CN117417193A - 一种多元过渡金属一硼化物粉体的低成本制备方法 - Google Patents
一种多元过渡金属一硼化物粉体的低成本制备方法 Download PDFInfo
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- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 17
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 35
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 48
- 229910002804 graphite Inorganic materials 0.000 claims description 36
- 239000010439 graphite Substances 0.000 claims description 36
- 239000011812 mixed powder Substances 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000002390 rotary evaporation Methods 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
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- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 7
- 238000000498 ball milling Methods 0.000 abstract description 20
- 239000000919 ceramic Substances 0.000 abstract description 14
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 2
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- 238000001238 wet grinding Methods 0.000 abstract description 2
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- 239000000463 material Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 7
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- 238000004321 preservation Methods 0.000 description 7
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- 229910052721 tungsten Inorganic materials 0.000 description 7
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- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
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- 230000008018 melting Effects 0.000 description 3
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- 238000003786 synthesis reaction Methods 0.000 description 3
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- 229910052796 boron Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
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- 229910052580 B4C Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开一种多元过渡金属一硼化物粉体的低成本制备方法,属于陶瓷材料技术领域。该方法包括采用微米级MoO3、WO3、Cr2O3、MOx、B4C和C为原料,将原料粉末混料、干燥、过筛后利用无压烧结进行热处理,得到所需一硼化物粉末。本发明首先通过摇摆球磨将过渡金属氧化物MoO3,WO3,Cr2O3,Ta2O5,B4C和C粉进行湿磨混合,然后将混合均匀的原料在旋转蒸发器中充分干燥,最后对混合均匀的原料进行热处理实现高熵陶瓷粉体的制备,通过调整工艺参数,获得单相结构的高熵陶瓷粉体。该方法首次成功合成出了一硼化物的高熵陶瓷粉体,通过多项技术表征,合成的(Mo0.25W0.25Cr0.25M0.25)B高熵陶瓷粉体具有较好的颗粒分散性和微观形貌。
Description
技术领域
本发明属于陶瓷材料技术领域,具体涉及一种多元过渡金属一硼化物粉体的低成本制备方法。
背景技术
高熵硼化物因独特的晶体结构和价键类型,往往展现出高熔点、优异的力学性能、较高的热稳定性等性能,如高熵二硼化物被认为是作为超高音速飞行器热防护部件、金属熔炼坩埚以及防弹装甲的候选材料。硼热-碳热还原作为制备二硼化物的一条常规途径,至今仍是十分成熟的一项工艺,无论是单相二硼化物还是高熵二硼化物都可以通过此法获得纯度很高的产物。Gild等人也是利用硼热-碳热还原成功制备出了高熵二硼化物(Hf0.2Zr0.2Ti0.2Ta0.2Nb0.2)B2、(Hf0.2Zr0.20.2Ti0.2Ta0.2Mo0.2)B2和(Hf0.2Zr0.2Ti0.2Ta0.2Cr0.2)B2。(Ceramics International,46(2020),6906-6913)。
由于过渡金属一硼化物独特的晶体结构和价键类型,具有高的硬度、高的熔点、耐磨损性能、良好的导电性、电磁屏蔽性能以及电化学性能等优异的物理化学性能,在刀具涂层、航空航天等领域有重要应用。2016年,Michael等人利用大原子半径的Ta取代WB中W原子制备了一种正交结构的一硼化物固溶体(W0.5Ta0.5)B,强化了双金属层晶面即(020)晶面,同时扭曲的共价键(B-B键)阻碍了(002)和(200)晶面的变形,最终成功获得了超硬的一硼化物材料。在二硼化物材料方面,高熵化可以在一定程度上增加材料的硬度。Zhao等以金属和硼粉为原料制备一硼化物粉体,并通过热压烧结成功制备了高熵一硼化物(Mo0.2Ta0.2Ni0.2Cr0.2W0.2)B,所获材料拥有48.5±4.1Gpa的维氏硬度,也进一步说明高熵一硼化物材料将会是超硬材料的一个重要的研究方向。(Ceramics International,46(2020),26626-26631)。
根据目前已报道的一硼化物陶瓷,合成方式仅有通过金属粉末与硼粉反应的方法。由于一硼化物可以与其他硼源如硼粉、碳化硼粉等发生反应,因此氧化物硼热-碳热还原制备一硼化物中不可避免的存在二硼化物杂质。因而使用此法合成一硼化物的方法还未曾有人报道。而通过金属粉末与硼粉反应的方法也存在一些缺陷,如反应温度高;硼粉价格昂贵,以及纯度问题尚待解决;金属粉体具有一定的延展性,在球磨过程中容易延展,加之球磨过程中金属粉体还存在氧化的可能等。
因此,为避开现有合成方法存在的问题,并寻找一种低温、简单、且成本更低的一硼化物高熵陶瓷粉体的制备技术是亟需解决的问题。
发明内容
针对现有技术中存在的不足,本发明目的在于提供一种微米级、纯度较高的多元过渡金属一硼化物粉体的低成本制备方法。
为实现上述目的,本发明通过下述技术方案实现:
一种多元过渡金属一硼化物粉体的低成本制备方法,包括:采用微米级MoO3、WO3、Cr2O3、MOx、B4C和C为原料,根据以下化学方程式进行粉末的配比:
