Bulk WC-Al2O3 composites prepared by spark plasma sintering

WC and WC-Al₂O₃ materials without metallic binder addition were densified by spark plasma sintering in the range of 1800-1900 °C. The densification behavior, phase constitution, microstructure and mechanical properties of pure WC and WC-Al₂O₃ composite were investigated. The addition of Al₂O₃ facilitates sintering and increases the fracture toughness of the composites to a certain extent. An interesting phenomenon is found that a proper content of Al₂O₃ additive helps to limit the formation of W₂C phase in sintered WC materials. The pure WC specimen possesses a hardness (HV₁₀) of 25.71 GPa, fracture toughness of 4.54 MPa·m^1/2, and transverse fracture strength of 862 MPa, while those of WC-6.8 vol.% Al₂O₃ composites are 24.48 GPa, 6.01 MPa·m^1/2, and 1245 MPa respectively. The higher fracture toughness and transverse fracture strength of WC-6.8 vol.% Al₂O₃ are thought to result from the reduction of W₂C phase, the crack-bridging by Al₂O₃ particles and the local change in fracture mode from intergranular to transgranular.     

Piezoelectric and dielectric properties of Dy2O3-doped (Bi0.5Na0.5)0.94Ba0.06TiO3 lead-free ceramics

(Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ + x wt% Dy₂O₃ with x = 0-0.3 ceramics were synthesized by conventional solid-state processes. The effects of Dy₂O₃ on the microstructure, the piezoelectric and dielectric properties were investigated. X-ray diffraction pattern confirmed that the coexistence of tetragonal and rhombohedral phases in the (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ composition was not changed by adding 0.05-0.3 wt% Dy₂O₃. SEM images indicate that all the ceramics have pore-free microstructures with high density, and that doping of Dy₂O₃ inhibits the grain growth of the ceramics. The addition of Dy₂O₃ shows the double effects on decreasing the piezoelectric and dielectric properties for 0 < x < 0.15 when Dy³⁺ ions substitute B-site Ti⁴⁺ ions, and increasing the properties for 0.15 < x < 0.3 when Dy³⁺ ions enters into A-site of the perovskite structure. The optimum electric properties of piezoelectric constant d₃₃ = 170 pC/N and the dielectric constant ?_r = 1900 (at a frequency of 1 kHz) are obtained at x = 0.3.     

Microstructure and mechanical properties of laminated ZrB2-SiC ceramics with ZrO2 interface layers

Laminated ZrB₂-SiC ceramics with ZrO₂ interface layers were successfully prepared by tape casting, laminating and hot pressing. The flexural strength and fracture toughness are 561 ± 20 MPa and 14.4 ± 0.3 MPa m^1/2 for parallel direction, and 432 ± 18 MPa and 5.8 ± 0.3 MPa m^1/2 for perpendicular direction. The fracture toughness for parallel direction is improved significantly compared to monolithic ZrB₂-SiC ceramics. The toughening mechanism was attributed to the deflection and branch of the crack and the new microcracks, which would increase the propagation path and fracture work.     

Sinterability and dielectric properties of Ba0.55Sr0.4Ca0.05TiO3-CaTiSiO5-Mg2TiO4 composite ceramics

The composite ceramics of Ba_0.55Sr_0.4Ca_0.05TiO₃-CaTiSiO₅-Mg₂TiO₄ (BSCT-CTS-MT) were prepared by the conventional solid-state route. The sintering performance, phase structures, morphologies, and dielectric properties of the composite ceramics were investigated. The BSCT-CTS-MT ceramics were sintered at 1100 °C and possessed dense microstructure. The dielectric constant was tailored from 1196 to 141 as the amount of Mg₂TiO₄ increased from 0 to 50 wt%. The dielectric constant and dielectric loss of 40 wt% Ba_0.55Sr_0.4Ca_0.05TiO₃-10 wt% CaTiSiO₅-50 wt% Mg₂TiO₄ was 141 and 0.0020, respectively, and the tunability was 8.64% under a DC electric field of 8.0 kV/cm. The Curie peaks were broadened and depressed after the addition of CaTiSiO₅. The optimistic dielectric properties made it a promising candidate for the application of tunable capacitors and phase shifters.     

