铝源孔容和焙烧升温过程对碳热还原法制备氮化铝粉体的影响

doi:10.11949/0438-1157.20200905

摘要/Abstract

摘要：

碳热还原氮化法是大规模制备高纯度氮化铝（AlN）粉体的主要方法，通过微反应器制备不同孔容的铝源，系统探究了前体孔容和微观形貌对AlN粉体产物的影响，并通过动力学模拟验证了筛选出的前体的活性。同时对氮化反应升温过程的影响也做了探究，最终通过对前体和焙烧升温过程的优化，得到纯度99%以上的AlN粉体，其平均粒径约为150 nm，O元素含量为0.55%。

关键词: 氮化铝, 碳热还原, 铝源孔容, 粉体技术, 微反应器, 制备

Abstract:

Carbothermal reduction nitriding method is the main method for industrial preparation of high-purity aluminum nitrite (AlN) powder. In this paper, the aluminum sources with different pore volumes were synthesized through a micro-reactor, and the influence of the pore volume and micro-morphology of the precursor on the AlN powder was systematically investigated, and the activity of the selected precursor was verified by kinetic simulation. At the same time, the influence of the heating process of the nitriding reaction was also explored. Finally, through optimizing the aluminum source and heating process, the AlN powder with a purity of more than 99% was obtained, with an average particle size of about 150 nm and element O content of 0.55%.

Key words: aluminum nitride, carbothermal reduction, aluminum source pore volume, powder technology, microreactor, preparation

中图分类号:

TQ 170.1

魏娟, 王玉军, 骆广生. 铝源孔容和焙烧升温过程对碳热还原法制备氮化铝粉体的影响[J]. 化工学报, 2021, 72(2): 1156-1168.

WEI Juan, WANG Yujun, LUO Guangsheng. Influence of pore volume and heating process on preparation of aluminum nitride powder by carbothermal reduction method[J]. CIESC Journal, 2021, 72(2): 1156-1168.

图/表 18

图1 微反应器实验装置示意图(a)；膜分散微反应器内的两相流型示意图(b)

Fig.1 Schematic diagram of microreactor(a). Two-phase flow pattern in the membrane dispersion microreactor(b)

图2 不同铝源的XRD谱图

Fig.2 XRD patterns of different aluminum source

图3 不同铝源在不同温度下保温3 h的氮化率曲线

Fig.3 Nitrading rate-temperature curves of different aluminum sources

表1 不同孔容的拟薄水铝石与炭黑混合前后的BET数据以及对应的产品氮化率(1400℃，3 h)

Table 1 BET data and nitrading rate of γ-AlOOH with different pore volumes before and after mixing with carbon black (1400℃, 3 h)

序号	组分	微反出口pH	比表面积/(m²/g)	孔容/(ml/g)	平均孔径/nm	产品氮化率
1	AlOOH	10.32	320.40	0.17	9.29	0.332
1	AlOOH+C	10.32	132.7	0.14	9.02	0.332
2	AlOOH	5.09	251.55	0.38	6.04	0.367
2	AlOOH+C	5.09	88.90	0.19	8.59	0.367
3	AlOOH	6.33	279.77	0.71	10.13	0.397
3	AlOOH+C	6.33	97.35	0.25	10.47	0.397
4	AlOOH	8.37	343.73	0.95	11.07	0.403
4	AlOOH+C	8.37	86.67	0.23	10.82	0.403
5	AlOOH	8.92	396.10	1.13	11.43	0.342
5	AlOOH+C	8.92	145.70	0.16	4.51	0.342
6	C	—	318.91	0.92	11.56	—

图4 不同孔容的拟薄水铝石作为铝源时的氮化率

Fig.4 Nitrading rate curve of γ-AlOOH with different pore volumes

图5 γ-AlOOH(a)和其对应AlN产物(b)的粒度分布图(1~4分别对应表1中的1~4号拟薄水铝石)

Fig.5 Grain size distribution of γ-AlOOH (a) and AlN (b)(1—4 respectively correspond to 1—4 in table 1)

表2 不同混合方式得到的前体BET数据以及对应的产品氮化率

Table 2 BET data and nitrading rate of different mixing methods

组分	编号	混合条件	比表面积/(m²/g)	孔容/(ml/g)	平均孔径/nm	产品氮化率
纯AlOOH	a	无处理	279.77	0.71	10.13	—
纯AlOOH	b	干磨10 min	49.07	0.13	10.51	—
纯炭黑	c	无处理	318.91	0.92	11.56	—
AlOOH+C	1	干磨3 min	232.17	0.51	8.78	0.351
	2	干磨10 min	97.35	0.25	10.47	0.397
	3	干磨30 min	56.32	0.19	13.5	0.321
	4	湿磨30 min	191.6	0.42	8.79	0.412
	5	微反后混合	96.17	0.13	3.8	0.404
	6	微反中混合	49.97	0.1	3.81	0.571

