Microstructure and physical properties of black-aluminum antireflective films.

The microstructure and physical properties of reflective and black aluminum were compared for layers of different thicknesses deposited by magnetron sputtering on fused silica substrates. Reflective Al layers followed the Volmer-Weber growth mechanism classically observed for polycrystalline metal films. On the contrary, the extra nitrogen gas used to deposit the black aluminum layers modified the growth mechanism and changed the film morphologies. Nitrogen cumulated in the grain boundaries, favoring the pinning effect and stopping crystallite growth. High defect concentration, especially vacancies, led to strong columnar growth. Properties reported for black aluminum tend to be promising for sensors and emissivity applications.

Preparation and Characteristics of High-Performance, Low-Density Metallo-Ceramics Composite.

By applying the physical vapour deposition method, hollow ceramic microspheres were coated with titanium, and subsequently, they were sintered using the spark plasma sintering technique to create a porous ceramic material that is lightweight and devoid of a matrix. The sintering process was carried out at temperatures ranging from 1050 to 1200 °C, with a holding time of 2 min. The samples were subjected to conventional thermal analyses (differential scanning calorimetry, thermogravimetry, dilatometry), oxidation resistance tests, and thermal diffusivity measurements. Phase analysis of the samples was performed using the XRD and the microstructure of the prepared specimens was examined using electron microscopy. The titanium coating on the microspheres increased the compressive strength and density of the resulting ceramic material as the sintering temperature increased. The morphology of the samples was carefully examined, and phase transitions were also identified during the analysis of the samples.

High-Temperature Corrosion Behavior of Selected HVOF-Sprayed Super-Alloy Based Coatings in Aggressive Environment at 800 °C.

This study is focused on the high-temperature corrosion evaluation of selected thermally sprayed coatings. NiCoCrAlYHfSi, NiCoCrAlY, NiCoCrAlTaReY, and CoCrAlYTaCSi coatings were sprayed on the base material 1.4923. This material is used as a cost-efficient construction material for components of power equipment. All evaluated coatings were sprayed using HP/HVOF (High-Pressure/High-Velocity Oxygen Fuel) technology. High-temperature corrosion testing was performed in a molten salt environment typical for coal-fired boilers. All coatings were exposed to the environment of 75% Na2SO4 and 25% NaCl at the temperature of 800 °C under cyclic conditions. Each cycle consisted of 1 h heating in a silicon carbide tube furnace followed by 20 min of cooling. The weight change measurement was performed after each cycle to establish the corrosion kinetics. Optical microscopy (OM), scanning electron microscopy (SEM), and elemental analysis (EDS) were used to analyze the corrosion mechanism. The CoCrAlYTaCSi coating showed the best corrosion resistance of all the evaluated coatings, followed by NiCoCrAlTaReY and NiCoCrAlY. All the evaluated coatings performed better in this environment than the reference P91 and H800 steels.

Hot Corrosion Behavior of TWAS and HVOF NiCr-Based Coatings in Molten Salt.

In order to extend the life of boilers by applying an anti-corrosion coating without the need to dismantle them, it is advisable to find coatings that can be applied using cheaper and portable techniques, such as Twin Wire Arc Spray technology (TWAS). In this study, we compare selected NiCr-based coatings and two uncoated steel substrates (steel 1.7715 and 1.4903). Two coatings, Cr3C2 - 25% NiCr and Hastelloy C-276 are deposited using High velocity oxygen-fuel technology (HVOF) and three coatings, NiCrTi, NiCrMo, and Inconel 625, are deposited using TWAS. In addition to the corrosion weight gain during 50 cycles of loading in an 18% Na2SO4 and 82% Fe2(SO4)3 salt environment at 690 °C evaluated using the gravimetric method, the microstructure and phase composition of the coatings were analyzed on the samples after the exposure in order to compare the properties and gain a deeper understanding of the corrosion kinetics. Coating cross-sections and free-surfaces were observed with a scanning electron microscope (SEM) with an energy-dispersive (EDX) system. The phase composition was investigated using X-ray diffraction (XRD) and Raman spectroscopy. No significant differences were observed between the TWAS and HVOF coating methods for the coatings compared. Due to the similar corrosion products found on all coatings, a very effective corrosion protective layer was formed on the surface, forming a barrier between the corrosive environment and the coating regardless of the used deposition technology. Therefore, for industrial use on the inner surface of coal-fired boilers we recommend NiCrTi, NiCrMo, or Inconel coatings prepared with the more cost-effective and portable TWAS technology.

