Key parameters of preparing flake alumina by molten salt method

doi:10.16085/j.issn.1000-6613.2020-1864

Abstract

Abstract:

Flake alumina with high aspect ratio has attracted great attentions as a high-end pearlescent pigment flake substrate. However, the preparation technology is controlled by other countries so that it is essential to develop new preparation method for flake alumina. The molten salt method is an ideal method for the flake alumina production. However, the systematic research of the key parameters of the method has not been reported. Based on the formation mechanism of flake alumina, this article systematically studies the influence of TiO₂ additives, Na₃P₃O₉ additives, calcination temperatures and molten salt dosages on the preparation of flake alumina. The scanning electron microscope and X-ray diffractometer are used to analyze the morphology, particle size and phase composition of flake Al₂O₃. The results show that hexagonal flake alumina can be obtained with molten salt (Na₂SO₄-K₂SO₄) and NaCO₃ as gelling agent, 3.0% Na₃P₃O₉ and 2.0% TiO₂ as additives after calcination at 1200℃ for 5h. The final product possesses the average particle size of 4μm, the thickness of 50—200nm and the aspect ratio of 20—80.

Key words: molten salt method, flake alumina, additive, calcination temperature, molten salt ratio

摘要：

高径厚比片状Al₂O₃在高端珠光颜料片状基材应用方面潜力巨大，但是其制备技术为国外所垄断，开发片状Al₂O₃商用生产技术迫在眉睫。熔盐法是制备片状Al₂O₃的理想方法，目前尚无系统研究熔盐法关键工艺参数对片状Al₂O₃影响规律的报道。本文通过片状Al₂O₃的形成机理，系统研究了TiO₂添加剂、Na₃P₃O₉添加剂、煅烧温度和熔盐用量4种关键工艺参数对制备片状Al₂O₃的影响规律，并进一步优化制备工艺，提出最优工艺参数。利用扫描电子显微镜和X射线衍射仪分析Al₂O₃的形貌、粒度和物相。结果表明：采用熔融盐（Na₂SO₄-K₂SO₄）添加NaCO₃为凝胶剂，再加入质量分数分别为3.0%的Na₃P₃O₉和2.0%的TiO₂为添加剂，在煅烧温度为1200℃、保温时间5h时，所制得的六角片状Al₂O₃粉体具有优异的品质，其平均粒径约为4μm，厚度为50～200nm，径厚比为20～80。

关键词: 熔盐法, 片状氧化铝, 添加剂, 煅烧温度, 熔盐比

CLC Number:

TQ110.2

ZHANG He, SHAO Guoqiang, SHI Hebang, WU Changzi, WU Hao, CHEN Jingbo, LYU Pengpeng. Key parameters of preparing flake alumina by molten salt method[J]. Chemical Industry and Engineering Progress, 2021, 40(8): 4187-4195.

张鹤, 邵国强, 史和邦, 吴昌梓, 吴昊, 陈敬波, 吕鹏鹏. 片状氧化铝的熔盐法制备关键参数[J]. 化工进展, 2021, 40(8): 4187-4195.

