Research Progress of High Entropy Ceramic Materials

High-entropy materials(HEMs)have better mechanical,thermal,and electrical properties than traditional materials due to their special"high entropy effect".They can also adjust the performance of high entropy ceramics by adjusting the proportion of raw materials,and have broad application prospects in many fields.This article provides a review of the high entropy effect,preparation methods,and main applications of high entropy ceramic materials,especially exploring relevant research on high entropy perovskite ceramics.It is expected to provide reference for the promotion of scientific research and the development of further large-scale applications of high-entropy ceramic materials.

High-entropy rare earth stannate ceramics:Acid corrosion resistant radiative cooling materials with high atmospheric transparency window emissivity and high near-infrared solar reflectivity

In response to the development of the concepts of“carbon neutrality”and“carbon peak”,it is critical to developing materials with high near-infrared(NIR)solar reflectivity and high emissivity in the atmospheric transparency window(ATW;8–13μm)to advance zero energy consumption radiative cooling technology.To regulate emission and reflection properties,a series of high-entropy rare earth stannate ceramics(HE-RE_(2)Sn_(2)O_(7):(Y_(0.2)La_(0.2)Nd_(0.2)Eu_(0.2)Gd_(0.2))_(2)Sn_(2)O_(7),(Y_(0.2)La_(0.2)Sm_(0.2)Eu_(0.2)Lu_(0.2))_(2)Sn_(2)O_(7),and(Y_(0.2)La_(0.2)Gd_(0.2)Yb_(0.2)Lu_(0.2))_(2)Sn_(2)O_(7))with severe lattice distortion were prepared using a solid phase reaction followed by a pressureless sintering method for the first time.Lattice distortion is accomplished by introducing rare earth elements with different cation radii and mass.The as-synthesized HE-RE_(2)Sn_(2)O_(7)ceramics possess high ATW emissivity(91.38%–95.41%),high NIR solar reflectivity(92.74%–97.62%),low thermal conductivity(1.080–1.619 W·m^(−1)·K^(−1)),and excellent chemical stability.On the one hand,the lattice distortion intensifies the asymmetry of the structural unit to cause a notable alteration in the electric dipole moment,ultimately enlarging the ATW emissivity.On the other hand,by selecting difficult excitation elements,HE-RE_(2)Sn_(2)O_(7),which has a wide band gap(Eg),exhibits high NIR solar reflectivity.Hence,the multi-component design can effectively enhance radiative cooling ability of HE-RE_(2)Sn_(2)O_(7)and provide a novel strategy for developing radiative cooling materials.

Influence of Composite Phosphate Inorganic Antibacterial Materials Containing Rare Earth on Activated Water Property of Ceramics

Antibacterial ceramic was prepared by doping enamel slurry with composite phosphate inorganic antibacterial materials containing rare earth (inorganic antibacterial additives), and then the mechanisms for activating water and improving seed germinative property were tested by nuclear magnetic resonance (NMR) and the method of testing oxygen dissolved in activated water. Results show that the half peak width of (()^(17)O-NMR) for tap water activated by the antibacterial ceramic drops from 115.36 to 99.15 Hz, and oxygen concentrations of activated water increase by 20%, germinate rate of horsebean and earthnut seeds increases by 12.5% and 7.5%, respectively. Therefore antibacterial ceramic doped enamel slurry with inorganic antibacterial additives containing rare earth can reduce the volume of clusters of water molecules, improve activation of tap water, and promote plant seeds germinate.

Effects of Rare Earth Elements on Wear Resistance of Ceramic Tool Materials

Through the addition of Y, Sm and Ce in Al2O3/(W, Ti)C ceramic matrix, it was found that the amount and kind of the added rare earth elements have some different influences on the mechanical properties and wear resistance of the composite. Under the present experimental conditions, the flank wear curves of the selected ceramic tool materials when machining the hardened tool steel obeyed the wear law well. But wear resistance of different ceramic materials varied with each other. Wear resistance of rare earth ceramic tool materials was higher than that of the corresponding materials without rare earth. Wear modes of the developed Al2O3/(W, Ti)C series rare earth ceramic tool materials were mainly flank wear and accompanied with slight crater wear.

