Spark plasma sintered tantalum carbide: Effect of pressure and nano-boron carbide addition on microstructure and mechanical properties

TaC and TaC-1 wt.% B₄C powders were consolidated using spark plasma sintering (SPS) at 1850 °C and varying pressure of 100, 255 and 363 MPa. The effect of pressure on the densification and grain size is evaluated. The role of nano-sized B₄C as sintering aid and grain growth inhibitor is studied by means of XRD, SEM and high resolution TEM. Fully dense TaC samples were produced at a pressure of 255 MPa and higher at 1850 °C. The increasing pressure also resulted in an increase in TaC grain size. Addition of B₄C leads to an increase in the density of 100 MPa sample from 89% to 97%. B₄C nano-powder resists grain growth even at high pressure of 363 MPa. The formation of TaB₂/Carbon at TaC grain boundaries helps in pinning the grain boundary and inhibiting grain growth. The effect of B₄C addition on hardness and elastic modulus measured by nanoindentation and the indentation fracture toughness has been studied. Relative fracture toughness increased by up to 93% on B₄C addition.     

Preparation of nanostructured TiO2 ceramics by spark plasma sintering

The effect of spark plasma sintering (SPS) on the densification of TiO₂ ceramics was investigated using a nanocrystalline TiO₂ powder. A fully-dense TiO₂ specimen with an average grain size of ∼200 nm was obtained by SPS at 700 °C for 1 h. In contrast, a theoretical density specimen could only be obtained using conventional sintering above 900 °C for 1 h with an average grain size of 1-2 μm.     

Transparent Lu2O3:Eu ceramics by sinter and HIP optimization

Evolution of porosity and microstructure was observed during densification of lutetium oxide ceramics doped with europium (Lu₂O₃:Eu) fabricated via vacuum sintering and hot isostatic pressing (HIP’ing). Nano-scale starting powder was uniaxially pressed and sintered under high vacuum at temperatures between 1575 and 1850 °C to obtain densities ranging between 94% and 99%, respectively. Sintered compacts were then subjected to 200 MPa argon gas at 1850 °C to reach full density. Vacuum sintering above 1650 °C led to rapid grain growth prior to densification, rendering the pores immobile. Sintering between 1600 and 1650 °C resulted in closed porosity yet a fine grain size to allow the pores to remain mobile during the subsequent HIP’ing step, resulting in a fully-dense highly transparent ceramic without the need for subsequent air anneal. Light yield performance was measured and Lu₂O₃:Eu showed ∼4 times higher light yield than commercially used scintillating glass indicating that this material has the potential to improve the performance of high energy radiography devices.     

Simultaneous synthesis and densification of transparent,photoluminescent polycrystalline YAG by current activated pressure assisted densification (CAPAD)

We report a method for the synthesis and processing of transparent bulk polycrystalline yttrium aluminum garnet (YAG) and photoluminescent Ce-doped YAG ceramics via solid-state reactive-current activated pressure assisted densification (CAPAD). The process uses commercially available γ-Al₂O₃, Y₂O₃, and CeO₂ nanopowders. The nanopowders were reacted and densified simultaneously at temperatures between 850 °C and 1550 °C and at a maximum pressure of 105 MPa. The solid-state reaction to phase pure YAG occurs in under 4 min at processing temperatures 1100 °C which is significantly faster (on the order of tens of hours) and occurs at much lower temperatures (∼600 °C) compared to conventional reaction sintering. We found that the reaction significantly improves densification – the shrinkage rate of reaction-produced YAG was three times higher than that of YAG using pre-reacted powder. The Ce additions were found to retard the reaction driven shrinkage kinetics by a factor ∼3, but are still faster (by a factor ∼1.6) than those associated with direct densification (no synthesis). Densities >99% were achieved in both pure YAG and Ce doped YAG (Ce:YAG). Results of optical measurements show good transparency in the visible and photoluminescence (PL) in the Ce:YAG. The PL peak is broad and appears white when excited using blue light confirming that the ceramics can be used in solid state lighting to produce white light.     

