Second-phase evolution and densification behavior of AlN with CaO–Y2O3–C multicomponent additive system

AlN compacts with different CaO–Y₂O₃–C mixtures were sintered between 1100 and 1850 °C to understand the effects of the in situ formed reducing atmosphere on the densification behavior and evolution of the second-phases. AlN with Y₂O₃ densified at 1750 °C, but the addition of C changed the second-phases evolution towards Y-rich phases that delayed the densification. For AlN containing CaO, the second-phases were little influenced by the reducing atmosphere, but the addition of C increased the evaporation of the second-phase compounds during sintering, limiting the densification due to the reduction of the liquid-phase fraction and the gas trapping inside the pores. AlN with CaO–Y₂O₃ mixtures could be completely densified at 1650 °C, but the addition of C inhibited the densification below this sintering temperature because liquid-phase had poor wetting and spreading characteristics and the second-phase a high melting point (>1800 °C).     

Effect of β to α phase transformation on microstructure and thermal conductivity of SiC ceramic densified with Y2O3-MgO additives in argon

SiC ceramic was fabricated by spark plasma sintering of β-SiC powder and Y₂O₃-MgO additives in argon. The effects of β→α phase transformation of SiC on microstructure and thermal conductivity of densified bulks were systematically investigated, in comparison to the counterparts using α-SiC as starting powder. The β→α phase transformation led to a “unimodal to bimodal” transition in grain size distribution. After sintering at 1850 ^oC, the incomplete β→α phase transformation induced the appearance of β/α heterophase boundary with strong effect of phonon-scattering. After sintering at 2050 ^oC, the completion of β→α phase transformation resulted in enlarged grains and disappearance of β/α heterophase boundary in SiC ceramic. The lattice oxygen content was decreased primarily by enhanced grain growth and oxygen picking-up of sintering additives, and possibly some contribution from β→α phase transformation. The optimized microstructure enabled SiC ceramic to obtain a remarkable increase in thermal conductivity from 126 to 204 W/mK after the replacement of α-SiC by β-SiC as starting powder and the accomplishment of β→α phase transformation.     

Low sintering of X7R ceramics based on barium titanate with SiO2–B2O3–Li2O sintering additives in reducing atmosphere

Development of a low-temperature sintered dielectric material derived from barium titanate for X7R characterized dielectric ceramics application is discussed in this paper. By addition of SiO₂–B₂O₃–Li₂O sintering additives to commercial BaTiO₃ powder, more than 95% of the theoretical density was obtained at a sintering temperature of 950 °C in H₂/N₂ atmosphere. The influence of the composition and procedures on the microstructures, lattice parameters and properties of ceramics materials were systemically studied. After explaining the reason for lower isolated resistivity (IR) in the previous experiment, several methods are tried out to improve the IR properties, which have reached the application requirement level of 10¹² Ω cm. These ceramics sintered between 900 °C and 950 °C in H₂/N₂ atmosphere are promising candidates for fabrication of Cu electrode MLCCs.     

Effect of adding Y2O3 on structural and mechanical properties of Al2O3–ZrO2 ceramics

The effects of adding 1–8 wt% Y₂O₃ on phase formation and fracture toughness of Al₂O₃–xZrO₂–Y₂O₃(AZY) ceramics were studied. Phase formations of the samples were characterized by the X-ray diffraction (XRD) technique. It was found that the major phase was rhombohedral-Al₂O₃, while the minor phase consisted of the monoclinic-ZrO₂, tetragonal-ZrO₂ and monoclinic-Y₂O₃. It was found that Y₂O₃ contents did not clearly influence grain shape of AZY ceramics. The results obtained from the microhardness test could be used to evaluate the fracture toughness. It was found that the smaller grains had high fracture toughness. The maximum fracture toughness of 4.827 MPa m^1/2 was obtained from 4 wt% Y₂O₃. Refinement of lattice parameters using Rietveld analysis revealed the quantitative phases of AZY ceramics. This shows that under adding Y₂O₃ conditions the proportion of tetragonal-ZrO₂ phase plays an important role for the mechanical properties of AZY ceramics.     

