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Yttrium oxide was sprayed by a plasma torch using a coarse thermal spray powder, which must be in size range of tens of micrometers to ensure good penetration into the plasma stream. Thick coatings on steel substrates were produced with two sprays systems facilitating gas stabilized plasma (GSP) and hybrid water-argon stabilized plasma (WSP–H) techniques. Additionally, an ultra-fine yttrium oxide powder was sprayed from a suspension. Hybrid water-argon stabilized plasma system was used for this purpose. Markedly thinner compact coatings were produced this way. All three sorts of plasma sprayed deposits were studied by the same methods. Dielectric properties were studied in a broad range of frequencies and temperatures. The microstructure aspects as well as crystallite size were analyzed and discussed in relation to electrical properties. All coatings exhibited stable dielectric parameters versus changing frequency and temperature, comparable with literature values for various samples. Concerning sintered bulks, and especially their thermal stability of capacitance, the plasma sprayed coatings were slightly worse. However due to shape and size variability of the plasma spraying are yttria coatings prospective for technical applications.

Titanium dioxide (TiO2) was plasma sprayed using a high feed-rate spray system with hybrid water–argon stabilization torch (WSP-H). TiO2 powder agglomerated from nanometric particles was used as the feedstock. The produced coating had thickness over 4 mm, to be comparable with bulk ceramic bodies. The deposit was removed from the substrate and annealed in air to reoxidize the oxygen deficient as-sprayed titania and to obtain material with a proper dielectric behavior. Besides the microstructure studies, radiofrequency dielectric spectroscopy and microwave dielectric spectroscopy were in the focus of investigation. The approach to annealing of an extremely thick coating is studied: The significance of annealing of a large-area thick coating is discussed, as the role of grain interior and grain boundaries in the charge transport is influenced. Relative permittivity er 94 and the Q*f product 12,800 GHz were reached at frequency 4 GHz, whereas the frequency response under 1 MHz was mapped continuously and the values (i.e., low and stable loss tangent) confirmed that a sprayed and air-annealed TiO2 is able to approach or also overperform dielectric parameters typical for TiO2 sintered bulk.

In this paper, we examined the dielectric properties of CaCu3Ti4O12 (CCTO) ceramics fabricated by various routes and discussed the most important conditions affecting their dielectric behavior. We prepared feedstock powder using a molten salt route and compared it with a commercial powder. Both powders were sintered using SPS. For some samples, annealing was applied after sintering. Other samples were obtained by high-pressure forming and conventional sintering, using both powders. Phase composition, porosity and microhardness were evaluated in comparison with the literature. The results showed that a sintering temperature just below or equal to 1000 °C should be set for the SPS process. However, the best dielectric characteristics were obtained in samples prepared by high-pressure forming and conventional sintering, which showed a relative permittivity of 22,000 and a loss tangent of 0.13 at 1 MHz.

Solution precursor plasma spraying (SPPS) presents a modern route to deposit coatings directly from liquid feedstock. In this study, unique ability of SPPS to intermix different precursors on the atomic scale was employed to deposit pure and Cr-doped Al2O3 (technically, synthetic ruby) from several mixtures of aluminum and chromium nitrates. Highly porous coatings (> 60% porosity) were deposited by high-enthalpy WSP-H torch. Homogeneous distribution of Cr atoms in Al2O3 resulted in coatings color ranging from pink to grayish-green correlated with increasing Cr content and change of lattice parameters as observed by x-ray diffraction. High content of over 80 wt.% of α-alumina phase was reached for all coatings. For the Cr-doped Al2O3 coatings, distinct and fully reversible thermochromic behavior was observed by temperature-resolved colorimetry. Further increase in α-phase content (up to 95 wt.%) and coating densification were achieved by additional surface remelting by plasma torch.

Precipitation reactions of the cast Al–3.4 at%Mg–2.7 at%Zn–0.80 at%Cu–0.10 at%Fe–0.05 at%Si alloy with and without addition of 0.14 at%Sc and 0.06 at%Zr were characterized by electrical resistometry, electron microscopy, X-ray diffraction, thermal analysis, microhardness testing, and positron annihilation. The AlMgZnCuScZr alloy contains a grain boundary T-phase (Mg32(Al,Cu,Zn)49) with a cubic and/or quasicrystalline structure. The AlMgZnCu alloy contains a mixture of MgZn2- and the T-phase. Primary multilayer Al3(Sc,Zr) particles precipitated during casting and subsequent cooling. The particles have a layered Al3(Sc,Zr) + α-Al + Al3(Sc,Zr) structure, i.e. consist of regions enriched with both Sc and Zr. Small atomic Mg,Zn(,Cu)-rich clusters coherent with the matrix were formed during the cooling of both alloys and/or in the course of their storage at ambient temperature. Their dissolution enables precipitation of the transient η′- and/or stable η-phases of the AlZnMgCu system in both investigated alloys. The effective activation energy for the dissolution of the clusters was calculated as ~ 103 kJ/mol. Annealing of the AlMgZnCuScZr alloy above 300 °C leads to a formation of the secondary Al3(Sc,Zr) particles which cause precipitation hardening and guarantee thermal stability of mechanical properties. Addition of Sc and Zr micro alloying elements resulted in a substantial grain refinement. The grain size remains unchanged up to isochronal annealing at 390 °C.