Preparation and Effect of Rare Earth Composite Ceramic Materials on Reducing Exhaust Emissions

Rare earth composite ceramic materials (RE/CM) were prepared by the method of firing the mixtures of the rare earth elements, polar crystal mineral materials and clays. The effects of processing method on the reducing exhaust emissions were studied. The results show that after dealt with the ceramic balls, the surface tension of gasoline, and the CO concentration among exhaust emissions during combustion, decrease by 2.7% and 11.5%, respectively; however the temperature of the inner flue increases by 4.8%.

Composition,Processing Technology and Property of Ceramic Die Materials Containing Rare Earth Additives

Development and application of new ceramic die materials is one of the important topics in the field of die research. The composition, processing technology, mechanical property and engineering performance of the ceramic materials such as cermet, ZTA, TZP, TZP/Al2O3, TZP/TiC/Al2O3, PSZ and Sialon, etc., with rare earth yttrium, lanthanum and cerium, and so on working as additives, were investigated and analyzed in the present study. Problems existed in the research and application of rare earth ceramic die materials were discussed. Rare earth additives can effectively improve the mechanical property and engineering performance of ceramic die materials. Thus, it will have further perspectives of wider application. More attention should be paid in the future to the toughening and strengthening of the ceramic die materials, the adding forms and kinds of rare earth elements and acting mechanisms of rare earth additives in ceramic die materials.

Fabrication and Characterization of Glass-Ceramics Doped with Rare Earth Oxide and Heavy Metal Oxide

Cordierite-based glass-ceramics with non-stoichiometric composition doped with rare earth oxide (REO_2) and heavy metal oxide (M_2O_3) respectively were fabricated from glass powders. After sintering and crystallization heat treatment, various physical properties, including compact density and apparent porosity, were examined to evaluate the sintering behavior of cordierite-based glass-ceramics. Results show that the additives both heavy metal oxide and rare earth oxide promote the sintering and lower the phase temperature from μ- to α-cordierite as well as affect the dielectric properties of sintered glass-ceramics. The complete-densification temperature for samples is as low as 900 ℃. The materials have a low dielectric constant (≈5), a low thermal expansion coefficient ((2.80～3.52)×10^(-6) ℃^(-1)) and a low dissipation factor (≤0.2%) and can be co-fired with high conductivity metals such as Au, Cu, Ag/Pd paste at low temperature (below 950 ℃), which makes it to be a promising material for low-temperature co-fired ceramic substrates.

Status of Research on Application of High Purity Rare Earth Oxides in Solid Oxide Fuel Cells

The solid oxide fuel cell (SOFC) is a high-efficient and environmentally friendly power generation system.The rare earth oxide materials are used extensively in the manufacturing of SOFC components.In particular, the CeO2doped with Gd2O3 or Sm2O3, lanthanide perovskite oxides are indispensable and key materials for developing the intermediate temperature SOFC.The research and development status of application of high purity rare earth oxides in SOFC was overviewed.The rare earth oxide-based and -doped materials were discussed for the SOFC components.Concerning the rare earth oxides applicable to SOFC, several topics were also pointed out for further researching and developing.

Studies on Gas Sensitive Materials of γ-Fe_2O_3 Doped with Rare Earth Oxides

Fine powders of γ-Fe_2O_3,doped with Y_2O_3,CeO_2,Eu_2O_3 or Tb_2O_3 have been prepared by the chemical co-precipitation method.The sensitivity of gas sensation has been measured with respect to the relative resist- ance change in the ceramic matrix upon introduction of inflammable gases.The structure of the materials has been studied with X-ray diffraction spectroscopy(XRD),electron diffraction spectroscopy( ED) and transmis- sion electron microscopy(TEM).The addition of rare earth oxides,which improves ceramic microstructure of γ-Fe_2O_3,improves gas sensitivity of γ-Fe_2O_3.The stability can be increased because of the increase of phase transition temperature.In addition,the selectivity of gas sensation of γ-Fe_2O_3 can be improved because of the variation of rare earth oxides.

A novel(Sm_(0.2)Eu_(0.2)Gd_(0.2)Ho_(0.2)Yb_(0.2))CrO_(3)high-entropy ceramic nanofiber as a negative temperature coefficient thermistor

The electrical properties of high-entropy ceramics(HECs)have been extensively studied in recent years due to their unique structural characteristics and fascinating functional properties induced by entropy engineering.Novel high-entropy(Sm_(0.2)Eu_(0.2)Gd_(0.2)Ho_(0.2)Yb_(0.2))CrO_(3)(HE-RECrO_(3))nanofibers were prepared by electro spinning.This work demonstrates that HE-RECrO_(3)nanofibe rs were successfully synthesized at a low temperature(800℃),which is approximately 400℃lower than the temperatures at which chromate ceramics were synthesized via the sol-gel method and the solid-state reaction method.The resistivity of HE-RECrO_(3)nanofibers decreases exponentially with increasing temperature from 25 to600℃.The logarithm of the resistivity is linearly related to the inverse of the temperature,confirming the negative temperature coefficient property of HE-RECrO_(3)nanofibers.The B_(25/50)value of the HERECrO_(3)nanofibers reaches 4072 K.In conclusion,HE-RECrO_(3)nanofibers are expected to be potential candidates for negative-temperature-coefficient(NTC)thermistors.