Effect of in-situ formed Y2O3 by metal hydride reduction reaction on thermal conductivity of β-Si3N4 ceramics

The effect of YH₂ on densification, microstructure, and thermal conductivity of Si₃N₄ ceramics were investigated by adjusting the amount of YH₂ in the range of 0–4 wt% using a two-step sintering method. Native SiO₂ was eliminated, and Y₂O₃ was in situ formed by a metal hydride reduction reaction, resulting in various Y₂O₃/SiO₂ ratios. Full densification of YH₂-doped samples could be achieved after sintering at 1900 °C for 4 h. The Y₂O₃/SiO₂ ratio had a significant influence on the composition of crystalline secondary phases. Besides, the increased Y₂O₃/SiO₂ ratio is conducive not only to the grain growth but also to the reduction of activity of SiO₂ in the liquid phase, resulting in enlarged purified grains, reduced volume fraction of intergranular phases and increased Si₃N₄-Si₃N₄ contiguity. Ultimately, the thermal conductivity increased by 29 % from 95.3 to 123.0 W m⁻¹ K⁻¹ after sintering at 1900 ℃ for 12 h by the substitution of Y₂O₃ with YH₂.     

Mechanical properties and thermal conductivity of dense β-SiAlON ceramics fabricated by two-stage spark plasma sintering with Al2O3-AlN-Y2O3 additives

Fully dense β-SiAlON ceramics with excellent mechanical properties and good thermal conductivity were fabricated by two-stage spark plasma sintering (SPS) processes without and with applying pressure respectively, using α-Si₃N₄ powder and 6 Al₂O₃-3 AlN-6 Y₂O₃ (in wt.%, label with 636), 424 and 422 additives. In the first stage SPS process without pressure, the relative dense β-SiAlON ceramics with interlock microstructures of elongated grains and density of 3.14˜3.18 g cm⁻³, hardness of 14.00˜14.82 GPa and fracture toughness of 6.00˜6.63 MPa m^1/2 were obtained by sintering at about 1600 °C for 20 min. In the second stage SPS process at about 1425 °C for 5 min under pressure of 24 MPa, the fully dese β-SiAlON ceramics with density of 3.22˜3.24 g cm⁻³, high hardness of 15.68˜15.95 GPa, high fracture toughness of 6.38˜7.03 MPa m^1/2 and thermal conductivity of 13.5˜19.6 Wm^-1K^-1 were obtained. The reaction between the samples and the graphite mold can be avoided in this fabrication method.     

Electrical resistivity of α-SiC ceramics sintered with Al2O3 or AlN additives

Highly resistive SiC ceramics were prepared by hot pressing α-SiC powders with Al₂O₃-Y₂O₃ additives with a 4:1 molar ratio. X-ray diffraction patterns, Raman spectra, electron probe microanalysis (EMPA), and scanning electron microscopy (SEM) images revealed that the bulk SiC ceramics consisted mostly of micron-sized 6H-SiC grains along with Y₂O₃ and Si clusters. As the additive content increased from 1 to 10 vol%, the electrical resistivity of the ceramics increased from 3.0 × 10⁶ to 1.3 × 10⁸ Ω cm at room temperature. Such high resistivity is ascribed to Al₂O₃ in which Al impurities substituting Si site act as deep acceptors for trapping carriers. More resistive α-SiC ceramics were produced by adding AlN instead of Al₂O₃. The highest resistivity (1.3 × 10¹⁰ Ω cm) was achieved by employing 3 vol% AlN-Y₃Al₅O₁₂ (yttrium aluminum garnet, YAG) as an additive.     

