Synthesis and thermal stability of Cr2AlC

A new reaction route with AlCr₂ and C as starting materials has been developed to produce Cr₂AlC. A Cr₂AlC bulk ceramic was achieved by hot pressing the AlCr₂ and C powders at 1400 °C with 20 MPa for 1 h in Ar. The mechanism to form Cr₂AlC in a temperature range of 1050-1400 °C was studied. It was confirmed that Cr₂AlC is formed directly by a reaction between C and AlCr₂. The reaction process, phase composition and microstructure were characterized with differential thermal analysis, X-ray diffractometry and scanning electron microscopy. The produced Cr₂AlC ceramic is stable up to 1500 °C in an Ar atmosphere, but decomposes into Al₈Cr₅ and Cr₂₃C₆ above 1500 °C.     

The effect of carbon and nickel additions on the precursor synthesis of Cr3C2-Ni nanopowder

Decreasing crystal size to nanoscale is a proven method to enhance material properties. In this study, nanosize Cr₃C₂ and Cr₃C₂-Ni were synthetized and the reaction sequence was studied. Aqueous precursors using only water-soluble raw materials with varying carbon contents and a nickel addition were spray-dried. Glycine was used as a carbon source and chromium acetate hydroxide as a chromium source in the precursor solutions. Nickel nitrate hexahydrate was introduced as a nickel source to yield a metallic binder into the carbide nanopowder.Resulting powders were heat-treating to identify an applicable precursor composition producing the targeted Cr₃C₂ phase with crystal size of tens of nanometers. Thermal synthesis tests of the precursor powders to yield Cr₃C₂ took place at a temperature between 900 and 1300?°C under an Argon atmosphere. The synthesis of nanosize Cr₃C₂-Ni powder was successful at 1000?°C in 30?min, in a case of the best precursor. In order to produce the carbide phase with no residual oxide traces, relative carbon load has to be 48?wt%, while the stoichiometric amount of carbon in Cr₃C₂ is 13?wt%. When also introducing the nickel source into the precursor, an even higher carbon load was required. The carbon surplus needed to enable the Cr₃C₂ synthesis attributes to the non-homogeneity of the precursor composition.The chemical synthesis starting from water-soluble raw materials is a promising way of preparing nanosize Cr₃C₂-Ni with the targeted phase configuration.     

Effects of PTFE activation and carbon sources on combustion synthesis of Cr2AlC/Al2O3 composites

Formation of Cr₂AlC/Al₂O₃ in situ composites was investigated by self-propagating high-temperature synthesis (SHS) involving both PTFE activation and aluminothermic reduction. In addition to Al and Cr₂O₃ as the starting materials, carbon black, graphite, and Al₄C₃ were used as the carbon sources. PTFE was employed not only as a reaction promoter, but also as a carburizing agent. Depending on different sources of carbon, the threshold amounts of PTFE for inducing self-sustaining combustion were 1.5, 4.0, and 3.0 wt% for the samples adopting carbon black, graphite, and Al₄C₃, respectively. The combustion front velocity and temperature increased with increasing PTFE content. Moreover, the sample using carbon black was the most exothermic, while the Al₄C₃-based sample was the least. For the powder compacts adopting carbon black or graphite, Cr₂AlC/Al₂O₃ composites were produced with no impurities. Due to relatively weak reaction exothermicity, however, the synthesized composites containing small amounts of Cr₇C₃ and Al₄C₃ were obtained from the Al₄C₃-based reaction scheme.     

Synthesis and ultra-high temperature ablation behavior of a ZrC/Cr2AlC composite

This work reports on the fabrication and high temperature ablation property of a new ZrC/Cr₂AlC composite. The ZrC/Cr₂AlC composite was obtained by hot pressing a mixture of 15 vol% ZrC and 85 vol% Cr₂AlC powders at 1300 °C with 20 MPa for 1 h in Ar atmosphere. The composite had a flexural strength of 622 MPa, higher than 400 MPa for Cr₂AlC. The high temperature ablation behavior of the composite was investigated using the oxyacetylene torch ablation test. During oxyacetylene torch testing, the composite underwent a series of thermal decomposition and oxidation. Microstructure and composition of the synthesized composite before and after the ablation test were characterized with scanning electron microscopy and X-ray diffractometry techniques.     