Fabrication of full density near-nanostructured cemented carbides by combination of VC/Cr3C2 addition and consolidation by SPS and HIP technologies

The aim of present work is to study the effect of VC and/or Cr₃C₂ in densification, microstructural development and mechanical behavior of nanocrystalline WC-12wt.%Co powders when they are sintered by spark plasma sintering (SPS) and hot isostatic pressing (HIP). The results were compared to those corresponding to conventional sintering in vacuum. The density, microstructure, X-ray diffraction, hardness and fracture toughness of the sintered materials were evaluated. Materials prepared by SPS exhibits full densification at lower temperature (1100 °C) and a shorter stay time (5 min), allowing the grain growth control. However, the effect of the inhibitors during SPS process is considerably lower than in conventional sintering. Materials prepared by HIP at 1100 °C and 30 min present full densification and a better control of microstructure in the presence of VC. The added amount of VC allows obtaining homogeneous microstructures with an average grain size of 120 nm. The hardness and fracture toughness values obtained were about 2100 HV₃₀ and close to 10 MPa m^1/2, respectively.     

Synthesis, microstructure and mechanical properties of reaction-infiltrated TiB2-SiC-Si composites

TiB₂-C preforms formed with different compositions and processing parameters were reactively infiltrated by Si melts at 1450 °C to fabricate TiB₂-SiC-Si composites. Phase constituent and microstructure of these composites were analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The resulting composites are generally composed of TiB₂ and reaction-formed β-SiC major phases, together with a quantity of residual Si. Unreacted carbon is detected in the samples with a starting composition of 2TiB₂ + 1C formed at higher pressure and in all of the ones at the composition of 1TiB₂ + 1C. The distribution of these phases is fairly homogeneous in microstructure. TiB₂-SiC-Si composites show good mechanical properties, with representative values of 19.9 GPa in hardness, 395 GPa in elastic modulus, 3.5 MPa m^1/2 in fracture toughness and 604 MPa in bending strength. The primary toughening and strengthening mechanism is attributed to the crack deflection of TiB₂ particles.     

Low temperature sintering and microwave dielectric properties of (Mg0.7Zn0.3)0.95Co0.05TiO3 ceramics with BaCu(B2O5) additions

The effects of BaCu(B₂O₅) additives on the sintering temperature and microwave dielectric properties of (Mg_0.7Zn_0.3)_0.95Co_0.05TiO₃ ceramics were investigated. The (Mg_0.7Zn_0.3)_0.95Co_0.05TiO₃ ceramics were not able to be sintered below 1000 °C. However, when BaCu(B₂O₅) were added, they were sintered below 1000 °C and had the good microwave dielectric properties. It was suggested that a liquid phase with the composition of BaCu(B₂O₅) was formed during the sintering and assisted the densification of the (Mg_0.7Zn_0.3)_0.95Co_0.05TiO₃ ceramics at low temperature. BaCu(B₂O₅) powders were produced and used to reduce the sintering temperature of the (Mg_0.7Zn_0.3)_0.95Co_0.05TiO₃ ceramics. Good microwave dielectric properties of Q × f = 35,000 GHz, ?_r = 18.5.0 and τ_f = −51 ppm/°C were obtained for the (Mg_0.7Zn_0.3)_0.95Co_0.05TiO₃ ceramics containing 7 wt.% mol% BaCu(B₂O₅) sintered at 950 °C for 4 h.     

Densification and mechanical properties of fine-grained Al2O3-ZrO2 composites consolidated by spark plasma sintering

Alumina matrix composites containing 5 and 10 wt% of ZrO₂ were sintered under 100 MPa pressure by spark plasma sintering process. Alumina powder with an average particle size of 600 nm and yttria-stabilized zirconia with 16 at% of Y₂O₃ and with a particle size of 40 nm were used as starting materials. The influence of ZrO₂ content and sintering temperature on microstructures and mechanical properties of the composites were investigated. All samples could be fully densified at a temperature lower than 1400 °C. The microstructure analysis indicated that the alumina grains had no significant growth (alumina size controlled in submicron level 0.66-0.79 μm), indicating that the zirconia particles provided a hindering effect on the grain growth of alumina. Vickers hardness and fracture toughness of composites increased with increasing ZrO₂ content, and the samples containing 10 wt% of ZrO₂ had the highest Vickers hardness of 18 GPa (5 kg load) and fracture toughness of 5.1 MPa m^1/2.     

Interface and defect characterization in hot-pressed ZrB2-SiC ceramics

ZrB₂ is interesting for thermal protection materials because of favorable thermal stability, mechanical properties and oxidation resistance. ZrB₂-20 vol.% SiC composite was prepared by hot-pressing at 2000 °C and 30 MPa. Microstructures and interfacial characterization were investigated by high resolution transmission electron microscopy. SiC polytype was formed as 6H structure in hot-pressed ZrB₂-SiC ceramics. Numerous edge dislocations were found in ZrB₂ grains. There was no interfacial amorphous layer or transition layer at the ZrB₂/6H-SiC interface. Note also that since only one of the constituents (ZrB₂ or SiC) was oriented along a proper zone axis, no evident orientation relationship was observed between SiC or ZrB₂.     