Effect of CaO doping on the properties and crystallization behavior of Y2O3–Al2O3–SiO2 glass

Nowadays, Y₂O₃–Al₂O₃–SiO₂ (YAS) glass joining is considered to be a promising scheme for nuclear-grade continuous silicon carbide (SiC) fiber reinforced SiC matrix composites (SiC/SiC). CaO has great potential for nuclear applications since it has low reactivity and low decay rate under nuclear irradiation. In this paper, the effect of CaO doping on the structure, thermophysical properties, and crystallization behavior of YAS glass was systematically studied. As the CaO doping content increased, the number of bridge oxygens and the viscosity at high temperatures reduced gradually. After heat treatment at 1400 °C, the main phases in YAS glass were β-Y₂Si₂O₇, mullite, and SiO₂ (coexistence of crystalline and glass phases), while that with 3.0% CaO doping turned into a single glassy phase under the same treatment conditions. Moreover, a structural model and the modification mechanism were proposed, which provided a theoretical basis for the subsequent component design and optimization.     

Effect of sintering temperature and dopant concentration on microstructure and electrical conductivity of ultra-fine-grained ZrO2–Sc2O3 ceramics

Phase transformations in ZrO₂ + xSc₂O₃ solid solutions (6.5 < x < 11 mol%) at sintering of ceramics obtained from nanopowders produced by laser evaporation of the ceramic targets have been studied. The Sc₂O₃ concentration increasing from 6.5 to 11 mol% is accompanied by the sintering temperature decreasing and the average grain size growth from 130 nm to 760 nm. At concentration of about 7 mol% Sc₂O₃ an abrupt increase of the average grain size and electric conductivity is observed. The sinterability of the ZrO₂ − хSc₂O₃ ceramics is affected by the prehistory of nanopowders preparation. The characteristics of ceramics obtained from nanopowders evaporated from the targets based on (ZrO₂ + xmol% Sc₂O₃) mixture and on the (ZrO₂ − 11mol% Sc₂O₃) solid solution significantly differ, namely, in the latter the sintering temperature is markedly lower and the shrinkage rate is higher. Besides, its average grain size is substantially lower and the conductivity is higher.     

Microstructure and properties of porous SiC ceramics with AlN–RE2O3 (RE = Sc,Y, Lu) additives

The intrinsic microstructure and crystalline phases of porous SiC ceramics with 5 vol% AlN–RE₂O₃ (RE = Sc, Y, Lu) additives were characterized by high-resolution transmission microscopy with energy-dispersive spectroscopy and X-ray diffraction. The homophase (SiC/SiC) and heterophase (SiC/junction) boundaries were found to be clean; that is, amorphous films were not observed in the specimens. In addition, ScN, YN, and LuN were formed as secondary phases. The flexural strength and thermal conductivity of the ceramics were successfully tuned using different additive compositions. The flexural strength of the ceramics improved by a factor of ~3, from 11.7 MPa for the specimen containing Y₂O₃ to 34.2 MPa for that containing Sc₂O₃, owing to the formation of a wide necking area between SiC grains. For the same reason, the thermal conductivity improved by ~56%, from 9.2 W·m^?1·K^?1 for the specimen containing Lu₂O₃ to 14.4 W·m^?1·K^?1 for that containing Sc₂O₃.     

High-strength AlN ceramics by low-temperature sintering with CaZrO3–Y2O3 co-additives

Aluminum nitride (AlN) ceramics with the concurrent addition of CaZrO₃ and Y₂O₃ were sintered at 1450-1700 °C. The degree of densification, microstructure, flexural strength, and thermal conductivity of the resulting ceramics were evaluated with respect to their composition and sintering temperature. Specimens prepared using both additives could be sintered to almost full density at relatively low temperature (3 h at 1550 °C under nitrogen at ambient pressure); grain growth was suppressed by grain-boundary pinning, and high flexural strength over 630 MPa could be obtained. With two-step sintering process, the morphology of second phase was changed from interconnected structure to isolated structure; this two-step process limited grain growth and increased thermal conductivity. The highest thermal conductivity (156 Wm⁻¹ K⁻¹) was achieved by two-step sintering, and the ceramic showed moderate flexural strength (560 MPa).     