Figures/Tables 15

References 36

1	孙敬会, 伊家飞, 卿培林, 等. 碳分法制备超细片状氧化铝粉体[J]. 人工晶体学报, 2019, 48(1): 122-126, 136.
	SUN Jinghui, YI Jiafei, QING Peilin, et al. Preparation of ultrafine flake aluminum oxide powder by carbonation[J]. Journal of Synthetic Crystals, 2019, 48(1): 122-126, 136.
2	GANGAR B V, NAGARAJAN K, KRISHNAN V R, et al. Preparation of alumina and alumina-ceria microspheres using an internal gelation process and their characterization[J]. Transactions of the Indian Ceramic Society, 2012, 71(2): 101-109.
3	李超, 刘红宇. 用于导热填料的片状氧化铝的制备[J]. 硅酸盐通报, 2020, 39(7): 2286-2290, 2307.
	LI Chao, LIU Hongyu. Preparation of flaky alumina for heat conducting filler[J]. Bulletin of the Chinese Ceramic Society, 2020, 39(7): 2286-2290, 2307.
4	王玲, 王千瑞, 刘冲, 等. 片状氧化铝的发展历程与应用前景[J]. 陶瓷学报, 2016, 37(6): 608-612.
	WANG Ling, WANG Qianrui, LIU Chong, et al. Development process and application prospect of flaky aluminum oxide[J]. Journal of Ceramics, 2016, 37(6): 608-612.
5	刘小杰, 黄婉霞, 张月, 等. 珠光颜料的最新研究进展[J]. 材料导报, 2008, 22(S2): 280-282.
	LIU Xiaojie, HUANG Wanxia, ZHANG Yue, et al. New research developments of pearlescent pigments[J]. Materials Review, 2008, 22(S2): 280-282.
6	FUKUDA T, SHIDO R. Flake-like alpha-alumina particles and method for producing the same: EP1148028[P]. 2004-04-14.
7	王梦迪, 罗瑾, 周靖辉, 等. 微反应器水热法耦合制备纳米片状氧化铝[J]. 无机盐工业, 2021, 53(3): 87-92.
	WANG Mengdi, LUO Jin, ZHOU Jinghui, et al. Microreactor-hydrothermal coupling preparation of nano-flaky alumina[J]. Inorganic Chemicals Industry, 2021, 53(3): 87-92.
8	YASUO S, KIICHI O, TAKESHI F. Verfahren zur herstellung feiner plättchenförmiger partikel sowie plastische werkstoffe basierend auf aluminiumoxid: DE69208753T2[P]. 1996-04-11.
9	CHO S B, VENIGALLA S, ADAIR J H. Morphological forms of α-alumina particles synthesized in 1,4-butanediol solution[J]. Journal of the American Ceramic Society, 1966, 79: 88-96.
10	苏界. 新型片状Al₂O₃材料的可控制备及其在新一代珠光颜料中的应用研究[D]. 武汉: 湖北大学, 2017.
	SU Jie. Controllable preparation of a new flake alumina materials and its application in the new generation of pearlescent pigment[D]. Wuhan: Hubei University, 2017.
11	赵燕禹, 胡兴兰, 张志鸿, 等. 高温固相法制备片状氧化铝及表征[J]. 无机盐工业, 2014, 46(4): 46-48.
	ZHAO Yanyu, HU Xinglan, ZHANG Zhihong, et al. Preparation and characterization of flaky alumina by high temperature solid phase method[J]. Inorganic Chemicals Industry, 2014, 46(4): 46-48.
12	KEBBEDE A, PARAI J, CARIM A H. Anisotropic grain growth in α-Al₂O₃ with SiO₂ and TiO₂ additions[J]. Journal of the American Ceramic Society, 2004, 83(11): 2845-2851.
13	SONG Huesup, COBLE R L. Origin and growth kinetics of platelike abnormal grains in liquid‐phase‐sintered alumina[J]. Journal of the American Ceramic Society, 1990, 73(7): 2077-2085.
14	潘志东, 范玉涛, 胡程, 等. 机械法制备无机纳米粉体[J]. 中国粉体技术, 2010, 16(2): 45-48.
	PAN Zhidong, FAN Yutao, HU Cheng, et al. Mechanical preparation of nano-sized powder of inorganic materials[J]. China Powder Science and Technology, 2010, 16(2): 45-48.
15	曹茂盛. 超微颗粒制备科学与技术[M]. 哈尔滨: 哈尔滨工业大学出版社, 1995.
	CAO Maosheng. Ultrafine particle preparation science and technology[M]. Harbin: Harbin Institute of Technology Press, 1995.
16	胡程, 王燕民. 机械法制备超细氧化铝粉体及其在ZTA陶瓷上的应用[J]. 硅酸盐学报, 2009, 37(10): 1628-1633.
	HU Cheng, WANG Yanmin. Mechanical preparation of ultra-fine powder of alumina and its application in ZTA ceramic[J]. Journal of the Chinese Ceramic Society, 2009, 37(10): 1628-1633.
17	刘学文, 郑经堂, 李长海, 等. 氧化铝粉体湿法球磨参数优化[J]. 硅酸盐通报, 2013, 32(5): 777-781.
