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Abstract:
Magnetron sputtered WB2 coatings doped with 8, 11 and 16 at.% zirconium were analysed using energy dispersive spectroscopy, X-ray diffraction and nanoindentation under the load of 4, 7 and 10 mN. It has been observed that these coatings crystallize in the α-AlB2 and ω-W2B5 prototype structure. Phenomenon responsible for this is an increase of the zirconium content which causes an increase in the ω-W2B5 phase. All the deposited coatings have a hardness of about 45 GPa while Young's modulus drops down from 497 to 480 GPa with increasing zirconium content. Coatings without doping and doped with 16 at.% zirconium were annealed at 650 °C and subjected to cyclic thermal loads using a maximum temperature 600 °C and cooling with a compressed air. It has been observed that addition of zirconium improved coatings phase stability.

Keywords:
superhard coatings, tungsten diboride, zirconia doping, magnetron sputtering, cycling thermal loads, annealing

Abstract:
Tungsten borides (WBx; x = 2.5 or 4.5) with an increasing substitution of tungsten by zirconium from 0 to 24 at.% were synthesized by spark plasma sintering (SPS) for the first time. The influence of the holding time (2.5–30 min) on the densification behavior, microstructure evolution and development of the properties of W–Zr–B compounds were studied. The samples were characterized using scanning electron microscopy (SEM) for microstructure analysis, X-ray diffraction (XRD) for phase identification, Vickers micro-indentation for microhardness measurements, tribological tests to determine the coefficient of friction and specific wear rate, as well as measurements of electrical conductivity. The XRD results confirm the presence of the WB4 phase in the microstructure, despite the high sintering temperature (1800 °C) and small overstoichiometric excess of boron (4.5) addition in the sintered samples. This is caused by the high heating rate (400 °C/min), short holding time (2.5 min) and addition of zirconium. The Vickers hardness (HV) values measured at 1 N are 24.8 ± 2.0 and 26.6 ± 1.8 GPa for 24 at.% zirconium in WB2.5 and for 0 at.% zirconium in WB4.5, respectively. In addition, the hardest sample (W0.76Zr0.24B2.5) showed electrical conductivity up to 3.961·10^6 S/m, which is similar to WC–Co cemented carbides. The friction and wear test results reveal the formation of a boron-based film which seems to play the role of a solid lubricant.

Abstract:
To enhance the properties of tungsten diboride, we have synthesized and characterized solid solutions of this material with chromium, molybdenum, rhenium and zirconium. The obtained materials were subsequently deposited as coatings. Various concentrations of these transition metal elements, ranging from 0.0 to 24.0 at.%, on a metals basis, were made. Spark plasma sintering was used to synthesize these refractory compounds from the pure elements. Elemental and phase purity of both samples (sintered compacts and coatings) were examined using energy dispersive X-ray spectroscopy and X-ray diffraction. Microindentation was utilized to measure the Vickers hardness. X-ray diffraction results indicate that the solubility limit is below 8 at.% for Mo, Re and Zr and below 16 at.% for Cr. Above this limit both diborides (W,TM)B2 are created. Addition of transition metals caused decrease of density and increase of hardness and electrical conductivity of sintered compacts. Deposited coatings W1−xTMxBy (TM = Cr, Mo, Re, Zr; x = 0.2; y = 1.7–2) are homogenous, smooth and hard. The maximal hardness was measured for W-Cr-B films and under the load of 10 g was 50.4 ± 4.7 GPa. Deposited films possess relatively high fracture toughness and for WB2 coatings alloyed with zirconium it is K1c = 2.11 MPa m^1/2.

Keywords:
ternary tungsten boride, spark plasma sintering, magnetron sputtering, electrical conductivity

Abstract:
In this work, (W,Ti)B2 films with different stoichiometric ratio Ti/W deposited on silicon and 304 stainless steel by radio frequency magnetron sputtering are presented. The coatings were deposited from plasma spark sintered targets obtained from the mixture of pure boron, tungsten and titanium powders. It is shown that during plasma spark sintering process using overstoichiometric boron and a low content of titanium change the WB2 to WB4 phase with almost no secondary phases. Subsequently, the impact of titanium content on the films properties is investigated systematically, including the chemical and phase composition, crystalline structure, surface and cross-section morphology. Simultaneously, nano-indentation test and ball-on-disk tribometery are performed to analyse the hardness and tribological properties of the films. It is shown that deposited films with titanium content of 3.6 and 5.5 at.% are formed in the zone T of the Thornton's Structural Zone Model. In opposite to α-WB2 magnetron sputtered coatings they are more flexible and hard nanocomposite coatings. The results show that the addition of titanium is apparently changing the film structure from nanocrystalline columnar to amorphous, very dense and compact structure with the addition of TiB2 phase. That films are simultaneously hard (H > 37.5 GPa), have high hardness to effective Young's modulus ratio values (H/E* > 0.1) and elastic recovery (We > 60%) appropriate for tough and resistant to cracking materials. The presented (W,Ti)B2 films exhibit also tribological and corrosion properties better than unalloyed coatings.