The equiatomic CoCrFeMnNi alloy is currently one of the most studied high-entropy alloys. In our previous work, a new grade of CoCrFeMnNi high-entropy alloy with yttria-based particle dispersion was introduced showing improved mechanical properties, especially high-temperature strength and creep rate. In this study, a detailed analysis of room to high-temperature thermal properties was performed, as it is important for defining the future application of the alloy and opening the discussion on tailoring the thermal response. Thermal properties are not well known for the original CoCrFeMnNi alloy or for CoCrFeMnNi with yttria dispersion. As a result of the analysis, thermal properties of both alloys and the effect of the oxide dispersion are discussed. Most of the thermal properties remain unchanged. However, it was found that the presence of 0.3% yttria influences the oxidation rate of CoCrFeMnNi alloy at the initial and intermediate oxidation times. The onset of the oxidation is described in detail. Yttria nano-oxide dispersion and related grain refinement also reduce the microstructural degradation caused by the formation of voids due to outward Mn diffusion.

Tungsten is a refractory metal, suitable for a broad range of high-temperature applications, due to its high melting point and high-temperature strength. Recently, tungsten alloys became of great interest in thermonuclear fusion research. The alloys maintain low sputtering yield and high melting point, but greatly improve some drawback properties comparing to pure tungsten. These alloys are commonly prepared by mechanical alloying and compacted using Spark Plasma Sintering/Field Assisted Sintering. Powder in a graphite die is consolidated by applying pulsed electric current and pressure. Graphite foil is commonly placed between the die and the powder, to prevent adhesion. However, for number of applications it is necessary to avoid carbon contamination. In the present study we have examined carbon contamination mechanism of W - 10 wt.%Cr - 1 wt.%Hf alloy during Field Assisted Sintering along with the alloy's properties. The experiments have shown that the graphite foil leads to significant dealloying via mechanism of liquid phase sintering. As a result, tailored properties of the material are deteriorated after several minutes of the consolidation process. Therefore, application of carbon diffusion barrier was proposed, examined and compared with the alloy sintered with graphite foil.

In suspension spraying, two most frequently used solvents are water and ethanol. In this study, we test the potential of using alternative, high molecular weight solvent and demonstrate the associated advantages. For that, two organic solvents are directly compared: ethanol (serving as a benchmark, suspension formulated at 10 wt.% solid load) and di-propylene glycol methyl ether (two suspensions at 10 wt.% and 20 wt.% solid load). As a model material, $$\hbox {Al}_{2}\hbox {O}_3$$ is selected, a frequently sprayed ceramics employed in many industrial sectors. Sub-micron 100% alpha-alumina powder is used to formulate the suspensions. Identical spray conditions are then used to deposit the coatings using hybrid water-stabilized plasma torch. Shadowgraphy monitoring of the suspension fragmentation as well as in situ measurement of the particle in-flight properties is employed, showing no significant differences between the three series. Further, it is shown that the ethanol- and ether-based-feedstock coatings are fully comparable in terms of their microstructure, porosity content, surface roughness as well as hardness and adhesion to the substrates. Importantly, the ether-based coatings exhibit slightly higher levels of $$\alpha$$ - $$\hbox {Al}_{2}\hbox {O}_3$$ phase when compared to their ethanol-based counterpart (17 wt.% vs. 6 wt.%). The use of 20 wt.% solid load in the ether solvent leads to twofold increase in the deposition rate while (as opposed to ethanol) successfully retaining a dense microstructure. Lastly, the ether is significantly cheaper and safer to handle than ethanol.

Harnessing nuclear fusion is a challenging task, in particular because of the demands put on the used materials. In tokamaks, future energy sources, the inner-most chambers are to be coated with dense coatings of W, or W-Cr-based alloys. So far, the attempts for such coatings formation by other methods failed due to oxidation, high porosity, insufficient adhesion, high specific surface, or even insufficient thickness below 10 &mu, m. Cold spraying seems a promising technology for the task. In our study, we demonstrate the first successful fabrication of thick pure W coatings. W-Cr and W-Cr-Ti coatings were further prepared without oxidation of the metals. All coatings exhibited high hardness levels, good interface quality with three tested substrates and, importantly, a promising potential for formation of stable Cr 2 WO x phases.

The aims of this study were: (1) to produce composite coatings by high velocity oxy fuel (HVOF) spraying with steel matrix reinforced by cermets (a) Cr3C2&ndash, 20%Ni and (b) TiC&ndash, 20%NiMo, manufactured by mechanically activated synthesis (MAS), (2) to synthesize in situ a carbide reinforcement for iron matrix from a mixture of titanium and carbon during HVOF reactive thermal spraying (RTS), (3) to compare the wear resistance of produced coatings. As a reference, HVOF sprayed coatings from commercial Cr3C2&ndash, 25%NiCr (Amperit 588.074) and AISI 316L were utilized. Study of microstructure revealed the inhomogeneity of the Cr-based MAS coating, the Ti-based MAS coating had typical carbide granular structure, and the Ti-based RTS coating possessed elongated structures of TiC. The X-ray diffraction revealed two main phases in the Cr-based MAS coating: Cr3C2 and austenite, and two phases in the Ti-based coatings: TiC and austenite. Among the studied coatings, the Cr-based MAS coating demonstrated the highest low-force hardness (490 HV0.3). During the abrasive rubber wheel test (ASTM G65), the Ti-based MAS coating showed the best wear resistance, followed by Cr3C2&ndash, 25%NiCr and Ti-based RTS coating. In the abrasive&ndash, erosive test (GOST 23.201-78), the Ti-based MAS coating was 44% better than Cr3C2&ndash, 25%NiCr coating. The Ti-based RTS coating was 11% more wear resistant than the reference Cr3C2&ndash, 25%NiCr coating.