Synthesis and characterization of nanocrystalline La2Mo2O9 fast oxide-ion conductor by an in-situ polymerization method

A nanocrystalline La₂Mo₂O₉ powder was synthesized via the pyrolysis of polyacrylate salt precursor prepared by an in situ polymerization of the metal salts and acrylic acid. The pyrolysis behavior of the polymeric precursor was studied by thermal (TG/DTA) analysis. The obtained product was characterized by X-ray diffraction (XRD) and transmission electron microscope (TEM) analysis. The results revealed that the average particle size is ∼25 nm for La₂Mo₂O₉ with good crystallinity. The synthesized nanocrystalline La₂Mo₂O₉ powder showed good sinterability and reached ∼99% of theoretical density when sintered at 800 °C for 4 h. The La₂Mo₂O₉ sample sintered at 800 °C, yield good microstructure with improved conductivity value of about 0.12 S/cm at 800 °C.     

Investigation of TaC–TaB<Subscript>2</Subscript> ceramic composites

The TaC–TaB₂ composition was sintered by spark plasma (SPS) at 1900–2100°C and applied pressure of 30 MPa. TaC and 2–3 wt% B₄C were used as starting powders. Densification process, phase evolution, microstructure and the mechanical properties of the composites were investigated. The results indicated that the TaC–TaB₂ composition could be SPS to 97% of theoretical density in 10 min at 2100°C. Addition of B₄C leads to an increase in the density sample from 76 to 97%. B₄C nano-powder resists grain growth even at high temperature 2100°C. The formation of TaB₂/carbon at TaC grain boundaries helps in pinning the grain boundary and inhibiting grain growth. The phase formation was associated with carbon and boron diffusion from the starting particles B₄C to form TaB₂ phases. TaC grain sizes decreased with increase in B₄C concentration. Samples with 2.0 wt% B₄C composition had highest flexure strength up to 520 MPa. The effect of B₄C addition on hardness measured by microhardness has been studied. Hardness of samples containing 3.0 wt% B₄C was 16.99 GPa.     

Synthesis, densification, and mechanical properties of TaB2

Tantalum diboride (TaB₂) was synthesized by reducing Ta₂O₅ using B₄C and graphite at 1600 °C under flowing Ar. The powder had an average particle size of 0.4 μm with both needle-like and rounded particles. The TaB₂ powder was hot pressed to relative densities of 97% at 2000 °C (3.6 μm grain size) and 98% at 2100 °C (5.3 μm grain size). Mechanical properties were measured for TaB₂ hot pressed at 2100 °C and were comparable to those of the commonly studied diborides, ZrB₂ and HfB₂. The Young's modulus was 551 GPa, Vickers' hardness was 25.6 GPa, flexure strength was 555 MPa, and fracture toughness was 4.5 MPa-m^1/2.     

Effect of the sintering temperature on the properties of Ce0.85La0.10Ca0.05O2−δ electrolyte material

Rare earth and alkaline earth co-doped Ce_0.85La_0.10Ca_0.05O_2−δ electrolyte material with the powder obtained by solid-state reaction method was sintered at 1300, 1400, 1500 and 1600 °C respectively. The results showed that the ionic conductivity of the sample sintered at 1400 °C was slightly lower compared to that sintered at 1500 °C in the temperature range of 300-550 °C, while the sample sintered at 1400 °C showed the highest ionic conductivity in all the samples above 550 °C. The ionic conductivity of ∼0.021 S/cm at 600 °C and the relative density of 98.2% were observed for the sample sintered at 1400 °C. In addition, the highest flexural strength with 145 MPa was also obtained for the sample sintered at 1400 °C. It suggested that the sintering temperature for Ce_0.85La_0.10Ca_0.05O_2−δ electrolyte may be reduced to as low as 1400 °C with desired properties.     

Reaction sintering fabrication of (AlN, TiN)-Al2O3 composite

The (AlN, TiN)-Al₂O₃ composites were fabricated by reaction sintering powder mixtures containing 10-30 wt.% (Al, Ti)-Al₂O₃ at 1420-1520°C in nitrogen. It was found that the densification and mechanical properties of the sintered composites depended strongly on the Al, Ti contents of the starting powder and hot pressing parameters. Reaction sintering 20 wt.% (Al, Ti)-Al₂O₃ powder in nitrogen in 1520°C for 30 min yields (AlN, TiN)-Al₂O₃ composites with the best mechanical properties, with a hardness HRA of 94.1, bending strength of 687 MPa, and fracture toughness of 6.5 MPa m^1/2. Microstructure analysis indicated that TiN is present as well dispersed particulates within a matrix of Al₂O₃. The AlN identified by XRD was not directly observed, but probably resides at the Al₂O₃ grain boundary. The fracture mode of these composites was observed to be transgranular.     

