites, a TaB₂–SiC–Si multiphase oxidation protective ceramic coating was prepared on the surface of SiC coated C/C composites by pack cementation. Results showed that the outer multiphase coating was mainly composed of TaB₂, SiC and Si. The multilayer coating is about 200 μm in thickness, which has no penetration crack or big hole. The coating could protect C/C from oxidation for 300 h with only 0.26 × 10^?2 g²/cm² mass loss at 1773 K in air. The formed silicate glass layer containing SiO₂ and tantalum oxides can not only seal the defects in the coating, but also reduce oxygen diffusion rates, thus improving the oxidation resistance.     

Grain size effect on electrical properties of Mn-modified 0.67BiFeO3–0.33BaTiO3 lead-free piezoelectric ceramics

To investigate how grain size affects the dielectric, ferroelectric, and piezoelectric properties of Mn-modified 0.67BiFeO₃–0.33BaTiO₃ ceramics, we prepared samples with a wide variety of grain sizes from 4.1 μm to 0.59 μm via a conventional solid-state process that use the normal and the two-step sintering methods. Small-signal dielectric measurements show that all the samples exhibit a relaxor-like behavior and that grain size has little influence on the room-temperature dielectric permittivity. For grain sizes below 2 μm, the remanent polarization P_r and piezoelectric coefficient d₃₃ decrease with the grain size, whereas they remain almost constant near P_r = 27 μC/cm² and d₃₃ = 70 pC/N in samples with grain sizes exceeding 2 μm. The mechanism underlying the observed grain size effect is discussed in terms of the electric-field-induced formation of macroscopic ferroelectric domains.     

Hardmetal woodcutting tool tips coated with tetrahedral amorphous carbon

Woodcutting tools with hardmetal (WC–Co) tool tips were coated with a high-quality (80% sp³ bonding fraction) tetrahedral amorphous carbon (ta-C) film. The coatings were produced by filtered cathodic vacuum-arc (FCVA) deposition. The problem with poor adhesion between the ta-C film and cobalt was solved by using an intermediate chromium layer structure. The adhesion was tested with a conventional scratch tester. In the case of a 1.2 μm thick ta-C film with intermediate layer structure the critical load value was 31.6 N; without the intermediate layer it was 16.2 N. The lifetime of the ta-C-coated woodcutting tool was tested under normal production conditions with a computer numerical control (CNC) woodcutting machine. The lifetime of the woodcutting tool tip improved by a factor of three in the case of a 2.1 μm thick multilayer (ta-C/Cr) film coating and by a factor of 1.5 in the case of a 1.0 μm thick ta-C film coating with an 0.5 μm thick intermediate chromium layer.     

Method of catalyst coating in micro-reactors for methanol steam reforming

Micro-channels of silicon-based micro-reactors were successfully coated with deionized (DI) water-based Cu–ZnO–Al₂O₃ catalyst slurry by a fill-and-dry coating method, applicable to pre-assembled micro-reactors, for steam reforming of methanol. The 10–20 μm thick catalyst layers could be formed on the inner walls of the micro-channels after the micro-channels were fully filled with catalyst slurry, because the catalyst particles in the slurry cohered to the walls of micro-channels by surface tension during drying and calcinations. The adhesion between the catalyst layer and silicon surface was improved by pre-coating the micro-channels with an alumina adhesion layer. The addition of polyvinyl alcohol (PVA) in the alumina sol resulted in better adhesion of the alumina layer at the corners of the channels. The critical minimum thickness of the alumina layer for catalyst coating was 0.15 μm. The highest catalytic activity without loss of intrinsic catalytic activity was obtained using 1:5 (catalyst to solvent) DI water-based catalyst layers coated by fill-and-dry coating. The maximum H₂ production rate was 85 ccm with 1650 ppm of CO measured at 300 °C using a methanol feed rate of 9 ml/h.     

Sintering behavior of La2O3–B2O3–TiO2 glass powders prepared by spray pyrolysis for low temperature co-fired ceramics

Fine-sized La₂O₃–B₂O₃–TiO₂ glass powders with spherical shape were directly prepared by spray pyrolysis at a temperature of 1500 °C. The optimum flow rate of the carrier gas to prepare the glass powders with dense inner structure and fine size by complete melting was 10 L/min. The ratio of La/Ti was identified to be 2.06:1, which was close to the original starting ratio of La/Ti in mixture of the spray solution. The T_g and T_c of the powders were 614 and 718 °C. The crystal structures within the powders were observed from the sintered disc at 630 °C. The mean sizes of the powders changed from 0.24 to 0.71 μm when the concentrations of the spray solution were changed from 0.025 to 0.5 M. The BET surface areas of the powders changed from 4.4 to 1.6 m²/g. The grain sizes of the sintered discs increased with increasing the sintering temperatures. The main crystal structure of the sintered discs was LaBO₃.     

