CN117105664A - 一种高熵碳化物陶瓷(MoNbTaTiW)C5及其制备方法 - Google Patents
一种高熵碳化物陶瓷(MoNbTaTiW)C5及其制备方法 Download PDFInfo
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Abstract
本发明属于金属碳化物陶瓷材料技术领域,具体涉及一种高熵碳化物陶瓷(MoNbTaTiW)C5及其制备方法。本发明采用过渡金属氧化物碳热还原制备高熵碳化物陶瓷(MoNbTaTiW)C5。本发明以微米级MoO3、Nb2O5、Ta2O5、TiO2、WO3和炭黑(C)粉末为原料,通过碳热还原反应,采用SPS烧结工艺制得。所得高熵碳化物陶瓷(MoNbTaTiW)C5为单相、面心立方结构相对密度大于96%,晶粒细小,金属元素分布均匀;具有较优的力学性能,其硬度,纳米硬度,弹性模量,断裂韧性分别为14‑15 GPa,25‑28 GPa,357‑418 GPa和4.7‑5.2 MPa·m1/2;具有较低的热导率,室温热导率低至5.9 W/mK,低于其金属组元对应的碳化物陶瓷。
Description
技术领域
本发明属于金属碳化物陶瓷技术领域,具体涉及一种高熵碳化物陶瓷(MoNbTaTiW)C5及其制备方法。
背景技术
近年来,研究人员将“高熵”概念应用于陶瓷领域,合成了多种高熵陶瓷,如,碳化物、氧化物、硼化物等。其中,高熵碳化物陶瓷通常具有高硬度,高强度,低导热系数,抗氧化等性能,可用作高温结构材料。
高熵过渡金属碳化物陶瓷是由4种或4种以上元素以接近等原子比组成,被证明具有高硬度、良好的高温抗弯强度、低热导率等性能。
过渡金属一元碳化物具有相似的晶体结构和良好的固溶性,有利于形成含4种或4种以上主金属组分的多元固溶体,被广泛用于制备高熵碳化物陶瓷。
Xiao-Feng Wei等人以金属与石墨为原料,通过放电等离子烧结(SPS)制备出(NbTiTaZrW)C5,致密度为98.2%,但以金属粉末作为原料在混合过程中会导致原料严重氧化。D.O. Moskovskikh等以高纯度的金属粉末与石墨运用高能球磨法制备出高熵先驱体(Hf0.2Ta0.2Ti0.2Nb0.2Zr0.2)C5-Zr(HECZr)和(Hf0.2Ta0.2Ti0.2Nb0.2Mo0.2)C5-Mo (HECMo) ,并通过SPS在2000℃进行烧结得到HECZr的致密度在94.8%,硬度为25.7±3.5GPa,杨氏模量为473±37GPa,热导率为5.6±0.1 W/m·K,HECMo的相对密度为93.8%、硬度为23.8±2.7GPa、杨氏模量为544±48GPa、热导率为5.9±0.2 W/m·K。提供金属粉末与碳粉合成高熵碳化物的可能性。Dusza等人报道了以金属碳化物通过球磨和SPS在烧结温度2300℃下制备Fm-3m晶体结构的 (Hf-Ta-Zr-Nb)C,其密度为99%,平均晶粒尺寸为12μm,硬度为36.1±1.6GPa。Chen等以金属碳化物为原料,采用SPS在1500℃至2200℃制备了(VNbTaMoW)C5高熵陶瓷,其中,1900℃制备的高熵陶瓷具有最佳的综合性能,其Vicker硬度、纳米硬度、断裂韧性和弹性模量分别达到19.6GPa、29.7GPa、5.4MPa·ml/2和551GPa。
现有技术无论是以金属粉末和石墨为原料,还是以金属碳化物为原料制备高熵碳化物陶瓷,都存在着烧结单相化和完全致密化的工艺复杂和温度较高,制备出的样品晶粒尺寸较大的问题。
发明内容
针对现有技术中制备的高熵碳化物陶瓷存在的问题,为了克服现有技术的不足,本发明的目的是提供一种高熵碳化物陶瓷(MoNbTaTiW)C5。本发明采用过渡金属氧化物碳热还原制备高熵碳化物陶瓷(MoNbTaTiW)C5。本发明所得高熵碳化物陶瓷(MoNbTaTiW)C5相对密度大于96%,晶粒细小,金属元素分布均匀,具有较优的力学性能,热导率低于其金属组元对应的碳化物陶瓷。
