Influence of pore volume and heating process on preparation of aluminum nitride powder by carbothermal reduction method

doi:10.11949/0438-1157.20200905

Abstract

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

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

CLC Number:

TQ 170.1

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.

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.

Figures/Tables 18

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

Fig.2 XRD patterns of different aluminum source

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

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	—

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

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

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

Fig.6 Pore size distribution of samples

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

Fig.8 SEM images of precursors by different mixing methods

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

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

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

Fig.11 SEM images of AlN heated under 1500℃

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

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)

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

Fig.14 Characterization results of final AlN product

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