杂凝聚法制备纳米复相陶瓷材料的微观组织及增韧机理研究

采用杂凝聚法制备了Al2O3-ZrO2(n)纳米复相陶瓷粉体,对经SPS烧结成型的纳米复相陶瓷材料块体进行了微观组织韧化机理的试验研究.研究表明,Al2O3-ZrO2(n)陶瓷中由于ZrO2的添加,改变了Al2O3的晶粒形状,提高了材料的致密度,并细化了晶粒;其微观组织为典型的晶内/晶界混合型纳米复相陶瓷,其中不规则的ZrO2团聚体主要存在于Al2O3的多晶粒相交的晶界处,一些细小、分散的球状ZrO2纳米颗粒(70~200 nm)分布在Al2O3晶粒内部.由于基体晶粒的细化以及因其形成的"内晶型"纳米结构,提高了基体的力学性能.研究认为,Al2O3-ZrO2(n)纳米复相陶瓷力学性能的改变是由于纳米粒子的增韧机制、ZrO2相变增韧机制和"内晶型"结构共同作用的结果.     

Electrically conductive and thermally stable SiC-TiC containing nanocomposites via flash pyrolysis

Flash pyrolysis, which combines conventional pyrolysis with flash sintering, was first conducted to produce polymer derived SiC-TiC nanocomposites. Pre-pyrolysis at 800℃ allows the conversion from titanium isopropoxide (TTIP) modified polysiloxane to an amorphous SiTiOC ceramic. The subsequent application of an electric field gives rise to the formation of turbostratic carbon and creates Joule heating to obtain a sample internal temperature of ~1400℃. The precipitation of β-SiC, TiC, as well as titanium oxides is realized upon carbothermal reduction of extensively phase separated SiO₂ and TiO₂ with carbon. Increasing TTIP content embodies the nanocomposites with prominent electrical percolation behaviors. The electrical transport of the synthesized ceramics follows an amorphous semiconductor mechanism. High thermal stability in air is guaranteed, thanks to the in-situ formed TiC nanocrystals and preferentially reduced amorphous carbon. Flash pyrolyzed nanocomposite with a Ti:Si molar ratio of 0.20 exhibits the highest electrical conductivity (0.696 S/cm) and minimum mass change (~2%) at 1000℃, serving as a competitive candidate for electro-discharge machining (EDM) applications or self-standing conducting devices that must withstand high temperature conditions.     

Structure-property relations for a phase-pure,nanograined tetragonal zirconia ceramic stabilized with minimum CaO doping

Dense (~97%) CaO-stabilized ZrO₂ ceramic was stabilized with minimum (3 mol%) doping (reported to date) and processed via conventional sintering at a low temperature (~1200°C); compositional analysis via X-ray florescence confirmed the CaO doping accuracy. Phase-pure tetragonal structure (characterized via both X-ray diffraction and Raman spectroscopy) along with uniform nanograins (90 nm) of the ceramic ensured the evolution of no monoclinic phase even after vigorous low-temperature degradation experiments (both thermal and hydrothermal aging for 80-100 h). The sintered ceramic recorded a high hardness (~15 GPa); the indentation toughness value was also comparable to a 3 mol% yttria-stabilized zirconia system. The remarkable structure–property correlations in the 3 mol% CaO-stabilized ZrO₂ ceramic suggests that the same may be worth examining for suitable future applications (e.g., in dental ceramics).     

Electric field assisted solid-state interfacial joining of TaC-HfC ceramics without filler

The application of ultra-high-temperature ceramics (UHTCs) demands effective ways of joining in overcoming the problems associated with the fabrication of complex-shaped components. In this study, we choose to investigate a new method of rapidly joining pre-sintered TaC and HfC ceramics without any filler material using the spark plasma sintering (SPS) technique. A well-bonded TaC–HfC interface was observed with no apparent cracking and porosity at the joint. The joining mechanisms were predominantly driven by solid-state diffusion and localized plastic deformation. The nanomechanical properties of the TaC-HfC joint are better than the HfC while comparable to that of the TaC. High-load indentation (up to 200 N) results suggest that the TaC–HfC interface is stronger than the parent UHTCs with no crack propagating at the interface. Upon comparison with the parent UHTCs, the damaged area and the average crack length at the interface, reduced up to ~94% and ~56%, respectively. This study shows that the SPS technique can also apply to joining other UHTCs without any filler, resulting in the new field of developing complex components for the thermal protection system (TPS).     

Sintering parameter optimization of Tb3Al5O12 magneto-optical ceramics by vacuum sintering and HIP post-treatment

Transparent terbium aluminum garnet (TAG) ceramics were achieved by the vacuum sintering plus HIP post-treating from the coprecipitated TAG nanoparticles. The influences of vacuum sintering temperature and sintering aid TEOS on the optical quality of the TAG ceramics were studied. The results show that with the increase of sintering temperature, the optical quality of TAG ceramics is improved gradually, and the in-line transmittance of the TAG ceramics treated at 1720°C for 20 hours under vacuum and then HIP post-treated at 1700°C for 3 hours under 200 MPa argon gas is 81.6% at 1064 nm. The sintering additive TEOS can improve the optical quality of TAG ceramics and inhibit the valence state change of Tb³⁺ ions to Tb⁴⁺ during the annealing process. The Verdet constant of the TAG ceramics at 632.8 nm is about −178 rad·T⁻¹·m⁻¹ at room temperature, which is 1.3 times that of the commercial TGG crystals (−134 rad·T⁻¹·m⁻¹).     