本发明的另一个目的是提供一种高熵碳化物陶瓷(MoNbTaTiW)C5的制备方法,包括称料、球磨、干燥、研磨、装料、烧结、卸压冷却七个步骤,其中烧结步骤包括碳热还原反应阶段和固溶阶段。
为实现上述目的,本发明采用的技术方案是:一种高熵碳化物陶瓷(MoNbTaTiW)C5,是以微米级MoO3、Nb2O5、Ta2O5、TiO2、WO3和炭黑 ( C ) 粉末为原料,通过碳热还原反应,采用SPS烧结工艺制得。
本发明一种高熵碳化物陶瓷(MoNbTaTiW)C5的制备方法,包括称料、球磨、干燥、研磨、装料、烧结、卸压冷却七个步骤,具体为:
S01. 称料:按照摩尔比MoO3 : Nb2O : Ta2O5 : TiO2 : WO3 : C = 1:0.5:0.5:1:1:(15.75-17.5)称取MoO3、Nb2O5、Ta2O5、TiO2、WO3、炭黑( C )粉末,混合。
S02. 球磨:将步骤S01混合得到的原料装入硬质合金球磨罐,加入无水乙醇,加入硬质合金球,球料比为(5-10):1,以300-400 r/min的转速球磨混合8 h-12 h。
S03. 干燥:将步骤S02球磨混合得到的浆料置于100 ℃真空干燥箱中,充分干燥。
S04. 研磨:将步骤S03干燥后得到的物料研磨成粉,过筛。
S05. 装料:将步骤S04研磨过筛后的粉末装入石墨模具中,模具内要预先装石墨纸将粉料与模具内壁隔开,且粉料与模具接触的上下两侧也需要用石墨纸隔开,便于脱模。
S06. 烧结:将步骤S05中装入石墨模具中的物料放入真空烧结炉中,采用SPS烧结;SPS烧结的过程中,先将温度从室温升至1600℃并在 1600℃保温10min-20min作为碳热还原反应阶段,再以30-60℃/min从1600℃升至1950℃-2050℃并保温5min-12min作为固溶阶段,烧结,烧结条件为真空气氛,压力范围在20MPa - 40MPa。
S07. 卸压冷却:待步骤S06烧结保温保压时间结束后,以80 - 100 ℃/min的速率降温至1000 ℃,同时在1-3 min内卸压至20 MPa,然后保持压力20 MPa,在5 min - 10 min内降温至1000 ℃;而后,同时停止加热和加压,随炉冷却到室温。
进一步,在步骤S06中,将温度从室温升至1600℃时,先以50-100℃/min的升温速率从室温升至600℃,再以40-90℃/min的升温速率从600℃升至1600℃。
进一步,在步骤S06中,当温度在室温至1600℃时压力保持20MPa不变,在1600℃-1950℃时压力随温度上升由20MPa逐步升至40MPa。
由上述SPS方法所得高熵碳化物陶瓷 (MoNbTaTiW)C5为单相、面心立方结构。
本发明的发明人团队采用过渡金属氧化物与炭黑进行碳热还原反应,通过SPS制备了具有优异力学性能的高熵碳化物陶瓷(MoNbTaTiW)C5,研究了烧结过程中保温温度、烧结温度、碳含量对于制备高熵碳化物陶瓷(MoNbTaTiW)C5物相、致密度、微观结构以及力学性能的影响。研究结果证明,采用SPS,在1950 ℃及以上得到单相、面心立方结构的高熵碳化物陶瓷(MoNbTaTiW)C5,相对密度大于96%;碳含量的减小能促进致密化,而固溶温度提高对致密化不利;本发明所得高熵陶瓷晶粒细小(平均晶粒尺寸3.7 μm),金属元素分布均匀,氧化物杂质富集于高熵陶瓷的孔隙内;减碳,较短的还原保温时间和较低的固溶温度,有利于获得力学性能较好的高熵陶瓷。研究结果对高熵碳化物材料的制备和应用具有很好的指导作用。
本发明与现有技术相比具有如下突出的实质性特点和显著进步。