Keywords:
superhard films, ternary tungsten borides, RF magnetron sputtering, wear resistance, corrosion

Abstract:
Tungsten borides belong to the group of potentially superhard materials which hardness could be compared to cubic boron nitride and diamond. However, difficulty in fabrication of single phase material using conventional methods is the main drawback of this group of ceramics. In order to overcome this problem material can be deposited as a thin layer e.g. in the pulsed laser deposition process. In this paper, the effect of laser wavelength and energy density of nanosecond Nd:YAG laser on the WBx-type layers were analyzed using wavelengths 355 and 1064 nm with the energy density of laser beam from 1.7 to 5 J/cm2 and from 1.7 to 9.3 J/cm2, respectively. The WB2.5 and WB4.5 targets synthesized in Spark Plasma Sintering process were used and the layers were deposited onto Si (100) substrate heated to a temperature of 570 °C. Layers' microstructure were analyzed using X-ray Diffraction and scanning electron microscope equipped with energy dispersive X-ray spectrometer. Change of laser wavelength and energy density resulted in variations of the chemical composition and morphology of deposited layers. Finally, W2B-βWB, αWB-WB-WB3 and WB3, and boron layers were deposited wherein WB3 structure is formed in a wide range of laser fluences and at both investigated wavelength. Next, WB3 layers were investigated in the indentation test at a load of 5–30 mN and its hardness was up to 50 ± 10 GPa

Keywords:
Pulsed laser deposition, Super-hard materials, Tungsten borides, Tungsten triboride

Abstract:
Reactive spark plasma sintering (SPS) of WB2/WB3 ceramics from elements is studied; the sintering pressure dependence of the ratio of WB3 to WB2 in samples produced by SPS is discussed. Regardless of the sintering pressure, the obtained samples are very hard ~20 GPa. WB3 superhard films prepared by pulsed laser deposition (PLD) from selected SPS targets are presented.

WB3 coatings were prepared on Si (100) substrates using a nanosecond, Nd:YAG laser operating at a 355 nm wavelength. The phase analysis, crystallography, and orientations have been studied using X-ray diffraction (XRD). A WB2 to WB3 phase transformation from 8.2% WB3 in a sintered target to 93.3% WB3 in a deposited film was observed. Additionally, the surface of a SPS sintered WBx target after the ablation process was examined. XRD studies show that already during the laser ablation there is a significant WB2 to WB3 phase transformation. Vickers hardness of sintered samples was measured in macro- and micro-scale, and PLD films in the nanoscale.

Keywords:
Films, Tungsten borides, SPS – sintering, Pulsed laser ablation/deposition

Abstract:
This work presents fabrication and characterization of Al–Al2O3 composite materials with a 5%, 10%, 15% and 20% volume fraction of reinforcing phase particles. The spark plasma sintering method was applied for the purpose of fabricating these materials. The obtained Al–Al2O3 composites were characterized with an porosity from 1.27% to 5.07%. It was proven that as the content of hard ceramic particles increases in the composite, its density, hardness, and compression as well as tensile strength increase. The conducted study showed that a composite with 20% alumina content is characterized by a larger hardness (1355 MPa) and compression strength (247 MPa).

Keywords:
Spark plasma sintering, Composite material, Aluminum, Alumina

Keywords:
tungsten boride, superhard materials, spark plasma sintering SPS, magnetron sputtering

Keywords:
RF magnetron sputtering, hard materials, PLD, tungsten boride

Abstract:
Tungsten boride compounds are very promising new hard and super - hard materials. This kind of materials could be used in production of high-speed tools, durable bearings and nonabrasive surfaces. The hardness of tungsten borides strongly depends on boron content as well as material microstructure. For example hardness of W2B is about 12.4 GPa, WB hardness is 18 – 36 GPa, WB2 hardness is 28.5–39.7 GPa and WB3 hardness is 28.6 – 36.9 GPa. Moreover production of tungsten borides in the form of layers or nano -grained structured increase its hardness even above 40 GPa. Although the properties of tungsten boride structures are known from theoretical calculations, the data concerning structures produced experimentally are scare. Therefore, the properties of tungsten boride layers deposited by pulsed laser deposition (PLD) process are investigated in this paper. Layers were deposited using two types of targets: with boron to tungsten ratio of 2.5:1 and 4.5:1 and with the use of two laser wavelengths: 355 and 1064 nm.

Keywords:
pulsed laser deposition, tungsten borides

Keywords:
pulsed laser deposition, rhenium borides, tungsten borides

Keywords:
pulsed laser deposition

Abstract:
Inexpensive Tungsten Tetraboride super hard coatings prepared by pulsed laser deposition (PLD) method are investigated. WB4 coatings were prepared on Si (100), by PLD technique using nanosecond, Nd:YAG laser operating at 355 nm wavelenght. Additionally the surface of SPS sintered WBx target before and after ablation process was examined. Phase change of WB2 to WB4 at the surface of target is observed. The phase analysis, crystallography and orientations have been studied using X-ray diffractometry. The surface layer of target after ablation and deposited films are found to be mostly WB4 phase with hardness HV>28 GPa.

Keywords:
laser mikro/nano engineering, thin films, pulsed laser ablation/deposition, tungsten tetraboride WB4