0.25MoO3+0.25WO3+0.125Cr2O3+0.25MOx+0.25B4C+aC=(Mo0.25W0.25Cr0.25M0.25)B+bCO;其中,参数a和b分别为对应不同氧化物时C和CO的计量系数;将原料粉末混料、干燥、过筛后利用无压烧结进行热处理,得到所需一硼化物粉末。
其中,获得的一硼化物粉体为正交结构,且需要多次热处理方能成功制备。
优选地,MOx中元素M为Ta、Nb、V、Ti中的任意一种。
优选地,参数a的取值范围为2.125-2.5,参数b的取值范围为2.375-2.5。
优选地,原料粉末的混料、干燥和过筛的具体步骤为:
以微米级MoO3、WO3、Cr2O3、MOx、B4C和C为原料,将各种原料粉体按设计的反应方程的配比进行称量,配料,以无水乙醇为溶剂,氧化锆球为混料介质,进行混料,混合后所得的浆料通过旋转蒸发烘干,破碎过筛后得到的混合均匀的粉料。
优选地,各种原料粉体的粒径均小于3μm,纯度均为99%。
优选地,无压烧结进行热处理的具体步骤为:
一次热处理:将过筛后的粉体进行压片,随后放入垫好石墨纸的石墨坩埚中,在石墨碳管炉中进行真空热处理,得到块体;
二次热处理:将得到的块体进行破碎、过筛,重新进行压片,随后放入垫好石墨纸的石墨坩埚中,在石墨碳管炉中再次进行真空热处理,热处理温度不高于第一次热处理温度。
相较于直接按照计量比合成一硼化物粉末,此处采用了多次真空热处理的方式,使得粉体纯度逐步提高。
优选地,粉体在压力3-20MPa下进行压片。
优选地,真空热处理的温度范围为1250-1750℃。
优选地,真空热处理的保温时间范围为30-90min。
优选地,真空热处理的升温速度范围为5-20℃/min。
本发明提供的技术方案具有如下优点及有益效果:
目前一硼化物合成仅能依靠金属粉末和硼粉反应合成,但此法仍存在一系列的问题:1)硼粉价格昂贵,并且反应对硼粉纯度要求很高。2)金属粉体具有一定的延展性,在球磨过程中容易延展,加之球磨过程中金属粉体还存在氧化的可能。对此,本发明方法通过硼热-碳热还原反应制得了微米级、纯度较高的一硼化物粉末,其原料成本低,方便易得,制备工艺简单,在1250-1750℃即可实现一硼化物粉末的合成。
本发明提出了一种(Mo0.25W0.25Cr0.25M0.25)B高熵陶瓷粉体材料,首先通过摇摆球磨将过渡金属氧化物MoO3,WO3,Cr2O3,Ta2O5,B4C和C粉进行湿磨混合,然后将混合均匀的原料在旋转蒸发器中充分干燥,最后对混合均匀的原料进行热处理实现高熵陶瓷粉体的制备,通过调整工艺参数,获得单相结构的高熵陶瓷粉体。该方法首次成功合成出了一硼化物的高熵陶瓷粉体,通过多项技术表征,合成的(Mo0.25W0.25Cr0.25M0.25)B高熵陶瓷粉体具有较好的颗粒分散性和微观形貌。
附图说明
图1为实施例1得到的(Mo0.25W0.25Cr0.25Ta0.25)B粉体的SEM图;
图2为实施例1得到的(Mo0.25W0.25Cr0.25Ta0.25)B粉体的元素分布图;
图3为实施例1得到的(Mo0.25W0.25Cr0.25Ta0.25)B粉体的XRD图;
图4为实施例2得到的(Mo0.25W0.25Cr0.25Ta0.25)B粉体的XRD图;
图5为实施例2得到的(Mo0.25W0.25Cr0.25Ta0.25)B粉体的XRD图。
具体实施方式
为了使本领域的技术人员更好地理解本发明的技术方案,下面结合具体实施例对本发明的优选实施方案进行描述,但是不能理解为对本发明的限制,仅作举例而已。
下述实施例中所述试验方法或测试方法,如无特殊说明,均为常规方法;所述试剂和材料,如无特殊说明,均从常规商业途径获得,或以常规方法制备。
实施例1
步骤1:分别称取市售的MoO3粉末3.44g、WO3粉末5.55g、Cr2O3粉末1.82g、Ta2O5粉末5.29g、B4C粉末1.32g、C粉末2.59g,并将称取的粉末(共20g)、50g无水乙醇和40g钇稳定氧化锆球(料球质量比约为1:2)一同加入球磨罐中球磨混料12h。然后,将混合后的料浆通过旋转蒸发在60℃烘干1h并过200目的筛网后得到均匀且干燥的混合粉末。
步骤2:将上述混合粉末,经过干压成型(成型压力3-20MPa,保压时间1min)得到混合粉末块体,随后放入垫好石墨纸的石墨坩埚中,在石墨碳管炉中进行真空热处理。其中热处理温度为1250-1750℃,保温时间范围为30-90min,升温速度范围为5-20℃/min。将得到的块体进行破碎、过筛,依旧在压力3-20MPa下进行压片,随后放入垫好石墨纸的石墨坩埚中,在石墨碳管炉中再次进行热处理,热处理温度不高于第一次热处理温度。