(1) 本发明所得高熵碳化物陶瓷 (MoNbTaTiW)C5,相对密度大于96%。高熵陶瓷晶粒细小(平均晶粒尺寸3.7 μm),金属元素分布均匀。
(2) 本发明所得高熵碳化物陶瓷(MoNbTaTiW)C5具有较优的力学性能,其硬度,纳米硬度,弹性模量,断裂韧性分别为14-15 GPa,25-28 GPa,357-418 GPa和4.7-5.2 MPa·m1/2。
(3) 本发明所得高熵碳化物陶瓷 (MoNbTaTiW)C5具有较低的热导率,室温热导率低至5.9 W/mK,低于其金属组元对应的碳化物陶瓷。
(4) 本发明通过碳热还原法制备高熵碳化物陶瓷,具有烧结温度低,样品纯度高、晶粒细小等优点。
附图说明
图1为由实施例6所得高熵碳化物陶瓷 (MoNbTaTiW)C5样品HEC-1、HEC-2、HEC-3、HEC-4和HEC-5的XRD图谱。
图2为由实施例6所得高熵碳化物陶瓷 (MoNbTaTiW)C5样品HEC-1抛光表面的SEM及对应的元素面分布图。
图3为由实施例6所得高熵碳化物陶瓷 (MoNbTaTiW)C5样品HEC-2抛光表面的SEM及对应的元素面分布图。
图4为由实施例6所得高熵碳化物陶瓷 (MoNbTaTiW)C5样品HEC-3抛光表面的SEM及对应的元素面分布图。
图5为由实施例6所得高熵碳化物陶瓷 (MoNbTaTiW)C5 样品HEC-4抛光表面的SEM及对应的元素面分布图。
图6为由实施例6所得高熵碳化物陶瓷 (MoNbTaTiW)C5样品HEC-5抛光表面的SEM及对应的元素面分布图。
图7 为由实施例6所得高熵碳化物陶瓷 (MoNbTaTiW)C5样品HEC-1、HEC-2、HEC-3、HEC-4和HEC-5断裂面的SEM图谱。
图8为由实施例6所得高熵碳化物陶瓷(MoNbTaTiW)C5 样品HEC-2的高角度环形暗场扫描透射电子显微镜图谱和能谱。
图9为由实施例6结合SAED的HEC-2的透射电镜图像、亮场透射电镜(a、b)和透射电镜图像(c、d、e、f、g、h、i、j)。
图10为由实施例6所得高熵碳化物陶瓷 (MoNbTaTiW)C5的热导率与温度的关系图。
实施方式
下面结合附图对本发明的技术方案进行详细说明,但本发明的内容并不局限于此。
在实施例中通过制备高熵碳化物陶瓷 (MoNbTaTiW)C5,对其性能进行检测,同时将所得结果进行对比分析,证明本发明所得金属碳化物陶瓷具有优异的性能。
实施例 1
采用SPS工艺制备高熵碳化物陶瓷 (MoNbTaTiW)C5:
本试验所使用的原料为微米级MoO3、Nb2O5、Ta2O5、TiO2、WO3和C粉。
按照各原料配比称取物料1,物料1中原料MoO3、Nb2O5、Ta2O5、TiO2、WO3和C粉的配比为:
物料1:MoO3 : Nb2O5 : Ta2O5 : TiO2 : WO3 : C = 1:0.5:0.5:1:1:17.5(摩尔比);
设置17.5 mol C为初始100%反应碳含量。
将物料1混合。然后装入硬质合金球磨罐,加入无水乙醇,加入硬质合金球,球料比为5:1,在硬质合金罐中以300 r/min的转速球磨混合8 h。然后将得到的混合浆料放入真空干燥箱中,温度设置为100 ℃,充分干燥后,研磨成粉,过筛。过筛后的粉末放入石墨模具中,模具内要预先装一层石墨纸将粉料与模具内壁隔开,且粉料与模具接触的上下两侧也需要用石墨纸隔开,便于脱模。将装好粉料的模具放入SPS烧结炉中,烧结。SPS烧结的过程中,以85℃/min的升温速率从室温升至600℃,再以80℃/min的升温速率从600℃升至1600℃,在 1600℃保温10min作为碳热还原反应阶段,再以50℃/min从1600℃升至1950℃并在1950℃保温10min作为固溶阶段,烧结,烧结条件为真空气氛,压力范围在20MPa~40MPa;其中,当温度在室温至1600℃时压力保持20MPa不变,在1600℃-1950℃时压力随温度上升由20MPa逐步升至40MPa。