A new temperature stable microwave dielectric ceramics: ZnTiNb2O8 sintered at low temperatures

The phases, microstructure and microwave dielectric properties of ZnTiNb₂O₈-xTiO₂ composite ceramics with different weight percentages of BaCu(B₂O₅) additive prepared by solid-state reaction method have been investigated using the X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy-dispersive spectroscopy (EDS). The results showed that the microwave dielectric properties were strongly dependent on densification, grain sizes and crystalline phases. The sintering temperature of ZnTiNb₂O₈ ceramics was reduced from 1250 °C to 950 °C by doping BaCu(B₂O₅) additive and the temperature coefficient of resonant frequency (τ_f) was adjusted from negative value of −52 ppm/°C to 0 ppm/°C by incorporating TiO₂. Addition of 2 wt% BaCu(B₂O₅) in ZnTiNb₂O₈-xTiO₂ (x = 0.8) ceramics sintered at 950 °C showed excellent dielectric properties of ?_r = 38.89, Q × f = 14,500 GHz (f = 4.715 GHz) and τ_f = 0 ppm/°C, which represented very promising candidates as LTCC dielectrics for LTCC applications.     

Sintering effect on electrical properties of ZnO-V2O5-MnO2-Nb2O5 ceramics

The microstructure and electrical properties of quaternary ZnO-V₂O₅-MnO₂-Nb₂O₅ ceramics were investigated at different sintering temperature (875-950 °C). The average grain size increased from 4.4 μm to 9.6 μm with increasing sintering temperature. The breakdown field decreased from 6991 V/cm to 943 V/cm with increasing sintering temperature. Proper sintering for quaternary ZnO-V₂O₅-MnO₂-Nb₂O₅ ceramics led to surprisingly high nonlinear coefficient (50). The donor concentration increased from 3.33 × 10¹⁷ cm⁻³ to 7.64 × 10¹⁷ cm⁻³ with increasing sintering temperature and the barrier height exhibited the maximum value (1.07 eV) at 900 °C.     

Synthesis of MoSi2/WSi2 nanocrystalline powder by mechanical-assistant combustion synthesis method

MoSi₂/WSi₂ nanocrystalline powder has been successfully synthesized by the mechanical-assistant combustion synthesis method. This method includes a ball-milling process followed by combustion synthesis. The composition and microstructure of the as-milled powder mixture were detected by X-ray diffraction and scanning electron microscopy analyses. Their results show that the Mo(W) solid solution and Si nanocrystals could be obtained during the ball-milling process. Compared with normal powder mixture (Mo + Si + W), it could be easily ignited and high maximum combustion temperature was achieved. It was also confirmed that MoSi₂/WSi₂ solid solution powder with nanometric structure could be prepared through combustion synthesis method from the mechanical activated powder mixture.     

Improved dielectric and non-ohmic properties of Ca2Cu2Ti4O12 ceramics prepared by a polymer pyrolysis method

Non-ohmic and dielectric properties of Ca₂Cu₂Ti₄O₁₂ (CaCu₃Ti₄O₁₂/CaTiO₃ composite) ceramics prepared by a polymer pyrolysis method (PP-ceramic samples) are investigated. The PP-ceramics show a highly dense structure and improved non-ohmic and dielectric properties compared to the ceramics obtained by a solid state reaction method (SSR-ceramic samples). ?′ (tan δ) of the PP-ceramic samples is found to be higher (lower) than that of the SSR-ceramic samples. Interestingly, the PP-ceramic sintered at 1050 °C for 10 h exhibits the high ?′ of 2530 with weak frequency dependence below 1 MHz, the low tan δ less than 0.05 in the frequency range of 160 Hz-177 kHz, and the little temperature coefficient, i.e., |Δ?′| ≤ 15 % in the temperature range from −55 to 85 °C. These results indicate that the CaCu₃Ti₄O₁₂/CaTiO₃ composite system prepared by PP method is a promising high-?′ material for practical capacitor application.     