In this work, CoCrNi, FeCoCrNi and CoCrFeMnNi concentrated alloys with a Y-Ti oxide particle dispersion were prepared by mechanical alloying and Spark Plasma Sintering. The alloy consists of an FCC Ni-based matrix with a Y-Ti oxide dispersion and additional phases of Cr23C6 and Cr2O3. The effect of Fe, Mn, and Y-Ti oxide particles on the formation of oxide scales and the composition of the adjacent CoCrNi and FeCoCrNi alloys was studied. It was found that alloys without Mn in their composition form a protective Cr2O3 scale. The Cr23C6 particles provide an alternative mechanism for balancing the chromium loss during the oxidation. Y and Ti from the oxide particles participate in the formation of the protective oxide scales. Fe promotes Y and especially Ti diffusion through the Cr2O3 scale, resulting in the formation of Ti-depleted regions in the alloy. The findings will serve for the further development of these new materials.

Barium titanate coatings were first time sprayed by a high feed-rate plasma torch with water stabilization. Two power levels of the torch were applied. Two substrate materials were used—stainless steel and carbon steel. Various substrate preheating levels from 125 to 450 °C were applied to change the cooling conditions. Microstructure, phase composition including crystallinity quantification, surface roughness and microhardness were evaluated. Dielectric measurements proved that coatings with medium-level relative permittivity and with stable loss factor course versus frequency of the AC electric field were fabricated by spraying. The cold substrates provided coatings with low reflectivity and visibly darker surface compare to the hot substrates. The coatings exhibited good dielectric properties—on the top of an expectable range for plasma-sprayed BaTiO3. This study is targeted to coatings prospective for electrical industry, namely via optimization of conditions at the high feed-rate spraying.

Vliv legování (10 wt% Mo) a následného zpracování povrchu (laserové přetavení povrchu) na vlastnosti a chování byl hodnocen u PTA návaru oceli M2. Vlivem legování Mo došlo ke změně charaketru a povahy jak matrice, tak karbidů v povlaku M2. Naopak, laserové zpracování vedlo ke zjemnění struktury a potalčení precipitace karbidických částic. Navzdory zvýšení povrchové trvrdosti vykazoval povlak po laserovém zpracování pokles odolnosti proti opotřebení. Naopak, návar legovaný Mo zlepšil odolnost proti opotřebení, ačkoli jeho tvrdost poklesla. Důvodem byla tvorba oxidického tribofilmu typu Magneli v Mo legované oceli. The influence of alloying (10 wt% Molybdenum) and post deposition treatment (Laser Surface Melting) on the structural characteristics and wear performance of Plasma Transfer Arc deposited M2 hardfacings have been investigated. The nature of matrix and carbides of M2 hardfacing had changed upon Molybdenum addition while the Laser Surface Melting caused structural refinement and a decrease in carbide volume fraction. Despite an increase in hardness, Laser Surface Melting has resulted in reduction in sliding wear resistance against alumina counterface, while the Molybdenum enhanced the wear resistance even with decrease in hardness. This counter intuitive behaviour is attributed to Magnelli oxide containing tribo-oxide layer formation on the worn surface of Molybdenum alloyed hardfacings.

Tungsten alloys currently represent prospective candidates to replace tungsten in the first wall applications in future fusion facilities. Tungsten has many advantageous features; however, it is rather susceptible to oxidation at temperatures above around 500 °C. To mitigate/suppress this, various oxide-forming elements are being added to tungsten to induce self-passivation. The most common ones are chromium, titanium and silicon. The alloyed powder is frequently prepared by mechanical alloying and then consolidated by a sintering method. Most of the published results are related to alloys consolidated by HIP process that leads to formation of multiphase material. In the presented study, W-10Cr alloy with hafnium oxide particle dispersion was prepared by spark plasma sintering. Unique features of the microstructure are discussed and compared with other processing methods Phase and thermal stability of the alloy was evaluated at three fusion-relevant temperatures using detailed X-ray diffraction analysis, differential thermal analysis and microstructural observations in a scanning electron microscope. Impact of the heat treatment on crucial properties such as thermal conductivity and heat capacity was evaluated.

Three commercially available chromium carbide-based powders with different kinds of matrix (Cr3C2-25%NiCr; Cr3C2-25%CoNiCrAlY and Cr3C2-50%NiCrMoNb) were deposited by an HVOF JP-5000 spraying gun, evaluated and compared. The influence of heat treatment on the microstructure and properties, as well as the oxidation resistance in a hot steam environment (p = 24 MPa; T = 609 °C), was evaluated by SEM and XRD with respect to their potential application in the steam power industry. The sliding wear resistance measured at room and elevated (T = 600 °C) temperatures according to ASTM G-133. For all three kinds of chromium carbide-based coatings, the precipitation of secondary carbides from the supersaturated matrix was observed during the heat treatment. For Cr3C2-25%NiCr coating annealed in hot steam environment as well as for Cr3C2-25%CoNiCrAlY coating in both environments, the inner carbide oxidation was recorded. The sliding wear resistance was found equal at room temperature, regardless of the matrix composition and content, while at elevated temperatures, the higher wear was measured, varying in dependence on the matrix composition and content. The chromium carbide-based coating with modified matrix composition Cr3C2-50%NiCrMoNb is suitable to replace the Cr3C2-25%NiCr coating in a hot steam environment to eliminate the risk of failure caused by inner carbide oxidation.

Introduction of suspension and solution plasma spraying led to a breakthrough in the deposition of yttria-stabilized zirconia (YSZ) coatings and enabled preparation of new types of layers. However, their deposition with high feed rates needed, for example, for the deposition of thermal barrier coatings (TBCs) on large-scale components, is still challenging. In this study, possibility of high-throughput plasma spraying of YSZ coatings is demonstrated for the latest generation of high-enthalpy hybrid water-stabilized plasma (WSP-H) torch technology. The results show that microstructure of the coatings prepared by WSP-H may be tailored for specific applications by the choice of deposition conditions, in particular formulation of the liquid feedstock. Porous and columnar coatings with low thermal conductivity (0.5-0.6 W/mK) were prepared from commercial ethanol-based suspension. Dense vertically cracked coatings with higher thermal conductivity but also higher internal cohesion were deposited from suspension containing ethanol/water mixture and coarser YSZ particles. Spraying of solution formulated from diluted zirconium acetate and yttrium nitrate hexahydrate led also to the successful deposition of YSZ coating combining regions of porous and denser microstructure and providing both low thermal conductivity and improved cohesion of the coating. Enthalpy content, liquid-plasma interaction and coating buildup mechanisms are also discussed.