Dielectric Spectroscopy of Calcium Titanate Processed by Spark Plasma Sintering.

Calcium titanate (CaTiO3) powder was compacted by spark plasma sintering (SPS). The resulting products were subjected to the phase stability study and dielectric characterization. The change in temperature of SPS between 1100 °C and 1250 °C had a clear and straightforward effect on density, porosity, relative permittivity, loss tangent, and DC resistivity. Since the SPS itself introduces certain oxygen deficiency into Ti-perovskites, all samples were annealed after SPS. However, this post-processing did not mask the effects of the SPS regime. Optical reflectance measurements were completed to compare and quantify the sample coloration and support the dielectric results with corresponding optical band gap estimations. Subtle changes in the CaTiO3 crystal lattice arrangement, completed between 1150 °C and 1250 °C and documented in the literature for conventionally sintered samples, could not be confirmed for SPS-prepared calcium titanate. The novelty of this research work is in producing very stable dielectric ceramics and an indication of the SPS processing parameters suitable for this. The best sample showed at 1 MHz frequency the combination of relative permittivity 370, loss tangent 0.008, and DC resistivity 3 × 1012 Ωm.

Thermal Properties of Illite-Zeolite Mixtures up to 1100 °C.

Illitic clays are the commonly used material in building ceramics. Zeolites are microporous, hydrated crystalline aluminosilicates, they are widely used due to their structure and absorption properties. In this study, illitic clay (Füzérradvány, Hungary) was mixed with natural zeolite (Nizný Hrabovec, Slovakia) with up to 50 wt.% of zeolite content. The samples were submitted to thermal analyses, such as differential thermal analysis, differential scanning calorimetry, thermogravimetry, and dilatometry. In addition, the evolution of thermal diffusivity, thermal conductivity, and specific heat capacity in the heating stage of firing were measured and discussed. The amount of the physically bound water in the samples increased along with the amount of zeolite. The temperature of the illite dehydroxylation (peak temperature) was slightly shifted to lower temperatures, from 609 °C to 575 °C (for sample IZ50). On the other hand, the mass loss and the shrinkage of the samples significantly increased with the zeolite content in the samples. Sample IZ50 reached 10.8% shrinkage, while the sample prepared only from the illitic clay contracted by 5.8%. Nevertheless, the temperature of the beginning of the sintering (taken from the dilatometric curves) decreased from 1021 °C (for illitic clay) to 1005 °C (for IZ50). The thermal diffusivity and thermal conductivity values decreased as the amount of zeolite increased in the samples, thus showing promising thermal insulating properties.

High-Temperature Cycling of Plasma Sprayed Multilayered NiCrAlY/YSZ/GZO/YAG Thermal Barrier Coatings Prepared from Liquid Feedstocks.

High-enthalpy hybrid water/argon-stabilized plasma (WSP-H) torch may be used for efficient deposition of coatings from dry powders, suspensions, and solutions. WSP-H torch was used to deposit two complete thermal barrier coatings (TBCs) with multilayered top-coat. NiCrAlY was used as bond-coat and deposited on nickel-based superalloy substrates. Top-coat consisted of up to three sublayers: (i) yttria-stabilized zirconia (ZrO2-8 wt.%Y2O3-YSZ) deposited from solution, (ii) gadolinium zirconate (Gd2Zr2O7-GZO) deposited from suspension, and (iii) optional yttrium aluminum garnet (Y3Al5O12-YAG) overlayer deposited from suspension. Each of the sublayers was intended to provide different functionalities, namely improved fracture toughness, low thermal conductivity, and high erosion resistance, respectively. High-temperature performance and thermal shock resistance of the deposited coatings were tested by thermal cycling fatigue "TCF" test (maximum temperature 1100 °C, 1 h dwell per cycle) and "laser-rig" test (maximum temperature ~ 1530 °C, 5 min dwell per cycle) exposing samples to isothermal and gradient thermal conditions, respectively. In both tests, coatings endured around 800 test cycles which shows great potential for further development of these layers and their application in demanding thermal conditions. Analysis of the samples after the test showed microstructural changes and identified reason of ultimate coating failure.

