高熵(Zr,Hf,Nb,Ta)C微米长方体的制备、吸波性能和抗氧化性研究

针对高熵碳化物制备困难,本文采用ZrC、HfC、NbC和TaC粉为原料,Ni粉为熔剂,通过低温无压烧结工艺成功制备出三种不同成分的高熵(Zr, Hf, Nb, Ta)C粉体。结果表明,三种粉体均为微米长方体,且暴露(100)晶面。(Zr_1/4Hf_1/4Nb_1/4Ta_1/4)C微米长方体因具有高介电常数而展现出优异的吸波性能,在厚度为3.5 mm、频率为6.16 GHz时,最低反射损耗值可达-48.86 dB。高熵(Zr, Hf, Nb, Ta)C微米长方体在800～1 200℃下展示出优异的抗氧化性,且氧化产物均由正交相(Nb_xTa_1-x)₂O₅固溶体、单斜相(Zr_xHf_1-x)O₂固溶体和正交相HfO₂所组成,与氧化温度和过渡金属的物质的量比无关。Zr、Hf、Nb和Ta的协同作用导致其氧化机制与单组元碳化物截然不同,Hf的存...     

(Ti1/6V1/6Nb1/6Ta1/6Mo1/3)C高熵陶瓷的制备、微观结构与抗磨损性能

过渡金属碳化物陶瓷是超高温陶瓷的典型代表,具有极高的熔点和硬度,而韧性和耐磨性有待提高。近年来,在高熵理论指导下合成的多元碳化物固溶体—高熵碳化物陶瓷具有更高的熔点和良好的韧性。本工作采用放电等离子烧结(SPS)制备了具有优异耐磨性能的(Ti_1/6V_1/6Nb_1/6Ta_1/6Mo_1/3)C 高熵陶瓷。研究了 1 600～2 100 ℃烧结的(Ti_1/6V_1/6Nb_1/6Ta_1/6Mo_1/3)C 高熵陶瓷的致密化行为、物相、微观形貌、力学和耐磨性能。结果表明,烧结温度为 1 700 ℃时,可得到面心立方结构的(Ti_1/6V_1/6Nb_1/6Ta_1/6Mo_1/3)C 高熵陶瓷。1 900 ℃以上时,高熵陶瓷相对密度大于 98%。烧结温度由 1 700 ℃升高至 2 1...     

Ti(C,N)基金属陶瓷氧化后的显微结构与力学性能

研究了Ti(C,N)基金属陶瓷的高温抗氧化性能。采用X R D、SEM分析了样品氧化后的物相组成及显微结构,并测试了试样氧化前后的抗弯强度和维氏硬度。实验结果表明:Ti(C,N)基金属陶瓷在800℃时氧化不明显,但抗弯强度开始下降;样品在900℃时开始剧烈氧化,材料的抗弯强度呈现明显的下降趋势,试样氧化前后的硬度变化较小。随着氧化温度的升高,氧化层厚度明显增加,Ti(C,N)被氧化变成TiO 2。     

高熵(TiVTaMoW)C陶瓷与不同配副间的摩擦磨损特性

为探究高熵碳化物陶瓷作为耐磨部件在摩擦学领域中的应用前景,以金属碳化物为原料,通过高能球磨和两步热压烧结法制备了一种元素分布均匀、无偏聚和偏析的高熵(Ti VTaMoW)C 陶瓷。研究了(Ti VTaMoW)C 与 Al₂O₃、Si C 和 Si₃N₄3 种配副材料在室温及 800 ℃条件下的摩擦磨损特性。结果表明：室温条件下,(Ti VTa Mo W)C 与 3 种配副对摩均表现出优异的摩擦学性能,尤其与 Si C 对摩具有最低的摩擦系数和磨损率,分别可低至(0.38±0.01)和(1.52±0.36)×10^–7 mm³/(N·m)。800 ℃条件下,(Ti VTa Mo W)C 表面氧化严重,磨损明显加剧,磨损率上升至 10^–4 mm³/(N·m)数量级。高温氧化生成的 Mo O₃和 V₂O₅具有较低剪切强度,摩擦过程转移至配副球接触面上形成转...     