待烧结保温时间结束后,以80 ℃/min的速率,同时在1 min内卸压至20 MPa,然后保持压力20 MPa,在8 min内降温至1000 ℃;而后,同时停止加热和加压,随炉冷却到室温。得到高熵碳化物陶瓷 (MoNbTaTiW)C5,并将由物料1制备得到的高熵碳化物陶瓷 (MoNbTaTiW)C5样品命名为HEC-1。制备高熵碳化物陶瓷 (MoNbTaTiW)C5样品所用原料配比及烧结工艺参数汇总见表1。
实施例 2
采用SPS工艺制备高熵碳化物陶瓷 (MoNbTaTiW)C5:
本试验所使用的原料为微米级MoO3、Nb2O5、Ta2O5、TiO2、WO3和C粉。
按照各原料配比称取物料2,物料2中原料MoO3、Nb2O5、Ta2O5、TiO2、WO3和C粉的配比为:
物料2:MoO3 : Nb2O5 : Ta2O5 : TiO2 : WO3 : C = 1:0.5:0.5:1:1:15.75(摩尔比);
相对于实施例1中17.5 mol C为初始100%反应碳含量,实施例2中的15.75 mol C为初始90%反应碳含量。
将物料2混合。然后装入硬质合金球磨罐,加入无水乙醇,加入硬质合金球,球料比为5:1,在硬质合金罐中以320 r/min的转速球磨混合9 h。然后将得到的混合浆料放入真空干燥箱中,温度设置为100 ℃,充分干燥后,研磨成粉,过筛。过筛后的粉末放入石墨模具中,模具内要预先装一层石墨纸将粉料与模具内壁隔开,且粉料与模具接触的上下两侧也需要用石墨纸隔开,便于脱模。将装好粉料的模具放入SPS烧结炉中,烧结。SPS烧结的过程中,以85℃/min的升温速率从室温升至600℃,再以80℃/min的升温速率从600℃升至1600℃,在 1600℃保温10min作为碳热还原反应阶段,再以50℃/min从1600℃升至1950℃并在1950℃保温10min作为固溶阶段,烧结,烧结条件为真空气氛,压力范围在20MPa~40MPa;其中,当温度在室温至1600℃时压力保持20MPa不变,在1600℃-1950℃时压力随温度上升由20MPa逐步升至40MPa。待烧结保温时间结束后,以90 ℃/min的速率,同时在1 min内卸压至20 MPa,然后保持压力20 MPa,在8 min内降温至1000 ℃;而后,同时停止加热和加压,随炉冷却到室温。得到高熵碳化物陶瓷 (MoNbTaTiW)C5,并将由物料2制备得到的高熵碳化物陶瓷 (MoNbTaTiW)C5样品命名为HEC-2。制备高熵碳化物陶瓷 (MoNbTaTiW)C5样品所用原料配比及烧结工艺参数汇总见表1。
实施例 3
采用SPS工艺制备高熵碳化物陶瓷 (MoNbTaTiW)C5:
本试验所使用的原料为微米级MoO3、Nb2O5、Ta2O5、TiO2、WO3和C粉。
按照各原料配比称取物料3,物料3中原料MoO3、Nb2O5、Ta2O5、TiO2、WO3和C粉的配比为:
物料3:MoO3 : Nb2O5 : Ta2O5 : TiO2 : WO3 : C = 1:0.5:0.5:1:1:15.75(摩尔比);