Strengthening and toughening forming of Al/Al2O3 composite in pseudo-semi-solid state

A new technology—thixo-die-forging of the composite in pseudo-semi-solid state was proposed based on the powder metallurgy technology combing with semi-solid metal process, and the cup shells with Al/Al₂O₃  composite was prepared successfully. The metallographic analysis and performance test show that the microstructure of parts is dense and mechanical properties are excellent with the volume fraction of Al is 37 %. The bend strength and fracture toughness of the composite are about 570-690 MPa and 8.5-16.8 MPa m^1/2, respectively. Comparing with reaction in situ and high temperature oxidation technologies the bending strength and fracture toughness are improved greatly. At the same time, it shows that the technology parameters have great influences on the properties. So it is feasible to prepare metal/ceramics composites by the proposed technology.     

Ti3AlC2掺杂SPS法制备Ti2AlC/TiAl复合材料的研究

通过2TiC-Ti-1.2Al体系的原位热压反应制备了Ti₃AlC₂陶瓷,然后以59.2Ti-30.8Al-10Ti₃AlC₂(wt%)为反应体系,采用放电等离子烧结技术制备出Ti₂AlC/TiAl基复合材料。借助XRD、SEM分析了产物的相组成和微观结构,并测量了其室温力学性能。结果表明：原位热压烧结产物由Ti₃AlC₂和TiC相组成,Ti₃AlC₂呈典型的层状结构,TiC颗粒分布在其间。SPS法制备的Ti₂AlC/TiAl基复合材料主要由TiAl、Ti₃Al和Ti₂AlC相组成,Ti₂AlC增强相主要分布于基体晶界处,表现为晶界/晶内强化作用。力学性能测试表明：Ti₂AlC/TiAl基复合材料的密度、维氏硬度、断裂韧性和抗弯强度分别为3.85 g/cm₃、5.37 GPa、7.17 MPa?m_1/2和494.85 MPa。     

Characterization of sol-gel synthesised lead-free (1 − x)Na0.5Bi0.5TiO3-xBaTiO3-based ceramics

The crystal structure, microstructure, dielectric and ferroelectric properties of (1 − x)Na_0.5Bi_0.5TiO₃-xBaTiO₃ ceramics with x = 0, 0.03, 0.05, 0.07 and 0.1 are investigated. A structural variation according to the system composition was investigated by X-ray diffraction (XRD) analyses. The results revealed that the synthesis temperature for pure perovskite phase powder prepared by the present sol-gel process is much lower (800 °C), and a rhombohedral-tetragonal morphotropic phase boundary (MPB) is found for x = 0.07 composition which showing the highest remanent polarization value and the smallest coercive field. The optimum dielectric and piezoelectric properties were found with the 0.93Na_0.5Bi_0.5TiO₃-0.07BaTiO₃ composition. The piezoelectric constant d₃₃ is 120 pC/N and good polarization behaviour was observed with remanent polarization (P_r) of 12.18 pC/cm², coercive field (E_c) of 2.11 kV/mm, and enhanced dielectric properties ?_r > 1500 at room temperature. The 0.93Na_0.5Bi_0.5TiO₃-0.07BaTiO₃-based ceramic is a promising lead-free piezoelectric candidate for applications in different devices.     

Microstructure and electrical properties of PLZT ceramics from Pb3O4 as the lead source

In this paper, Pb₃O₄, rather than conventional PbO, was introduced in the solid phase synthesis of (Pb_0.92La_0.08)(Zr_0.35Ti_0.65)_0.98O₃ (PLZT) ceramics. The microstructure and electrical properties of the PLZT ceramics were investigated. Results showed that due to the activity of Pb₃O₄, pyrochlore phase PLZT was depressed effectively. The PLZT ceramics with 5.0 wt.% excess Pb₃O₄ in the original materials had a well-crystallized pure perovskite structure when being sintered at 1100 °C for 6 h. In addition, the amount of Pb₃O₄ had an influence on the electrical properties of the PLZT ceramics. Residual polarization as high as 36.9 μC/cm² was obtained from the samples with 5.0 wt.% excess Pb₃O₄.     

Dielectric relaxation behaviors of pure and Pr6O11-doped CaCu3Ti4O12 ceramics in high temperature range

Pure and Pr₆O₁₁-doped CaCu₃Ti₄O₁₂ (CCTO) ceramics were prepared by conventional solid-state reaction method. The compositions and structures were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The influences of Pr-ion concentration on dielectric properties of CCTO were measured in the ranges of 60 Hz-3 MHz and 290-490 K. The third phase of Ca₂CuO₃ was observed from the XRD of CCTO ceramics. From SEM, the grain size was decreased obviously with high valence Pr-ion (mixing valence of Pr³⁺ and Pr⁴⁺) substituting Ca²⁺. The room temperature dielectric constant of Pr-doped CCTO ceramics, sintered at 1323 K, was an order of magnitude lower than the pure CCTO ceramics due to the grain size decreasing and Schottky potential increasing. The dielectric spectra of Pr-doped CCTO were flatter than that of pure CCTO. The loss tangent of Pr-doped CCTO ceramics was less than 0.20 in 2 × 10²-10⁵ Hz region below 440 K. The complex impedance spectra of pure and Pr-doped CCTOs were fitted by ZView. From low to high frequency, three semicircles were observed corresponding to three different conducting regions: electrode interface, grain boundary and grain. By fitting the resistors R and capacitors C, the activation energies of grain boundary and electrode contact were calculated. All doped CCTOs showed higher activation energies of grain boundary and electrode than those of pure CCTO ceramics, which were concordant with the decreasing of dielectric constant after Pr₆O₁₁ doping.     