IR transmission prediction,processing, and characterization of dense La2Ce2O7

High-throughput computation, based on density functional theory (HT-DFT), is used to predict the bounds for optical transparency, from the ultraviolet to the infrared, for materials in the pyrochlore family. The HT-DFT approach adopted here uses an initial screening from Materials-Project database, with millions of calculated properties. Band gaps and phonon spectra were calculated from selected pyrochlore crystal structures taken from the Materials Project database. Short and long wavelength bounds for optical transparency were calculated for chemistries with stable, cubic structures. The calculations predict that La₂Ce₂O₇ has one of the broadest range of transparency for the pyrochlore family. Based on these calculations, dense polycrystalline samples of La₂Ce₂O₇ were produced by sintering and hot-isostatic pressing. Transparency was characterized by methods that did not require large samples with high optical quality, obtaining 7.15 and 7.5 µm at 95% and 90% normalized transmittance, respectively. Bandgap calculations suggest a lower bound of UV transparency cut-off of 0.3 µm. The infrared wavelength cut-off is higher than that reported for other pyrochlores, and higher than for yttria, zirconia, or other common infrared transparent ceramics. We discuss our prediction and characterization methods as well as the suitability of pyrochlores for mid- and far-infrared optical applications.     

Ti4+ modified MgZrNb2O8 microwave dielectric ceramics with an ultra-high quality factor

Ti⁴⁺-modified MgZrNb₂O₈ (MgZr_1-xTi_xNb₂O₈, x = 0, 0.1, 0.2, 0.3, 0.4) ceramics were synthesized using the traditional solid-state reaction method. Pure MgZr_1–xTi_xNb₂O₈ was detected without any secondary phase via the X-ray diffraction patterns. According to the sintering behavior and the surface morphology results, the introduction of Ti⁴⁺ reduced the sintering temperature and promoted the grain growth. The correlations between the dielectric properties and the crystal structure were analyzed through the Rietveld refinement and Raman spectroscopy. The slight shifts of the Raman peaks, corresponding to different vibration modes, were induced by the substitution of Ti⁴⁺ for Zr⁴⁺ and related to the improved quality factor. In general, the sample of MgZr_0.9Ti_0.1Nb₂O₈ sintered at 1320°C for 4 h exhibited promising microwave dielectric properties with an ultra-high Q × f value of 130 123 GHz (at 7.308 GHz, 20°C), which is potential for 5G communication applications.     

Rapid preparation of hierarchically porous ceramic microspheres based on UV-curing-assisted molding

Ceramic microspheres have attracted significant attention, while the preparation of hierarchically porous ceramic microspheres with high porosity, good sphericity, and controllable size or shape in a short time remains a challenge. Herein, we developed a highly adaptable methodology for the preparation hierarchically porous ceramic microspheres with high porosity and favorable shape in a short time. The UV-curing assisted molding method combined with the Pickering emulsion method was utilized to prepare hierarchically porous ceramic microspheres. Under the irradiation of a UV-curing lamp (395 nm, 50 W), the Pickering emulsion can be cured within as short as 10 s. The microstructures of the three microspheres with different shapes were characterized by scanning electron microscopes (SEM). The as-prepared microspheres had a high sphericity, the interconnectivity of pores was as high as 54 %, and its porosity was as high as 73.4 % ± 3.0 %, while the density was quite low at ∼ 1.02 g/cm³.     

Effect of SiCnws on flexural strength of SiCf/HfC-SiC composites after impact and ablation

SiC nanowires (SiC_nws) modified SiC_f/HfC-SiC composites were prepared by precursor infiltration and pyrolysis (PIP) and chemical vapor infiltration (CVI) methods. The microstructure, flexural strengths, impact and impact-ablation tests of the composites with and without SiC_nws were investigated. The results showed that after introducing SiC_nws, not only the retention rate of HfC ceramic produced by PIP was increased obviously, but also the fracture displacement of the modified composites was reduced due to the enhancement effect of SiC_nws at interface between SiC fiber and matrix. After impact and impact-ablation, the strength retention of SiC_nws modified composites was 91.6 % and 69.1 % respectively, higher than that of the composites without SiC_nws (85.2 % and 54.8 %). As the impact resistance of the modified composites was improved by the pull-out and bridging of SiC_nws, the ablation resistance of the impacted composites was enhanced as well.     

Design of Lu2O3-reinforced Cf/SiC-ZrB2-ZrC ultra-high temperature ceramic matrix composites: Wetting and interfacial reactivity by ZrSi2 based alloys

The wettability and infiltration of molten ZrSi₂ and ZrSi₂-Lu₂O₃ alloys into C_f/SiC and B₄C-infiltrated C_f/SiC composites were investigated to understand the interfacial interactions that occur during the development of C_f/SiC-ZrC and C_f/SiC-ZrB₂-ZrC-Lu₂O₃ materials. A significant evaporation of Si from the liquid affected the wetting behaviour of the alloy when tested in a vacuum at 1670 °C. The better wetting and spreading of the alloy over the surface was observed for the composites with lower overall porosity (12 %). On the other hand, the formation of an outer dense layer, followed up by the uniform infiltrated region up to ～ 1 mm was observed for the C_f/SiC with higher porosity (21 %). The infiltrated alloy reacted with SiC matrix to form ZrC or with B₄C-infiltrated SiC matrix to form ZrB₂-ZrC-SiC. The Lu₂O₃ particles were not wetted by the melt, and were pushed away of the reaction zone by the solidification front.