Institute of Fundamental Technological Research

Carbon nanodots (CNDs) produced in pure water by the ablation of graphite with a nanosecond laser pulse exhibit weak photoluminescence. A small addition of polyethyleneimine (PEI) to the aqueous suspension of CNDs causes a significant increase in emissions. This paper presents experimental and theoretical studies of the emission properties of CND/PEI systems. The obtained CNDs responded to even trace amounts of PEI in solution (~0.014% v/v), resulting in a significant increase in the initial weak blue emission of CNDs and PEI taken separately. Morphology and size measurements showed that particle aggregation occurred in the presence of the polymer. A decrease in the calculated Stokes shift values was observed with increasing PEI content in the solution. This indicates a reduction in the number of non-radiative transitions, which explains the increase in the emission intensity of the CND/PEI systems. These results therefore confirmed that the increase in the emission of CND/PEI systems is caused by particle aggregation. Kinetic studies proved that the process is controlled mainly by diffusion, the initial stage of which has a dominant influence on determining the optical properties of the system.

aggregation-induced emission, carbon nanodots, polyethyleneimine, intrinsic fluorescence, adsorption kinetic study

In this work, tantalum-doped tungsten boride ceramic coatings were deposited from a single sputtering target with the radio frequency (RF) and high-power impulse magnetron sputtering (HiPIMS) methods. Two-inch torus targets were synthesised from pure elements with the spark plasma sintering (SPS) method with a stoichiometric composition of W1-xTaxB2.5 (x = 0, 0.08, 0.16, 0.24). Films were deposited with RF and HiPIMS power suppliers at process temperatures from RT to 600 °C. The substrate heating and the energy of the ionised material impacting the substrate increase the surface diffusivity of adatoms and are crucial in the deposition process. The results of SEM and XRD investigations clearly show that the addition of tantalum also changes the microstructure of the deposited films. The coatings without tantalum possess a finer microstructure than those with 24% of tantalum. The structure of films is homogeneous along the film thickness and composed mainly of columns with a (0001) preferred orientation. Deposited coatings are composed mainly of P6/mmm α-WB2 structures. The analysis of nanoindentation results allowed us to determine that ceramic coatings obtained with the HiPIMS method possess hardness above 41 GPa and a ratio of hardness to reduced Young modulus above 0.1. The thickness of HiPIMS-deposited films is relatively small: only around 60% of the RF magnetron sputtered coatings even when the average power input was two times higher. However, it has been shown that the RF coatings require heating the substrate above 400 °C to obtain a crystalline structure, while the HiPIMS method allows for a reduction of the substrate temperature to 300 °C.

RF magnetron sputtering, HiPIMS magnetron sputtering, Superhard ceramic coatings, Transition metal borides, Deposition temperature

Electrospark coatings alloyed with MoS2 have been studied. The coatings were obtained by the following two strategies: the first consisted of pre-applying molybdenum disulfide to the treated surface and alloying with a molybdenum electrode (Mo + MoS2 coating); the second consisted of applying a paste with a sulfur content of 33.3% to the treated surface and alloying with a molybdenum electrode (Mo + S coating). The structure, phase composition, and tribological properties of the coatings were investigated. The coatings have a complex structure consisting of an upper soft layer, a hardened white layer, a diffusion zone, and a substrate. Element analysis and cross-sectional hardness changes indicated that element diffusion occurred at the coating/substrate interface. The phase composition of the coatings is represented by BCC and FCC solid solutions on Fe, and MoS2 is also detected. In Mo + S coatings, the molybdenum disulfide on the surface is about 8%; in Mo + MoS2 coatings, it is 27%–46%. The obtained coatings show very good tribological properties compared to molybdenum ESA coatings. The frictional forces and coefficients are reduced by a factor of 10 and 40, depending on the test conditions.

electrospark alloying, coating, structure, molybdenum disulfide, tribological properties, energy conservation

Tungsten diboride alloyed with transition metals provides an opportunity to obtain exceptional mechanical, physical, and chemical properties. We report a strategy for designing and synthesizing of superhard and low-compressible ceramic thin films with increased toughness and lowered residual stresses (σ < −0.9 GPa) deposited with high-power impulse magnetron sputtering (HiPIMS) from one target. The addition of 7–12 % titanium promotes additional strengthening mechanisms of the layers in one material, leading to the improvement of wear resistance compared to an alloyed WB2-z yet at even higher hardness 43.8 ± 2.1 GPa and nanoindentation toughness 4.9 ± 0.2 MPa√m. The compression of the micropillar shows that titanium addition changed the type of nanoindentation from cracking along the slip plane to bulging on the top of the pillar and next the crack initiation along column boundaries. The highest adhesion of the layers is obtained for addition of 7 % titanium and in all cases the wear has abrasive character. The controlled use of 200 μs pulses during synthesis with HiPIMS allows for an increase in the deposition rate and maintaining exceptional mechanical properties of the layers even at a substrate temperature of 300 °C.