Microwave dielectric properties of (ABi)1/2MoO4 (A = Li,Na, K,Rb, Ag) type ceramics with ultra-low firing temperatures

A series of (ABi)_1/2MoO₄ (A = Li, Na, K, Rb, Ag) compositions were studied in regard to the sintering behavior, phase composition, microwave dielectric properties and chemical compatibility with silver and/or aluminum for electrodes. All the (ABi)_1/2MoO₄ (A = Li, Na, K, Rb, Ag) ceramics could be sintered below 700 °C with relative densities above 93%. Whereas the (KBi)_1/2MoO₄ ceramic can be sintered to a high density at around 630 °C/2 hrs with a relative permittivity ∼37, a Qf value of 4000 GHz and a temperature coefficient of resonant frequency (TCF) ∼ +117 ppm/°C. Furthermore, from the XRD analysis of co-fired ceramics, the (KBi)_1/2MoO₄ ceramic reacts with silver but not with aluminum at its densification temperature. The (ABi)_1/2MoO₄ (A = Li, Na, K, Rb, Ag) type ceramics can all be considered into the new field of ultra-low temperature co-firing dielectrics for multilayer applications.     

Synthesis reactions for Ti3SiC2 through pulse discharge sintering TiH2/Si/TiC powder mixture

Ternary compound Ti₃SiC₂ was rapidly synthesized by pulse discharge sintering the powder mixture of 1TiH₂/1Si/1.8TiC without preliminary dehydrogenation. Almost single-phase dense Ti₃SiC₂ was synthesized at 1400 °C for 20 min. The grain size of synthesized Ti₃SiC₂ strongly depends on sintering temperature. The synthesis mechanism of Ti₃SiC₂ was revealed to be completed via the reactions among the intermediate phases of Ti₅Si₃, TiSi₂ and the other reactants in the starting powder. The Ti-Si liquid reaction occurring above the Ti-Ti₅Si₃ eutectic temperature at 1330 °C was found to assist the synthesis reaction and densification of Ti₃SiC₂. The dehydrogenation of TiH₂ was accelerated by the synthesis reactions.     

The effect of Tb doping on the structure and spectroscopic properties of MgAl2O4 nanopowders

In this paper, a modified sol-gel method was employed to prepare nanostructured MgAl₂O₄ spinel powders doped with Tb³⁺ ions and thermally treated at 700 and 1000 °C for 3 h. The structural properties of the prepared at 700 and 1000 °C powders where characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). According to obtained XRD patterns the formation of single-phase spinels after calcination was confirmed. The XRD analyses demonstrated that the powders were single-phase spinel nanopowders with high crystallite dispersion. The Rietveld method was applied to calculate lattice parameters. The averaged spinel particle size was determined to be ∼10 nm for calcination at 700 °C and ∼20 nm at 1000 °C. The emission and excitation spectra measured at room and low temperature (77 K) for the samples calcined at 700 and 1000 °C demonstrated characteristic spectra of Tb³⁺ ions. The effect of MgAl₂O₄:Tb³⁺ grain sizes on luminescence properties was noticed.     

Chemical stability and dielectric properties of RO-La2O3-B2O3 (R = Ca, Mg, Zn)-based ceramics

New lanthanum borate (La₂O₃-B₂O₃) glasses modified with divalent oxides, such as CaO, MgO and ZnO were investigated as potential low temperature dielectrics by understanding compositional dependence of dielectric properties and chemical leaching resistance. Firing behavior, such as densification and crystallization, depended strongly on the glass composition and is found to influence the resultant dielectric performance. Specifically, the dielectric composition of 20ZnO-20La₂O₃-60B₂O₃ glass with 40 wt% Al₂O₃ as a filler showed distinct enhancements of dielectric properties, i.e., k ∼ 8.3 and Q ∼ 1091 at the resonant frequency of 17.1 GHz, as a result of 850 °C firing. The result was believed related to earlier densification and unexpected evolvements of ZnAl₂O₄ and La(BO₂)₃ phases during firing. The Mg-containing glass sample was most stable in strong acid solutions and did not show any significant changes in microstructure even after 300 min exposure. The Ca-containing glass sample was not regarded as a promising candidate for low temperature dielectrics from the observed low quality factor and weak chemical durability.     

