CN115159990A - 一种高韧性高熵金属二硼化物及其制备方法 - Google Patents
一种高韧性高熵金属二硼化物及其制备方法 Download PDFInfo
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- 229910052796 boron Inorganic materials 0.000 claims abstract description 5
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
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- 239000011215 ultra-high-temperature ceramic Substances 0.000 abstract description 3
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Abstract
本发明涉及一种高韧性高熵金属二硼化物，属于超高温陶瓷材料技术领域。所述高韧性高熵金属二硼化物材料化学式记为(Hf0.2Zr0.2Ta0.2Nb0.2Tm0.2)B2，元素组成为Hf、Zr、Ta、Sc、Tm以及B六种元素。制备得到的(Hf0.2Zr0.2Ta0.2Sc0.2Tm0.2)B2的粉体和块体的相结构中主要为AlB2型结构，含有少量TmB4相结构。(Hf0.2Zr0.2Ta0.2Nb0.2Tm0.2)B2除了具有较高的硬度和强度外，由于由于Tm原子的加入，导致共价键的减弱改善了高熵金属二硼化物的脆性，显著提高了金属硼化物的断裂韧性(8.25MPa·m1/2)，比HfB2(4MPa·m1/2)，ZrB2(4MPa·m1/2)，NbB2(4.5MPa·m1/2)等传统金属二硼化物高出约83％。因此，本发明涉及的(Hf0.2Zr0.2Ta0.2Sc0.2Tm0.2)B2可以显著改善金属二硼化物的韧性，并且制备工艺简单，适合工业推广应用。
Description
技术领域
本发明涉及一种高韧性高熵金属二硼化物及其制备方法，属于超高温陶瓷材料技术领域。
背景技术
过渡金属二硼化物(TMB2)属于超高温陶瓷的一种，具有高熔点、高电导率、高导热率、优异的力学性能和良好的化学稳定性等优点。这种独特的性能组合使得过渡金属二硼化物适用于各种应用，如熔融金属坩埚、切削工具、耐磨部件、电火花加工电极、霍尔-赫罗特电池阴极材料、电气设备、装甲材料、铝蒸发船、核用中子屏蔽、火箭喷嘴、耐火材料部件、太阳能吸收应用、高温结构部件等。虽然，TMB2具有优异的硬度和强度，但是作为需要考虑的结构应用，仅仅提高TMB2硬度和强度是不够的。因此，必须注意其他基本力学性能，其中最重要的就是断裂韧性。然而，对于TMB2由于存在强共价键导致其断裂韧性普遍较低。因此，寻找更加有效、便利和可行的方法在改善TMB2的断裂韧性对TMB2在结构应用极为重要。高熵金属二硼化物(HE TMB2)不仅可以扩大不同元素之间的固溶极限，还能为无序单相结构的形成提供稳定性，并且有望克服传统TMB2的应用瓶颈。
发明内容
有鉴于此，本发明提供一种高韧性的高熵金属二硼化物及其制备方法，该金属二硼化物是由Hf、Zr、Ta、Sc、Tm以及B组成的，可以通过简单的管式炉在低温下合成，不仅致密度高，且具有优异的断裂韧性。
本发明的目的是通过以下技术方案实现的。
一种高韧性的高熵金属二硼化物，所述高熵金属二硼化物化学式记为(Hf0.2Zr0.2Ta0.2Sc0.2Tm0.2)B2。
一种高韧性的高熵金属二硼化物的制备方法，所述方法包括以下步骤：
将HfO2,ZrO2,Ta2O5,Sc2O3,Tm2O3和B4C粉体按照化学计量比配料，B4C粉体的加入料过量20％以保证反应的充分和弥补高温下B源的损失。将五种粉体先混合均匀，然后将混合粉体装入石墨磨坩埚中，连同石墨坩埚放入至管式炉中并冲入氩气作为保护气氛，最后升温至1600℃并保温1h～3h，得到高熵金属二硼化物的粉体；
将高熵金属二硼化物粉体装入石墨模具中，采用放电感应等离子烧结在真空或惰性气体保护气氛下烧结，烧结温度为1900℃～2200℃，烧结压力为30MPa～50MPa，烧结时间(或者保温保压时间)为20min～30min，得到高熵金属二硼化物块体。