Ternary transition metal diboride thin films, Mechanical properties, HiPIMS magnetron sputtering, Wear resistance and adhesion

The quality parameters of surface layers synthesised using electrospark alloying (ESA) technology were analysed in this paper. The main focus was on the influence of equipment energy parameters on structure formation, specifically the effect of discharge energy and productivity. Microstructural analysis of the modified surface of C40 steel after nitriding by ESA using a paste containing nitrogen compounds injected into the interelectrode gap was conducted. The layer structure for all studied ESA parameters includes three areas: the upper “white layer”, the diffusion zone below it, and the substrate. The roughness of the surface is Ra ∼ 0.9 μm at low discharge energy Wp = 0.13 J and Ra ∼ 6 μm at Wp = 3.4 J. The microhardness, continuity, and surface roughness of the layers varied with Wp. The influence of ESA productivity on the structure was studied. The thickness of the hardened layer and the diffusion zone, as well as the microhardness and continuity, are affected by reduced productivity. For the same discharge energy, the thickness of the hardened layer increases by 10-18% with a decrease in productivity compared to the classical mode.

electrospark alloying, discharge energy, productivity, coating, structure

We present the deposition and characterization of tungsten-tantalum diboride (W,Ta)B2 coatings prepared by the high-power impulse magnetron sputtering technique. We evaluated the influence of pulse duration and substrate bias on the properties of (W,Ta)B2 films. A high hardness of up to 35 GPa measured by nanoindentation was simultaneously obtained with good elastic properties. Changing the pulse duration greatly affected the B/(W+Ta) atomic ratio, which influenced the properties of the coatings. The deposited films are thermally stable at up to 1000 ◦C in vacuum and are able to withstand oxidation at 500 ◦C.

tungsten diboride, high power impulse magnetron sputtering (HiPIMS), hardness, thermal stability, oxidation resistance

This work presents a growth of Fe3O4 nanoparticle films on silicon substrate. The iron oxide is deposited applying a pulsed laser deposition technique. The process is performed in open air in the absence and presence of external magnetic field. In fact, the morphologies of the obtained Fe3O4–Si samples are similar. The Fe3O4 nanoparticles are spherical with average diameters of 30 nm and are densely agglomerated on the Si substrate. The Fe3O4–Si material prepared in the absence of magnetic field has revealed more intense signals during X-ray diffraction and Raman measurements. The magnetic investigations indicate that the Fe3O4 nanoparticles are significantly coupled with the Si substrate and do not exhibit superparamagnetic behavior. Moreover, the Verwey transition is 98 K for both investigated Fe3O4–Si samples.

Fe3O4 nanoparticles,magnetic materials,pulsed laser deposition

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.

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

Potentially superhard W1−xZrxB2 polymorphs, hP6-P63/mmc-WB2 and hP3-P6/mmm-WB2 , were thoroughly analyzed with zirconium doping in the range of x=0-25%, within the framework of the first-principles density functional theory, from both a structural and a mechanical point of view. The obtained results were subsequently compared with the properties of material deposited by the magnetron sputtering method. All predicted structures are mechanically and thermodynamically stable. Theoretical calculations suggest a decrease in hardness Hv and fracture toughness KIC of the hP6 phase with zirconium doping but no such effect on the hP3 phase. It was observed that an additional defect in the analyzed structure significantly weakens the hP6 phase but strengthens the hP3 phase. The deposited films are characterized by greater hardness but lower fracture toughness. The results of experiments show that not only is solid solution hardening responsible for strengthening the predicted new material but also the change in microstructure, the Hall–Petch effect and vacancies.

Ab initio, Transition metal borides, Mechanical properties, Magnetron sputtered coatings, Hardness

Fluorescent carbon dots (CDs) synthesized by pulsed laser ablation in liquid (PLAL) are still interesting materials due to their possible applications. However, unlike CDs produced by the hydrothermal method, CDs produced the synthesis products by the PLAL method were never separated by dialysis, which differentiates the synthesis products and allows the identification of the main source of fluorescence. In this work, the synthesis of fluorescent carbon dots (CDs) was performed by nanosecond laser ablation of a graphite target immersed in polyethyleneimine (PEI) and ethylenediamine (EDA), and the synthesis products were separated by dialysis. The results of optical measurements showed that the main source of luminescence of the obtained nanostructures are fluorescent particles or quasi-molecular fluorophores created in the ablation process. In the case of ablation in PEI, most of the produced molecular fluorophores are associated with carbogenic nanostructures, while in the case of EDA, free fluorescent molecules dominate.

carbon dots, photoluminescence, laser ablation

An improved method for the production of luminescent carbon nanoparticles is proposed in this work. The new method overcomes the disadvantages of commonly used approaches. It involves two-stage laser ablation in water and in aqueous solutions, where the first stage is the laser ablation of a graphite target and the second is the shredding of particles produced in the first step. The two-stage method offers the optimization of the laser pulse fluence for the performance of each process. It was found that the two-stage process of laser ablation allows producing photoluminescent carbon structures in pure water. The additional reagent may be added either in the first or second stage. The first stage performed in pure water allows avoiding the contamination of the target. Moreover, it simplifies the identification of the origin of photoluminescence. Two synthesis routes for the preparation of carbon nanoparticles by the proposed method using pure water as well as urea aqueous solution are investigated. It was found that the use of urea as a reagent results in luminescence properties similar to those obtained with other more hazardous amine-based reagents. The influence of the synthesis approach and process parameters on the structural and luminescent properties of nanoparticles is also explored in this work.

pulsed laser ablation in liquid, carbon nanoparticles, photoluminescent particles

The article presents theoretical and experimental study of shock waves induced by a nanosecond laser pulse. Generation of surface plasma pressure by ablation of the graphite absorption layer in water medium and shock wave formation were analyzed theoretically and experimentally. The amplitude and temporal variation of the shock wave pressure was determined basing on a proposed hydrodynamic model of nanosecond laser ablation and experimentally verified with use of a polyvinylidene fluoride (PVDF) piezoelectric-film sensor. The determined pressure wave was used for examination of adhesive strength of tungsten–zirconium–boride coatings on steel substrate. The magnetron sputtered (MS) W–Zr–B coatings show good adhesion to the steel substrate. The obtained experimental results prove the correctness of the proposed model as well as the suitability of the procedure for assessment of adhesive strength.