Effect of Y2O3 on the physical properties and biocompatibility of β–SiAlON ceramics

To investigate the effects of Y₂O₃ on the physical properties and biocompatibility of β–SiAlON ceramics, β–SiAlON ceramics were prepared with Al, Si, and α–Al₂O₃ powders using a direct nitriding technique. As a sintering additive, Y₂O₃ helps lower the sintering temperature and forms β–SiAlON ceramics. In this study, the physical and biological properties of the prepared ceramics were investigated to evaluate their use as bone-repairing material. Experiments revealed that the main crystal composition of the sample was Si₄Al₂O₂N₆, containing small amount of additional phases Y₃Al₅O₁₂ with increasing content of Y₂O₃. The porosity and compressive strength initially decrease and then increase to their initial values, whereas the bulk density exhibits the opposite trend with an increased proportion of Y₂O₃. The proliferation of osteoblastic and angiogenic cells demonstrates that β–SiAlON and Y₃Al₅O₁₂ have good biocompatibility; however, the sample porosity has a slight effect on the cell proliferation rate. This implies that in human tissues, bone-repairing speed can be adjusted by modifying the sample porosity or material surface roughness. Therefore, Y₂O₃ can be added to β–SiAlON ceramics to regulate their microstructure, physical properties, and biological properties for tissue engineering applications.     

ZrSi2–MgO as novel additives for high thermal conductivity of β-Si3N4 ceramics

A novel ZrSi₂–MgO system was used as sintering additive for fabricating high thermal conductivity silicon nitride ceramics by gas pressure sintering at 1900°C for 12 hours. By keeping the total amount of additives at 7 mol% and adjusting the amount of ZrSi₂ in the range of 0-7 mol%, the effect of ZrSi₂ addition on sintering behaviors and thermal conductivity of silicon nitride were investigated. It was found that binary additives ZrSi₂–MgO were effective for the densification of Si₃N₄ ceramics. XRD observations demonstrated that ZrSi₂ reacted with native silica on the Si₃N₄ surface to generate ZrO₂ and β-Si₃N₄ grains. TEM and in situ dilatometry confirmed that the as formed ZrO₂ collaborated with MgO and Si₃N₄ to form Si–Zr–Mg–O–N liquid phase promoting the densification of Si₃N₄. Abnormal grain growth was promoted by in situ generated β-Si₃N₄ grains. Consequently, compared to ZrO₂-doped materials, the addition of ZrSi₂ led to enlarged grains, extremely thin grain boundary film and high contiguity of Si₃N₄–Si₃N₄ grains. Ultimately, the thermal conductivity increased by 34.6% from 84.58 to 113.91 W·(m·K)⁻¹ when ZrO₂ was substituted by ZrSi₂.     

Sintering behavior of Cr2O3–Al2O3 ceramics

We investigated the sintering behavior of Cr₂O₃–Al₂O₃ ceramic materials. In our observation of the isothermal shrinkage behavior of Cr₂O₃–Al₂O₃ ceramic, the activation energy of sintering reaction was measured to be 102 kJ/mol, that is, the near value of the activation energy of diffusion of Al ions in Al₂O₃ single crystal. Therefore the diffusion of cations is believed to control the sintering behavior of this material. With the addition of TiO₂, (the compound chosen to accelerate the diffusion of cations) to Cr₂O₃–Al₂O₃, the sintering behavior was accelerated.     