图6 样品的孔径分布图

Fig.6 Pore size distribution of samples

图7 不同混合方式制备的前体的孔径分布图

Fig.7 Pore size distribution of precursors with different mixing methods

图8 不同混合方式制备的前体的SEM图

Fig.8 SEM images of precursors by different mixing methods

表3 不同混合方式得到的AlN产品的O、C杂质含量

Table 3 O and C content of AlN by different mixing methods

混合方式	O/%（质量）	C/%（质量）
干磨10 min	0.62	0.063
微反应器中混合	0.57	0.114

图9 不同反应温度保温3 h产物XRD谱图

Fig.9 XRD patterns of products heated in different temperatures for 3 h

图10 在1450℃下保温不同时间的产物XRD谱图

Fig.10 XRD patterns of products heated for different heating time under 1450℃

图11 不同反应时间下产物SEM图(1500℃)

Fig.11 SEM images of AlN heated under 1500℃

图12 不同焙烧曲线及其对应的产物SEM图和粒径统计分析

Fig.12 Different heating curves and corresponding SEM images and partical size statistical analysis of products

图13 不同温度下RN(a)、1-(1-RN)1/3(b)、1-2/3RN-(1-RN)2/3(c)随反应时间的变化，lnDe'对T-1拟合直线(d)

Fig.13 Plots of RN (a), 1-(1-RN)1/3 (b), 1-2/3RN-(1-RN)2/3 (c) against reaction time. Arrhenius plots of lnDe' against T-1 (d)

表4 表面化学反应控制和内扩散控制条件下的线性拟合R2值

Table 4 Linear fitting R2 values under surface chemical reaction control and internal diffusion control

反应机理	R²
反应机理	1300℃	1400℃	1450℃	1500℃	1550℃
表面化学反应控制	0.940	0.982	0.940	0.942	0.983
内扩散控制	0.932	0.976	0.994	0.998	0.996