High power density in a piezoelectric energy harvesting ceramic by optimizing the sintering temperature of nanocrystalline powders

Piezoelectric energy harvesting is the research hotspot in the field of new energy, and its core is to prepare piezoelectric ceramics with high transduction coefficient (d₃₃ × g₃₃) and large mechanical quality factor (Q_m) as well. In addition, the miniaturization of the piezoelectric energy harvester also requires the material to have a submicron fine grain structure. In this work, submicron-structured ternary system, MnO₂-doped Pb(Zn_1/3Nb_2/3)O₃-Pb(Zr_0.5Ti_0.5)O₃ was constructed by pressureless sintering of nanocrystalline powders, which has been synthesized for the first time by high-energy ball milling route thereby evading the calcination stage. The microstructure and the energy harvesting characteristics were tailored through changing the sintering temperature. It was found that 1000 °C sintered fine-grained specimen (mean grain size ∼0.95 μm) showed the maximum d₃₃ × g₃₃ value of 9627 × 10⁻¹⁵ m²/N, meanwhile Q_m was as large as 774, which was almost seven times larger than pure counterpart. In the mode of the cantilever-type energy harvester, a high power density of 1.5 μW/mm³ were obtained for 1000 °C sintered specimen at a low resonance frequency of 90 Hz and acceleration of 10 m/s², which were further increased to 29.2 μW/mm³ when the acceleration increased to 50 m/s², showing the potential applications as a next generation high power multilayer energy harvester.     

Effects of tailored nitriding layers on comprehensive properties of duplex plasma-treated AlTiN coatings

Duplex-treated AlTiN coatings were deposited by advanced plasma assisted arc (APA-Arc) technology on pre-plasma nitrided AISI-H13 steel substrates using different N₂/H₂ flow ratios. The microstructures and properties of the AlTiN coatings were comprehensively characterized and analyzed. The results show that the N₂/H₂ flow ratios can tailor the thickness of compound layer during plasma nitriding process and the bright nitriding layer without compound layer is achieved. The properties of duplex-treated AlTiN coatings are well improved compared with monolayer AlTiN coating. The adhesion of the AlTiN coating is well enhanced by duplex treatment process, and adhesion grade increases from HF3-4 for monolayer AlTiN coating to HF1 for composite coatings. Moreover, the composite coatings with various thickness compound layers show different load-bearing capacities, and the interfacial adhesion force of the composite coating without compound layer reaches 61 N. The hardness of AlTiN coating is also enhanced by duplex treatment with the highest hardness of 2935 HV_0.05. Meanwhile, tribological properties of AlTiN coatings are also slightly improved by duplex treatments.     

Growth and electron field emission properties of ultrananocrystalline diamond on silicon nanostructures

The electron field emission (EFE) properties of Si nanostructures (SiNS), such as Si nanorods (SiNR) and Si nanowire (SiNW) bundles were investigated. Additionally, ultrananocrystalline diamond (UNCD) growth on SiNS was carried out to improve the EFE properties of SiNS via forming a combined UNCD/SiNS structure. The EFE properties of SiNS were improved after the deposition of UNCD at specific growth conditions. The EFE performance of SiNR (turn-on field, E₀ = 5.3 V/μm and current density, J_e = 0.53 mA/cm² at an applied field of 15 V/μm) was better than SiNW bundles (turn-on field, E₀ = 10.9 V/μm and current density, J_e < 0.01 mA/cm² at an applied field of 15 V/μm). The improved EFE properties with turn-on field, E₀ = 4.7 V/μm, current density, J_e = 1.1 mA/cm² at an applied field of 15 V/μm was achieved for UNCD coated (UNCD grown for 60 min at 1200 W) SiNR. The EFE property of SiNW bundles was improved to a turn-on field, E₀ = 8.0 V/μm, and current density, J_e = 0.12 mA/cm² at an applied field of 15 V/μm (UNCD grown for 30 min at 1200 W).     

CO2 laser peeling of Al2O3 ceramic and an application for the polishing of laser cut surfaces

A laser controlled fracture peeling technique is demonstrated to smooth the Al₂O₃ ceramic surface without thermal damages. It was found that a chip can be separated and curled from the ceramic surface during a focused CO₂ continuous wave (CW) laser dual-scanning. The thickness of the curled chip is ～50 μm and the formed subsurface roughness (R_a ≈ 2 μm) is close to the surface machined by mechanical breaking (R_a = 1.84 μm). The chip formation is attributed to the controlled fracture by the residual tensile stress in the recast layer, whereas the chip curling only occurs when the melting depth is shallower than the position of lateral cracks. The peeling technique can be applied to polish the cut surface of laser fusion cutting in ceramics. The polished cut surface (R_a = 2.18 μm) is free from recast, crack and heat effects. The microstructure is similar to the base material. The material removal rate during polishing is up to 0.125 mm³/s.