Effects of Al2O3–Y2O3/Yb2O3 additives on microstructures and mechanical properties of silicon nitride ceramics prepared by hot-pressing sintering

Silicon nitride (Si₃N₄) ceramics doped with two different sintering additive systems (Al₂O₃–Y₂O₃ and Al₂O₃–Yb₂O₃) were prepared by hot-pressing sintering at 1800℃ for 2 h and 30 MPa. The microstructures, nano-indentation test, and mechanical properties of the as-prepared Si₃N₄ ceramics were systematically investigated. The X-ray diffraction analyses of the as-prepared Si₃N₄ ceramics doped with the two sintering additives showed a large number of phase transformations of α-Si₃N₄ to β-Si₃N₄. Grain size distributions and aspect ratios as well as their effects on mechanical properties are presented in this study. The specimen doped with the Al₂O₃–Yb₂O₃ sintering additive has a larger aspect ratio and higher fracture toughness, while the Vickers hardness is relatively lower. It can be seen from the nano-indentation tests that the stronger the elastic deformation ability of the specimens, the higher the fracture toughness. At the same time, the mechanical properties are greatly enhanced by specific interlocking microstructures formed by the high aspect ratio β-Si₃N₄ grains. In addition, the density, relative density, and flexural strength of the as-prepared Si₃N₄ ceramics doped with Al₂O₃–Y₂O₃ were 3.25 g/cm³, 99.9%, and 1053 ± 53 MPa, respectively. When Al₂O₃–Yb₂O₃ additives were introduced, the above properties reached 3.33 g/cm³, 99.9%, and 1150 ± 106 MPa, respectively. It reveals that microstructure control and mechanical property optimization for Si₃N₄ ceramics are feasible by tailoring sintering additives.     

Effect of properties and crystallization behavior of BaO–ZnO–B2O3–SiO2 glass on the electrical conductivity of Cu paste

The extensive application of multilayer ceramic capacitors provides an attractive development for terminal electrode pastes. However, the growing requirement for advanced glass materials used in terminal electrode pastes is substantiated. Therefore, to advance the development of electrode pastes, better development and deeper exploration of glass powder are required. Here, a series of BaO–ZnO–B₂O₃–SiO₂ (BZBS) glasses were prepared by melt-quenching technique, which are used to investigate the effect of the introduction of BaO on structure and properties of the ZnO–B₂O₃–SiO₂ (ZBS) glass. With the introduction of BaO, the relative amount of [BO₄] was much less, which made the glass network structure loosen, decreased the glass transition temperature (T_g) and increased the coefficient of thermal expansion of the glass. The decreasing contact angle was observed on the surface of a barium titanate (BaTiO₃) substrate. When the BaO content was around 3–7 mol%, the stability of ZBS glass frit could be strengthened by inhibiting the precipitation of Zn₂SiO₄ crystal. In addition, to further characterize the effect of glass on terminal electrode paste, BZBS glass powder was adopted to prepare copper electrode paste, which was printed on the BaTiO₃ substrate and subsequently fired at 800°C for 10 min. With the related copper paste containing ZBS glass doped with 7 mol% BaO, the optimum value of acid resistance and sheet resistance (1.99 mΩ) were exhibited, at which the coated copper paste formed a dense conducting layer.     

Gelcasting and pressureless sintering of silicon carbide ceramics using Al2O3–Y2O3 as the sintering additives

In this paper, silicon carbide ceramics were prepared by aqueous gelcasting and pressureless sintering using Al₂O₃ and Y₂O₃ as the sintering additives. In order to develop well dispersed SiC slurries in the presence of sintering additives, the Al₂O₃ and Y₂O₃ powder was treated in the citric acid solution in advance. Zeta potential measurement showed that the isoelectric point (IEP) of Al₂O₃ and Y₂O₃ powder moved toward low pH region after treatment. Rheological measurement confirmed that the addition of as-treated powder showed very limited influence on the slurry properties as compared to that of untreated powder. SiC slurries with solid content of 54 vol% and enough fluidity can be developed. After gelcasting and pressureless sintering, SiC ceramics with nearly full density, fine grained and homogeneous microstructure can be obtained. Results showed that the surface treatment of Al₂O₃ and Y₂O₃ with citric acid is effective for the gelcasting process of SiC.     