Young's Modulus of Different Illitic Clays during Heating and Cooling Stage of Firing.

Dynamical thermomechanical analysis of 5 illite-based clays from deposits in Slovakia, Estonia, Latvia, and Hungary is presented. The clays consist of illite (37-80 mass%), quartz (12-48 mass%), K-feldspar (4-13 mass%), kaolinite (0-18 mass%), and calcite (0-3 mass%). Young's modulus is measured during the heating and cooling stages of firing (25 °C → 1100 °C → 25 °C). The liberation of the physically bound water increases Young's modulus by ∼70% for all studied clays. By increasing the temperature, dehydroxylation and the α → ß transition of quartz take place without a significant effect on Young's modulus. Sintering, which starts at 800 °C, leads to an intensive increase in Young's modulus up to the highest temperature (1100 °C). The increase remains also in the early stage of cooling (1100 °C → 800 °C). This increase of Young's modulus is also the result of solidification of the glassy phase, which is finished at ∼750 °C. A sharp minimum of Young's modulus is observed at around the ß â†’ α transition of quartz. Then, Young's modulus still decreases its value down to the room temperature. The physical processes observed during heating and cooling do not differ in nature for the studied clays. Values of Young's modulus vary at around 8 GPa, up to 800 °C. During sintering, Young's modulus reaches values from 30 GPa to 70 GPa for the studied clays. The microstructure and composition given by the origin of the clay play a cardinal role for the Young's modulus of the final ceramic body.

Effect of Short Attritor-Milling of Magnesium Alloy Powder Prior to Spark Plasma Sintering.

The spark plasma sintering (SPS) technique was employed to prepare compacts from (i) gas-atomized and (ii) attritor-milled AE42 magnesium powder. Short attritor-milling was used mainly to disrupt the MgO shell covering the powder particles and, in turn, to enhance consolidation during sintering. Compacts prepared by SPS from the milled powder featured finer microstructures than compacts consolidated from gas-atomized powder (i.e., without milling), regardless of the sintering temperatures in the range of 400-550 °C. Furthermore, the grain growth associated with the increase in the sintering temperature in these samples was less pronounced than in the samples prepared from gas-atomized particles. Consequently, the mechanical properties were significantly enhanced in the material made of milled powder. Apart from grain refinement, the improvements in mechanical performance were attributed to the synergic effect of the irregular shape of the milled particles and better consolidation due to effectively disrupted MgO shells, thus suppressing the crack formation and propagation during loading. These results suggest that relatively short milling of magnesium alloy powder can be effectively used to achieve superior mechanical properties during consolidation by SPS even at relatively low temperatures.

Phase, Composition and Structure Changes of CoCrNi-Based Concentrated Alloys Resulting from High Temperature Oxidation.

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.

Influence of Glass Additions on Illitic Clay Ceramics.