laser pulse, shock wave, MS coatings, ternary borides, laser adhesion test

In this work, novel W-Zr-B coatings were developed by a hybrid process combining pulsed laser deposited ZrB2 and radio frequency magnetron sputtered W2B5. The influence of the laser power density on the structure and mechanical properties of the deposited films was studied. Addition of zirconium causes a change in the structure of the deposited films from columnar to mainly amorphous. The nanoindentation tests and compression of nanopillars showed that doped W-Zr-B layers are still super-hard and incompressible in comparison to WB2 films without doping, but they change their behaviour from brittle to ductile. Films obtained with a fluence of 1.06 J/cm2 are superhard (H = 40 ± 4 GPa) and incompressible (12 ± 1 GPa), but possess a relatively low Young’s modulus (E = 330 ± 32 GPa) and a high elastic recovery (We = 0.9). Further increase in the fluence causes films to consist of deeply embedded fragments of laser ablated ZrB2 target in the deposited layer. Taking into account that the particles are made of ZrB2 which possess extraordinary thermal properties, and the matrix is made of W-Zr-B, a super-hard material, such a composite can also be interesting for industrial applications.

superhard tungsten borides, hybrid magnetron sputtering – pulsed laser deposition, nanopillar compression

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.

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.

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

Two new hypothetical zirconium diboride (ZrB 2) polymorphs: (hP6-P6 3 /mmc-space group, no. 194) and (oP6-Pmmn-space group, no. 59), were thoroughly studied under the first-principles density functional theory calculations from the structural, mechanical and thermodynamic properties point of view. The proposed phases are thermodynamically stable (negative formation enthalpy). Studies of mechanical properties indicate that new polymorphs are less hard than the known phase (hP3-P6/mmm-space group, no. 191) and are not brittle. Analysis of phonon band structure and density of states (DOS) also show that the phonon modes have positive frequencies everywhere and the new ZrB 2 phases are not only mechanically but also dynamically stable. The estimated acoustic Debye temperature, ΘD, for the two new proposed ZrB 2 phases is about 760 K. The thermodynamic properties such as internal energy, free energy, entropy and constant-volume specific heat are also presented.

zirconium diboride, ab initio calculations, mechanical properties, elastic properties, phonons

In this work, α-WB2 and (W,Ti)B2 borides were applied as wear-resistant coatings to commercial WC–Co cutting inserts. Properties of coatings deposited by magnetron sputtering on WC–Co tools were studied. The crystal structure and chemical composition were analyzed. Vickers hardness and surface roughness were determined and wear test in semi-dry conditions was performed. The W–B and W–Ti–B coatings deposited on WC–Co substrate were smooth and very hard. However, titanium alloy W-B films with Vickers hardness of 3630 ± 260 HV0.02 were characterized by lower adhesion to the substrate, influencing the wear mechanism. Turning tests carried out on 304 stainless steel showed that the W–B film caused less wear compared to uncoated insert. Moreover, when W–B coating was applied, flank wear was reduced by 30% compared to uncoated WC–Co insert. Additionally, coating prevented chipping of the edge during cutting under test conditions. The research shows that W–B film deposited by magnetron sputtering has great potential as a coating for cutting tools for difficult-to-cut materials.

PVD coatings, wear resistance, transition metal borides, cutting tools

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.

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

The coatings of tungsten borides (WBx) and tungsten borides doped with titanium (WyTi1−yBx) were deposited by using combined magnetron sputtering - pulsed laser deposition technique. In the case of WBx coatings, pure tungsten target was evaporated by a laser pulse at 1064 nm wavelength and pure boron target was sputtered by a magnetron. In the case of WyTi1−yBx coatings, the W2B5 target was sputtered by the magnetron and titanium target was evaporated by the laser pulse at 1064 nm wavelength. The content of titanium dopant changed from 1.1 to 5.5 at.%. The microstructure, chemical and phase composition of deposited coatings were investigated by means of Scanning Electron Microscopy, Energy Dispersive X-Ray Spectroscopy, X-Ray Photoelectron Spectroscopy and X-Ray Diffractometry, respectively. The Vickers hardness and Young's modulus were determined by using the nanoindentation test. Nanocrystalline WB coatings with dominant WB2 phase were obtained at a substrate temperature of 520 °C. The coatings were superhard with a hardness of 47–50 GPa and the mean value of surface roughness was <6 nm. The WBx coatings doped with 5.5 at.% Ti had hardness similar to the coatings sputtered by magnetron from W2B5 target.

The superhard WyBx thin films was deposited with hybrid laser-magnetron technology, The MS-PLD method allows for the deposition of ternary borides such as WyTi1−yBx, The MS-PLD method enables to control the chemical and phase composition of films, The deposited films are smooth with hardness above 50 GPa, Crystalline films were deposited only on a substrate kept an elevated temperature