通过以上步骤制备的(Mo,W,Cr,Ta)B粉体的SEM、元素分布图以及XRD图,如图1-3所示,其中一硼化物纯度可达95%以上。
实施例2
步骤1:分别称取市售的MoO3粉末3.43g、WO3粉末5.52g、Cr2O3粉末1.90g、Ta2O5粉末5.26g、B4C粉末1.32g、C粉末2.57g,并将称取的粉末(共20g)、50g无水乙醇和40g钇稳定氧化锆球(料球质量比约为1:2)一同加入球磨罐中球磨混料12h。然后,将混合后的料浆通过旋转蒸发在60℃烘干1h并过200目的筛网后得到均匀且干燥的混合粉末。
步骤2:将上述混合粉末,经过干压成型(成型压力3-20MPa,保压时间1min)得到混合粉末块体,随后放入垫好石墨纸的石墨坩埚中,在石墨碳管炉中进行真空热处理。其中热处理温度为1250-1750℃,保温时间范围为30-90min,升温速度范围为5-20℃/min。
通过以上步骤制备的(Mo,W,Cr,Ta)B粉体的XRD图,如图4所示,其中一硼化物纯度可达95%以上。
实施例3
步骤1:分别称取市售的MoO3粉末3.57g、WO3粉末5.74g、Cr2O3粉末1.88g、Ta2O5粉末5.47g、B4C粉末1.72g、C粉末1.61g,并将称取的粉末(共20g)、50g无水乙醇和40g钇稳定氧化锆球(料球质量比约为1:2)一同加入球磨罐中球磨混料12h。然后,将混合后的料浆通过旋转蒸发在60℃烘干1h并过200目的筛网后得到均匀且干燥的混合粉末。
步骤2:将上述混合粉末,经过干压成型(成型压力3-20MPa,保压时间1min)得到混合粉末块体,随后放入垫好石墨纸的石墨坩埚中,在石墨碳管炉中进行真空热处理。其中热处理温度为1250-1750℃,保温时间范围为30-90min,升温速度范围为5-20℃/min。
通过以上步骤制备的(Mo,W,Cr,Ta)B粉体的XRD图,如图5所示。
实施例4
步骤1:分别称取市售的MoO3粉末3.85g、WO3粉末6.20g、Cr2O3粉末2.03g、Nb2O5粉末3.55g、B4C粉末1.48g、C粉末2.89g,并将称取的粉末(共20g)、50g无水乙醇和40g钇稳定氧化锆球(料球质量比约为1:2)一同加入球磨罐中球磨混料12h。然后,将混合后的料浆通过旋转蒸发在60℃烘干1h并过200目的筛网后得到均匀且干燥的混合粉末。
步骤2:将上述混合粉末,经过干压成型(成型压力3-20MPa,保压时间1min)得到混合粉末块体,随后放入垫好石墨纸的石墨坩埚中,在石墨碳管炉中进行真空热处理。其中热处理温度为1250-1750℃,保温时间范围为30-90min,升温速度范围为5-20℃/min。
通过以上步骤制备的粉体通过XRD测试确认为(Mo,W,Cr,Nb)B。
实施例5
步骤1:分别称取市售的MoO3粉末4.11g、WO3粉末7.11g、Cr2O3粉末2.33g、V2O5粉末1.14g、B4C粉末1.69g、C粉末3.31g,并将称取的粉末(共20g)、50g无水乙醇和40g钇稳定氧化锆球(料球质量比约为1:2)一同加入球磨罐中球磨混料12h。然后,将混合后的料浆通过旋转蒸发在60℃烘干1h并过200目的筛网后得到均匀且干燥的混合粉末。
步骤2:将上述混合粉末,经过干压成型(成型压力3-20MPa,保压时间1min)得到混合粉末块体,随后放入垫好石墨纸的石墨坩埚中,在石墨碳管炉中进行真空热处理。其中热处理温度为1250-1750℃,保温时间范围为30-90min,升温速度范围为5-20℃/min。
通过以上步骤制备的粉体通过XRD测试确认为(Mo,W,Cr,V)B。
实施例6
步骤1:分别称取市售的MoO3粉末4.21g、WO3粉末6.78g、Cr2O3粉末2.22g、TiO2粉末2.18g、B4C粉末1.62g、C粉末2.99g,并将称取的粉末(共20g)、50g无水乙醇和40g钇稳定氧化锆球(料球质量比约为1:2)一同加入球磨罐中球磨混料12h。然后,将混合后的料浆通过旋转蒸发在60℃烘干1h并过200目的筛网后得到均匀且干燥的混合粉末。