图14 最终AlN产品的表征结果

Fig.14 Characterization results of final AlN product

参考文献 31

1	Sheppard L M. Aluminum nitride - a versatile but challenging material [J]. American Ceramic Society Bulletin, 1990, 69(11): 1801-1812.
2	严光能, 邓先友, 林金堵. 高导热氮化铝基板在航空工业的应用研究[J]. 印制电路信息, 2017, 25(10): 32-37.
	Yan G N, Deng X Y, Lin J D. The research of high-thermal-conductive aluminum nitride substrate in airport power electronics [J]. Printed Circuit Information, 2017, 25(10): 32-37.
3	He X, Shi L, Guo Y, et al. Study on microstructure and dielectric properties of aluminum nitride ceramics [J]. Materials Characterization, 2015, 106, 404-410.
4	Son H W, Kim B N, Suzuki T S, et al. Fabrication of translucent AlN ceramics with MgF₂ additive by spark plasma sintering [J]. Journal of the American Ceramic Society, 2018, 101(10): 4430-4433.
5	Jackson T B, Virkar A V, More K L, et al. High-thermal-conductivity aluminum nitride ceramics: the effect of thermodynamic, kinetic, and microstructural factors [J]. Journal of the American Ceramic Society, 1997, 80(6): 1421-1435.
6	Fei C L, Liu X L, Zhu B P, et al. AlN piezoelectric thin films for energy harvesting and acoustic devices [J]. Nano Energy, 2018, 51(1): 146-161.
7	张浩, 崔嵩, 何金奇. 高性能氮化铝粉体技术发展现状[J]. 真空电子技术, 2015, (5): 14-18.
	Zhang H, Cui S, He J Q. Technology development of high-performance AlN powders [J]. Vacuum Electronics, 2015, (5): 14-18.
8	王毅, 李东红, 张岩岩. 碳热还原法制备氮化铝的影响因素[J]. 真空电子技术, 2019, (3): 64-66+72.
	Wang Y, Li D H, Zhang Y Y. Influencing factors of carbothermic reduction for AlN synthesis [J]. Vacuum Electronics, 2019, (3): 64-66+72.
9	Cinar F S, Kizilirmak V, Derin B, et al. Carbothermal reduction - nitridation study of seydisehir alumina [J]. Silicates Industries, 2004, 69(7/8): 305-310.
10	侯海兰, 冯月斌, 字富庭, 等. 碳热还原氮化法制备氮化铝的研究进展[J].粉末冶金工业, 2019, 29(1): 69-72.
	Hou H L, Feng Y B, Zi F T, et al. Research progress in preparation of aluminum nitride by carbothermal reduction nitridation [J]. Powder Metallurgy Industry, 2019, 29(1): 69-72.
11	张笑. 氧化铝碳热还原氮化的机理研究[D]. 昆明: 昆明理工大学, 2017.
	Zhang X. Research on mechanism of carbothermal reduction nitriding of alumina [D]. Kunming: Kunming University of Science and Technology, 2017.
12	马丁. 适合于导热基板用AlN粉体的制备与表征[D]. 北京: 北京交通大学, 2019.
	Ma D. Preparation and characterization of AlN powders for thermally conductive substrates [D]. Beijing: Beijing Jiaotong University, 2019.
13	秦明礼, 曲选辉, 林健凉, 等. 原料对碳热还原法合成氮化铝粉末的影响[J].中南工业大学学报(自然科学版), 2002, (5): 505-508.
	Qin M L, Qu X H, Lin J L, et al. Effect of starting materials on the synthesis of aluminum nitride powders by carbothermal reduction method[J]. J. Cent. South. Univ. Technol., 2002, (5): 505-508.
14	Kimura I, Ichiya K, Ishii M, et al. Synthesis of fine AlN powder by a floating nitridation technique using an N₂/NH₃ gas mixture [J]. Journal of Materials Science Letters, 1989, 8(3): 303-304.
15	Tsuge A, Inoue H, Kasori M, et al. Raw-material effect on AlN powder synthesis from Al₂O₃ carbothermal reduction [J]. Journal of Materials Science, 1990, 25(5): 2359-2361.
16	Mylinh D T, Yoon D H, Kim C Y. Aluminum nitride formation from aluminum oxide/phenol resin solid-gel mixture by carbothermal reduction nitridation method [J]. Archives of Metallurgy and Materials, 2015, 60(2): 1551-1555.
17	Pathak L C, Ray A K, Das S, et al. Carbothermal synthesis of nanocrystalline aluminum nitride powders [J]. Journal of the American Ceramic Society, 1999, 82(1): 257-260.
18	Xi S Q, Liu X K, Li P L, et al. AlN ceramics synthesized by carbothermal reduction of mechanical activated Al₂O₃ [J]. Journal of Alloys and Compounds, 2008, 457(1/2): 452-456.
19	刘新宽, 马明亮, 周敬恩, 等. 高能球磨对碳热还原合成氮化铝的作用[J]. 兵器材料科学与工程, 1999, (3): 23-27.
	Liu X K, Ma M L, Zhou J E. Effects of high energy ball milling on ain snythesis from Al₂O₃ by carbothermal reduction nitridation[J]. Ordnance Material Science and Engineering, 1999, (3): 24-28.
20	Mao X X, Li J, Zhang H L, et al. Synthesis of AlN powder by carbothermal reduction-nitridation of alumina/carbon black foam [J]. Journal of Inorganic Materials, 2017, 32(10): 1115-1120.
21	Chikami H, Fukushima J, Hayashi Y, et al. Kinetics of microwave synthesis of AlN by carbothermal-reduction-nitridation at low temperature [J]. Journal of the American Ceramic Society, 2018, 101(11): 4905-4910.
22	马艳红, 陈玮. 溶胶-凝胶法制备氮化铝粉体[J]. 真空电子技术, 2009, (4): 78-80.
	Ma Y H, Chen W. Preparation of AlN by the sol-gel method [J]. Vacuum Electronics, 2009, (4): 78-80.
23	李亚伟, 李楠, 袁润章. Al₂O₃-C-N₂系统反应热力学初步探讨[J]. 硅酸盐通报, 2001, (4): 3-8.
	Li Y W, Li N, Yuan R Z. Thermodynamical discussion of the reaction evolution in Al₂O₃-C-N-2 system [J]. Bulletin of the Chinese Ceramic Society, 2001, (4): 3-8.
24	Yu J K, Ueno S, Li H X, et al. Improvement of graphitization of isotropic carbon by Al₂O₃ formed from aluminium chelate compound [J]. Journal of the European Ceramic Society, 1999, 19(16): 2843-2848.
25	傅仁利, 于洪珍, 张月铭, 等. 碳热还原法合成氮化铝的机理与热力学条件[J]. 中国矿业大学学报, 2002, (5): 415-420.
	Fu R L, Yu H Z, Zhang Y M, et al. Mechanisms and thermodynamics conditions of carbothermal reduction nitridation reactions [J]. Journal of China University of Mining and Technology, 2002, (5): 415-420.
26	Shen C Y, Qiu T, Lu Y M. Morphology and reaction mechanism of AIN fibers synthesized by carbothermal reduction [J]. Key Engineering Materials, 2005, 280/283(2): 1399-1402.
27	Suehiro T, Hirosaki N, Terao R, et al. Synthesis of aluminum nitride nanopowder by gas-reduction-nitridation method [J]. Journal of the American Ceramic Society, 2003, 86(6): 1046-1048.
28	匡加才. AlN粉体及陶瓷的制备、结构与性能研究[D]. 长沙: 国防科学技术大学, 2004.
	Kuang J C. Processing, microstructure and thermal properties of AlN ceramics and AlN powder prepared by modified carbothermal reduction method[D]. Changsha: National University of Defense Technology, 2004.
29	Lefort P, Tetard D, Tristant P. Formation of aluminium carbide by carbothermal reduction of alumina - role of the gaseous aluminium phase [J]. Journal of the European Ceramic Society, 1993, 12(2): 123-129.
30	Wan Y, Liu Y, Wang Y, et al. Preparation of large-pore-volume gamma-alumina vanofibers with a varrow pore size distribution in a membrane sispersion microreactor [J]. Industrial & Engineering Chemistry Research, 2017, 56(31): 8888-8894.
31	Galvez M E, Frei A, Halmann M, et al. Ammonia production via a two-step Al₂O₃/AlN thermochemical cycle. 2. Kinetic analysis [J]. Industrial & Engineering Chemistry Research, 2007, 46(7): 2047-2053.