Deposition of aluminium oxide (Al 2 O 3 ) coatings from liquid feedstocks using a high enthalpy hybrid water-stabilized plasma torch was investigated. The entire process included the optimization of spraying parameters using a commercial ready-to-spray suspension, optimization and deposition of custom-made suspensions and one solution and evaluation of mechanical properties of the most durable coatings. Acquired coating microstructures varied from porous with typical columnar morphology to well-sintered dense structures with low porosity. The microstructural features were clearly linked to the feedstock formulation. The most durable coating with the highest density microstructure prepared from ethanol-based suspension showed outstanding mechanical properties, e.g. high values of hardness (up to 1211 HV0.3), tensile adhesion strength (up to 51 MPa) and wear resistance (material removal rate as low as 1.94·10 − 5 mm 3 ·N − 1 ·m − 1 as measured by pin-on-disc test). Moreover, deposition from a water-based solution of aluminium nitrate resulted in deposition of highly porous coating composed predominantly of stable α-alumina phase.

Mg-Gd alloy containing 22 wt.% Gd was studied in the present work. As cast alloy contains Mg 46 Gd 9 phase located at pockets along grain boundaries. In addition the as-cast alloy contains a low concentration of rectangular GdH 2 particles. Solution treatment at 530° C was performed in order to dissolve Gd in the Mg matrix. The solution treatment in air enhanced the volume fraction of GdH 2 particles by one order of magnitude. The formation of GdH 2 particles is caused by hydrogen-induced decomposition of the Mg 46 Gd 9 intermetallic phase. The source of hydrogen is water vapor reacting with Mg surface. A Gd-rich oxide layer was formed during solution treatment in air. Building of the oxide layer requires diffusion of Gd solutes from bulk to the surface and leads to formation of a Gd-depleted sub-surface region. It was found that solution treatment in vacuum results in substantially lower volume fraction of GdH 2 particles. Alternative methods of formation of GdH 2 particles in Mg-Gd alloy were examined as well and are discussed in the paper.

In the present work positron annihilation spectroscopy was employed for investigation of defects created in titanium by hydrogen loading. Pure titanium samples were firstly annealed to remove dislocations introduced by cutting and polishing. Subsequently the samples were loaded with hydrogen up to various hydrogen concentrations. Ti samples with different microstructures were compared: (i) conventional coarse grained sample, (ii) ultra fine grained material with microstructure refined by severe plastic deformation. Hydrogen gas loading of coarse grained and ultra fine grained samples was performed at hydrogen gas pressure of 103 bar and temperature of 150 °C. This resulted in formation of δ-TiH x phase in Ti matrix. The hydrogen content absorbed in the samples was determined by thermogravimetric analysis. The phase composition of hydrogen-loaded samples was characterized by X-ray diffraction. Hydrogen loading introduced vacancies which agglomerated in the sample into small vacancy clusters. In addition to vacancies, dislocations were created by α-Ti → δ-TiH x phase transition. Differential thermal analysis revealed that hydrogen is trapped at several kinds of traps characterized by different binding energies. The release of hydrogen from these traps precedes the decomposition of the δ-TiH x phase.

Magnesium alloys are, due to high specific strength and stiffness, materials suitable for lightweight applications in automotive and aeronautical industries. Very poor corrosion resistance of magnesium and magnesium alloys significantly limits their wide utilization. Magnesium alloys are very susceptible to galvanic corrosion that can result in serious pitting corrosion, particularly in wet and salty environment. Magnesium and its alloys can be protected by formation of protective surface layers which can be achieved by plasma spraying capable of preparing metal and/or ceramic coatings. In this work, plasma coatings of NiAl10 and NiAl40 on AZ91 magnesium alloy substrate were prepared by the hybrid plasma spraying system WSP®-H 500. Present results show a significant effect of the preheat temperature of the AZ91 substrate during plasma spraying on development of a diffusion bonding due to the formation of sub-layer composed of Mg 3 AlNi 2 , Al 12 Mg 17 phases and of Mg and Al solid solutions. The plasma sprayed coatings were observed by scanning electron microscope with elements point analysis and by X-ray phase analysis. The mechanical properties of prepared coatings were evaluated by adhesion tests. The corrosion resistance of prepared coatings was evaluated using the method of potentiodynamic measurements performed in the 0.5 mol·l − 1 NaCl solution while the long-term corrosion resistance was assessed in condensation chamber in wet air atmosphere at the temperature of 35 °C. Both the tests showed significant effect of present sub-layers on resulting corrosion resistance.

Positron annihilation spectroscopy was employed for investigation of vacancy-like defects in plasma-sprayed barium titanate. Defect studies were combined with measurement of dielectric properties of barium titanate coatings. Samples prepared by gas-stabilized plasma spray (GSP) torch and by plasma torch with the hybrid water-argon stabilization (WSP-H) were studied. Processing parameters were selected so that GSP coatings were sprayed in reductive conditions, whereas WSP-H coatings were prepared in oxidizing environment. As-sprayed GSP coating is dark, whereas WSP-H one is light. The dielectric properties of WSP-H coating are superior to those for GSP one. Defect studies revealed that both GSP and WSP-H coatings contain titanium vacancies. However, GSP coating contains in addition a considerable concentration of oxygen vacancies. Some fraction of oxygen vacancies in GSP coating is coupled with titanium vacancies forming partial Schottky defect. The structure of WSP-H coating is less disordered and contains only a low concentration of oxygen vacancies. This is consistent with reductive and oxidizing conditions in GSP and WSP-H spraying, respectively. Annealing at elevated temperatures in air leads to removal of oxygen vacancies which are filled by oxygen diffusing into the samples.