With increasing demand for high-performance and long-lasting cutting and forming tools, the members of this expanding class of superhard metals hold promise to address the shortcomings of traditional tool materials. Those shortcoming include their high cost (silicon nitride, cubic boron nitride, and diamond), their inability to cut ferrous metals due to chemical reactions (diamond), instability in the presence of humidity (cubic boron nitride) and relatively low hardness (tungsten carbide). Also the increasing industrial demand for protective coatings with high hardness, good elastic properties and thermal stability calls for the investigation of new material systems. Although transition metal (TM) nitrides are successfully applied for different tasks in automotive or aero-space industries, the search for improved materials is an ongoing topic, being far from its end. In this work the study on deposition of thin films made of new super-hard materials (SHM) such as tungsten boride are presented. Additionally, the influence of doping by titanium of those materials is investigated. Investigated films were deposited by the pulsed laser deposition method. The used targets were synthetized by SPS method. The powders of boron and tungsten in 4.5 to 1 molar faction were used. The films deposited by PLD method have stoichiometric composition such as used targets. The WB2 and WB3 phase are dominant. Research carried out using SEM, XRD and nanoindentation test showed that the phase composition of the targets is more important in the case of laser deposition than magnetron. All obtained layers are very hard and thermally stable. In the case of magnetron sputtering, smooth layers were obtained while the layers deposited by the laser have a very high roughness. Titanium doping increases the amount of WB3 phase in the sintered discs, while it has no significant effect on the properties of the deposited layers.
Z rosnącym zapotrzebowaniem na niezawodne, a jednocześnie zapewniające dużą wydajność, narzędzia do skrawania i obróbki plastycznej, coraz większego znaczenia nabiera rozszerzająca się grupa supertwardych ceramik przewodzących prąd. Materiały te dobrze rokują w związku z rozwiązaniem problemów tradycyjnych materiałów narzędziowych, których niedoskonałości obejmują wysoką cenę (azotek krzemu, azotek boru), niezdolność do cięcia stopów żelaza w wyniku reakcji chemicznych (diament), niestabilność w obecności wilgoci (azotek boru) i względnie małą twardość (węglik wolframu). Również rosnący popyt na powłoki ochronne o wysokiej twardości, o dobrych właściwościach sprężystych i stabilności termicznej powoduje, że badania nad nowymi systemami materiałowymi prowadzone są coraz intensywniej. Pomimo że azotki metali przejściowych są już z powodzeniem stosowane do różnych zadań w przemyśle samochodowym i lotniczym, poszukiwanie ulepszonych materiałów jest tematem wciąż aktualnym. W pracy przedstawiono badania nad osadzaniem cienkich powłok z nowych supertwardych materiałów (SHM), którymi są borki wolframu. Dodatkowo zbadano wpływ domieszkowania tych materiałów tytanem. Warstwy osadzane były metodą ablacji laserowej PLD. Tarcze do osadzania zsyntetyzowane zostały metodą spiekania plazmowego SPS proszków boru i wolframu o stosunku atomów 4,5 do 1. Osadzane z użyciem lasera warstwy mają skład stechiometryczny podobny do użytych tarcz. W warstwach tych dominuje faza WB3. Badania przeprowadzone z użyciem SEM, XRD i nanoindentacji wykazały, że skład fazowy tarcz jest odwzorowany w warstwach osadzonych laserem. Wszystkie uzyskane warstwy są bardzo twarde i stabilne termicznie. Warstwy osadzane laserem odznaczają się dużą chropowatością. Domieszkowanie tytanem zwiększa ilość fazy WB3 w spiekanych tarczach i osadzanych warstwach oraz zmniejsza ilość i wielkość naniesionych na powierzchnię cząstek.

laser ablation, tungsten borides doped titanium, plasma sintering / ablacja laserowa, borki wolframu domieszkowane tytanem, spiekanie plazmowe

The laser ablation of graphite in ambient argon is studied both experimentally and theoretically in conditions corresponding to the initial conditions of carbon nanotube synthesis by the laser vaporization method. The results of the experiment show that the maximum plasma temperature of 24 000 K is reached 25 ns after the beginning of the laser pulse and decreases to about 4000–4500 K after 10 μs. The maximum electron density of 8 × 1025 m−3 is reached 15 ns from the beginning of the laser pulse. The hydrodynamic model applied shows comparable plasma temperatures and electron densities. The model also replicates well a shock wave and plume confinement—intrinsic features of supersonic flow of the ablated plume in an ambient gas. The results show that the theoretical model can be used to simulate nanosecond laser ablation in an ambient gas from the beginning of the process up to several microseconds.

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

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

The plasma induced during underwater pulsed laser ablation of graphite is studied both experimentally and theoretically. The results of the experiment show that the maximum plasma temperature of 25000 K is reached 20 ns from the beginning of the laser pulse and decreases to 6500 K after 1000 ns. The observed OH absorption band shows that the plasma plume is surrounded by the thin layer of dissociated water vapour at a temperature around 5500 K. The hydrodynamic model applied shows similar maximum plasma temperature at delay times between 14 ns and 30 ns. The calculations show also that already at 14th ns, the plasma electron density reaches 0.97·1027 m−3, which is the critical density for 1064 nm radiation. At the same time the plasma pressure is 2 GPa, which is consisted with earlier measurements of the peak pressure exerted on a target in similar conditions.

underwater laser processing, pulsed laser ablation in liquid, laser induced plasma, numerical modelling

The numerical model of laser welding is presented. The time dependent set of equations describing heating, melting and solidification is solved using ANSYS-Fluent package and adopted to the problem using the external user-defined functions. The developed model is used for investigation of laser welding of Ir pad with spark plug electrode made of Ni. These spark plugs are key parts of industrial internal combustion engines using biogas as fuel. Problems in welding arise from significant difference of melting points of both metals; moreover, the boiling point of Ni is close to melting point of Ir. Theoretical model of the welding process is a useful and cost lowering tool providing guidance for selection of parameters and reducing significantly number of expensive and time consuming experiments

Nd:YAG laser, iridium, Ir, nickel, Ni, spark plug, laser welding, numerical model, dissimilar metals welding, temperature dependent material properties