[1]	吴文涛, 褚良永, 张玲洁, 谭伟民, 沈丽明, 暴宁钟. 腰果酚生物基自愈合微胶囊的高效制备工艺研究[J]. 化工学报, 2023, 74(7): 3103-3115.
[2]	王志龙, 杨烨, 赵真真, 田涛, 赵桐, 崔亚辉. 搅拌时间和混合顺序对锂离子电池正极浆料分散特性的影响[J]. 化工学报, 2023, 74(7): 3127-3138.
[3]	朱风, 陈凯琳, 黄小凤, 鲍银珠, 李文斌, 刘嘉鑫, 吴玮强, 高王伟. KOH改性电石渣脱除羰基硫的性能研究[J]. 化工学报, 2023, 74(6): 2668-2679.
[4]	衣思敏, 马亚丽, 刘伟强, 张金帅, 岳岩, 郑强, 贾松岩, 李雪. 微晶菱镁矿蒸氨及水化动力学研究[J]. 化工学报, 2023, 74(4): 1578-1586.
[5]	张雪婷, 胡激江, 赵晶, 李伯耿. 高分子量聚丙二醇在微通道反应器中的制备[J]. 化工学报, 2023, 74(3): 1343-1351.
[6]	章承浩, 罗京, 张吉松. 微反应器内基于氮氧自由基催化剂连续氧气/空气氧化反应的研究进展[J]. 化工学报, 2023, 74(2): 511-524.
[7]	谢煜, 张民, 胡卫国, 王玉军, 骆广生. 利用膜分散微反应器高效溶解D-7-ACA的研究[J]. 化工学报, 2023, 74(2): 748-755.
[8]	杨星宇, 马优, 朱春英, 付涛涛, 马友光. 梳状并行微通道内液液分布规律研究[J]. 化工学报, 2023, 74(2): 698-706.
[9]	靳志远, 单国荣, 潘鹏举. AM/AMPS/SSS三元共聚物的制备及耐温耐盐性能[J]. 化工学报, 2023, 74(2): 916-923.
[10]	付家崴, 陈帅帅, 方凯伦, 蒋新. 微反应器共沉淀反应制备铜锰催化剂[J]. 化工学报, 2023, 74(2): 776-783.
[11]	张浩, 王子悦, 程钰洁, 何晓辉, 纪红兵. 单原子催化剂规模化制备的研究进展[J]. 化工学报, 2023, 74(1): 276-289.
[12]	刘佳宁, 马嘉浩, 张军营, 程珏. 顺序双重热固化的硫醇-丙烯酸酯-环氧树脂三维网络的构建及性能[J]. 化工学报, 2022, 73(9): 4173-4186.
[13]	李承威, 骆华勇, 张铭轩, 廖鹏, 方茜, 荣宏伟, 王竞茵. 氢氧化镧交联壳聚糖微球的微流控制备及其除磷性能[J]. 化工学报, 2022, 73(9): 3929-3939.
[14]	张经纬, 周弋惟, 陈卓, 徐建鸿. 微反应器内的有机合成前沿进展[J]. 化工学报, 2022, 73(8): 3472-3482.
[15]	侯跃辉, 刘璇, 廉应江, 韩梅, 尧超群, 陈光文. 超声微反应器内三硝基间苯三酚合成工艺研究[J]. 化工学报, 2022, 73(8): 3597-3607.