原位生成陶瓷相结合Ti(C,N)复合材料及其性能研究

以TiO₂粉、鳞片石墨和Si粉为原料,采用碳热还原氮化法在1 450℃保温2 h制备了陶瓷相结合Ti(C,N)复合材料。研究了Si粉加入量(加入质量分数分别为0、5%、15%、25%)对材料物相组成、显微结构、物理性能及抗氧化性的影响。结果表明：适量Si粉的引入有利于细化Ti(C,N)晶粒,提高Ti(C,N)复合材料的常温力学性能与抗氧化性。当Si粉加入量为5%(w)时,原位生成陶瓷相结合Ti(C,N)复合材料的综合性能较优,其显气孔率、常温抗折强度和常温弹性模量分别约为(38.8±1.6)%、(62.5±2.4)MPa及(59.6±2.2)GPa。随Si粉加入量(w)进一步增加至15%或25%,复合材料的体积密度和力学性能下降。     

(Ti,Zr,Hf)B2粉体的制备及B4C含量对中熵陶瓷高温弯曲强度的影响

高熵陶瓷是陶瓷领域近几年的研究热点,过渡金属硼化物中熵、高熵陶瓷以其优异的性能、化学反应惰性和极高的熔点,成为耐极端环境的重要候选材料。本工作首次研究了B₄C过量含量对中熵硼化物粉体合成、陶瓷致密化、微结构演变和高温弯曲强度的影响,确定了低氧含量、高烧结活性(Ti,Zr,Hf)B₂粉体的制备工艺。采用热压烧结工艺在1800℃制备的(Ti,Zr,Hf)B₂中熵陶瓷致密度高达99%以上。B₄C过量15wt%的(Ti,Zr,Hf)B₂陶瓷晶粒尺寸为5.0±2.1μm,随着B₄C过量含量增加到25wt%,晶粒尺寸明显细化至2.4±0.7μm。过量的B₄C一部分与球磨引入的Si₃N₄原位反应生成BN相,另一部分B₄C以第二相形式存在,BN和B₄C相的引入可以有效抑制中熵陶瓷烧结过程中的晶粒生长,同时也提升了材料的高温弯曲强度。B₄C过量...     

碳热还原氮化攀钢高钛高炉渣制取Ti(C,N)的研究

以攀钢高炉渣(粒度≤0.074mm,w(TiO2)=21.19%)和炭黑(w(C)=98%)为原料,在密封管式炉中通入流量0.5L·min-1的工业N2(纯度>95%),分别在1300℃、1350℃、1400℃、1450℃、1500℃保温2h以及在1450℃下分别保温0、2h、4h、6h、8h的条件下,采用碳热还原氮化法制备了Ti(C,N)。用X射线衍射仪、电子探针、图像分析仪等研究了碳氮化处理温度及保温时间对Ti(C,N)的形成及其晶粒大小的影响。结果表明碳氮化处理温度对高炉渣中Ti(C,N)的形成过程产生显著影响,温度从1300℃升至1500℃时,产物中Ti(C,N)的相对含量增大,其晶粒也逐渐长大,但超过1450℃后,影响又不太显著;在1450℃下延长保温时间能促进Ti(C,N)的生成与晶粒长大,但保温时间超过2h后,此促进作用又不太明显。     

掺杂W~(6+)的Zr(WV)_xO_y质复相陶瓷的制备及特性研究

以WO3、V2O5及ZrO2粉末为原料,用氧化物煅烧法制备了掺杂W6+的Zr(WV)xOy质复相陶瓷。结果表明,复相陶瓷纯度高,杂质含量少;采取W元素和V元素的不同配比的两种配方分别实现了W元素的少量掺杂和以W元素为主、ZrV2O7为辅的良好复合;复相陶瓷在室温到100℃呈现正热膨胀特性,继续升高温度到420℃,材料表现出负热膨胀特性。但平均线膨胀系数与纯ZrV2O7的线膨胀系数相比有明显的增大。     

(Ba0.85Ca0.15)(Ti0.90Zr0.06Sn0.04)O3-Fe2O3无铅压电陶瓷的性能研究

采用固相法制备了(Ba0.85Ca0.15) (Ti0.90Zr0.06Sn0.04)O3-xmol％Fe2O3(简写为BCTZS-xFe)无铅压电陶瓷.研究了不同掺杂量对该陶瓷的显微结构、介电、铁电及压电性能的影响.结果表明,所有样品均具有单一的钙钛矿结构,少量掺杂能使晶粒长大,提高电性能.在x=0.025时,具有最佳的综合电性能,压电常数d33 =515 pC/N,机电耦合系数kp=48.2％,机械品质因数Qm =182,2Pr=18.2 μC/cm2,2Ec =4.3 kV/cm,介电常数εr=5175.     