The most promising areas of research of new super-hard materials are transition metal borides. These materials are one of the candidates for future superhard layers that will be competitive to DLC and c-BN layers. In this paper MoB-type tungsten boride (WB) layers were examined. WB layers have been deposited by radio frequency magnetron sputtering on Silicon (100), 304 stainless steel (SS 304) and Inconel 601 substrates. Measured thickness of herein prepared layers was about 1 µm, and all studied samples were dense, uniform and smooth. Surface investigation was performed by using an optical profilometer, atomic force microscopy, and scanning electron microscopy. The structure analysis was examined by using X-ray diffractometer (XRD) and transmission electron microscopy (TEM) techniques. Results from the XRD and TEM analysis showed that WB layers were dominated by (101) reflection and indicated a fine grain structure with a grain size of 20–40 nm. The effect of target sputtering power and ambient gas pressure was investigated. The hardness of WB layers deposited on silicon substrate was compared under the load from 1 mN to 5 mN. The hardness of WB layers deposited on SS 304 and Inconel was measured up to 50 mN. All layers of WB revealed excellent hardness exceeding 40 GPa.

Borides, Nanohardness, RF magnetron sputtering, Superhard layers, Tungsten boride

Three mechanically and dynamically stable polymorphs of rhenium diboride (ReB2) (space group: P63/mmc, No: 194), (space group: R-3m, No: 166) and (space group: Pmmn, No: 59) were thoroughly analysed within the framework of Density Functional Theory from the structural, mechanical, optical, thermodynamical and phonon properties point of view. The calculated hardness of rhombohedral structure suggests that it can be even harder than well known hexagonal ReB2.

Rhenium diboride, Phase stability, Density Functional Theory (DFT), Physical properties, Phonons

Five potentially superhard WBx polymorphs: hP10-P63/mmc-WB4, hP16-P63/mmc-WB3, View the MathML sourcehR24-R3¯ m-WB3, hP6-P63/mmc-WB2 and oP6-Pmmn-WB2 were thoroughly analyzed within the framework of First Principles Density Functional Theory from the structural, mechanical and optical properties point of view. None of the analyzed polymorphs have a hardness greater than 40 GPa, for the hardest one hP6-P63/mmc-WB2, Hv = 39 GPa. The most stable WBx polymorph is oP6-Pmmn-WB2 with the lowest cohesive energy Ecoh = −8.299 eV/Atom. Due to our knowledge, the optical properties of WB2 and cohesive energy of tungsten borides were presented for the first time. The best optical properties for Pulsed Laser Ablation possess hP6-P63/mmc-WB2 with the lowest reflectivity 0.343 for 355 nm laser radiation.

Ab initio calculations, Mechanical properties, Hardness, Optical properties

The first attempt to the deposition of WB3 films using nanosecond Nd:YAG laser demonstrated that deposited coatings are superhard. However, they have very high roughness. The deposited films consisted mainly of droplets. Therefore, in the present work, the explanation of this phenomenon is conducted. The interaction of Nd:YAG nanosecond laser pulse with tungsten, boron, and WB2/B target during ablation is investigated. The studies show the fundamental differences in ablation of those materials. The ablation of tungsten is thermal and occurs due to only evaporation. In the same conditions, during ablation of boron, the phase explosion and/or fragmentation due to recoil pressure is observed. The deposited films have a significant contribution of big debris with irregular shape. In the case of WB2/B composite, ablation is significantly different. The ablation seems to be the detonation in the liquid phase. The deposition mechanism is related mainly to the mechanical transport of the target material in the form of droplets, while the gaseous phase plays marginal role. The main origin of differences is optical properties of studied materials. A method estimating phase explosion occurrence based on material data such as critical temperature, thermal diffusivity, and optical properties is shown. Moreover, the effect of laser wavelength on the ablation process and the quality of the deposited films is discussed.

ablation mechanism, boron, critical temperature, plasma velocity, pulsed laser deposition, tungsten

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.

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

Rhenium diboride (ReB2) thin films have been deposited by a nanosecond pulsed laser deposition method on Si (100) substrate heated to 570°C. The coatings were formed in the ablation process of SPS sintered ReB2 target. The effect of laser wavelength, energy density and postannealing on the films' properties was studied. Investigated wavelengths were 355 and 1064 nm of Nd:YAG nanosecond laser. Laser beam energy density varied from 2.1 to 6.1 J cm− 2 and from 4.1 to 9.4 J cm− 2 at 355 and 1064 nm, respectively. Layer thickness was of the order of several hundred nanometres. Deposition efficiency increases with an energy density in quasi linear way and strongly grows for shorter wavelength. The layers consist of two characteristic microstructures: a smooth basis and stick debris (typical diameters of several hundred nanometres). Lower energy density of laser beam and longer wavelength favour dominance of smooth basis and minimization of debris. The XRD analysis of all samples indicate the crystalline ReB2 with preferred (002) orientation and fine grain size of about 20 nm. Shorter wavelength and higher energy density foster stronger (002) orientation. Moreover, an annealing right after the deposition (25 min in 350°C) causes minimization of degree of orientation and decrease of hardness. The Vickers hardness of ReB2 films is at about 60 GPa and is reduced to about 40 GPa after the annealing process. Deposition efficiency and physical and chemical structures of layers produced under variety of conditions were studied and compared.

