碳源对碳热还原法制备二硼化锆中硼损失的影响

喻冲; 冷科; 王怡; 曾强; 唐彦; 刘喆

doi:10.13832/j.jnpe.2022.S2.0088

碳源对碳热还原法制备二硼化锆中硼损失的影响

doi: 10.13832/j.jnpe.2022.S2.0088

中国核动力研究设计院反应堆燃料及材料重点实验室，成都，610213

详细信息

作者简介:
喻　冲（1987—），男，硕士研究生，现从事核燃料及材料制备方面研究，Email：yucongy@126.com

中图分类号: TL345
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- 被引次数: 0
出版历程
- 收稿日期: 2022-08-23
- 修回日期: 2022-10-10
- 刊出日期: 2022-12-31

Effect of Carbon Source on Boron Loss in Preparation of Zirconium Diboride by Carbothermal Reduction

Science and Technology on Reactor Fuel and Materials Laboratory, Nuclear Power Institute of China, Chengdu, 610213, China

摘要

摘要: 针对第三代核电堆型AP1000所用的核级ZrB₂靶材制备过程中硼易损失问题，以ZrO₂、B₄C和C为原料，采用碳热还原法制备ZrB₂粉体，研究了碳源种类、碳加入量对高温合成过程中硼损失的影响。采用X射线衍射（XRD）、扫描电镜（SEM）、化学滴定仪等分析了样品的相组成、微观形貌和元素含量，根据合成前后硼含量以及质量守恒原则计算了粉末合成过程中硼含量的损失。结果表明：采用碳热还原法制备ZrB₂粉体会引起硼的损失；相较于石墨，采用炭黑作为碳源且适当过量，能有效降低合成过程中硼的损失，当B₄C过量5%、C过量20%时，合成过程中硼的损失率最低（4.4%），ZrB₂粉体颗粒大小均匀，粒径为1~2 μm，纯度较高。
- 碳热还原 /
- ZrB₂粉体 /
- 石墨 /
- 炭黑 /
- 硼损失
Abstract: In order to solve the problem of easy loss of boron in the preparation of nuclear grade ZrB₂ target used in the third-generation nuclear power reactor AP1000, ZrO₂ powder was prepared by carbothermal reduction method using ZrO₂, B₄C and C as raw materials. The effects of carbon source and carbon addition on boron loss during high temperature synthesis were studied. The phase composition, micro morphology and element content of the samples were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM) and chemical titrator. The loss of boron content in the process of powder synthesis was calculated according to the boron content before and after synthesis and the principle of mass conservation. The results show that the loss of boron can be caused by the preparation of ZrB₂ powder by carbothermal reduction; Compared with graphite, using carbon black as the carbon source with appropriate excess can effectively reduce the loss of boron in the synthesis process; When B₄C exceeds by 5% and carbon exceeds by 20%, the boron loss rate in the synthesis process is the lowest 4.4%, and the particle size of ZrB₂ powder is uniform, the particle size is 1-2 1~2 μm, and the purity is high.
- Carbothermal reduction /
- ZrB₂ powder /
- Graphite /
- Carbon black /
- Boron loss

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图 1 在不同温度下合成ZrB₂粉末的XRD图谱

2θ—衍射角

Figure 1. XRD Spectra of ZrB₂ Powder Synthesized at Different Temperatures

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图 2 不同碳源及不同硼含量合成ZrB₂粉末的XRD图谱

Figure 2. XRD Spectra of ZrB₂ Powder Synthesized from Different Carbon Sources and Different Boron Content

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图 3 硼含量不同的原料在1600℃合成的ZrB₂粉体XRD图谱　　　　　　　　　

Figure 3. XRD Spectra of ZrB₂ Powder Synthesized from Raw Materials with Different Boron Content at 1600 ℃

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图 4 合成ZrB₂粉末的SEM图

Figure 4. SEM Diagram of Synthesized ZrB₂ Powder

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表 1 研究原料

Table 1. Raw Materials of Research

原料	纯度	中位径（D50）	制备公司
商业用ZrO₂粉	≥99.9%	3 μm	致磨新材料科技有限公司
B₄C粉	96%	1.07 μm	郑州嵩山硼业科技有限公司
炭黑	除去水分后纯度≥99.0%	50 nm	中橡集团炭黑工业研究设计院
石墨	≥99.0%	1 μm	自贡东新电碳

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表 2 原料摩尔配比

Table 2. Molar Ratio of Raw Materials

编号	ZrO₂粉	B₄C粉	C粉
T1	2	1	3
T2	2	1.05	3
T3	2	1.1	3
T4	2	1.15	3
T5	2	1	3.3
T6	2	1	3.6
T7	2	1.05	3.3
T8	2	1.05	3.6
S1	2	1	3
S2	2	1.05	3
S3	2	1.1	3
S4	2	1.15	3