Mechanism of Cracking Resistance of Hardfacing Specimens of Steel 5CrNiMo Improved by Rare Earth Oxide

The cracking morphology of the hardfacing specimens taken from steel 5CrNiMo was observed. Meanwhile, the residual stress fields were measured and simulated. Based on experiment mentioned above, the improved structure and modified inclusion in hardfacing metal with rare earth （RE） oxide were analyzed. The results show that, the hardfacing crack is initiated from the coarse dendritic crystal grain boundary, inclusions and coarse austenite grain boundary in the HAZ and propagated by the residual stress existing in the center of the hardfacing metal and HAZ. The primary columnar grain structure can be refined by adding RE oxide in the coating of the electrode. The inclusion in the hardfacing metal can be modified as well. Meanwhile, if the martensite transformation temperature is decreased, the largest value of the residual tensile stress in the dangerous region can be reduced.

Corrosion Resistance of Ceramic Materials in Metallic Neodymium and NdF_3-LiF-Nd_2O_3 System

Corrosion resistant properties of Si3N4-SiC and TiB2 at high temperature were studied. The experiments were carried out in metallic neodymium and NdF3-LiF-Nd2O3 system, respectively. Corrosion temperature was 1100 ℃ and the holding time of corrosion experiments was 24 h. Corrosion products were analyzed by XRD and SEM, and corrosion behavior and corrosion mechanism of the experiments were studied. The results showed that Si3N4-SiC was corroded seriously in the above-mentioned two systems. A few of compounds were found on the surface of Si3N4-SiC, and surface structure of the Si3N4-SiC samples was loosened. The corrosion resistance of TiB2 was better than that of Si3N4-SiC. Oxidation resistance of TiB2 at high temperature should be enhanced.

Study on Thermal Expansion Coefficient of Sealing Materials for Ceramic Metal Halide Lamps

With Al2O3, Dy2O3, and SiO2 as starting materials, the basic glass of Al2O3-Dy2O3-SiO2 system was prepared by conventional melting technology, and their thermal expansion coefficients （TECs） at different anneal time were investigated. TECs of the basic glass, which were heat-treated under different temperature, were also investigated. The result showed that TECs of the basic glass gradually approached a fixed value as the anneal time was extended, which suggested that most of the inner stress had been eliminated. After heat treatment, the contents of Dy2O3, Dy2Si2O7, and a new crystal increased up to 1200 ℃ and decreased below 1250 ℃, which was consistent with the TEC change of crystallized samples. This suggests that the crystal has a direct effect on TECs of the crystallized samples.

Study on Rare Earth Electrolyte of Ce_(0.9)RE_(0.1)O_(2-δ) (RE=Pr, Nd, Sm, Gd, Dy)

The solid solutions Ce_(0.9)RE_(0.1)O_(2-δ)(RE=Pr, Nd,Sm, Gd, Dy) were prepared by sol-gel method. The XRD measurement shows that the solid solution is crystallized in cubic fluorite-type structure and the cell volume of Ce_(0.9)RE_(0.1)O_(2-δ) decreases with the increase of atomic number of RE. The ionic conduction for Ce_(0.9)RE_(0.1)O_(2-δ) was measured by impedance spectroscopy and Ce_(0.9)Pr_(0.1)O_(2-δ) has better conductivity. The linear thermal expansion of Ce_(0.9)RE_(0.1)O_(2-δ) decreases with the increase of atomic number of RE.