Ceramics ablation, Pulsed laser deposition, Rhenium diboride, ReB2 optical properties, Super-hard films, Wavelength influence

In this paper, the effect of absorption of the laser beam and subsequent radiation on the dynamics of a tungsten plasma plume during pulsed laser ablation is analyzed. Different laser wavelengths are taken into consideration. The absorption and emission coefficients of tungsten plasma in a pressure range of 0.1–100 MPa and temperature up to 70 000 K are presented. The shielding effects due to the absorption and radiation of plasma may have an impact on the course of ablation. The numerical model that describes the tungsten target heating and the formation of the plasma and its expansion were made for 355 nm and 1064 nm wavelengths of a Nd:YAG laser. The laser beam with a Gaussian profile was focused to a spot size of 0.055 mm2 with a power density of 1 × 109 W/cm2 (10 ns full width half maximum pulse duration). The plasma expands into air at ambient pressure of 1 mPa. The use of the shorter wavelength causes faster heating of the target, thus the higher ablation rate. The consequences of a higher ablation rate are slower expansion and smaller dimensions of the plasma plume. The higher plasma temperature in the case of 1064 nm is due to the lower density and lower plasma radiation. In the initial phase of propagation of the plasma plume, when both the temperature and pressure are very high, the dominant radiation is emission due to photo-recombination. However, for a 1064 nm laser wavelength after 100 ns of plasma expansion, the radiation of the spectral lines is up to 46.5% of the total plasma radiation and should not be neglected.

Plasma temperature, Tungsten, Laser ablation, Laser beams, Plasma pressure

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).

Spark plasma sintering, Composite material, Aluminum, Alumina

The ablation of graphite is studied as a function of laser fluence for 355, 532 and 1,064 nm wavelength generated by a nanosecond Nd:YAG laser. It has been found that in the case of lower wavelengths, the transition from the thermal ablation to the phase explosion takes place at lower laser fluences. The change of crater shape due to the effect of deep drilling in the proximity of the phase explosion threshold was observed. The calculations of plasma radiation flux to the target surface were made, and the considerable increase of absorbed energy density was found in the case of 355 nm wavelength.

laser ablation, ablation rate, carbon

Laser ablation of boron and tungsten is studied theoretically. The effect of disparate masses of boron and tungsten on parameters of the laser-ablated plasma plume is studied. A theoretical model is applied, which describes both the target heating and formation of the plasma and its expansion. Calculations are made for the third harmonic of a nanosecond Nd:YAG laser. The calculated distributions of plasma temperature, velocity and electron density in the early phase of expansion show that the plasma temperature is higher in the case of heavier tungsten, but the velocity is higher in the case of lighter boron, which is in agreement with experimental findings. In addition, the absorption coefficient of 355 nm radiation, the emission coefficient, the mass density and heat capacity of boron and tungsten plasma are compared.

laser ablation, tungsten plasma properties, boron plasma properties, superhard borides

The effect of laser wavelength on parameters of laser-ablated carbon plume is studied. A theoretical model is applied, which describes the target heating and formation of the plasma and its expansion, and calculations are made for the fundamental and third harmonic of a Nd:YAG laser. The calculated distributions of plasma temperature and electron density in the early phase of expansion show that plasma temperatures are higher in the case of 1064 nm but the electron densities are higher in the case of 355 nm, which is in agreement with experimental findings. It has been shown that while a higher plasma temperature in the case of 1064 nm is the result of stronger plasma absorption, the greater ablation rate in the case of 355 nm results in larger mass density of the ablated plume and hence, in higher electron densities. An additional consequence of a higher ablation rate is slower expansion and smaller dimensions of the plume.

Plasma temperature, Laser ablation, Laser beams, Absorption coefficient, Carbon

In this paper the simultaneous laser melting and burnishing of a stainless steel is studied both experimentally and theoretically. A continuous CO2 laser beam is moving either along a straight line or criss-crossing it. It has been shown that the oscillatory movement of the laser source together with the burnishing results in a better surface topography comparing to the non-oscillatory process. A theoretical modelling is applied to calculate the temperature field during the process. Theresults oftheoretical analysis are verifiedbyanalyzing microstructure changes of the material in laser heated zone. It has been found that a very good agreement between theoretical and experimental results is achieved when the change of the absorptivity of the laser beam with the temperature of the melted zone is taken into account.

laser treatment, hybridtreatment, surface structure, mathematical modelling

The plasma plume induced during laser ablation of graphite is studied both experimentally and theoretically. The hydrodynamic model applied shows that the high velocities of the plume observed in the experiment result from the large pressure gradient built up during laser–plume interaction. This means that at a low laser intensity of ∼109 W cm−2 the acceleration mechanism is rather gasdynamical than electrostatic. The calculated temporal profiles of plasma temperature and electron density in the early phase of expansion are in reasonable agreement with experimental profiles obtained from emission spectroscopy. The effect of evolution of the plasma temperature on time-of-flight signals is presented. It has been shown that the appearance of ions with higher charge prior to ions with lower charge often ascribed to the effect of the induced electric field can be explained by the evolution of the plume temperature.

carbon, laser ablation, plasma plume acceleration, hydrodynamic model

Laser ablation of graphite is studied both theoretically and experimentally. Plasma temperature and electron density in the early phase of expansion into vacuum are measured as a function of distance from the target. The experimental results agree well with the theoretical simulations. The simulation of ablation shows that plasma plume considerably affects the ablation rate

laser ablation, plasma plume

The effect of laser wavelength on heating of the ablated carbon plume is studied. The plasma absorption coefficients are calculated in order to analyze the results and an experiment is conducted using the first, second, and third harmonic of a Nd:YAG laser. Plasma temperature and electron density in the early phase of expansion in vacuum are studied as a function of distance from the target. The calculations show that the ratio between absorption coefficients for 1064, 532, and 355 nm is approximately 9:2:1. The experimental results do not agree well with the theoretical predictions. Indeed, the plasma temperatures are highest in the case of 1064 nm but no clear differences between 532 nm and 355 nm have been found.