优选地，过量的B4C粉体为按照化学计量比加入的B4C粉体质量的115％～140％。
优选地，HfO2,ZrO2,Ta2O5,Sc2O3,Tm2O3和B4C粉体在球磨罐中球磨混合，球料比为(3～7)：1，转速为300rpm～500rpm，球磨时间为1h～5h。
优选地，单相高熵金属二硼化物粉体制备过程中，以5℃/min～10℃/min的升温速率加热至1600℃。
优选地，HfO2,ZrO2,Ta2O5,Sc2O3,Tm2O3和B4C粉体的粒径均为500nm～3μm。
有益效果：
(1)TmB2作为稀土金属二硼化物其相结构在常温常压无法存在，因此TmB2的性能无法被应用。本发明首次提出将TmB2和其他三种过渡金属二硼化物TMB2(TM＝Hf，Ta，Zr，Sc)固溶形成高熵金属二硼化物，不仅能够发挥TmB2的特性，还能通过高熵结构改善金属二硼化物的断裂韧性。这主要归因于TmB2与TMB2(TM＝Hf，Ta，Zr，Sc)具有良好的相稳定性，且TmB2比其他TMB2具有更低的熔点，提高了高熵金属二硼化物烧结性和致密度。
(2)本发明设计的高熵金属二硼化物，由于Tm原子的加入，导致共价键的减少改善了高熵金属二硼化物的脆性，显著提高了断裂韧性；Tm原子比其他四种TM原子的半径更大，造成较高的晶格畸变，导致固溶强化和裂纹扩展作用，从而提高了其硬度。
(3)本发明所述高熵金属二硼化物的制备过程中添加过量的B4C，因为硼碳热还原反应过程会生成硼的氧化物，即B2O3和BO，在真空和高温下快速挥发导致硼源的流失，此外为了使金属氧化物与B4C能够充分反应，不残留金属氧化物，所以添加了过量的B4C。
(4)本发明所述高熵金属二硼化物能够在管式炉中较低温度下(1600℃)制备成粉体，制备工艺易于操作，制备成本低，适宜工业推广。
附图说明
图1为实施例1制备的(Hf0.2Zr0.2Ta0.2Sc0.2Tm0.2)B2粉体的X射线衍射(XRD)谱图。
图2为实施例1制备的(Hf0.2Zr0.2Ta0.2Sc0.2Tm0.2)B2块体的X射线衍射(XRD)谱图。
图3为实施例1制备的(Hf0.2Zr0.2Ta0.2Sc0.2Tm0.2)B2块体的元素分析图谱。
具体实施方式
下面结合具体实施方式对本发明作进一步阐述，其中，所述方法如无特别说明均为常规方法，所述原材料如无特别说明均能从公开商业途径获得。
以下实施例中：
HfO2,ZrO2,Ta2O5,Sc2O3,Tm2O3和B4C粉体的粒径均为500nm～3μm；
弹性模量采用脉冲激发共振法测得，测试样品尺寸为3mm×15mm×40mm的长方体；
弯曲强度通过三点弯曲实验得到，测试设备为万能力学试验机，用于测试的长条样品尺寸为3mm×4mm×36mm，跨距为30mm，压头移动速度为0.5mm/min；其中，在测试前，样品进行三面抛光，且受拉面作45°倒角处理以降低边缘性破坏的可能性；
断裂韧性通过三点弯曲实验得到，测试设备为万能力学试验机，采用单边切口梁法测试，样品尺寸为3mm×6mm×40mm，切口深度为3mm，宽度为0.15mm，跨距为24mm，压头移动速度为0.05mm/min。
实施例1
(1)将HfO2,ZrO2,Ta2O5,Sc2O3,Tm2O3和B4C粉体按照化学式配比加入尼龙球磨罐中，球料比为5:1，在350rpm转速下球磨混合5h，得到混合均匀的混合粉体；
(2)将混合粉体装入石墨坩埚中，并放入管式炉中，冲入氩气作为保护气氛，然后以10℃/min的升温速率加热至1600℃并保温3h，得到(Hf0.2Zr0.2Ta0.2Sc0.2Tm0.2)B2粉体；
(3)将(Hf0.2Zr0.2Ta0.2Sc0.2Tm0.2)B2粉体装入石墨模具中，采用放电感应等离子烧结在氩气保护气氛下烧结，烧结温度为2000℃，烧结压力为50MPa，烧结时间30min，得到单相(Hf0.2Zr0.2Ta0.2Sc0.2Tm0.2)B2块体。
对步骤(2)获得的(Hf0.2Zr0.2Ta0.2Sc0.2Tm0.2)B2粉体进行XRD表征，从图1中可以看出，(Hf0.2Zr0.2Ta0.2Sc0.2Tm0.2)B2粉体的主要衍射峰为六方AlB2型结构，并存在一定量的中间产物稀土硼酸盐。
步骤(3)所获得的(Hf0.2Zr0.2Ta0.2Sc0.2Tm0.2)B2块体进行XRD表征，发现(Hf0.2Zr0.2Ta0.2Sc0.2Tm0.2)B2块体稀土硼酸盐消失，主要物相结构为六方AlB2型结构，并存在少量四硼化铥。