将物料3混合。然后装入硬质合金球磨罐,加入无水乙醇,加入硬质合金球,球料比为5:1,在硬质合金罐中以350 r/min的转速球磨混合10 h。然后将得到的混合浆料放入真空干燥箱中,温度设置为100 ℃,充分干燥后,研磨成粉,过筛。过筛后的粉末放入石墨模具中,模具内要预先装一层石墨纸将粉料与模具内壁隔开,且粉料与模具接触的上下两侧也需要用石墨纸隔开,便于脱模。将装好粉料的模具放入SPS烧结炉中,烧结。SPS烧结的过程中,以85℃/min的升温速率从室温升至600℃,再以80℃/min的升温速率从600℃升至1600℃,在 1600℃保温20min作为碳热还原反应阶段,再以50℃/min从1600℃升至1950℃并在1950℃保温10min作为固溶阶段,烧结,烧结条件为真空气氛,压力范围在20MPa~40MPa;其中,当温度在室温至1600℃时压力保持20MPa不变,在1600℃-1950℃时压力随温度上升由20MPa逐步升至40MPa。待烧结保温时间结束后,以80 ℃/min的速率,同时在1 min内卸压至20 MPa,然后保持压力20 MPa,在8 min内降温至1000 ℃;而后,同时停止加热和加压,随炉冷却到室温。得到高熵碳化物陶瓷 (MoNbTaTiW)C5,并将由物料3制备得到的高熵碳化物陶瓷 (MoNbTaTiW)C5样品命名为HEC-3。制备高熵碳化物陶瓷 (MoNbTaTiW)C5样品所用原料配比及烧结工艺参数汇总见表1。
实施例 4
采用SPS工艺制备高熵碳化物陶瓷 (MoNbTaTiW)C5:
本试验所使用的原料为微米级MoO3、Nb2O5、Ta2O5、TiO2、WO3和C粉。
按照各原料配比称取物料4,物料4中原料MoO3、Nb2O5、Ta2O5、TiO2、WO3和C粉的配比为:
物料4:MoO3 : Nb2O5 : Ta2O5 : TiO2 : WO3 : C = 1:0.5:0.5:1:1:15.75(摩尔比);
将物料4混合。然后装入硬质合金球磨罐,加入无水乙醇,加入硬质合金球,球料比为5:1,在硬质合金罐中以360 r/min的转速球磨混合10 h。然后将得到的混合浆料放入真空干燥箱中,温度设置为100 ℃,充分干燥后,研磨成粉,过筛。过筛后的粉末放入石墨模具中,模具内要预先装一层石墨纸将粉料与模具内壁隔开,且粉料与模具接触的上下两侧也需要用石墨纸隔开,便于脱模。将装好粉料的模具放入SPS烧结炉中,烧结。SPS烧结的过程中,以85℃/min的升温速率从室温升至600℃,再以70℃/min的升温速率从600℃升至1600℃,在 1600℃保温10min作为碳热还原反应阶段,再以50℃/min从1600℃升至2050℃并在2050℃保温10min作为固溶阶段,烧结,烧结条件为真空气氛,压力范围在20MPa~40MPa;其中,当温度在室温至1600℃时压力保持20MPa不变,在1600℃-1950℃时压力随温度上升由20MPa逐步升至40MPa。待烧结保温时间结束后,以100 ℃/min的速率,同时在1 min内卸压至20 MPa,然后保持压力20 MPa,在8 min内降温至1000 ℃;而后,同时停止加热和加压,随炉冷却到室温。得到高熵碳化物陶瓷 (MoNbTaTiW)C5,并将由物料4制备得到的高熵碳化物陶瓷 (MoNbTaTiW)C5样品命名为HEC-4。制备高熵碳化物陶瓷 (MoNbTaTiW)C5样品所用原料配比及烧结工艺参数汇总见表1。
实施例 5
采用SPS工艺制备高熵碳化物陶瓷 (MoNbTaTiW)C5:
本试验所使用的原料为微米级MoO3、Nb2O5、Ta2O5、TiO2、WO3和C粉。
按照各原料配比称取物料5,物料5中原料MoO3、Nb2O5、Ta2O5、TiO2、WO3和C粉的配比为:
物料5:MoO3 : Nb2O5 : Ta2O5 : TiO2 : WO3 : C = 1:0.5:0.5:1:1:15.75(摩尔比);