The aim of this work was investigation of hydrogen interaction with defects in Ti. Well-annealed Ti samples were loaded with hydrogen either electrochemically or using H2 gas phase. The hydrogen content and the phase composition of hydrogen loaded samples was determined by thermogravimetric analysis and by X-ray diffraction (XRD) respectively. Positron lifetime (LT) spectroscopy was employed for investigation of defects created by hydrogen loading. High-temperature H2 gas loading led to complete transformation of the whole sample into δ-TiH2 while low-temperature H2 gas loading and the electrochemical loading resulted in a non-uniform structure with most of the hydrogen absorbed in a sub-surface layer. All hydrogen-loaded samples exhibit positron lifetime component of ≈ 170 ps corresponding to positrons trapped at dislocations. Vacancy clusters were observed in the electrochemically loaded sample and the H2 gas phase loaded sample at low temperature.

Tungsten-based materials are the prime candidate plasma-facing materials for future fusion reactors, such as DEMO. Spark plasma sintering is a prospective fabrication technology with several advantageous features. The concurrent application of electric current, temperature and pressure enhances the sintering process, allowing for lower temperatures and shorter sintering times than traditional powder metallurgy processes. This in turn helps to avoid excessive grain growth and phase segregation in W-alloys. This study is focused on several factors that may influence the homogeneity of the sintered compacts&mdash, namely the diffusion of carbon from the graphite die, purity of the powder and sintering conditions. The following characteristics of spark plasma-sintered tungsten compacts were studied: composition (especially carbon and oxygen content), porosity, mechanical properties (hardness and fracture strength), and thermal diffusivity. The effects of the abovementioned processing factors were quantified, and local variations of selected properties were assessed.

High entropy alloys represent a new type of materials with a unique combination of physical properties originating from the occurrence of single-phase solid solutions of numerous elements. The preparation of nanostructured or amorphous structure in a form of thin films promises increased effective surface and high intergranular diffusion of elements as well as a high affinity to oxidation. In this work, we studied HfNbTaTiZr thin films, deposited at room temperature by DC magnetron sputtering from a single bcc phase target. Films exhibit cellular structure (∼100 nm) with fine substructure (∼10 nm) made of round-shape amorphous clusters. The composition is close to equimolar with slight Ti enrichment and without any mutual segregation of elements. Oxidation at the ambient atmosphere leads to the formation of Ti, Zr, Nb, Hf, and Ta oxide clusters in the film up to the depth of 200–350 nm out of the total film thickness of 1650 nm. Oxygen absorption takes place preferentially in the large vacancy clusters located in between the amorphous cluster aggregates. The dominant type of defect are small open volumes with a size comparable with vacancy. The distribution of these defects is uniform with depth and is not influenced by the presence of oxygen in the film.

Sintering of magnesium powder is often affected by the oxide layer, which is present on the powder already after gas-atomization. Its negative consequence demonstrates itself usually by limited diffusion between the individual powder particles and formation of compact 3D net-like structures, which promote crack propagation during mechanical loading. This work shows that magnesium-rare earth metals alloys, in this case Mg-4Y-3Nd, can benefit from the utilization of sufficiently high sintering temperature and pressure during the spark plasma sintering. A thorough analysis of the powder boundaries morphology and chemical composition revealed that application of temperature near the eutectic point of Mg-Y/Nd system together with high pressure results in severe diffusion of both Y and Nd into the powder boundaries. Consequently, local change in the chemical composition led to partial melting and the oxide shells became unstable and shattered. As a result, the interparticle diffusion was intensified and the powder consolidation became successful.

Thermal spray is a versatile and cost-effective process to deposit wear and corrosion resistant coatings. In this work, a relatively new ‘Fe-based’ chemistry comprising boride and carbides, is explored as a ‘greener’ alternative to the relatively expensive and carcinogenic Co-based coatings to mitigate wear. The emergent thermal spray process of high-velocity air-fuel (HVAF) spraying was chosen to deposit the Fe-based coatings, with the high-velocity oxy-fuel (HVOF) also being employed solely for the purpose of preliminary comparison. Detailed characterization of the HVOF and HVAF sprayed Fe-based coatings was carried out. Microstructure, porosity, hardness and phase analysis results demonstrate the influence of processing conditions, where specific spray conditions yielded minimal undeformed particulates content, high hardness, low porosity and feedstock phase retention. Differences in microstructural features of the as-deposited coatings in relation to their processing conditions are discussed in detail. The coatings were subjected to ball-on-disc tribometry tests at different load conditions and their friction and wear performance were evaluated. The coefficient of friction results of investigated coatings concurred with their respective microstructural features. Post-mortem of the worn coating surface, the mating alumina ball surface and wear debris was performed using SEM/EDS analysis to understand the associated wear mechanisms and material transfer. This work provides new insights on identifying appropriate HVAF processing conditions to achieve acceptable microstructural features and phases in Fe-based coatings for improved wear performance.

This paper deals with the compaction of ceramics based on lithium-silicate by spark plasma sintering (SPS). The initial powder was prepared by calcination in a resistance furnace at a temperature of 1300 °C with the ratio of Li/Si = 1. Compacting by SPS was carried out at temperatures of 800 - 1000 °C with a maximum pressure of 80 MPa. Samples with open porosity of less than 1 % were prepared at the temperature of 1000 °C. According to the quantitative Rietveld refinement of x-ray diffraction data, the dominant phases in all samples were Li₂Si₂O₅ and Li₂SiO₃, together representing over 80 wt. % of the sintered material.