A mixture of an illitic clay and waste glass was prepared and studied during the sintering process. The illitic clay, from the Liepa deposit (Latvia), and green glass waste (GW) were disintegrated to obtain a homogeneous mixture. The addition of disintegrated GW (5-15 wt% in the mixture) led to a reduction in the intensive sintering temperature, from 900 to 860 °C, due to a significant decrease in the glass viscosity. The addition of GW slightly decreased the intensities of the endo- and exothermic reactions in the temperature range from 20 to 1000 °C due to the reduced concentration of clay minerals. GW reduced the plasticity of the clay and reduced the risk of structural breakage. The increase in sintering temperature from 700 to 1000 °C decreased the apparent porosity and water uptake capacity of the ceramics from 35% and 22%, down to 24% and 13%, respectively. The apparent porosities of all the sintered mixtures showed a decrease of between 6% to 9% after the addition of GW with concentrations from 5 up to 15 wt% respectively, while the water uptake capacities decreased from between 4% and 10%. The addition of GW led to an increase in the apparent density of the ceramic materials, up to 2.2 g/cm3. Furthermore, the compressive strength increased by more than two times, reaching a highest value of 240 MPa after the sintering of the 15 wt% GW-containing mixture at 1000 °C.

The Effect of Processing Route on Properties of HfNbTaTiZr High Entropy Alloy.

High entropy alloys (HEA) have been one of the most attractive groups of materials for researchers in the last several years. Since HEAs are potential candidates for many (e.g., refractory, cryogenic, medical) applications, their properties are studied intensively. The most frequent method of HEA synthesis is arc or induction melting. Powder metallurgy is a perspective technique of alloy synthesis and therefore in this work the possibilities of synthesis of HfNbTaTiZr HEA from powders were studied. Blended elemental powders were sintered, hot isostatically pressed, and subsequently swaged using a special technique of swaging where the sample is enveloped by a titanium alloy. This method does not result in a full density alloy due to cracking during swaging. Spark plasma sintering (SPS) of mechanically alloyed powders resulted in a fully dense but brittle specimen. The most promising result was obtained by SPS treatment of gas atomized powder with low oxygen content. The microstructure of HfNbTaTiZr specimen prepared this way can be refined by high pressure torsion deformation resulting in a high hardness of 410 HV10 and very fine microstructure with grain size well below 500 nm.

Improvement of Mechanical Properties of Plasma Sprayed Al2O3-ZrO2-SiO2 Amorphous Coatings by Surface Crystallization.

Ceramic Al2O3-ZrO2-SiO2 coatings with near eutectic composition were plasma sprayed using hybrid water stabilized plasma torch (WSP-H). The as-sprayed coatings possessed fully amorphous microstructure which can be transformed to nanocrystalline by further heat treatment. The amorphous/crystalline content ratio and the crystallite sizes can be controlled by a specific choice of heat treatment conditions, subsequently leading to significant changes in the microstructure and mechanical properties of the coatings, such as hardness or wear resistance. In this study, two advanced methods of surface heat treatment were realized by plasma jet or by high energy laser heating. As opposed to the traditional furnace treatments, inducing homogeneous changes throughout the material, both approaches lead to a formation of gradient microstructure within the coatings; from dominantly amorphous at the substrate-coating interface vicinity to fully nanocrystalline near its surface. The processes can also be applied for large-scale applications and do not induce detrimental changes to the underlying substrate materials. The respective mechanical response was evaluated by measuring coating hardness profile and wear resistance. For some of the heat treatment conditions, an increase in the coating microhardness by factor up to 1.8 was observed, as well as improvement of wear resistance behaviour up to 6.5 times. The phase composition changes were analysed by X-ray diffraction and the microstructure was investigated by scanning electron microscopy.

Microstructure and Room Temperature Mechanical Properties of Different 3 and 4 Element Medium Entropy Alloys from HfNbTaTiZr System.

Refractory high entropy alloys (HEA) are promising materials for high temperature applications. This work presents investigations of the room temperature tensile mechanical properties of selected 3 and 4 elements medium entropy alloys (MEA) derived from the HfNbTaTiZr system. Tensile testing was combined with fractographic and microstructure analysis, using scanning electron microscope (SEM), wavelength dispersive spectroscope (WDS) and X-Ray powder diffraction (XRD). The 5 element HEA alloy HfNbTaTiZr exhibits the best combination of strength and elongation while 4 and 3 element MEAs have lower strength. Some of them are ductile, some of them brittle, depending on microstructure. Simultaneous presence of Ta and Zr in the alloy resulted in a significant reduction of ductility caused by reduction of the BCC phase content. Precipitation of Ta rich particles on grain boundaries reduces further the maximum elongation to failure down to zero values.