Influence of porosity on the electrical properties of La9.33(SiO4)6O2 oxyapatite

Oxyapatites are very promising materials in terms of ionic conductivity. They can be considered as a potential electrolyte for fuel cells as SOFC. The influence of porosity on the electrical properties of La_9.33(SiO₄)₆O₂ oxyapatite is reported here. Hot pressed pellets with various densification ratios have been characterized by the complex impedance method. The high frequency response associated with the bulk contribution is much more affected by the porosity than the grain boundaries contribution: as a consequence, the electrical behaviour of the samples has been considered in assimilating the porous ceramics to composite materials made of apatite with various amounts of air inclusions. Thus, the porosity dependence of conductivity, activation energy and permittivity are reported here. A percolation threshold has been highlighted for porosity values greater than 30%, involving great lowering of the electrical performances.     

Investigations of SiC aggregates oxidation: Influence on SiC castables refractories life time at high temperature

This paper reports results concerning the oxidation of silicon carbide of pure SiC powder (98% of SiC) and the oxidation of two silicon carbide castables, used in waste-to-energy plants (WTE), and containing 60% and 85% of SiC, respectively. The investigated temperature range (800-1200 °C) corresponds to typical service conditions in WTE. Thanks to thermogravimetric and thermal expansion tests, kinetics of oxidation of the powder of SiC and of the castables has been investigated. According to these tests, several important points have been underlined. Firstly, the oxidation of SiC aggregates has a high influence on the thermal expansion and on the weight gain of SiC castables. Secondly, the grain size distribution of SiC aggregates within castables plays a dominating role (especially enhanced for the fine particles) in castable expansion behaviour induced by oxidation. This is a key point according to the evolution of thermal expansion of such materials.     

Hot-pressing sintered BN-SiO2 composite ceramics with excellent thermal conductivity and dielectric properties for high frequency substrate

High thermal conductivity and low dielectric constant are the more and more important properties for high-frequency substrate materials to enhance their heat radiation and reduce signal delay. In this work, a series of BN-SiO₂ composite ceramics for high frequency application were successfully synthesized by hot-pressing sintering method. And their structures, thermal and dielectric properties were systematically studied. According to the results, the excellent thermal conductivity with low dielectric constant and low dielectric loss has been obtained in the BN-SiO₂ ceramic. Compared to the pure SiO₂, the sample with 50?wt% BN addition sintered at 1650?℃ exhibited excellent physical properties, including a high thermal conductivity of 6.75?W/m?K which is almost five times higher than that of pure SiO₂ and a low dielectric constant of 3.73. The achieved high thermal conductivity and appropriate dielectric property of the BN-SiO₂ composite ceramic make it a promising candidate for high-frequency substrate application.     

The influence of MgO,Y2O3 and ZrO2 additions on densification and grain growth of submicrometre alumina sintered by SPS and HIP

Spark plasma sintering followed by hot isostatic pressing was applied for preparation of polycrystalline alumina with submicron grain size. The effect of additives known to influence both densification and grain growth of alumina, such as MgO, ZrO₂ and Y₂O₃ on microstructure development was studied. In the reference undoped alumina the SPS resulted in some microstructure refinement in comparison to conventionally sintered materials. Relative density >99% was achieved at temperatures >1200 °C, but high temperatures led to rapid grain growth. Addition of 500 ppm of MgO, ZrO₂ and Y₂O₃ led, under the same sintering conditions, to microstructure refinement, but inhibited densification. Doped materials with mean grain size <400 nm were prepared, but the relative density did not exceed 97.9%. Subsequent hot isostatic pressing (HIP) at 1200 and 1250 °C led to quick attainment of full density followed by rapid grain growth. The temperature of 1250 °C was required for complete densification of Y₂O₃ and ZrO₂-doped polycrystalline alumina by HIP (relative density >99.8%), and resulted in fully dense opaque materials with mean grain size<500 nm.     