plasma plume absorption, PLD, carbon, laser wavelength dependence

The interaction of laser beam with a target and next with the evaporated material is studied theoretically. In the case of a nanosecond laser pulse with 1064 nm wavelength, the ablation is thermal and therefore the interaction of the laser beam with a target is studied with the use of thermal model. The model which describes both the target heating, formation of the plasma and its expansion consists of equations of conservation of mass, momentum and energy and is solved with the use of Fluent software package. The calculations show a sharp increase of the plume temperature and pressure after plasma formation and following it, a considerable increase of the velocity of plasma plume. Maximum plasma pressure of 2 × 108 Pa, temperature of 61 500 K and front velocity of 3.8 × 104 m · s−1 have been found. The results show that the Mie absorption cannot be neglected in the phase of plasma formation. The shape of the plume and plasma front velocity obtained from the model are close to that observed in the experiment carried out in similar conditions.

laser ablation, plasma formation, plasma expansion

The characteristics of hydroxyapatite (Ca10(PO4)6(OH)2) thin films deposited by the pulsed laser deposition technique have been describrd. The laser used was a Nd:YAG, operating at the wavelength of 355 nm. All films were deposited at room temperature, either in ambient water vapour or in vacuum, and were annealed, after deposition in air, at 600 °C. Next, they were examined with the use of an X-ray diffractometer, Fourier transform infrared spectrometer, atomic force microscope, micro scratch tester and scanning electron microscope. The analyses showed that crystalline films exhibiting very strong
adhesion to the substrate have been obtained.

pulsed laser deposition, hydroxyapatite, biomaterials

Net emission coefficients of low temperature thermal iron-helium plasma mixture at atmospheric pressure are presented. The calculations are made assuming the plasma is in the local thermodynamic equilibrium at a pressure of 0.1 MPa. The results are presented for several values of helium mass fraction in the mixture (between 0 and 1), for a temperature range 3000–25000 K and three characteristic plasma dimensions; 0 – corresponding to the optically thin case, and 1 mm and 10 mm. The values of net emission coefficients allow the estimations of total radiation losses in iron-helium plasmas.

net emission coefficients, iron-helium plasma

A theoretical modelling of the plasma plume induced during welding of iron sheets with CO2 laser is presented. The set of equations consists of the equations of conservation of mass, energy, momentum and the diffusion equation and is solved with the use of the commercially available program Fluent 6.1. The computations are made for a laser power of 1700 W and for two shielding gases—argon and helium. The results show a significant difference between these two cases. When helium is used as the shielding gas, the plasma is much smaller and burns only where the metal vapour is slightly diluted by helium. In the case when argon is the shielding gas, there are actually two plasmas: argon plasma and metal plasma. The flowfield shows that the velocity increases in the hot region but only part of the mass flux enters the plasma core. In the case when argon is used as the shielding gas, the total absorption of the laser radiation amounts to 18–33% of the laser power depending on argon and iron vapour velocities. In the case of helium the total absorption is much lower and amounts to ~5% of the laser power.

laser welding, CFD, numerical model

Theoretical modelling of the plasma plume induced during welding of iron sheets with CO2 laser are presented. The set of equations consists of equation of conservation of mass,energy, momentum and the diffusion equation and is solved with the use of commercially available program Fluent 6.1. The computations are made for the laser power of 1700 W and shielding gas argon. Two solutions are taken into account stationary and non–stationary. The results show significant difference between these two cases.

laser welding, simulations, plasma

Iron plasma appears during material processing with laser, electric arc etc., and has considerable influence on the processing conditions. In this paper emission coefficients of low temperature thermal iron plasma at atmospheric pressure are presented. Net emission coefficients εN have been calculated for pure iron plasma as well as for Fe–Ar and Fe–He plasma mixtures. To calculate the recombination radiation the knowledge of the Biberman factors ξz fb(Te, λ) is necessary and they have been calculated from the iron photo–ionization cross sections. The calculations allow estimation of energy losses, energy radiated by plasma plume and its comparison with the energy absorbed from laser beam.

absorption coefficient, plasma emission, Biberman factor

The dynamics of the plasma plume produced during laserwelding is quite complex. The keyhole wall oscillates and this results in oscillations of the plasma plume over the keyhole mouth. The metal vapour, which appears in irregular bursts, interacts with the shielding gas flowing from the opposite direction. In the present work, temporary electron densities and temperatures are determined in the peaks of plasma bursts during welding with a continuous wave CO2 laser. It has been found that during strong bursts the plasma plume over the keyhole consists of metal vapour only, without being diluted by the shielding gas. The results, together with the analysis of the colour pictures from sreak camera, allow interpretation of the dynamics of the plasma plume. No apparent mixing of metal vapour and the shielding gas has been observed. In typical bursts the electron density determined from the Stark broadening of Ar I lines varies from 0.9x1023 m-3 near the metal surface to 0.5x1023 m-3 at a distance of 1.5 mm from the surface. Assuming that argon is not mixed with the metal vapour and is in local thermal equilibrium these electron densities correspond to temperatures 12.7 kK and 11.5 kK, respectively. In strong bursts the electron density varies, along the same distance, from 1.6x1023 m-3 to 0.6x1023 m-3, which corresponds to the temperatures of 14.2 kK, respectively.