Low-temperature hot-press sintering of AlN ceramics with MgO–CaO–Al2O3–SiO2 glass additives for ceramic heater applications

Aluminum nitride (AlN) is used a ceramic heater material for the semiconductor industry. Because extremely high temperatures are required to achieve dense AlN components, sintering aids such as Y₂O₃ are typically added to reduce the sintering temperature and time. To further reduce the sintering temperature, in this study, a low-melting-temperature glass (MgO–CaO–Al₂O₃–SiO₂; MCAS) was used as a sintering additive for AlN. With MCAS addition, fully dense AlN was obtained by hot-press sintering at 1500 °C for 3 h at 30 MPa. The mechanical properties, thermal conductivity, and volume resistance of the sintered AlN–MCAS sample were evaluated and compared with those of a reference sample (AlN prepared with 5 wt% Y2O3 sintering aid sintered at 1750 °C for 8 h at 10 MPa). The thermal conductivity of AlN prepared with 0.5 wt% MCAS was 91.2 W/m?K, which was 84.8 W/m?K lower than that of the reference sample at 25 °C; however, the difference in thermal conductivity between the samples was only 14.2 W/m?K at the ceramic-heater operating temperature of 500 °C. The flexural strength of AlN–MCAS was 550 MPa, which was higher than that of the reference sample (425 MPa); this was attributed to the smaller grain size achieved by low-temperature sintering. The volume resistance of AlN–MCAS was lower than that of the reference sample in the range of 200–400 °C. However, the resistivity of the proposed AlN–MCAS sample was higher than that of the reference sample (500 °C) owing to grain-boundary scattering of phonons. In summary, the proposed sintering strategy produces AlN materials for heater applications with low production cost, while achieving the properties required by the semiconductor industry.     

Effect of solid loading on properties of Y2O3–Al2O3–Nd2O3 powder mixtures obtained by planetary ball milling and ceramics based on them

The effect of the solid loading (41–50 wt%) of the slurry on granulometric composition and physico-chemical characteristics of Y₂O₃–Al₂O₃–Nd₂O₃ powder mixtures obtained by planetary ball milling has been studied for the first time. It was shown that the particle size distribution of powder, its Zeta potential, and specific surface area depend on the solid loading of the milled slurry and, consequently, on the interparticle distance during milling. The interparticle distance decreases from 200 nm to 142 nm with an increase of solid loading in the range of 41–50 wt%. It was shown that for the solid loading of 47 wt%, the convergence of particles to a distance comparable to their median diameter promotes subsequent clustering of particles. This facilitates the sintering of highly-homogenous ceramics. It was found that solid loadings in the 46–50 wt% range is useful for obtaining high-quality Nd:YAG transparent ceramics. The lowest optical losses optical losses of 1 × 10^?3 cm^?1 and the highest in-line transmittance of 84.1%@1064 nm were obtained for 1 at.% Nd:YAG transparent ceramics (22 × 3 × 4 mm³) prepared from slurries with 47 wt% solid loading (taking all other ball milling parameters fixed). If the interparticle distance in the powder is higher (solid loading of 41 wt%) than the median particle diameter, the ceramics are characterized by significant residual porosity due to the survival of large particles (insufficient milling).     

Effect of additives on the thermal conductivity of zirconium diboride based composites – A review

Re-entry space vehicle necessities sharp leading edges for better aerodynamic performance and, hence, require advanced thermal protection materials with improved safety for crew members. Material possessing high thermal conductivity and oxidation resistance are desirable at nose cap and wings leading edge of spacecraft. Consequently, the thermal shock resistance improves due to reduced thermal gradient and stresses. ZrB₂ has drawn strong impetus for futuristic space vehicles as thermal protection materials under extreme thermal environments. This study reviews the effect of the incorporation of non-carbonaceous and carbon additives on the thermal conductivity of ZrB₂ ceramics and based composites. Several factors such as the purity of starting powder, initial particle size, amount of sintering aids, processing route, porosity, the grain size of ZrB₂ matrix, distribution of secondary phases in the matrix and sinter density of the final composite, controls the overall thermal conductivity of ZrB₂ based composites.