高熵稀土氧化物热障涂层材料研究进展

热障涂层(Thermal barrier coating,TBC)材料在航空发动机和燃气轮机的热防护中具有保护高温合金基底免受氧化及腐蚀,并降低高温合金的工作温度的重要作用。新型热障涂层材料中存在许多高熵稀土氧化物,能够实现比单一主成分稀土氧化物更优异的热学、力学、高温相稳定性以及抗烧结、耐腐蚀等性能。但是目前对高熵稀土氧化物的研究仍然停留在初步阶段,其中稀土元素对材料性能的作用尚未完全明确,且没有形成统一标准。简要概述了热障涂层的基本结构,并重点总结了高熵锆酸盐、铈酸盐、铪酸盐、钽酸盐和铌酸盐等5种高熵稀土酸盐的晶体结构、热物理性能与力学性能。对比分析了其与相应的单一组分稀土酸盐的差异,并探讨了影响其性能优劣的多种因素。相比于单一组分稀土氧化物,高熵稀土氧化物的热导率、热膨胀系数和相稳定性均有明显改善。最后,展望了未来高熵稀土热障涂层的发展方向。

高湿度下具有荧光指示功能的PET复合膜的制备与性能

为了制备出能在高湿度、易结雾环境下可持续发光的薄膜,以聚对苯二甲酸乙二醇酯(PET)膜为基底,将具有优异疏水功能的新型稀土发光配合物和聚甲基丙烯酸甲酯(PMMA)均匀分散制成发光涂覆液,通过涂覆刮膜技术,制备出PET-PMMA发光复合膜,并对其进行测试表征。荧光分光光度计和共聚焦显微镜测试的结果表明:发光材料占聚合物PMMA的质量分数为1.50%时所制备的PET发光膜具有良好的表面均匀性和最佳的荧光性能,荧光强度可达到9979 a.u.,在不同激发波长下PET-PMMA发光复合膜均可以显现出发光材料中Eu3+的特征荧光发射峰;测得发光复合膜的最佳紫外激发波长为350 nm,在最佳激发波长下发光复合膜具有较好的色纯度;通过对比发光复合膜浸泡在水溶液7 d内每天的荧光强度值,发现在发光材料仅有1.50%的前提下,样品的荧光强度损失仅有5%,这表明所制备的发光复合膜遇水易猝灭的弊端得到极大改善,这为PET农膜在潮湿、易结雾环境下实现长期稳定的荧光指示功能提供了重要基础。

(La0.2Ce0.2Nd0.2Sm0.2Eu0.2)PO4: A high-entropy rare-earth phosphate monazite ceramic with low thermal conductivity and good compatibility with Al2O3

Low thermal conductivity, matched thermal expansion coefficient and good compatibility are general requirements for the environmental/thermal barrier coatings(EBCs/TBCs) and interphases for Al2O3 f/Al2O3 composites. In this work, a novel high-entropy(HE) rare-earth phosphate monazite ceramic (La0.2Ce0.2Nd0.2Sm0.2Eu0.2)PO4 is designed and successfully synthesized. This new type of HE rare-earth phosphate monazite exhibits good chemical compatibility with Al2O3, without reaction with Al2O3 as high as 1600℃ in air. Moreover, the thermal expansion coefficient(TEC) of HE (La0.2Ce0.2Nd0.2Sm0.2Eu0.2)PO4(8.9 × 10^-6/℃ at 300–1000℃) is close to that of Al2O3. The thermal conductivity of HE (La0.2Ce0.2Nd0.2Sm0.2Eu0.2)PO4 at room temperature is as low as 2.08 W·m^-1·K^-1, which is about 42% lower than that of La PO4. Good chemical compatibility, close TEC to that of Al2O3, and low thermal conductivity indicate that HE (La0.2Ce0.2Nd0.2Sm0.2Eu0.2)PO4 is suitable as a candidate EBC/TBC material and an interphase for Al2O3 f/Al2O3 composites.

(Si_(0.2)Ti_(0.2)Nb_(0.2)Ta_(0.2)V_(0.2))C高熵陶瓷的低温制备及吸波性能

寻求具有良好耐高温及力学性能的新型陶瓷材料是吸波材料领域的研究热点之一。高熵碳化物陶瓷具有高温热稳定性及抗氧化性好等优点,但合成温度高且吸波性能研究较少,限制了其在高温吸波材料领域的应用。本工作采用熔盐法合成了多晶岩盐晶型(Si_(0.2)Ti_(0.2)Nb_(0.2)Ta_(0.2)V_(0.2))C高熵碳化物陶瓷,研究了其物相组成、微观形貌及吸波特性。结果表明:随着反应温度的升高,样品的衍射峰逐渐锐化,吸波性能明显提高。当反应温度为1500℃时,3.72 GHz时最低反射损耗达-34.68 dB;与已报道的高熵碳化物陶瓷相比,在相同的有效吸收带宽(2.3 GHz)下,涂层厚度减少了13.3%(1.5 mm降低到1.3 mm),其介电损耗主要来源于极化损耗和导电损耗。本工作制备的高熵碳化物陶瓷可以为研究制备新型环境适应、耐高温、抗冲击的高性能单相吸波材料提供新途径。