非等摩尔比Sr(Ti,Zr,Y,Sn,Hf)O3-σ高熵钙钛矿氧化物的制备及电学性能研究

本研究采用非等摩尔混料结合两步法烧结制备了一系列非等摩尔比高熵钙钛矿氧化物Sr(Ti,Zr,Y,Sn,Hf)O3-σ。通过XRD、TG-DSC、SEM及TEM分析了其物相转变、表面形貌及晶体结构,并且采用电化学交流阻抗谱(EIS)对其电导率进行分析。研究结果表明Sr(Ti,Zr,Y,Sn,Hf)O3-σ在1480℃左右形成了单相钙钛矿结构,并且各元素分布均匀。在测试温度范围为300~750℃的条件下,Sr(Ti,Zr,Y,Sn,Hf)O3-σ单相钙钛矿结构稳定,其电导率符合阿伦尼乌斯方程,电导机理保持稳定。相较于其他三种高熵钙钛矿氧化物,Sr(Ti0.20Zr0.20Y0.20 Sn0.20Hf0.20)O3-σ(HEOY1)表现出最高的电导率,其750℃的电导率为3.55×10-3S/cm,与文献报道中的高熵钙钛矿氧化物的电导率(2.41×10-3S/cm)相比有较大提升。     

Low-temperature sintered (Ti,Zr, Nb,Ta, Mo)C-based composites toughened with damage-free SiCw

The high sintering temperature would have a great tendency to damage the morphology and thus properties of the silicon carbide whisker (SiC_w) in high entropy carbide-silicon carbide whisker (HEC-SiC_w) composites, which, in turn, would impact the effectiveness of the operative toughening mechanisms. The objective of this study was to achieve full contributions to the toughening effects of SiC_w by preparing (Ti, Zr, Nb, Ta, Mo)C-SiC_w composites at low temperature (1600 ℃) using cobalt as additives. Results showed that the fracture toughness of the (Ti, Zr, Nb, Ta, Mo)C bulk reinforced with 20 vol% SiC_w and 5 vol% Co was 7.2 MPa?m^1/2, which was much higher than that of the (Ti, Zr, Nb, Ta, Mo)C bulk only sintered with 5 vol% Co (3.4 MPa?m^1/2). Meanwhile, it was also higher than that of the reported HEC-20 vol% SiC_w composite sintered at 2000 ℃ (4.3 MPa?m^1/2). For the fracture toughness of HEC-SiC_w composites, it was significantly increased by the introduction of damage-free SiC_w.     

(Hf0.2Zr0.2Ta0.2Nb0.2Ti0.2)C high‐entropy ceramics with low thermal conductivity

A novel high‐entropy carbide ceramic, (Hf_0.2Zr_0.2Ta_0.2Nb_0.2Ti_0.2)C, with a single‐phase rock salt structure, was synthesized by spark plasma sintering. X‐ray diffraction confirmed the formation of a single‐phase rock salt structure at 26‐1140°C in Argon atmosphere, in which the 5 metal elements may share a cation position while the C element occupies the anion position. (Hf_0.2Zr_0.2Ta_0.2Nb_0.2Ti_0.2)C exhibits a much lower thermal diffusivity and conductivity than the binary carbides HfC, ZrC, TaC, and TiC, which may result from the significant phonon scattering at its distorted anion sublattice. (Hf_0.2Zr_0.2Ta_0.2Nb_0.2Ti_0.2)C inherits the high elastic modulus and hardness of the binary carbide ceramics.     

Mechanisms responsible for enhancing low-temperature oxidation resistance of nonstoichiometric (Zr,Ti)C

A series of (Zr,Ti)C_x (x = 0.7–1.0) samples were fabricated by a modified spark plasma sintering apparatus to investigate the effects of carbon concentration and Ti substitutions on the oxidation behavior. Crushed powders of (Zr,Ti)C_x were oxidized in lab air (N₂–20-vol.% O₂) from room temperature to 900°C. The results indicated that Zr_0.8Ti_0.2C_0.8, with a nominal carbon concentration x = 0.8, displayed good oxidation resistance, which was attributed to the formation of dense t-(Zr,Ti)O₂ oxide solid solution. During the oxidation of (Zr,Ti)C_x, Ti substitutions for Zr enhanced the outward diffusion of carbon, enabling a uniform carbon layer and a Zr–Ti–C–O layer on the surface of carbides. The formed carbon layer improved the oxidation resistance of (Zr,Ti)C_x below 550°C, where carbon is relatively oxidation resistant. Increasing the Ti concentration was found to enhance the oxidation resistance of (Zr,Ti)C_x with an increased oxidation onset temperature (672 ± 2°C for Zr_0.8Ti_0.2C_0.8).     