A series of samples was sintered from nanometric BaTiO 3 powder by spark plasma sintering (SPS). Porosity on ultra-fine size scales, hardly accessible for quantification by conventional techniques, was measured by small angle neutron scattering (SANS). Band gap was estimated from diffuse reflectance measurements. Sintered tablets were polished, sputtered by aluminum to create electrode system and tested in DC and AC electric fields. The results were correlated with the SPS processing parameters and are discussed in connection with other BaTiO 3 samples produced by SPS with or without additional heat treatment. Majority of our SPS fired samples had, even without subsequent thermal treatment, advantageous combination of high permittivity, DC resistivity and low loss factor, seldom reported for SPS technology.

Wet-milling of magnesium powder was performed at room temperature in ethanol covered by argon atmosphere. It is shown that the wet-milling in ethanol can produce highly deformed powder of flake-like morphology. Subsequently, bulk samples were consolidated by spark plasma sintering technique in the temperature range 400–550 °C. It is shown that milling caused severe microstructural refinement. The flake-like shape of the milled particles was transferred into the compacts and caused formation of a layer-like microstructure which was predominantly perpendicular to the external force applied during sintering. Grain growth was highly limited by powder particles’ interface and secondary phase particles present in the matrix. Formation of texture in the compacts was attributed to the combination of SPS thermo-mechanical effect and continuous static recrystallization acting during the sintering.

Gas phase loading of nanocrystalline and epitaxial 20 nm Pd films deposited on single crystalline sapphire substrates was studied in this work. The nanocrystalline film was deposited at room temperature and the epitaxial film deposited at 800 °C. The nanocrystalline film suffers from in-plane compressive stress imposed by atomic peening processes. The epitaxial film exhibits tensile stress caused by the different thermal expansion coefficients of Pd and sapphire substrate. Coherent phase transition into the hydride phase was observed both for the nanocrystalline and for the epitaxial film. For both films, the lattice parameters continuously increase during the phase transition to the hydride phase. Both films exhibit enhanced hydride formation pressure compared to bulk Pd. Misfit dislocations are formed at interface between Pd film and substrate during hydrogenation. This leads to irreversible change of stress state of the films subjected to sorption and desorption cycle with hydrogen.

A Pd-H system is a model system suitable for studying interactions of hydrogen with metals. In the present work, we studied hydrogen-induced buckling of thin Pd films deposited on various substrates with different bonding strengths (sapphire, glimmer) and also the effect of deposition temperature. Lattice expansion and phase transitions were investigated by X-ray diffraction of synchrotron radiation. The influence of the substrate and microstructure of the film on the buckling process and phase transformation to palladium hydride are discussed.

Nanocrystalline Fe82Al18 powders were prepared by high energy ball milling in various atmospheres. Two preparation techniques were compared: (i) mechanical milling of pre-alloyed Fe82Al18 pieces and (ii) mechanical alloying of pure Fe and Al powders. Single phase Fe82Al18 nano-powder was formed by mechanical alloying in H2 atmosphere while milling in N2 or air environment suppressed mechanical alloying due to passivation of Fe surfaces. Positron annihilation spectroscopy revealed that mechanical alloying of Fe and Al in H2 atmosphere is mediated by hydrogen-induced vacancies.

Permeation barriers represent one of the crucial fields in materials development for thermonuclear fusion. Primary objective of the barriers is to suppress the permeation of hydrogen isotopes (mainly tritium) from future thermonuclear fusion facilities. Secondary objective is to reduce hydrogen retention in structural materials, potentially also improving their corrosion resistance. Expected reactor conditions put high demands on the material, as well as on the final barrier quality. Key properties are tritium permeation reduction, absence of defects (especially cracks), high-temperature stability and corrosion resistance, and compatibility with structural materials (mostly ferritic-martensitic steels). Regarding industrial scale production, ability of the deposition method to coat large complex surfaces is desirable. Thin nitride layers, identified as promising permeation barriers, were prepared by diffusion-based nitridation and physical vapour deposition (PVD) and characterized.

Nanocrystalline powders of iron aluminum alloy of the Fe82Al18 nominal composition were prepared under air, hydrogen and nitrogen atmospheres from the Fe and Al elemental powders by mechanical alloying and also from the conventionally cast Fe82Al18 alloy by the high-energy ball milling. The intensive plastic deformation during high-energy mechanical treatment has introduced high concentrations of open volume defects and contributed to a rapid decrease in the crystallite size down to a nanoscopic range.The hydrogen atmosphere was found to be the most efficient for the Fe-Al mechanical alloying since it has resulted into the fully alloyed Fe82Al18 after 30 h of milling. On the other hand, the nitrogen and air atmosphere have slightly prevented mechanical alloying and after the same milling time the pure iron particles were still detected in the powder mixtures. This partial suppression of the mechanical alloying process is explained by a formation of thin iron nitride and/or oxide layers on the surface of Fe particles preventing mutual inter-diffusion of Fe and Al atoms.

Hydrogen interaction with defects and structural development of Pd films with various microstructures were investigated. Nanocrystalline, polycrystalline and epitaxial Pd films were prepared and electrochemically loaded with hydrogen. Structural changes of Pd films caused by absorbed hydrogen were studied by in-situ X-ray diffraction combined with acoustic emission and measurement of electromotorical force. Development of defects during hydrogen loading was investigated by positron annihilation spectroscopy. It was found that hydrogen firstly fills open volume defects existing already in the films and subsequently it occupies also interstitial sites in Pd lattice. Absorbed hydrogen causes volume expansion, which is strongly anisotropic in thin films. This introduces high stress into the films loaded with hydrogen. Acoustic emission measurements revealed that when hydrogen-induced stress achieves a certain critical level rearrangement of misfit dislocations takes place. The stress which grows with increasing hydrogen concentration can be further released by plastic deformation and also by detachment of the film from the substrate.

