碳源对先驱体转化法制备TaC陶瓷粉体微观结构及性能影响

doi:10.15541/jim20220553

无机材料学报 ›› 2023, Vol. 38 ›› Issue (2): 184-192.DOI: 10.15541/jim20220553

碳源对先驱体转化法制备TaC陶瓷粉体微观结构及性能影响

孙敬伟¹(), 王洪磊¹(), 孙楚函¹, 周新贵¹, 纪小宇¹^,²()

1.国防科技大学空天科学学院, 新型陶瓷纤维及其复合材料重点实验室, 长沙410073
2.海军工程大学舰船综合电力技术国防科技重点实验室, 武汉 430033

收稿日期:2022-09-22 修回日期:2022-11-07 出版日期:2023-02-20 网络出版日期:2022-11-16
通讯作者: 王洪磊, 副教授. E-mail: honglei.wang@163.com;
纪小宇, 讲师. E-mail: jixiaoyu15@nudt.edu.cn
作者简介:孙敬伟(2000-), 男, 硕士研究生. E-mail: sunjingwei0120@163.com
基金资助:
湖南省自然科学基金(2020JJ4667)

Effects of Carbon Sources on Structure and Properties of TaC Ceramic Powder Prepared by Polymer Derived Ceramics

SUN Jingwei¹(), WANG Honglei¹(), SUN Chuhan¹, ZHOU Xingui¹, JI Xiaoyu¹^,²()

1. Science and Technology on Advanced Ceramic Fibers and Composites Laboratory, College of Aerospace Science and Engineering, National University of Defense Technology, Changsha 410073, China
2. National Key Laboratory of Science and Technology on Vessel Integrated Power System, Naval University of Engineering, Wuhan 430033, China

Received:2022-09-22 Revised:2022-11-07 Published:2023-02-20 Online:2022-11-16
Contact: WANG Honglei, associate professor. E-mail: honglei.wang@163.com;
JI Xiaoyu, lecturer. E-mail: jixiaoyu15@nudt.edu.cn
About author:SUN Jingwei (2000-), male, Master candidate. E-mail: sunjingwei0120@163.com
Supported by:
Natural Science Foundation of Hunan Province(2020JJ4667)

摘要/Abstract

摘要：

先驱体转化法是制备耐超高温陶瓷和粉体的有效方法之一, 但原料种类对先驱体交联固化程度和陶瓷产率的影响鲜有报道。本研究分别采用两种碳源与聚钽氧烷(PTO)合成了TaC先驱体, 研究了碳源种类、裂解温度和钽碳比例等因素对先驱体转化法制备TaC陶瓷粉体微观结构及性能的影响。结果表明, 含C=C的PF-3树脂可以有效促进PTO的交联固化, 提高先驱体的陶瓷产率。当钽碳质量比分别为PTO : PF-3树脂=1 : 0.25和PTO : 2402树脂=1 : 0.4时, 在1400 ℃下裂解获得的TaC陶瓷粉体不含残余Ta₂O₅, 陶瓷产率分别为54.02%和49.64%, 晶粒尺寸分别为47.2和60.9 nm。PF-3树脂在提高陶瓷产率的同时能够减小晶粒尺寸, 但对粉体纯度与粒度影响较小。不同碳源制备的TaC陶瓷粉体纯度分别为96.50%和97.36%, 中位径分别为131和129 nm。

关键词: 聚钽氧烷(PTO), 先驱体转化法, TaC, 交联, 固化, 陶瓷产率

Abstract:

Polymer derived ceramic is one of the effective methods for producing ultra-high temperature ceramics and powders, but effect of source material type on precursor cross-linking degree and ceramic yield has rarely been reported. Here, TaC precursors were synthesized using two carbon sources and poly-tantalumoxane (PTO). Phase composition and microstructure of TaC ceramic powders from different carbon sources, tantalum/carbon mass ratios, and pyrolysis temperatures were characterized. It was found that PF-3 resin with C=C was effective in promoting the cross-linking of PTO and increasing the ceramic yield. When the mass ratio of PTO to PF-3 Resin was 1 : 0.25 and PTO to 2402 Resin was 1 : 0.4, TaC ceramic powders could be obtained at 1400 ℃ without residue Ta₂O₅. Ceramic yields of ceramic powders were 54.02% and 49.64%, and the crystal sizes were 47.2 and 60.9 nm, respectively. Therefore, PF-3 resin is able to reduce crystal size while increasing ceramic yield, but has less impact on the powder purity and particle size. The purity of TaC ceramic powders derived from different carbon sources are 96.50% and 97.36%, respectively, meanwhile the median diameters are 131 and 129 nm, respectively.