Effect of chromium additive on sintering and oxidation behavior of HfB2-SiC ceramics

The effect of chromium admixture on the processes in the HfB₂-SiC ceramic powder system during its pressureless sintering at 1600?°C was studied. It was shown that an increase in chromium content from 0% to 15.5% in the HfB₂-SiC ceramic powder mixture leads to a continuous increase in its relative density up to 90%. A transient liquid phase Cr-Si-C-B is formed at 1600?°C, and it promotes intense sintering of HfB₂ and SiC powders. The oxidation resistance of HfB₂-SiC-Cr ceramics was studied in static air at 1000–1500?°C. It was shown that the oxidation resistance is greatly improved due to a decrease in the porosity of the sintered ceramic system because of chromium additive. The presence of chromium oxide in the formed surface glassy layer can also lead to the increase in the oxidation resistance. These results suggest that chromium can be considered as a promising sintering additive for HfB₂-SiC and similar systems.     

Highly textured (Na1/2Bi1/2)0.94Ba0.06TiO3 ceramics prepared by the screen-printing multilayer grain growth technique

The screen-printing multilayer grain growth (MLGG) technique was successfully applied to perovskite-structured lead-free piezoelectric ceramics. Highly textured (Na_1/2Bi_1/2)_0.94Ba_0.06TiO₃ ceramics with (1 0 0) orientation were firstly fabricated by MLGG method with (or without) template particles. The MLGG approach using anisotropic Bi₄Ti₃O₁₂ templates resulted in >90% grain orientation, whereas the same approach without template particles resulted in high orientation degree. The grain orientation mechanism of MLGG using screen-printing was different form that of tape-casting and extrusion in templated grain growth (TGG) and reactive templated grain growth (RTGG) techniques. The interface between adjacent layers, which were formed by screen-printing, was the main mechanism for the texture development in MLGG technique. Compared with other grain orientation techniques, screen-printing was a simple, inexpensive and effective method to fabricate grain oriented lead-free piezoelectric ceramics.     

Formation, densification, and selected mechanical properties of hot pressed Al4SiC4, Al4SiC4 with 30 vol.% WC, and Al4SiC4 with 30 vol.% TiC

Powders of Al₄C₃ and SiC were combined by high-energy milling to produce Al₄SiC₄, Al₄SiC₄ + 30 vol.% TiC, and Al₄SiC₄ + 30 vol.% WC. Five different temperatures were used to hot press the constituents. XRD, SEM, relative density, and hardness measurements showed that formation of single-phase Al₄SiC₄ occurred at 1450 °C and full densification (99%) was achieved at 1500 °C. Both of these temperatures are lower than previously reported. Adding TiC and WC increases hardness, while WC improves densification (99.5%).     

Effect of 1 wt% LiF additive on the densification of nanocrystalline Y2O3 ceramics by spark plasma sintering

Densification of nanocrystalline cubic yttria (nc-Y₂O₃) powder, with 18 nm crystal size and 1 wt% LiF as a sintering additive was investigated. Specimens were fabricated by spark plasma sintering at 100 MPa, within the temperature range of 700-1500 °C. Sintering at 700 °C for 5 and 20 min resulted in 95% and 99.7% dense specimens, with an average grain size of 84 and 130 nm, respectively. nc-Y₂O₃ without additive was only 65% dense at 700 °C for 5 min. The presence of LiF at low sintering temperatures facilitated rapid densification by particle sliding and jamming release. Sintering at high temperatures resulted in segregation of LiF to the grain boundaries and its entrapment as globular phase within the fast growing Y₂O₃ grains. The sintering enhancement advantage of LiF was lost at high SPS temperatures.     