Synthesis,mechanical, and thermophysical properties of high-entropy (Zr,Ti,Nb,Ta,Hf)C0.8 ceramic

Two high-entropy carbides, including stoichiometric (Zr,Ti,Nb,Ta,Hf)C and nonstoichiometric (Zr,Ti,Nb,Ta,Hf)C_0.8, were prepared from monocarbides and ZrH₂. Their sinterability, microstructures, mechanical properties, thermophysical properties, and oxidation behaviors were systematically compared. With the introduction of carbon vacancy, the sintering temperature was lowered up to 300°C, Vickers hardness was almost unaffected, whereas the strength decreased significantly generally due to the decrease of covalent bonds. The thermal conductivity shows a 50% decrease for nonstoichiometry high-entropy carbide, which is a major consequence of the lower electrical conductivity. The oxidation resistance in high temperature water vapor was not sensitive to carbon stoichiometry.     

(K,Na) (Nb,Ta,Sb)O3粉体制备及陶瓷介电性能研究

Ta/Sb掺杂的K0.5Na0.5Nb0.7TaxSb0.3-xO3(KNNSTx,x＝0.06,0.09,0.12,0.15,0.18,0.21, 0.24)粉体经水热合成,Ta、Sb对粉体物相、微观结构的影响被系统研究,烧结后陶瓷的微观结构、介电性能表明:陶瓷物相均具有纯钙钛矿结构;随着Ta含量的增加陶瓷晶粒尺寸逐渐增大,x＝0.09、0.12时较小粒径颗粒均匀分布在大颗粒的空隙之间,陶瓷密度增加;样品的介电常数随着Ta含量的增加x＝0.06～0.12逐渐降低,x＝0.15～0.24逐渐增加,居里温度均在350 ℃左右,且x＝0.09、0.12时陶瓷介电损耗较小.     

In situ reaction and solid solution induced hardening in (Ti,Zr)B2-(Zr,Ti)C composites

(Ti,Zr)B₂ - (Zr,Ti)C ceramics were synthesized by reactive hot-pressing and solid solution coupling effect using ZrB₂ and TiC powders as starting materials. Effects of sintering temperature on phase relations, microstructure and mechanical properties were reported. The equimolar ZrB₂ and TiC reactants ensured a complete in situ reaction to form (Ti,Zr)B₂ and (Zr,Ti)C solid solutions. The (Ti,Zr)B₂ - (Zr,Ti)C composite sintered at 1750°C was fully densified, and exhibited a high hardness of 29.1 GPa due to fine-grain hardening and solid solution hardening. The optimized comprehensive mechanical properties such as a hardness of 27.9 GPa, a strength of 705 MPa and an indentation fracture toughness of 5.3 MPa m^1/2 were achieved in (Ti,Zr)B₂ - (Zr,Ti)C composites sintered at 1800°C for 1 hour.     

High-temperature oxidation behavior of (Hf0.2Zr0.2Ta0.2Nb0.2Ti0.2)C high-entropy ceramics in air

High-entropy metal carbides have recently been arousing considerable interest. Nevertheless, their high-temperature oxidation behavior is rarely studied. Herein the high-temperature oxidation behavior of (Hf_0.2Zr_0.2Ta_0.2Nb_0.2Ti_0.2)C high-entropy metal carbide (HEC-1) was investigated at 1573-1773 K in air for 120 minutes. The results showed that HEC-1 had good oxidation resistance and its oxidation obeyed a parabolic law at 1573-1673 K, while HEC-1 was completely oxidized after isothermal oxidation at 1773 K for 60 minutes and thereby its oxidation followed a parabolic-linear law at 1773 K. An interesting triple-layered structure was observed within the formed oxide layer at 1673 K, which was attributed to the inward diffusion of O₂ and the outward diffusion of Ti element and CO or CO₂ gaseous products.     

Spark plasma sintering of LaB6-(Ti,Zr)B2 composites

The LaB₆-(Ti_, Zr)B₂ composite was fabricated from LaB₆, TiB₂ and ZrB₂ powders by spark plasma sintering (SPS) at 1600–1900°C holding for 5?min under 40?MPa. The densification behaviour, microstructure, mechanical properties were investigated. The complete solid solution phase of (Ti, Zr)B₂ was identified. The morphologies of LaB₆ and (Ti, Zr)B₂ grains were equiaxed and elongated, respectively. The highest relative density of 98.43% and Vickers hardness of 19.56?GPa were obtained at 1900°C. The fracture toughness of 4.43?MPa?m^1/2 was obtained at 1800°C.