Phase stability study of Bi0.15Sr0.85-xAexCoO3-δ (x = 0 and Ae = Ba0.28; Ca0.17) perovskites by in-situ neutron diffraction

The oxygen deficient perovskites, Bi_0.15Sr_0.85-xAe_xCoO_3-δ, x = 0 and Ae_x = Ba_0.28, Ca_0.17, were studied with in-situ neutron powder diffraction and combined TGA/DSC in order to investigate their behaviour at elevated temperatures in oxidising conditions. The phase stability of the I4/mmm supercell structure adopted by Bi_0.15Sr_0.85CoO_3-δ is shown to be dependent on temperature and the oxygen content of the phase, with three structural events, at T ∼ 250, 590 and 880 °C, detected. The first transition occurs as the perovskite supercell vanishes due to oxygen absorption; the second transition is also associated with oxidation and involves the decomposition of the perovskite phase via an exothermic process to yield a dominant hexagonal phase. Finally, at T ∼ 900 °C the perovskite phase re-forms. For the Ba and Ca containing materials the decomposition to the hexagonal phase occurs at T ∼ 600 °C and ∼ 650 °C respectively. The presence of Ca at the A-site is found to stabilise the I4/mmm supercell structure in the range RT - 650 °C. The antiferromagnetic to paramagnetic transitions occur at T_N ∼ 250 °C, T_N ∼ 175 °C and T_N ∼ 145 °C for the samples with Ae_x = Ba_0.28, x = 0 and Ae_x = Ca_0.17, respectively.     

Structural and optical properties of Er-doped Y2Ti2O7 thin films by sol-gel method

Er³⁺-doped Y₂Ti₂O₇ and Er₂Ti₂O₇ thin films were fabricated by sol-gel spin-coating method. A well-defined pyrochlore phase Er_xY_2-xTi₂O₇ was observed while the annealing temperature exceeded 800 °C. The average transmittance of the Er_xY_2-xTi₂O₇ thin films annealed at 400 to 900 °C reduces from ∼ 87 to ∼ 77%. The refractive indices and optical band gaps of Er_xY_2-xTi₂O₇ (x = 0-2) annealed at 800 °C/1 h vary from 2.20 to 2.09 and 4.11 to 4.07 eV, respectively. The ∼ 1.53 μm photoluminescence spectrum of Er³⁺ (5 mol%)-doped Y₂Ti₂O₇ thin films annealed at 700 °C/1 h exhibits the maximum intensity and full-width at half maximum (∼ 60 nm).     

Optimization of Bi2Te3 and Sb2Te3 thin films deposited by co-evaporation on polyimide for thermoelectric applications

The optimization of the deposition process of n-type Bismuth Telluride and p-type Antimony Telluride thin films for thermoelectric applications is reported. The films were deposited on a 25 μm-thick flexible polyimide (kapton) substrate by co-evaporation of Bi and Te, for the n-type element, and Sb and Te, for the p-type element. The evaporation rate of each material was monitorized by an oscillating crystal sensor and the power supplied to each evaporation boat was controlled with a PID algorithm in order to achieve a precise user-defined constant evaporation rate.The influence of substrate temperature (in the range 240-300 °C) and evaporation rates of Bi, Te and Sb on the electronic properties of the films was studied and optimized to obtain the highest Seebeck coefficient. The best n-type Bi₂Te₃ films were deposited at 300 °C with a polycrystalline structure, a composition close to stoichiometry, electrical resistivity ∼20 μΩ m and Seebeck coefficient −195 μV/°C. The best p-type Sb₂Te₃ films were deposited at 240 °C, are slightly Te-rich, have electrical resistivity ∼20 μΩ m and Seebeck coefficient +153 μV/°C. These high Seebeck coefficients and low electrical resistivities make these materials suitable for fabrication of Peltier coolers and thermopile devices.     

Synthesis, structure, and electrochemical characteristics of LiNi1/3Co1/3Mn1/3O2 prepared by thermal polymerization

A thermal polymerization route was adopted to synthesize layered LiNi_1/3Co_1/3Mn_1/3O₂ materials. After annealing the polymer gel containing metal salts at different temperatures from 850 to 1000 °C for different time between 6 and 25 h, powders of pure α-NaFeO₂ phase were obtained. The crystal structure, morphology and electrochemical properties of the products were investigated by XRD, SEM, electrochemical cell cycling and AC impedance spectroscopy. It is found that the powder annealed at 950 °C for 15 h shows the best electrochemical property with the first specific discharge capacity of 188 mAh/g at C/10 and 87% retention after 100 cycles. It exhibits good rate capability with the specific capacity of 169 mAh/g at 1 C and 110 mAh/g at 6 C. Adopting a slowly cooling procedure during the powder annealing can improve the electrochemical performance of the LiNi_1/3Co_1/3Mn_1/3O₂ powder.     