Investigation on the origin of the giant dielectric constant in CaCu3Ti4O12 ceramics through analyzing CaCu3Ti4O12-HfO2 composites

A full range of CaCu₃Ti₄O₁₂-HfO₂ (CCTO-HfO₂) composites were prepared by sintering mixtures of the two components at 1000 °C for 10 h. X-ray diffraction studies confirmed the two-phase nature of the composites. The evolution of the microstructure in the composites, in particular, the size distribution of CCTO grains, was examined by scanning electron microscopy. The studies showed that, as more HfO₂ was added, the abnormal grain growth of CCTO and coarsening of the microstructure were gradually suppressed. As a result, the average CCTO grain size was reduced from 50 to 1 μm. The measured dielectric constants agree well with the values calculated from Lichtenecker's logarithmic law, using only the dielectric constants of pure CCTO and HfO₂ as two end points. The agreement suggests to us that the dielectric constant of CCTO is dominated by domain boundaries within the grains rather than by grain boundaries between the grains.     

Influence of surface roughness and temperature on the oxidation behavior of ZrC/SiC samples

New composites were elaborated using ZrC and SiC powders and the Spark Plasma Sintering process. The samples were polished at 4 different levels in order to compare the influence of surface roughness and temperature (1400 and 1600 K) on the characteristics of the oxide layers. By XRD analysis, it was confirmed that polishing and temperature level provoked changes in the crystalline structure. SEM imaging coupled to EDS microanalysis showed that the oxide layer was made of zirconia grains with silica at the grain boundaries. Nano-indentation was used to analyze the influence of the initial surface roughness and temperature on the hardness of the oxide layer. At 1400 K, the initial polishing has favored the growth of a hard oxide layer, which could be probably correlated to the higher crystallinity of the oxide. At 1600 K, it seems that a rougher initial surface favors the hardness of the oxide layer, which could be correlated to a better adherence between the oxide layer and the substrate. Both phenomena (crystallinity and adherence) would be in competition to reduce the fragility of the oxide layer.     

Influence of copper concentration on sprayed CZTS thin films deposited at high temperature

In this study, Cu₂ZnSnS₄ (CZTS) thin films were deposited by spray pyrolysis technique at constant substrate temperature. The effects of the copper concentration on the structural, morphological and optical properties of the films were investigated. The copper concentration was varied from 0.15 to 0.25 M in the steps of 0.05 M. The structural studies revealed that the Cu poor film shows low intense peaks, but as Cu concentration increases a relatively more intense and sharper diffraction peaks (112), (200), (220), and (312) of the kesterite crystal structure were observed. Raman spectroscopy analysis confirmed the formation of phase-pure CZTS films. From the morphological studies, it is found that the grain size increased as the Cu concentration increases from 0.15 to 0.25 M. The optical band-gap values were estimated to be 1.61, 1.52 and 1.45 eV for copper concentration 0.15, 0.20 and 0.25 M, respectively. Photoelectrochemical cells using films of different copper concentrations were fabricated and the best cell exhibited an efficiency of 1.09% for 0.25 M of copper concentration.     

Phase analysis and wear behavior of in-situ spark plasma sintered Ti3SiC2

In-situ synthesis of dense near-single phase Ti₃SiC₂ ceramics from 3Ti/SiC/C/0.15Al starting powder using spark plasma sintering (SPS) at 1250 °C is reported. Systematic analysis of the phase development over a range of sintering temperatures (1050–1450 °C) suggested that solid state reactions between intermediate TiC and Ti₅Si₃ phases lead to the formations of Ti₃SiC₂. The effect of starting powder composition on phase development after SPS at 1150 °C was also investigated using three distinct compositions (3Ti/SiC/C, 2Ti/SiC/TiC, and Ti/Si/2TiC). The results indicate that the starting powder compositions, with higher amounts of intermediate phase such as TiC, favor the formation of Ti₃SiC₂ at relatively lower sintering temperature. Detailed analysis of wear behavior indicated that samples with higher percentage of TiC, present either as an intermediate phase or a product of Ti₃SiC₂ decomposition, exhibited higher microhardness and better wear resistance compared to near single phase Ti₃SiC₂.     