稀土高熵氧化物用于能源和环境催化

随着工业技术的快速发展,能源短缺与环境污染问题日益凸显,对人类生活和社会经济发展造成了严重影响.在这一背景下,加速能源系统转型、积极开发与利用可再生能源变得至关重要,成为当前研究领域的热点.同时,消除环境中的有毒有害物质也具有较高的研究价值,对维护生态平衡和人类健康具有重要意义.催化技术因在去除污染物和能源转换方面具有巨大的应用潜力而备受关注.其中,高熵氧化物因其具有多样可调的晶体结构和丰富的表面活性位点,展现出较好的催化性能,从而备受研究者关注.此外,稀土元素因以其相近的离子半径、独特的电子轨道和可变的氧化态,常被用作高熵氧化物的组成元素.通过引入稀土元素,可以有效改善高熵氧化物的结构和性能.近年来,稀土高熵氧化物在催化应用中取得较多的研究成果,然而却缺少对该方面工作系统全面的综述.本文旨在系统总结稀土高熵氧化物的结构特点、合成方法及其在催化领域的应用,以期为该领域的进一步发展提供有益的参考.本文从结构、合成及应用等方面,对稀土高熵氧化物在催化领域的研究进展进行了总结.首先,详细介绍了钙钛矿型、萤石型和烧绿石型三种类型稀土高熵氧化物的结构特征,并探讨了结构对催化反应过程的重要影响.研究表明,多组分的高熵效应保证了单相固溶体的形成和高温下的催化稳定性,而晶格畸变效应则促进了氧空位等活性位点的形成,进而提升了催化活性.复杂多变的晶体结构导致了离子扩散延迟,这也使得高熵材料在催化过程中具有优异稳定性.此外,揭示了多种元素间的协同作用对催化性能的提升作用.值得一提的是,非等摩尔金属成分也可形成高熵氧化物,为稀土高熵氧化物研究开辟了新的方向.其次,讨论了稀土高熵氧化物的合成方法,主要包括固相反应合成法、喷雾热解法、化学共沉淀法和溶液燃烧法,合成方法的选择和优化对于建立高熵系统至关重要.目前,众多简单快速的合成方法已取代耗时耗力的合成过程,为稀土高熵氧化物的制备提供了便利.最后,重点概述了稀土高熵氧化物在电催化、热催化和光催化中的应用进展,并详细介绍了多元素可调材料对反应活性的影响.同时,指出了稀土高熵氧化物未来发展所面临的挑战,并提出了相应的应对策略,以期为高熵系统的理论研究提供有力支撑.综上,稀土高熵氧化物因其复杂结构而展现出丰富的潜在催化反应性能,具有巨大的应用潜力.未来研究可以加强开发设计、精准调控结构以及深入分析反应机理,从而提升高熵氧化物的催化性能.希望本文能够为稀土高熵氧化物催化体系研究提供有益的参考.

Effect of Y_(2)O_(3) on microstructure and properties of CoCrFeNiTiNb high entropy alloy coating on Ti-6Al-4V surface by laser cladding

The effects of Y_(2)O_(3) on the microstructure, microhardness, wear resistance, high-temperature oxidation resistance, hot corrosion resistance, and electrochemical corrosion behaviour of CoCrFeNiTiNb high entropy alloy coatings formed on Ti-6Al-4V alloy surfaces were studied. The results show that the addition of Y_(2)O_(3) changes the proportion of the phase but does not change its type. The average grain size is only 1/4.7 of that of the high entropy alloy(HEA) coating, and the fine-grained strengthening leads to increases in the microhardness and wear resistance of 21.8% and 26.9%, respectively. The addition of Y_(2)O_(3) enhances the denseness and bonding properties of the oxide and corrosion product layers, reducing the oxidation and hot corrosion rates by 60.3% and 40.3%, respectively. The addition of Y_(2)O_(3) doubles the corrosion resistance which is attributed to the refinement of the grains, the increased proportion of HCP and TiN, and the weakening of galvanic coupling corrosion.