Preparation of the rod-like β-Si3N4 particles favoring the self-reinforcing Si3N4 ceramics

The β-Si₃N₄ particles were prepared by heating original α-Si₃N₄ powder with rare earth oxide Nd₂O₃ or Yb₂O₃ additives at 1600-1700 °C for 1.5 h. The transformation ratio of α-Si₃N₄ was also investigated by XRD. The results showed that Yb₂O₃ could accelerate the transformation of Si₃N₄ more effectively than Nd₂O₃ and the powder heated at 1700 °C with over 4 wt.% Yb₂O₃ has a high transformation ratio of over 98%. The morphologies of the heated powders were observed by scanning electron microscopy. The results showed that the powder heated at 1700 °C with 4 wt.% Yb₂O₃ had ideal β-Si₃N₄ rod-like morphology particles. This heated powder was used as a seed by adding it to the original α-Si₃N₄ powder to prepare self-reinforced Si₃N₄ ceramic by hot-pressed sintering. The fracture toughness of the seeded Si₃N₄ ceramics increased to 9.1 MPa m^1/2 from 7.6 MPa m^1/2 of the unseeded Si₃N₄ ceramics, while the high value of strength was still kept at 1200 °C.     

Sol-gel preparation of near-infrared broadband emitting Er-doped SiO2-Ta2O5 nanocomposite films

This article reports a study on the preparation, densification process, and structural and optical properties of SiO₂-Ta₂O₅ nanocomposite films obtained by the sol-gel process. The films were doped with Er³⁺, and the Si:Ta molar ratio was 90:10. Values of refractive index, thickness and vibrational modes in terms of the number of layers and thermal annealing time are described for the films. The densification process is accompanied by OH group elimination, increase in the refractive index, and changes in film thickness. Full densification of the film is acquired after 90 min of annealing at 900 °C. The onset of crystallization and devitrification, with the growth of Ta₂O₅ nanocrystals occurs with film densification, evidenced by high-resolution transmission electron microscopy. The Er³⁺-doped nanocomposite annealed at 900 °C consists of Ta₂O₅ nanoparticles, with sizes around 2 nm, dispersed in the SiO₂ amorphous phase. The main emission peak of the film is detected at around 1532 nm, which can be assigned to the ⁴I_13/2 → ⁴I_15/2 transition of the Er³⁺ ions present in the nanocomposites. This band has a full width at half medium of 64 nm, and the lifetime measured for the ⁴I_13/2 levels is 5.4 ms, which is broader compared to those of other silicate systems. In conclusion, the films obtained in this work are excellent candidates for use as active planar waveguide.     

Effect of copper-oxide segregation on the dielectric properties of CaCu3Ti4O12 thin films fabricated by pulsed-laser deposition

We investigated the effects of post-deposition cooling conditions on the surface morphologies and dielectric properties of CaCu₃Ti₄O₁₂ (CCTO) thin films grown by pulsed-laser deposition on Pt/TiO₂/SiO₂/Si substrates. CCTO thin films cooled under the typical cooling parameters, i.e., slow cooling (3 °C/min) at high oxygen pressure (66 kPa) showed a severe segregation of nanoparticles near the grain boundaries, which was identified to be copper oxide from electron probe micro analyzer mapping. On the other hand, we could not observe any segregation on the film surface when the samples were cooled fast (∼ 20 °C/min) at relatively low oxygen pressure (100 Pa). The dielectric constant, ε_r, of CCTO thin films deposited at 750 °C with severe surface segregation (ε_r ∼ 750 at 10 kHz) was found to be much lower than that (ε_r ∼ 2000 at 10 kHz) of CCTO thin films with smooth surface. As the copper-oxide segregation becomes more serious, which preferentially occurs at relatively high ambient oxygen pressure and temperature, the degradation in the dielectric properties of CCTO films becomes larger. The variation of dielectric constant of CCTO films with no copper-oxide segregation could be related to the presence of an impurity phase at grain boundaries.