ZnO single crystals electrochemically charged with hydrogen were characterized. The concentration of hydrogen introduced into the crystals was determined by nuclear reaction analysis and was found to be in a reasonable agreement with the value estimated from the Faraday’s law. Moreover, a sub-surface layer with very high concentration of hydrogen and very high density of open-volume defects was formed by plastic deformation caused by hydrogen-induced stress. Specific surface modification caused by hydrogen-induced slip in the c-direction was observed on hydrogen loaded crystals. Hydrogen diffusion coefficient in ZnO was estimated by in situ electrical resistivity measurement. It was found that hydrogen diffusion in the c-direction is faster than in the a-direction most probably due to open channels existing in the wurtzite structure along the c-axis.

ZnO films with thickness of80 nm were grown by pulsed laser deposition (PLD) on MgO (1 0 0) single crys- tal and amorphous fused silica (FS) substrates. Structural studies of ZnO films and a high quality reference ZnO single crystal were performed by slow positron implantation spectroscopy (SPIS). It was found that ZnO films exhibit significantly higher density of defects than the reference ZnO crystal. Moreover, the ZnO film deposited on MgO substrate exhibits higher concentration of defects than the film deposited on amorphous FS substrate most probably due to a dense network of misfit dislocations. The ZnO films and the reference ZnO crystal were subsequently loaded with hydrogen by electrochemical cathodic charging. SPIS character- izations revealed that absorbed hydrogen introduces new defects into ZnO.

The development of the microstructure in nanocrystalline, polycrystalline and epitaxial Pd films loaded with hydrogen is investigated. Structural changes in Pd films loaded with hydrogen were characterized by positron annihilation spectroscopy combined with electron microscopy and X-ray diffraction. It was found that hydrogen charging causes plastic deformation which leads to an increase of the defect density in all Pd films studied. Moreover, the formation of buckles was observed in nanocrystalline and polycrystalline Pd films loaded above a certain critical hydrogen concentration. Buckling leads to detachment of the film from the substrate and this is accompanied with in-plane stress relaxation and plastic deformation of the film.

Hydrogen absorption and diffusivity in high quality ZnO crystals were investigated in this work by X-ray diffraction combined with slow positron implantation spectroscopy and electrical resistometry. ZnO crystals were covered by a thin Pd over-layer and electrochemically charged with hydrogen. It was found that absorbed hydrogen causes plastic deformation in a sub-surface region. The depth profile of hydrogen concentration introduced into the crystal was determined by nuclear reaction analysis. Enhanced hydrogen concentration was found in the sub-surface region due to excess hydrogen atoms trapped at defects introduced by plastic deformation. Hydrogen diffusion in ZnO crystals with various orientations was studied by in-situ electrical resistometry. It was found that hydrogen diffusion in the c-direction is faster than hydrogen diffusion in the a-direction most probably due to open channels existing in the wurtzite structure along the c-axis.

W alloys are currently widely studied materials for their potential application in future fusion reactors. In the presented study, we report on the preparation and properties of mechanically alloyed W-Ti powders compacted by pulsed electric current sintering. Four different powder compositions of W-(3%–7%)Ti with Hf or HfC were prepared. The alloys’ structure contains only high-melting-point phases, namely the W-Ti matrix, complex carbide (Ti,W,Hf)C and HfO2 particle dispersion; Ti in the form of a separate phase is not present. The bending strength of the alloys depends on the amount of Ti added. The addition of 3 wt. % Ti led to an increase whereas 7 wt. % Ti led to a major decrease in strength when compared to unalloyed tungsten sintered at similar conditions. The addition of Ti significantly lowered the room-temperature thermal conductivity of all prepared materials. However, unlike pure tungsten, the conductivity of the prepared alloys increased with the temperature. Thus, the thermal conductivity of the alloys at 1300 °C approached the value of the unalloyed tungsten.

Magnesium alloys are promising candidates for biodegradable medical implants which reduce the necessity of second surgery to remove the implants. Yttrium in solid solution is an attractive alloying element because it improves mechanical properties and exhibits suitable corrosion properties. Silver was shown to have an antibacterial effect and can also enhance the mechanical properties of magnesium alloys. Measurements of microhardness and electrical resistivity were used to study the response of Mg-4Y and Mg-4Y-1Ag alloys to isochronal or isothermal heat treatments. Hardening response and electrical resistivity annealing curves in these alloys were compared in order to investigate the effect of silver addition. Procedures for solid solution annealing and artificial aging of the Mg-4Y-1Ag alloy were developed. The corrosion rate of the as-cast and heat-treated Mg-4Y-1Ag alloy was measured by the mass loss method. It was found out that solid solution heat treatment, as well artificial aging to peak hardness, lead to substantial improvement in the corrosion properties of the Mg-4Y-1Ag alloy.

In the present work hydrothermally grown ZnO single crystals were electrochemically charged with hydrogen. The influence of hydrogen on ZnO microstructure was investigated by positron annihilation spectroscopy (PAS) combined with X-ray diffraction (XRD) using synchrotron radiation. Hydrogen concentration in the samples was determined by nuclear reaction analysis (NRA). It was found that a high concentration of hydrogen can be introduced into ZnO by electrochemical loading. At low concentrations, absorbed hydrogen causes elastic volume expansion of ZnO crystal. At higher concentration, hydrogen-induced stresses exceed the yield stress in ZnO and plastic deformation of the crystal takes place leading to formation of a defected subsurface layer in the crystals.