步骤2:将上述混合粉末,经过干压成型(成型压力3-20MPa,保压时间1min)得到混合粉末块体,随后放入垫好石墨纸的石墨坩埚中,在石墨碳管炉中进行真空热处理。其中热处理温度为1250-1750℃,保温时间范围为30-90min,升温速度范围为5-20℃/min。
通过以上步骤制备的粉体通过XRD测试确认为(Mo,W,Cr,Ti)B。
实施例7
步骤1:分别称取市售的MoO3粉末2.85g、WO3粉末4.59g、Cr2O3粉末1.51g、Ta2O5粉末4.38g、Nb2O5粉末2.63g、B4C粉末1.62g、C粉末2.99g,并将称取的粉末(共20g)、50g无水乙醇和40g钇稳定氧化锆球(料球质量比约为1:2)一同加入球磨罐中球磨混料12h。然后,将混合后的料浆通过旋转蒸发在60℃烘干1h并过200目的筛网后得到均匀且干燥的混合粉末。
步骤2:将上述混合粉末,经过干压成型(成型压力3-20MPa,保压时间1min)得到混合粉末块体,随后放入垫好石墨纸的石墨坩埚中,在石墨碳管炉中进行真空热处理。其中热处理温度为1250-1750℃,保温时间范围为30-90min,升温速度范围为5-20℃/min。
通过以上步骤制备的粉体通过XRD测试确认为(Mo,W,Cr,Ta,Nb)B。
以上仅是本发明的优选实施方式,应当指出的是,上述优选实施方式不应视为对本发明的限制,本发明的保护范围应当以权利要求所限定的范围为准。对于本技术领域的普通技术人员来说,在不脱离本发明的精神和范围内,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (10)
1.一种多元过渡金属一硼化物粉体的低成本制备方法,其特征在于,包括:采用微米级MoO3、WO3、Cr2O3、MOx、B4C和C为原料,根据以下化学方程式进行粉末的配比:0.25MoO3+0.25WO3+0.125Cr2O3+0.25MOx+0.25B4C+aC=(Mo0.25W0.25Cr0.25M0.25)B+bCO;其中,参数a和b分别为对应不同氧化物时C和CO的计量系数;将原料粉末混料、干燥、过筛后利用无压烧结进行热处理,得到所需一硼化物粉末。
2.根据权利要求1所述的多元过渡金属一硼化物粉体的低成本制备方法,其特征在于,MOx中元素M为Ta、Nb、V、Ti中的任意一种。
3.根据权利要求1所述的多元过渡金属一硼化物粉体的低成本制备方法,其特征在于,参数a的取值范围为2.125-2.5,参数b的取值范围为2.375-2.5。
4.根据权利要求1所述的多元过渡金属一硼化物粉体的低成本制备方法,其特征在于,原料粉末的混料、干燥和过筛的具体步骤为:
以微米级MoO3、WO3、Cr2O3、MOx、B4C和C为原料,将各种原料粉体按设计的反应方程的配比进行称量,配料,以无水乙醇为溶剂,氧化锆球为混料介质,进行混料,混合后所得的浆料通过旋转蒸发烘干,破碎过筛后得到的混合均匀的粉料。
5.根据权利要求4所述的多元过渡金属一硼化物粉体的低成本制备方法,其特征在于,各种原料粉体的粒径均小于3μm,纯度均为99%。
6.根据权利要求1所述的多元过渡金属一硼化物粉体的低成本制备方法,其特征在于,无压烧结进行热处理的具体步骤为:
一次热处理:将过筛后的粉体进行压片,随后放入垫好石墨纸的石墨坩埚中,在石墨碳管炉中进行真空热处理,得到块体;
二次热处理:将得到的块体进行破碎、过筛,重新进行压片,随后放入垫好石墨纸的石墨坩埚中,在石墨碳管炉中再次进行真空热处理,热处理温度不高于第一次热处理温度。
7.根据权利要求6所述的多元过渡金属一硼化物粉体的低成本制备方法,其特征在于,粉体在压力3-20MPa下进行压片。
8.根据权利要求6所述的多元过渡金属一硼化物粉体的低成本制备方法,其特征在于,真空热处理的温度范围为1250-1750℃。
9.根据权利要求6所述的多元过渡金属一硼化物粉体的低成本制备方法,其特征在于,真空热处理的保温时间范围为30-90min。
10.根据权利要求6所述的多元过渡金属一硼化物粉体的低成本制备方法,其特征在于,真空热处理的升温速度范围为5-20℃/min。
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