The Influence of Milling and Spark Plasma Sintering on the Microstructure and Properties of the Al7075 Alloy.

The compact samples of an Al7075 alloy were prepared by a combination of gas atomization, high energy milling, and spark plasma sintering. The predominantly cellular morphology observed in gas atomized powder particles was completely changed by mechanical milling. The continuous-like intermetallic phases present along intercellular boundaries were destroyed; nevertheless, a small amount of Mg(Zn,Cu,Al)2 phase was observed also in the milled powder. Milling resulted in a severe plastic deformation of the material and led to a reduction of grain size from several µm into the nanocrystalline region. The combination of these microstructural characteristics resulted in abnormally high microhardness values exceeding 300 HV. Consolidation through spark plasma sintering (SPS) resulted in bulk samples with negligible porosity. The heat exposition during SPS led to precipitation of intermetallic phases from the non-equilibrium microstructure of both gas atomized and milled powders. SPS of the milled powder resulted in a recrystallization of the severely deformed structure. An ultra-fine grained structure (grain size close to 500 nm) with grains divided primarily by high-angle boundaries was formed. A simultaneous release of stored deformation energy and an increase in the grain size caused a drop of microhardness to values close to 150 HV. This value was retained even after annealing at 425 °C.

Nanocrystalline Al7075 + 1 wt % Zr Alloy Prepared Using Mechanical Milling and Spark Plasma Sintering.

The microstructure, phase composition, and microhardness of both gas-atomized and mechanically milled powders of the Al7075 + 1 wt % Zr alloy were investigated. The gas-atomized powder exhibited a cellular microstructure (grain size of a few µm) with layers of intermetallic phases along the cell boundaries. Mechanical milling (400 revolutions per minute (RPM)/8 h) resulted in a grain size reduction to the nanocrystalline range (20 to 100 nm) along with the dissolution of the intermetallic phases. Milling led to an increase in the powder's microhardness from 97 to 343 HV. Compacts prepared by spark plasma sintering (SPS) exhibited negligible porosity. The grain size of the originally gas-atomized material was retained, but the continuous layers of intermetallic phases were replaced by individual particles. Recrystallization led to a grain size increase to 365 nm in the SPS compact prepared from the originally milled powder. Small precipitates of the Al3Zr phase were observed in the SPS compacts, and they are believed to be responsible for the retainment of the sub-microcrystalline microstructure during SPS. A more intensive precipitation in this SPS compact can be attributed to a faster diffusion due to a high density of dislocations and grain boundaries in the milled powder.

Microhardness and In Vitro Corrosion of Heat-Treated Mg-Y-Ag Biodegradable Alloy.

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.

Spark Plasma Sintering of a Gas Atomized Al7075 Alloy: Microstructure and Properties.

The powder of an Al7075 alloy was prepared by gas atomization. A combination of cellular, columnar, and equiaxed dendritic-like morphology was observed in individual powder particles with continuous layers of intermetallic phases along boundaries. The cells are separated predominantly by high-angle boundaries, the areas with dendritic-like morphology usually have a similar crystallographic orientation. Spark plasma sintering resulted in a fully dense material with a microstructure similar to that of the powder material. The continuous layers of intermetallic phases are replaced by individual particles located along internal boundaries, coarse particles are formed at the surface of original powder particles. Microhardness measurements revealed both artificial and natural ageing behavior similar to that observed in ingot metallurgy material. The minimum microhardness of 81 HV, observed in the sample annealed at 300 °C, reflects the presence of coarse particles. The peak microhardness of 160 HV was observed in the sample annealed at 500 °C and then aged at room temperature. Compression tests confirmed high strength combined with sufficient plasticity. Annealing even at 500 °C does not significantly influence the distribution of grain sizes-about 45% of the area is occupied by grains with the size below 10 µm.