Key words: poly-tantalumoxane (PTO), polymer derived ceramics, TaC, cross-linking, curing, ceramic yield

中图分类号:

TH145

孙敬伟, 王洪磊, 孙楚函, 周新贵, 纪小宇. 碳源对先驱体转化法制备TaC陶瓷粉体微观结构及性能影响[J]. 无机材料学报, 2023, 38(2): 184-192.

SUN Jingwei, WANG Honglei, SUN Chuhan, ZHOU Xingui, JI Xiaoyu. Effects of Carbon Sources on Structure and Properties of TaC Ceramic Powder Prepared by Polymer Derived Ceramics[J]. Journal of Inorganic Materials, 2023, 38(2): 184-192.

图/表 12

图1 TaC陶瓷粉体制备流程

Fig. 1 Preparation process of TaC ceramic powder

图2 不同碳源及交联产物红外谱图

Fig. 2 FT-IR of different carbon sources and crosslinked products (a) PTO, PF-3, PTC1 pioneer; (b) PTO, 2402 Resin, PTC2 pioneer

图3 不同钽碳源及交联产物热重曲线

Fig. 3 TG curves of different tantalum carbon sources and crosslinked products (a) PTO, PF-3, 2402 Resin, PTC1-25 (220 ℃), PTC2-40(220 ℃); (b) PTC1-25 (1000 ℃); (c) PTC2-40(1000 ℃) Colorful figures are available on website

图4 不同裂解温度及不同钽碳比例所得陶瓷产物的XRD图谱

Fig. 4 XRD patterns of ceramic products obtained at different pyrolysis temperatures and tantalum/carbon ratios (a) PTC1-25, 800~1500 ℃; (b) PTC1-(10~40), 1400 ℃, 2 h; (c) PTC2-(20~45), 1400 ℃ 2 h

表1 不同碳源比例所得TaC粉体的平均晶粒尺寸

Table 1 Average grain size of TaC powder with different carbon source ratios

Sample	L/nm	Sample	L/nm
PTC1-10	62.5	PTC2-20	71.3
PTC1-15	73.9	PTC2-30	67.9
PTC1-20	67.2	PTC2-35	66.0
PTC1-25	47.2	PTC2-40	60.9
PTC1-30	45.5	PTC2-45	54.8
PTC1-35	39.7
PTC1-40	37.5

图5 不同钽碳比例所得TaC粉体的拉曼图谱

Fig. 5 Raman spectra of TaC powders obtained at different tantalum/carbon ratios (a) PTC1-(10-40); (b) PTC2-(25-45)

表2 不同裂解温度PTC1-25产物D、G峰中心位置及${{I}_{\mathbf{D}}}/{{I}_{\mathbf{G}}}$比值

Table 2 Center positions of D and G peaks of PTC1-25 products obtained at different pyrolysis temperatures and ratios of ${{I}_{\mathbf{D}}}/{{I}_{\mathbf{G}}}$

Temperature/℃	ω_D/cm^-1	ω_G/cm^-1	${{I}_{\text{D}}}/{{I}_{\text{G}}}$
1200	1313	1576	2.045
1300	1315	1579	1.641
1400	1313	1580	1.605

表3 最佳钽碳比例所得TaC粉体中元素的质量含量

Table 3 Elements mass contents of TaC powders obtained at optimal tantalum/carbon ratio

Sample	Ta/%	C/%	O/%	C_free/%
PTC1-25	91.72	5.02	1.31	2.19
PTC2-40	92.14	6.42	0.89	1.75

图6 最佳钽碳质量比所得TaC粉体粒度分布直方图

Fig. 6 Histograms of the granularity distributions of TaC powders obtained at optimal tantalum/carbon mass ratios (a) PTC1-25; (b) PTC2-40

图7 不同钽碳质量比所得TaC粉体的SEM照片

Fig. 7 SEM images of TaC powders obtained at different tantalum/carbon mass ratios (a) PTO; (b) PTC1-25; (c) PTC1-40; (d) PTC2-40; (e) PTC2-45

图8 最佳钽碳质量比所得TaC粉体的元素分布

Fig. 8 Elemental distributions of TaC powders obtained at optimal tantalum/carbon mass ratios (a) PTC1-25; (b) PTC2-40

图9 最佳钽碳比例所得陶瓷产物的TEM和HRTEM照片

Fig. 9 TEM and HRTEM images of TaC powders obtained at optimal tantalum/carbon ratios (a, b) PTC1-25; (c, d) PTC2-40

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碳源对先驱体转化法制备TaC陶瓷粉体微观结构及性能影响

Effects of Carbon Sources on Structure and Properties of TaC Ceramic Powder Prepared by Polymer Derived Ceramics

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