采用扫描电子显微镜的EDS模式对步骤(3)获得的(Hf0.2Zr0.2Ta0.2Sc0.2Tm0.2)B2块体进行元素粉体，根据图3的测试结果可知，Hf、Ta、Zr和Sc四种金属元素分布均匀，没有发现团聚或偏析的现象，但是Tm元素有少量的偏聚，这是少量四硼化铥存在导致的。
对步骤(3)制备的(Hf0.2Zr0.2Ta0.2Sc0.2Tm0.2)B2块体进行力学性能测试，测试结果详见表1。从表1中可以看出，(Hf0.2Zr0.2Ta0.2Sc0.2Tm0.2)B2整体的力学性能都非常优异，其中断裂韧性为8.25MPa·m1/2，比HfB2(4MPa·m1/2)，ZrB2(4MPa·m1/2)，NbB2(4.5MPa·m1/2)等传统金属二硼化物高出约83％。因此，本发明涉及的(Hf0.2Zr0.2Ta0.2Sc0.2Tm0.2)B2可以显著改善金属二硼化物的韧性，并且制备工艺简单，适合工业推广应用。
表1
Claims (8)
1.一种四元高熵金属二硼化物，其特征在于：所述四元高熵金属二硼化物化学式为(Hf0.2Zr0.2Ta0.2Sc0.2Tm0.2)B2，由Hf、Zr、Ta、Sc、Tm以及B元素组成。
2.一种如权利要求1所述的四元高熵金属二硼化物的制备方法，其特征在于：所述方法包括以下步骤：
将HfO2,ZrO2,Ta2O5,Sc2O3,Tm2O3和B4C粉体按照化学计量比配料，B4C粉体的加入料过量20％以保证反应的充分和弥补高温下B源的损失。将五种粉体先混合均匀，然后将混合粉体装入石墨磨坩埚中，连同石墨坩埚放入至管式炉中并冲入氩气作为保护气氛，最后升温至1600℃并保温1h～3h，得到高熵金属二硼化物的粉体；
将高熵金属二硼化物粉体装入石墨模具中，采用放电感应等离子烧结在真空或惰性气体保护气氛下烧结，烧结温度为1900℃～2200℃，烧结压力为30MPa～50MPa，烧结时间(或者保温保压时间)为20min～30min，得到高熵金属二硼化物块体。
3.根据权利要求2所述的(Hf0.2Zr0.2Ta0.2Sc0.2Tm0.2)B2的制备方法，其特征在于：过量的B4C粉体为按照化学计量比加入的B4C粉体质量的115％～135％。
4.根据权利要求2所述的一种四元高熵金属二硼化物的制备方法，其特征在于HfO2,ZrO2,Ta2O5,Sc2O3,Tm2O3和B4C粉体在球磨罐中球磨混合，球料比为(3～6)：1，转速为300rpm～500rpm，球磨时间为2h～6h。
5.根据权利要求2所述的一种(Hf0.2Zr0.2Ta0.2Sc0.2Tm0.2)B2的制备方法，其特征在于：四元高熵金属二硼化物粉体制备过程中，以5℃/min～10℃/min的升温速率加热至1700℃以上。
6.根据权利要求2所述的一种(Hf0.2Zr0.2Ta0.2Sc0.2Tm0.2)B2的制备方法，其特征在于：(Hf0.2Zr0.2Ta0.2Sc0.2Tm0.2)B2粉体制备过程中，加热温度为1700℃～1950℃。
7.根据权利要求2所述的一种(Hf0.2Zr0.2Ta0.2Sc0.2Tm0.2)B2的制备方法，其特征在于：将制备得到的(Hf0.2Zr0.2Ta0.2Sc0.2Tm0.2)B2粉体研磨并通过100-300目的筛子过筛，再采用放电感应等离子烧结制备成块体。
8.根据权利要求2所述的一种(Hf0.2Zr0.2Ta0.2Sc0.2Tm0.2)B2的制备方法，其特征在于：HfO2,ZrO2,Ta2O5,Sc2O3和B4C粉体的粒径均为500nm～3μm。
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190024198A1 (en) * | 2017-07-19 | 2019-01-24 | The Industry & Academic Cooperation In Chungnam National University (Iac) | Precipitation Hardening High Entropy Alloy and Method of Manufacturing the Same |
| CN109516812A (zh) * | 2018-10-15 | 2019-03-26 | 广东工业大学 | 一种超细高熵固熔体粉末及其制备方法和应用 |
