基于Ti-Si-Fe合金与B粉的TiB<sub>2</sub>熔盐法合成制备研究

程登峰; 张锦化; 王景然; 柯昌明

doi:10.7513/j.issn.1004-7638.2022.02.008

基于Ti-Si-Fe合金与B粉的TiB₂熔盐法合成制备研究

doi: 10.7513/j.issn.1004-7638.2022.02.008

程登峰^{1, 2,},
张锦化¹,
王景然¹,
柯昌明^1, ,

1.
武汉科技大学, 省部共建耐火材料与冶金国家重点实验室, 湖北武汉430081
2.
九江金鹭硬质合金有限公司, 江西九江 332000

基金项目: 国家十一五重点支撑计划项目（2006BAB02B02）；国家十二五科技支撑计划项目（2011BAB05B05）；攀枝花市科技局重大科技攻关计划项目（2008CY-G-1）。

详细信息

作者简介:
程登峰（1983—），男，湖北天门人，博士生，长期从事陶瓷及其复合材料的基础研究工作，E-mail: amicay@163.com

通讯作者:
柯昌明（1955—），男，博士，教授，从事非氧化物陶瓷及耐火材料的研究工作，E-mail: kechangming@wust.edu.cn

中图分类号: TF823,TQ174.4
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- 被引次数: 0
出版历程
- 收稿日期: 2022-02-15
- 网络出版日期: 2022-05-11
- 刊出日期: 2022-04-28

Molten salt assisted preparation of TiB₂ powder from Ti-Si-Fe and B

1.
The State Key Laboratory of Refractories and Metallurgy, Wuhan University of Science and Technology, Wuhan 430081, Hubei, China
2.
Jiujiang Golden Egret Hard Material Co., Ltd., Jiujiang 332000, Jiangxi, China

摘要

摘要: 以从高钛型高炉渣中提取的Ti-Si-Fe合金和无定形硼粉为原料，在NaCl-KCl熔盐中合成了TiB₂粉体，研究了反应温度、保温时间、熔盐量、B/Ti摩尔比对反应进程的影响。结果表明：提高反应温度或延长保温时间均能促进反应进行，在850 ℃时开始有TiB₂生成，1100 ℃时反应完全。熔盐有促进反应过程的作用。元素分布表明，含Fe的颗粒同时含Si，这与产物FeSi₂相对应；大多数颗粒同时含有Si、Ti、B，说明在这些颗粒中产物TiB₂和Si是伴生在一起的；少数颗粒只含有Ti、B，对应产物TiB₂。产物颗粒形貌有两种，一种颗粒表面呈龟裂状，有裂缝或微米级孔洞与颗粒内部相连，这种颗粒同时含有TiB₂、Si或FeSi₂；另一种颗粒由片状TiB₂组成。Ti-Si-Fe合金与B在熔盐中的反应机制为：在熔盐促进作用下，含钛物中的Ti与B反应生成TiB₂，释放出Si及FeSi₂，大部分TiB₂以Si、FeSi₂为骨架形核并长大，从而维持了颗粒原有形貌，少量TiB₂在熔盐中形核并长大形成片状TiB₂的聚集体。合金相与B反应完全的先后顺序依次为：Ti₅Si₃、TiSi、TiFeSi₂和TiSi₂。
- 二硼化钛 /
- 熔盐法 /
- Ti-Si-Fe合金 /
- B粉 /
- 高钛型高炉渣
Abstract: TiB₂ powders were synthesized in NaCl-KCl molten salt by amorphous boron and Ti-Si-Fe alloy extracted from high titanium blast furnace slag. The effects of reaction temperature, holding time, molten salt amount and mole ratio of B to Ti on the reaction process were investigated. The results show that increasing the reaction temperature or extending the holding time can promote the reaction process. TiB₂ begins to form at 850 ℃ and the reaction completes at 1 100 ℃. Molten salt can facilitate the reaction process. The distribution of elements shows that the particles containing Fe also contain Si, corresponding to the product FeSi₂. Most of the particles contain Si, Ti and B at the same time, indicating that TiB₂ and Si are associated in these particles. A few particles contain only Ti and B, corresponding to TiB₂. There are two kinds of particle morphology of the product. One kind of particle presents cracking appearance with cracks or micron holes connected to the interior, which contains TiB₂, Si or FeSi₂. The other particle is composed of flake TiB₂. The reaction mechanism of Ti-Si-Fe alloy with B in molten salt is described below. First of all, titanium reacts with B to form TiB₂ , then Si and FeSi₂ are released. Most TiB₂ nucleate and grow with Si and FeSi₂ as the skeleton which maintain the original morphology of Ti-Si-Fe particles. A small amount of TiB₂ nucleate and grow in molten salt to form flake TiB₂ aggregates. The sequence of reaction between alloy phase and B is Ti₅Si₃, TiSi, TiFeSi₂ and TiSi₂.
- titanium diboride /
- molten salt method /
- Ti-Si-Fe alloy /
- B powder /
- high titanium blast furnace slag