laser welding, plasma diagnostics

W pracy został przedstawiony model teoretyczny oddziaływania wiązki laserowej z materiałami różnoimiennymi w procesie spawania. W celu wyznaczenia rozkładu pola temperatur, wymiarów spoiny oraz strefy mieszania się materiałów zbudowano trójwymiarowy, niestacjonarny model numeryczny uwzględniający proces wymiany ciepła i masy. Model został wykorzystany do zbadania przebiegu i optymalizacji parametrów procesu spawania niklowo - platynowych nakładek na świece zapłonowe dla silników na biopaliwo. Zbadano pływ czasu trwania impulsu, średnicy plamki oraz kąta nachylenia wiązki na rozkład pola temperatury. Kształt strefy przetopionej otrzymany z modelu teoretycznego jest w dobrej zgodności z wynikami eksperymentalnymi

To determine the distribution of the temperature field and shape of the melting zone during the laser welding process of 304 stainless steel a three-dimensional numerical model was bilt and numerical simulation was performed. In order to improve the accuracy of the calculations temperature dependent material properties, heat loosdue to vaporization and heat exchange with surrounding medium due to the convection and radiation was considered.

Theoretical Model, Laser Welding, CFD

In recent years, the search for improved materials for green energy, aerospace and automotive has been the focus of interest of scientists and industry. As an example transition metal borides such us ZrB2, TiB2, WB2 can be mentioned with their extraordinary thermal, mechanical properties and oxidation resistance even above 500˚C. Also in the form of thin films they are competitive with commercially used nitrides. The last studies have been show that disadvantages like low fracture toughness can be improved by alloying them with other transition metals TM= Ti, Cr, Zr, Mo, Ta, Hf etc. or the choosing of suitable deposition method. In this work the doping of tungsten diboride with titanium is presented. Also, two different method of deposition like High-Power Impulse Magnetron Sputtering (HiPIMS) and hybrid PLD-MS, which give possibility to produce a plasma with the higher energy than conventional DC magnetron sputtering are studied. Such solution allows to obtain coatings which are very hard and fracture resistant simultaneously. Deposited by HIPIMS coatings are smooth and possess lower hardness (40 GPa) than films deposited with PLD-MS method (51±8 GPa). However produced by hybrid method films are rougher and are characterized by higher Young modulus (520 GPa vs. 354 GPa) what cause that they are characterized by lower fracture resistance. Additionally, HIPIMS crystalline films can be obtained in 300˚C (520˚C for PLD-MS) what increase possibility of their future application. I should be noted that tungsten borides have very high potential for its implementation as a wear protecting coatings on tools and also in nuclear energy solutions

magnetron sputtering, transition metal borides, protective coatings

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

carbon nanoparticles, C-dots, laser ablation in liquid, photoluminescence

magnetron sputtering, pulsed laser deposition, superhard materials, tungsten borides

RF magnetron sputtering, hard materials, PLD, tungsten boride

laser ablation, plasma plume

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.

pulsed laser deposition, tungsten borides

In this paper the interaction of Nd - YAG nanosecond laser pulse with tungsten or boron target and lasma induced during ablation are studied theoretically. Tungsten and boron were chosen because of the significant differences in their chemical and physical properties. Both materials are of a great practical importance. The model consists of equations of conservation of mass, momentum and energy and is solved with the use of commercially available program Ansys - Fluent. The calculations show the fundamental differences in ablation of both specie s. In case of tungsten the material evaporation is controlled by the plasma formation and consequently the absorption coefficient. The dense plasma plume can block laser radiation and limit energy transfer from the laser beam to the material. In case of bo ron the explosive ablation is observed. The calculations also show the sharp increase of the plume pressure after plasma formation and resulting significant increase of the velocity of plasma plume. The lume velocity obtained from the model is close to th at observed in the experiment carried out in similar conditions. Moreover, the effect of laser wavelength on the quality of the deposited boron and tungsten films has been discussed on the base of ablation model.

ablation mechanism, boron, critical temperature, plasma velocity, pulsed laser deposition, tungsten

pulsed laser deposition

Pulsed laser deposition is a method frequently used for creating thin films of various materials on
solid substrates. High energy laser pulse causes evaporation of the target material, forming a
plume which subsequently
expands and moves with high speed from the target. Thin film of the
evaporated material is deposited on the substrate placed at some distance in front of the target.
The behavior of the plume influences both the stoichiometry and homogeneity of the deposit
ed
layer
–
the final product of the process. Better understanding of the process of expansion of the
plume, variation of its structure as well as deposition of the material itself is therefore very
important and should give us opportunity for better contro
l of formation of the deposited layer.

laser ablation, plume expansion, DSMC

pulsed laser deposition, RF magnsteron sputtering, tungsten borides

pulsed laser deposition, rhenium borides

pulsed laser deposition, rhenium borides, tungsten borides

In answer to research interest in production of super hard coatings prepared by pulsed laser deposition (PLD) method, Rhenium Diboride was taken under consideration. PLD is characteristic by necessity to define deposition parameters best for particular substance. ReB2 coatings were prepared with the use of 355 nm and 1064 nm wavelengths of Nd:YAG laser and the influence of laser wavelength on those films preparation was investigated. Deposition efficiency increased with shorter wavelength, however layer’s smoothness was better for longer wavelength. The XRD analysis shows crystalline ReB2 character of achieved samples.

pulsed laser deposition, rhenium diboride

The interaction of laser beam with dissimilar metals during welding process was studied theoretically. A finite element based three-dimensional transient heat transfer and fluid flow model was applied for prediction temperature distribution and material mixing field as well as weld dimensions. The model was used for study and optimization process parameters of welding of Ni – Pt spark plug for bio-fuel engine. The laser pulse duration and energy, and the angle of incidence of the laser beam to thesurface were analyzed. The shape of the melting pool obtained from the theoretical model was close to experimental results.

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.

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