Hydrogen absorption in Pd causes a significant volume expansion. In free-standing bulk Pd, the hydrogen-induced volume expansion is isotropic. However, the situation becomes more complicated in thin Pd films. Contrary to bulk samples, thin films are clamped to an elastically stiff substrate, which prevents in-plane expansion. Hence, the volume expansion of a thin film is strongly anisotropic because it expands in the out-of-plane direction only. Internal stresses introduced by absorbed hydrogen may become so high that detachment of a film from the substrate is energetically favorable and buckles of various morphologies are formed. In the present work, we studied hydrogen-induced buckling in a nanocrystalline thin Pd film deposited on a sapphire substrate. Slow positron implantation spectroscopy (SPIS) was employed as a principal tool for the characterization of defects and investigation of defect interactions with hydrogen. SPIS studies were combined with X-ray diffraction and direct observations of buckling by light microscopy. It was found that buckling of thin Pd film occurs at hydrogen concentrations xH > 0.1 and is accompanied by a strong increase of dislocation density.

Hydrogen diffusivity in ZnO (0001) single crystal was investigated using electrical resistometry and nuclear reaction analysis (NRA). ZnO crystals were covered with a thin Pd over-layer and electrochemically charged with hydrogen. The net concentration of hydrogen determined by NRA was found to be in a reasonable agreement with the value estimated from the transported charge using the Faradays law. The hydrogen diffusion coefficient in ZnO was estimated from in-situ electrical resistivity measurements. Moreover, NRA investigations revealed existence of a subsurface layer with very high concentration of hydrogen (up to 40 at.%). Typical surface modification observed on hydrogen loaded crystal by light microscope indicates hydrogen-induced plastic deformation realized by a slip in the c-direction. Open-volume defects introduced by hydrogen-induced plastic deformation trap diffusing hydrogen and cause an enhancement of hydrogen concentration in the deformed subsurface layer.

In the present work hydrothermally grown ZnO single crystals covered with Pd over-layer were electrochemically loaded with hydrogen and the influence of hydrogen on ZnO micro structure was investigated by positron annihilation spectroscopy (PAS). Nuclear reaction analysis (NRA) was employed for determination of depth profile of hydrogen concentration in the sample. NRA measurements confirmed that a substantial amount of hydrogen was introduced into ZnO by electrochemical charging. The bulk hydrogen concentration in ZnO determined by NRA agrees well with the concentration estimated from the transported charge using the Faraday's law. Moreover, a subsurface region with enhanced hydrogen concentration was found in the loaded crystals. Slow positron implantation spectroscopy (SPIS) investigations of hydrogen-loaded crystal revealed enhanced concentration of defects in the subsurface region. This testifies hydrogen-induced plastic deformation of the loaded crystal. Absorbed hydrogen causes a significant lattice expansion. At low hydrogen concentrations this expansion is accommodated by elastic straining, but at higher concentrations hydrogen-induced stress exceeds the yield stress in ZnO and plastic deformation of the loaded crystal takes place. Enhanced hydrogen concentration detected in the subsurface region by NRA is, therefore, due to excess hydrogen trapped at open volume defects introduced by plastic deformation. Moreover, it was found that hydrogen-induced plastic deformation in the subsurface layer leads to typical surface modification: formation of hexagonal shape pyramids on the surface due to hydrogen-induced slip in the [0001] direction.

The thermodynamics of structural phase transformations in thin films depends on the mechanical stress that can be released by plastic deformation. For thin films below a critical film thickness, plastic deformation is energetically unfavourable: thus, the system stays coherent and stress remains. For PdHc films less than 22 nm thick, a new situation emerges: while the interfaces between matrix and hydride precipitates remain coherent throughout the complete phase transition, misfit dislocations form between the hydride phase and the substrate.

Pd films can be used as a model system to examine the influence of microstructure and stress on the hydrogen absorption. In this work we study 500 nm Pd films deposited on different substrates with different binding strengths. The films were electrochemically loaded with hydrogen up to hydride concentration. Development of lattice constant during hydrogen loading of Pd films was investigated by in situ X-ray diffraction using synchrotron radiation. The influence of microstructure and mechanical stress in the films on the phase transition from Pd to Pd hydride was examined.

In this work variable energy positron annihilation spectroscopy was employed for investigation of defects created in Pd films electrochemically charged with hydrogen. The development of hydrogen-induced defects in nanocrystalline, polycrystalline and epitaxial Pd films were compared. It was found that absorbed hydrogen causes plastic deformation and increases defect density in all Pd films studied. Moreover, buckling was observed in nanocrystalline and polycrystalline films loaded above certain critical hydrogen concentration.

In the present work point defects in ZnO crystals were characterized by positron lifetime spectroscopy combined with back-diffusion measurement of slow positrons. Defects in ZnO crystals grown by various techniques were compared. Hydrothermally grown ZnO crystals contain defects characterized by lifetime of ≈181 ps. These defects were attributed to Zn vacancies associated with hydrogen. ZnO crystals prepared by other techniques (Bridgman, pressurized melt growth, and seeded chemical vapour transport) exhibit shorter lifetime of ≈165 ps. Positron back-diffusion studies revealed that hydrothermally grown ZnO crystals contain higher density of defects than the crystals grown by other techniques. The lowest concentration of defects was detected in the crystal grown by seeded chemical vapor transport.

In the present work hydrogen interaction with vacancies was investigated in Fe-Al alloys with various concentration of vacancies. The Fe-Al samples were implanted with low energy H+ ions (100 keV). This procedure introduced high hydrogen concentration into relatively narrow sub-surface region in the depth of ~500 nm. Variable energy positron annihilation spectroscopy (VEPAS) was employed for investigation of hydrogen interaction with vacancies in the sub-surface region. This study revealed formation of vacancy hydrogen complexes in the sub-surface region. Thermal stability of vacancy-hydrogen complexes was investigated as well.