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图 1 Ti-Si-Fe合金的XRD谱

Figure 1. The XRD pattern of Ti-Si-Fe alloy

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图 2 Ti-Si-Fe合金与B在不同温度下反应4 h后产物的XRD谱

Figure 2. XRD patterns of samples prepared by Ti-Si-Fe alloy reacting with B at different firing temperature for 4 h

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图 3 950 ℃保温不同时间下产物的XRD谱

Figure 3. XRD patterns of samples prepared at 950 ℃ for different dwell time

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图 4 1100 ℃保温不同时间下产物的XRD谱

Figure 4. XRD patterns of samples prepared at 1 100 ℃ for different dwell time

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图 5 不同熔盐/反应物质量比下，950 ℃反应1 h后产物的XRD谱

Figure 5. XRD patterns of samples prepared at 950 ℃ for 1 h with different mass ratios of salt to reactant

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图 6 不同熔盐/反应物质量比下，1100 ℃反应4 h后产物的XRD谱

Figure 6. XRD patterns of samples prepared at 1 100 ℃ for 4 h with different mass ratios of salt to reactant

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图 7 不同B/Ti原子比下，1100 ℃反应4 h后产物的XRD谱

Figure 7. XRD patterns of samples prepared at 1 100 ℃ for 4 h with different atomic ratios of B to Ti

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图 8 熔盐/反应物比例2.5，1100 ℃反应1 h产物粉末元素分布

Figure 8. Sample element distribution firing at 1 100 ℃ for 1h with 2.5 of mass ration of salt to reactant

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图 9 Ti-Si-Fe合金与B粉1100 ℃保温4 h后反应产物的SEM显微形貌

(a) Ti-Si-Fe合金颗粒；(b)～(f) 反应产物颗粒

Figure 9. The SEM microtopography of sample prepared at 1100 ℃ for 4 h

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图 10 Ti-Si-Fe合金与B粉在熔盐中反应的过程示意

Figure 10. Schematic reaction process of Ti-Si-Fe alloy and B powder in molten salt

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表 1 Ti-Si-Fe合金粉的化学成分

Table 1. Chemical compositions of Ti-Si-Fe alloy powder %

Ti	Si	Fe	Al	其他
43.80	41.26	10.55	3.1	1.29

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表 2 试验参数

Table 2. Experimental parameters

试验目的	反应温度/℃	保温时间/h	B/Ti摩尔比	熔盐/反应物质量比
考察温度对反应的影响	800、850、950、1000、1050、1100	4.0	2.1	2.5
考察保温时间对反应的影响	950、1100	1.0、2.5、 4.0、5.5	2.1	2.5
考察熔盐/反应物质量比对反应的影响	950、1100	1.0、4.0	2.1	0、1.5、2.5、3.5
考察B/Ti摩尔比对反应的影响	1100	4.0	2.0、2.1、2.2、2.3	2.5

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