将物料5混合。然后装入硬质合金球磨罐,加入无水乙醇,加入硬质合金球,球料比为5:1,在硬质合金罐中以400 r/min的转速球磨混合12 h。然后将得到的混合浆料放入真空干燥箱中,温度设置为100 ℃,充分干燥后,研磨成粉,过筛。过筛后的粉末放入石墨模具中,模具内要预先装一层石墨纸将粉料与模具内壁隔开,且粉料与模具接触的上下两侧也需要用石墨纸隔开,便于脱模。将装好粉料的模具放入SPS烧结炉中,烧结。SPS烧结的过程中,以85℃/min的升温速率从室温升至600℃,再以60℃/min的升温速率从600℃升至1600℃,在 1600℃保温20min作为碳热还原反应阶段,再以50℃/min从1600℃升至2050℃并在2050℃保温10min作为固溶阶段,烧结,烧结条件为真空气氛,压力范围在20MPa~40MPa;其中,当温度在室温至1600℃时压力保持20MPa不变,在1600℃-1950℃时压力随温度上升由20MPa逐步升至40MPa。待烧结保温时间结束后,以80 - 100 ℃/min的速率,同时在1 min内卸压至20 MPa,然后保持压力20 MPa,在8 min内降温至1000 ℃;而后,同时停止加热和加压,随炉冷却到室温。得到高熵碳化物陶瓷 (MoNbTaTiW)C5,并将由物料5制备得到的高熵碳化物陶瓷 (MoNbTaTiW)C5样品命名为HEC-5。制备高熵碳化物陶瓷 (MoNbTaTiW)C5样品所用原料配比及烧结工艺参数汇总见表1。
实施例 6
性能检测:对实施例1-5所得高熵碳化物陶瓷 (MoNbTaTiW)C5进行物相、微结构、力学性能和热性能检测,并将所得结果进行了对比分析。所得样品分析检测结果如下:
1. 物相
在实施例1-5碳热还原制备高熵碳化物陶瓷 (MoNbTaTiW)C5实验的基础上,发明人对所得高熵碳化物陶瓷 (MoNbTaTiW)C5的物相进行了检测,所得高熵碳化物陶瓷(MoNbTaTiW)C5 样品HEC-1、HEC-2、HEC-3、HEC-4和HEC-5的XRD图谱,见图1,其晶格常数列于表2。由图1(a)可见,20 °~80 °范围显示出面心立方结构(fcc)晶型的5个特征峰,34.6°、40.4 °、59.0 °、70.7 °和74.5 °的峰值分别对应(111)、(200)、(220)、(311)、(222)晶面。由此可知,在表1所示的条件下烧结形成了单相的高熵碳化物。在图1(a)所示的XRD图谱中,由HEC-1的XRD图谱未观察到氧化物对应的衍射峰,说明在1600 ℃保温,在最终烧结体中,氧化物被完全还原为碳化物,但在26°处存在一个衍射峰归属为碳峰,说明制备HEC-1的配料中碳过量。碳过量可能是由于金属氧化物熔点较低,在烧结过程中的挥发导致的。相对于HEC-1的原料配料配方,HEC-2至HEC-5的原料配方中减少了10%的碳。由图1(a)可见,在HEC-2至HEC-5的XRD衍射花样中,未观察到碳对应的衍射峰。另外,由图1(b)可见,在34 °-37 °范围内,HEC-2至HEC-5的衍射峰相对于HEC-1呈现左移,说明其晶格常数变大,具体晶格常数见表2。
2. 微结构
2.1 致密度
在实施例1-5碳热还原制备高熵碳化物陶瓷 (MoNbTaTiW)C5的基础上,发明人对所得高熵碳化物陶瓷 (MoNbTaTiW)C5的致密度进行了检测,所得高熵陶瓷的理论密度、实际密度和相对密度具体数据,见表2。由表2可知,由实施例1所得高熵碳化物陶瓷(MoNbTaTiW)C5样品HEC-1的相对密度仅为91.6%。由实施例2-实施例5所得高熵碳化物陶瓷(MoNbTaTiW)C5样品HEC-2、HEC-3、HEC-4和HEC-5为减小原料配比中碳含量后所得,由表2可以看出,在相同工艺下所得的HEC-2的相对密度上升为96.9%。在HEC-2的制备工艺基础上,延长碳热还原阶段的保温时间,所得HEC-3的相对密度比HEC-2略高,为97.2%;相对地,提高固溶阶段的温度,所得HEC-5的相对密度比HEC-2略低,为96.4%。同时延长碳热还原阶段的保温时间和提高固溶阶段的温度,所得HEC-5的相对密度与HEC-2相等。
2.2 SEM