Fabrication of Yb-doped Lu2O3-Y2O3-La2O3 solid solutions transparent ceramics by self-propagating high-temperature synthesis and vacuum sintering

A comparative analysis of sintering and grain growth processes of lutetium oxide and lutetium-yttrium-lanthanum oxides solid solutions, as well as optical properties, luminescence and laser generation of (Lu_xY_0.9-xLa_0.05Yb_0.05)₂O₃ transparent ceramics are reported. Fabrication of highly dispersed initial powders of these compounds was performed via nitrate-glycine self-propagating high-temperature synthesis (SHS) method. The powders were compacted at 300?MPa and vacuum sintered at temperatures up to 1750?°С. Optical ceramics of (Lu_0.65Y_0.25La_0.05Yb_0.05)₂O₃ elemental composition were shown to have the highest in-line transmittance, which achieved 78% at the wavelength of 800?nm. Generation of laser radiation at a wavelength of 1032?nm with the differential efficiency of 20% was demonstrated in the (Lu_0.65Y_0.25La_0.05Yb_0.05)₂O₃ ceramics.     

Size effect on dielectric properties of fine-grained BaTiO3 ceramics

The effect of grain size on the dielectric behavior of high-purity, fine-grained BaTiO₃ ceramic has been investigated. It was found that the dielectric constant and dissipation factor changed much with the decreasing of average grain size. The specimen with grain size of 280 nm had a high dielectric constant at room temperature, and the _r-T and tanδ-T curves remarkably changed with the grain size. Part of the grains remaining ferroelectric structure was ascribed to the high value of dielectric constant. ©     

Effect of the excess of bismuth on the morphology and properties of the BaBi2Nb2O9 thin films

In this study, the effect of bismuth content on the crystal structure, morphology and electric properties of barium bismuth niobate (BaBi₂Nb₂O₉) thin films was explored with the aid of X-ray diffraction (XRD), scanning electron microcopy (SEM), atomic force microscopy (AFM) and dielectric properties. BaBi₂Nb₂O₉ (BBN) thin films have been successfully prepared by the polymeric precursor methods and deposited by spin coating on Pt/Ti/SiO₂/Si (1 0 0) substrates. The phase formation, the grain size and morphology of the thin films were influenced by the addition of bismuth in excess. It was observed that the formation of single phase BBN for films was prepared with excess of bismuth up to 2 wt%. The films prepared with excess of the bismuth showed higher grain size and better dielectric properties. The 2 wt% bismuth excess BBN thin film exhibited dielectric constant of about 335 with a loss of 0.049 at a frequency of 100 kHz at room temperature.     

Temperature dependences of piezoelectric properties of vanadium substituted SrBi2Nb2O9 ceramics with grain orientation

The temperature dependence of the piezoelectric properties of vanadium substituted strontium bismuth niobate, SrBi₂Nb_1.95V_0.05O₉ (SBNV) ceramics, were investigated in various vibration modes. The effects of grain orientation in SBNV ceramics on the piezoelectric properties were also studied by the hot-forging (HF) method. The anisotropy of the piezoelectric properties of each vibration mode was confirmed by observing the grain orientation. In particular, HF-SBNV ceramics of the (33) and (15) modes showed excellent piezoelectric properties with relatively high mechanical quality factors, Q_m (2200, 4600), and high electrical quality factors, Q_{e max} (66.0, 21.6), respectively. In addition, HF-SBNV ceramics showed low temperature coefficients of resonance frequency TC-f_r (−16.5, −27.0). HF-SBNV ceramics are considered to be superior candidates for the lead-free piezoelectric application of ceramic resonators.