| CN110002879A (zh) * | 2019-03-22 | 2019-07-12 | 广东工业大学 | 一种致密超硬的高熵硼化物陶瓷及其制备方法和应用 |
| CN110511035A (zh) * | 2019-08-05 | 2019-11-29 | 广东工业大学 | 一种高韧性高耐磨性的高熵陶瓷及其制备方法和应用 |
| CN111344432A (zh) * | 2017-10-06 | 2020-06-26 | 欧瑞康表面处理解决方案股份公司普费菲孔 | 三元过渡金属二硼化物涂覆膜 |
| CN114507074A (zh) * | 2022-03-14 | 2022-05-17 | 北京理工大学 | 一种高熵过渡-稀土金属二硼化物陶瓷材料及其制备方法 |
| CN114715907A (zh) * | 2022-03-18 | 2022-07-08 | 北京理工大学 | 一种单相高熵金属二硼化物及其制备方法 |
-
2022
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- 2022-08-23 CN CN202311355059.8A patent/CN117303908A/zh active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190024198A1 (en) * | 2017-07-19 | 2019-01-24 | The Industry & Academic Cooperation In Chungnam National University (Iac) | Precipitation Hardening High Entropy Alloy and Method of Manufacturing the Same |
| CN111344432A (zh) * | 2017-10-06 | 2020-06-26 | 欧瑞康表面处理解决方案股份公司普费菲孔 | 三元过渡金属二硼化物涂覆膜 |
| US20200332407A1 (en) * | 2017-10-06 | 2020-10-22 | Oerlikon Surface Solutions Ag, Pfäffikon | Ternary tm-diboride coating films |
| CN109516812A (zh) * | 2018-10-15 | 2019-03-26 | 广东工业大学 | 一种超细高熵固熔体粉末及其制备方法和应用 |
| CN110002879A (zh) * | 2019-03-22 | 2019-07-12 | 广东工业大学 | 一种致密超硬的高熵硼化物陶瓷及其制备方法和应用 |
| CN110511035A (zh) * | 2019-08-05 | 2019-11-29 | 广东工业大学 | 一种高韧性高耐磨性的高熵陶瓷及其制备方法和应用 |
| CN114507074A (zh) * | 2022-03-14 | 2022-05-17 | 北京理工大学 | 一种高熵过渡-稀土金属二硼化物陶瓷材料及其制备方法 |
| CN114715907A (zh) * | 2022-03-18 | 2022-07-08 | 北京理工大学 | 一种单相高熵金属二硼化物及其制备方法 |
Non-Patent Citations (1)
| Title |
|---|
| ZHANG ET AL.: "Phase structure, mechanical properties and thermal properties of high-entropy diboride (Hf0.25Zr0.25Ta0.25Sc0.25)B2", 《JOURNAL OF THE EUROPEAN CERAMIC SOCIETY》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116354730A (zh) * | 2023-03-31 | 2023-06-30 | 中国科学院上海硅酸盐研究所 | 一种(Ti,Zr,Hf)B2中熵陶瓷基复相材料及其制备方法 |
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