在实施例1-5碳热还原制备高熵碳化物陶瓷 (MoNbTaTiW)C5的基础上,发明人对所得高熵碳化物陶瓷 (MoNbTaTiW)C5的表面及断裂面进行了扫描电子显微镜 (SEM) 检测,检测所得高熵碳化物陶瓷 (MoNbTaTiW)C5样品HEC-1、HEC-2、HEC-3、HEC-4和HEC-5抛光表面的SEM及对应的元素面分布图,分别如图2、图3、图4、图5、图6所示。其中,图2(a)、图2(b) 为高熵碳化物陶瓷HEC-1的抛光面的SEM及对应的元素面分布图;图3(c)、图3(d) 为高熵碳化物陶瓷HEC-2的抛光面的SEM及对应的元素面分布图;图4(e)、图4(f) 为高熵碳化物陶瓷HEC-3的抛光面的SEM及对应的元素面分布图;图5(g)、图5(h) 为高熵碳化物陶瓷HEC-3的抛光面的SEM及对应的元素面分布图;图6(i)、图6(k) 为高熵碳化物陶瓷HEC-1的抛光面的SEM及对应的元素面分布图。所得高熵碳化物陶瓷的平均晶粒尺寸列于表2。由各SEM图对应的元素面分布来看,各高熵碳化物陶瓷中的金属元素均匀分布。
所得高熵碳化物陶瓷 (MoNbTaTiW)C5样品HEC-1、HEC-2、HEC-3、HEC-4和HEC-5断裂面的SEM图谱,如图7所示。其中,图7(a)为高熵碳化物陶瓷 HEC-1的断裂面的SEM;图7(b)为高熵碳化物陶瓷HEC-2的断裂面的SEM;图7(c)为高熵碳化物陶瓷 HEC-3的断裂面的SEM;图7(d)为高熵碳化物陶瓷HEC-4的断裂面的SEM;图7(e)为高熵碳化物陶瓷 HEC-5的断裂面的SEM;由图7可见,HEC-1至HEC-4断裂方式为穿晶断裂的混合断裂方式,HEC-5断裂方式为沿晶断裂。说明烧结温度升高,晶界强度降低。由表2可知,HEC-1至HEC-4中,高熵碳化物陶瓷相的晶粒尺寸为3.4-3.7μm,HEC-5的晶粒尺寸为6.5μm,提示碳热还原反应阶段保温时间延长,有利于晶粒的长大。
2.3 TEM
在实施例2碳热还原制备高熵碳化物陶瓷 (MoNbTaTiW)C5的基础上,发明人对所得高熵碳化物陶瓷 (MoNbTaTiW)C5样品HEC-2进行了透射电子显微镜 (TEM) 检测,所得高熵碳化物陶瓷 (MoNbTaTiW)C5 样品HEC-2的高角度环形暗场扫描透射电子显微镜图谱和能谱,如图8所示。所得结合SAED的HEC-2的透射电镜图像、亮场透射电镜(a、b)和透射电镜图像(c、d、e、f、g、h、i、j),如图9所示,其中图9(a)为透射电镜图像,图9(b)为亮场透射电镜,图9(c)、9(d)、9(e)、9(f)、9(g)、9(h)、9(i)、9(j) 为透射电镜图像。由图9可以观察到Mo、Nb、Ti、Ta和W元素在纳米尺度上分布均匀,在整个扫描区域内未发现偏析或聚集现象。由图9(b)可见,P1和P2为具有面心立方结构的高熵区域,由图9的(c),(d),(g),(h),(i)可以看出晶化良好。
3. 力学性能
在实施例2-5碳热还原制备高熵碳化物陶瓷 (MoNbTaTiW)C5实验的基础上,发明人对所得高熵碳化物陶瓷 (MoNbTaTiW)C5 样品HEC-2、HEC-3、HEC-4和HEC-5的力学性能进行了检测,力学性能数据,见表3。由表3可知,4种高熵碳化物陶瓷HEC-2、HEC-3、HEC-4和HEC-5的断裂韧性均处于4.7-5.2 MPa·m1/2范围内,均明显高于其金属组元对应的二元碳化物的断裂韧性。
4.热性能
在实施例1-5碳热还原制备高熵碳化物陶瓷 (MoNbTaTiW)C5实验的基础上,发明人对所得高熵碳化物陶瓷 (MoNbTaTiW)C5样品HEC-1、HEC-2、HEC-3、HEC-4和HEC-5的热性能进行了检测,所得高熵碳化物陶瓷 (MoNbTaTiW)C5的热导率与温度的关系图,如图10所示。由图10可见,高熵碳化物陶瓷的热导率随温度的升高而增加。高熵碳化物陶瓷的室温热导率约为6-7 W/mK。说明本发明所制备的高熵碳化物陶瓷为低热导材料。