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表 3 反应（1）~反应（5）在标准状态下的起始温度

Table 3. Initial Temperatures of Reactions （1）~（5） Under Standard State

反应	（1）	（2）	（3）	（4）	（5）
起始温度/℃	1458	1218	1429	1649	1376

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表 4 不同原料合成纯ZrB₂粉体时硼的质量损失率

Table 4. Mass Loss Rate of Boron in Pure ZrB₂ Powder Synthesized from Different Raw Materials

原料	合成温度/℃	合成前硼含量/%	合成后总质量损失率/%	合成后硼含量/%	硼质量损失率/%
S4	1700	13.78	35.76	17.84	20.24
T3	1600	13.29	35.21	18.69	9.75
T4	1600	13.78	35.46	19.4	10.06
T8	1600	12.52	36.21	18.80	4.40

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参考文献(15)

[1]	黄华伟,王晓敏,杨静,等. 可燃毒物现状[J]. 材料开发与应用,2010, 25(4): 87-91,104. doi: 10.3969/j.issn.1003-1545.2010.04.021
[2]	郑继师,甄树权,朱关仁. 国外压水堆燃料组件的发展动向[J]. 原子能科学技术,2000, 34(6): 557-562. doi: 10.3969/j.issn.1000-6931.2000.06.014
[3]	喻冲,杨静,张良,等. 溶胶-凝胶法制备核级ZrB₂粉体[J]. 粉末冶金技术,2018, 36(5): 377-381.
[4]	马成良,封鉴秋,王成春,等. 二硼化锆粉体的工业合成[J]. 硅酸盐通报,2008, 27(3): 622-625. doi: 10.16552/j.cnki.issn1001-1625.2008.03.019
[5]	冯慧丽,黄启忠,苏哲安. 温度与原料组成对硼/碳热还原法制备高纯ZrB₂粉体的影响[J]. 粉末冶金材料科学与工程,2017, 22(2): 212-220. doi: 10.3969/j.issn.1673-0224.2017.02.010
[6]	方舟,傅正义,王皓,等. 原料配比与温度对热压烧结ZrB₂陶瓷的影响[J]. 武汉理工大学学报,2005, 27(3): 1-4. doi: 10.3321/j.issn:1671-4431.2005.03.001
[7]	ÇAMURLU H E, MAGLIA F. Preparation of nano-size ZrB₂ powder by self-propagating high-temperature synthesis[J]. Journal of the European Ceramic Society, 2009, 29(8): 1501-1506. doi: 10.1016/j.jeurceramsoc.2008.09.006
[8]	JI H M, YANG M, LI M M, et al. Low-temperature synthesis of ZrB₂ nano-powders using a sorbitol modified sol–gel processing route[J]. Advanced Powder Technology, 2014, 25(3): 910-915. doi: 10.1016/j.apt.2014.01.005
[9]	贾全利,张海军,贾晓林,等. 溶胶−凝胶微波碳热还原制备二硼化锆粉体[J]. 材料导报,2007, 21(11A): 65-67.
[10]	SETOUDEH N, WELHAM N J. Formation of zirconium diboride (ZrB₂) by room temperature mechanochemical reaction between ZrO₂, B₂O₃ and Mg[J]. Journal of Alloys and Compounds, 2006, 420(1-2): 225-228. doi: 10.1016/j.jallcom.2005.07.083
[11]	SINHA A, MAHATA T, SHARMA B P. Carbothermal route for preparation of boron carbide powder from boric acid-citric acid gel precursor[J]. Journal of Nuclear Materials, 2002, 301(2-3): 165-169. doi: 10.1016/S0022-3115(02)00704-3
[12]	QIU H Y, GUO W M, ZOU J, et al. ZrB₂ powders prepared by boro/carbothermal reduction of ZrO₂: the effects of carbon source and reaction atmosphere[J]. Powder Technology, 2012, 217: 462-466. doi: 10.1016/j.powtec.2011.11.002
[13]	叶大伦, 胡建华. 实用无机物热力学数据手册[M]. 第二版. 北京: 冶金工业出版社, 2002: 132-228, 1946-1957.
[14]	ZHAO H, HE Y, JIN Z Z. Preparation of zirconium boride powder[J]. Journal of the American Ceramic Society, 1995, 78(9): 2534-2536. doi: 10.1111/j.1151-2916.1995.tb08696.x
[15]	张海军,贾全利,贾晓林,等. 微波碳热还原低温合成ZrB₂粉体的研究[J]. 材料导报,2007, 21(11A): 61-64.