Preparation, structure and electrical conductivity of the pyrochlore-type phase Sm2Zr2O7 codoped with bivalent magnesium and trivalent dysprosium cations

The pyrochlore-type phases with the compositions of SmDy_1−xMg_xZr₂O_7−x/2 (0 ≤ x ≤ 0.20) have been prepared by pressureless-sintering method for the first time as possible solid electrolytes. The structure and electrical conductivity of SmDy_1−xMg_xZr₂O_7−x/2 ceramics have been studied by the X-ray diffraction (XRD), scanning electron microscopy (SEM) and impedance spectroscopy measurements. SmDy_1−xMg_xZr₂O_7−x/2 (x = 0, 0.05, 0.10) ceramics exhibit a single phase of pyrochlore-type structure, and SmDy_1−xMg_xZr₂O_7−x/2 (x = 0.15, 0.20) ceramics consist of pyrochlore phase and a small amount of the second phase magnesia. The total conductivity of SmDy_1−xMg_xZr₂O_7−x/2 ceramics obeys the Arrhenius relation, and the total conductivity of each composition increases with increasing temperature from 673 to 1173 K. SmDy_1−xMg_xZr₂O_7−x/2 ceramics are oxide-ion conductors in the oxygen partial pressure range of 1.0 × 10⁻⁴ to 1.0 atm at all test temperature levels. The highest total conductivity value is about 8 × 10⁻³ S cm⁻¹ at 1173 K for SmDy_1−xMg_xZr₂O_7−x/2 ceramics.     

Investigations on synthesis of ZrB2 and development of new composites with HfB2 and TiSi2

This paper presents the results of experimental investigations carried out on the synthesis of pure ZrB₂ by boron carbide reduction of ZrO₂ and densification with the addition of HfB₂ and TiSi₂. Process parameters and charge composition were optimized to obtain pure ZrB₂ powder. Monolithic ZrB₂ was hot pressed to full density and characterized. Effects of HfB₂ and TiSi₂ addition on densification and properties of ZrB₂ composites were studied. Four compositions namely monolithic ZrB₂, ZrB₂ + 10% TiSi₂, ZrB₂ + 10% TiSi₂ + 10% HfB₂ and ZrB₂ + 10% TiSi₂ + 20% HfB₂ were prepared by hot pressing. Near theoretical density (99.8%) was obtained in the case of monolithic ZrB₂ by hot pressing at 1850 °C and 35 MPa. Addition of 10 wt.% TiSi₂ resulted in an equally high density of 98.9% at a lower temperature (1650 °C) and pressure (20 MPa). Similar densities were obtained for ZrB₂ + HfB₂ mixtures also with TiSi₂ under similar conditions. The hardness of monolithic ZrB₂ was measured as 23.95 GPa which decreased to 19.45 GPa on addition of 10% TiSi₂. With the addition of 10% HfB₂ to this composition, the hardness increased to 23.08 GPa, close to that of monolithic ZrB₂. Increase of HfB₂ content to 20% did not change the hardness value. Fracture toughness of monolithic sample was measured as 3.31 MPa m^1/2, which increased to 6.36 MPa m^1/2 on addition of 10% TiSi₂. With 10% HfB₂ addition the value of K_IC was measured as 6.44 MPa m^1/2, which further improved to 6.59 MPa m^1/2 with higher addition of HfB₂ (20%). Fracture surface of the dense bodies was examined by scanning electron microscope. Intergranular fracture was found to be a predominant mode in all the samples. Crack propagation in composites has shown considerable deflection indicating high fracture toughness. An oxidation study of ZrB₂ composites was carried out at 900 °C in air for 64 h. Specific weight gain vs time plot was obtained and the oxidized surface was examined by XRD and SEM. ZrB₂ composites have shown a much better resistance to oxidation as compared to monolithic ZrB₂. A protective glassy layer was seen on the oxidized surfaces of the composites.