以上所述,仅是本发明的较佳实施例,并非用以限制本发明的权利范围。任何以本申请专利范围所涵盖的权利范围实施的技术方案,或者任何熟悉本领域的技术人员,利用上述揭示的方法内容做出许多可能的变动和修饰的方案,均属于本发明的保护范围。
Claims (7)
1.一种高熵碳化物陶瓷(MoNbTaTiW)C5,其特征在于:所述高熵碳化物陶瓷(MoNbTaTiW)C5是以微米级MoO3、Nb2O5、Ta2O5、TiO2、WO3和炭黑粉末为原料,通过碳热还原反应,采用SPS烧结工艺制得。
2. 一种高熵碳化物陶瓷(MoNbTaTiW)C5,其特征在于:所述高熵碳化物陶瓷(MoNbTaTiW)C5为单相、面心立方结构。
3.一种高熵碳化物陶瓷(MoNbTaTiW)C5的制备方法,包括称料、球磨、干燥、研磨、装料、烧结、卸压冷却七个步骤,其特征在于,所述七个步骤具体按如下方法操作:
S01. 称料:按照摩尔比MoO3 : Nb2O : Ta2O5 : TiO2 : WO3 : C = 1:0.5:0.5:1:1:(15.75-17.5)称取MoO3、Nb2O5、Ta2O5、TiO2、WO3、炭黑粉末,混合;
S02. 球磨:将步骤S01混合得到的原料装入硬质合金球磨罐,加入无水乙醇,加入硬质合金球,球料比为(5-10):1,以300-400 r/min的转速球磨混合8 h-12 h;
S03. 干燥:将步骤S02球磨混合得到的浆料置于100 ℃真空干燥箱中,充分干燥;
S04. 研磨:将步骤S03干燥后得到的物料研磨成粉,过筛;
S05. 装料:将步骤S04研磨过筛后的粉末装入石墨模具中,模具内要预先装石墨纸将粉料与模具内壁隔开,且粉料与模具接触的上下两侧也需要用石墨纸隔开,便于脱模;
S06. 烧结:将步骤S05中装入石墨模具中的物料放入真空烧结炉中,采用SPS烧结;SPS烧结的过程中,先将温度从室温升至1600℃并在1600℃保温10min-20min作为碳热还原反应阶段,再以30-60℃/min从1600℃升至1950℃-2050℃并保温5min-12min作为固溶阶段,烧结,烧结条件为真空气氛,压力范围在20MPa - 40MPa;
S07. 卸压冷却:待步骤S06烧结保温保压时间结束后,以80 - 100 ℃/min的速率降温至1000 ℃,同时在1-3 min内卸压至20 MPa,然后保持压力20 MPa,在5 min - 10 min内降温至1000 ℃;而后,同时停止加热和加压,随炉冷却到室温。
4.如权利要求3所述的一种高熵碳化物陶瓷(MoNbTaTiW)C5的制备方法,其特征在于,在步骤S06中,SPS烧结的过程中,在将温度从室温升至1600℃时,先以50-100℃/min的升温速率从室温升至600℃,再以40-90℃/min的升温速率从600℃升至1600℃。
5.如权利要求3所述的一种高熵碳化物陶瓷(MoNbTaTiW)C5的制备方法,其特征在于,在步骤S06中,当温度在室温至1600℃时压力保持20MPa不变,在1600℃-1950℃时压力随温度上升由20MPa逐步升至40MPa。
6. 如权利要求3所述的一种高熵碳化物陶瓷(MoNbTaTiW)C5的制备方法,其特征在于,所得高熵碳化物陶瓷 (MoNbTaTiW)C5的相对密度大于96%。
7. 如权利要求3所述的一种高熵碳化物陶瓷(MoNbTaTiW)C5的制备方法,其特征在于,所得高熵碳化物陶瓷 (MoNbTaTiW)C5的室温热导率低至5.9 W/mK。
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