	LIU Xuewen, ZHENG Jingtang, LI Changhai, et al. Optimization on wet ball milling conditions for alumina powder[J]. Bulletin of the Chinese Ceramic Society, 2013, 32(5): 777-781.
18	李悦, 叶红齐, 刘辉. 溶胶-凝胶涂膜法制备片状TiO₂的研究[J]. 上海涂料, 2007(1): 13-17.
	LI Yue, YE Hongqi, LIU Hui. Preparation of flake TiO₂ by sol-gel method[J]. Shanghai Coatings, 2007(1): 13-17.
19	王喜娜, 敬承斌, 刘爱云, 等. 溶胶-凝胶法制备氧化铝涂层的镀膜新工艺研究[J]. 硅酸盐通报, 2004(2): 14-16.
	WANG Xina, JING Chengbin, LIU Aiyun, et al. A new coating technique used for preparation of sol-gel alumina films[J]. Bulletin of the Chinese Ceramic Society, 2004(2): 14-16.
20	SAEGUSA K. A method for producing a flaky material: EP0236952A2[P]. 1987-04-03.
21	YOON Ki Hyun, Yong Soo CHO, KANG Dong Heon. Molten salt synthesis of lead-based relaxors[J]. Journal of Materials Science, 1998, 33(12): 2977-2984.
22	HASHIMOTO S, YAMAGUCHI A. Synthesis of α-Al₂O₃ platelets using sodium sulfate flux[J]. Journal of Materials Research, 1999, 14(12): 4667-4672.
23	龙翔, 陈雯, 叶红齐. 熔盐法制备珠光颜料用片状氧化铝[J]. 粉末冶金材料科学与工程, 2011, 16(1): 73-79.
	LONG Xiang, CHEN Wen, YE Hongqi. Preparation of lamellar aluminium oxide through molten salt synthesis[J]. Materials Science and Engineering of Powder Metallurgy, 2011, 16(1): 73-79.
24	张集发, 程小苏, 曾令可. 用于珠光颜料的片状氧化铝制备[J]. 中国陶瓷工业, 2014, 21(6): 1-5.
	ZHANG Jifa, CHENG Xiaosu, ZENG Lingke. Preparation of flaky aluminum oxide for pearlescent pigment[J]. China Ceramic Industry, 2014, 21(6): 1-5.
25	杨鹰, 苏周, 刘辉, 等. 片状氧化铝粉体的熔盐法合成[J]. 过程工程学报, 2004, 4(S1): 279-283.
	YANG Ying, SU Zhou, LIU Hui, et al. Preparation of flaky alumina powder by molten salt synthesis method[J]. The Chinese Journal of Process Engineering, 2004, 4(S1): 279-283.
26	苏周. 熔盐法合成片状氧化铝粉体的研究[D]. 长沙: 中南大学, 2004.
	SU Zhou. Preparation of flaky alumina powder by molten salt synthesis method[D]. Changsha: Central South University, 2004.
27	于闽. 新型片状氧化铝材料的合成及在珠光颜料中的应用[D]. 上海: 复旦大学, 2010.
	YU Min. Preparation of novel flaky alumina and its application in pearlescent pigment[D]. Shanghai: Fudan University, 2010.
28	ZHONG Weizhuo, TANG Dingyuan. Growth units and morphology of lithium triborate (LBO) crystals[J]. Journal of Crystal Growth, 1996, 166(1/2/3/4): 91-98.
29	王步国, 田明原. 水热条件下直接制备的α-Al₂O₃微晶的形态特征[J]. 科学通报, 1997, 42(24): 2663-2667.
	WANG Buguo, TIAN Mingyuan. Morphological characteristics of α-Al₂O₃ crystallites directly prepared under hydrothermal conditions[J]. Chinese Science Bulletin, 1997, 42(24): 2663-2667.
30	袁晰, 叶红齐, 刘辉, 等. 珠光颜料用片状氧化铁的助熔剂法合成研究[J]. 涂料工业, 2009, 39(8): 34-37.
	YUAN Xi, YE Hongqi, LIU Hui, et al. Preparation of flake iron oxide pearlescent pigment by flux salt process[J]. Paint &Coatings Industry, 2009, 39(8): 34-37.
31	HSIANG Hsing-I, CHUANG Chia Che, CHEN Tsung Hao, et al. Ti⁴⁺ addition effect on α-Al₂O₃ flakes synthesis using a mixture of boehmite and potassium sulfate[J]. Ceramics International, 2010, 36(4): 1467-1472.
32	阚艳梅, 王佩玲, 李永祥, 等. 工艺参数对熔盐法制备钛酸铋粉体影响的研究[J]. 无机材料学报, 2002(5): 1063-1067.
	KAN Yanmei, WANG Peiling, LI Yongxiang, et al. Influences of processing parameters on Bi₄Ti₃O₁₂ powder prepared by molten salt methods[J]. Journal of Inorganic Materials, 2002(5): 1063-1067.
33	于海洋, 隋万美, 翟会深, 等. 熔盐法二氧化钛针状晶的制备及表征[J]. 青岛大学学报（自然科学版）, 2006(3): 44-47.
	YU Haiyang, Wanmei SUI, ZHAI Huishen, et al. Characterization of salt flux method prepared titania needle-like crystals[J]. Journal of Qingdao University: Natural Science Edition, 2006(3): 44-47.
34	仲维卓, 华素坤. 晶体生长形态学[M]. 北京: 科学出版社, 1999: 208.
	ZHONG Weizhuo, HUA Sukun. Crystal growth morphology[M]. Beijing: Science Press, 1999: 208.
35	张倩影, 朱丽慧, 刘伟, 等. 添加剂在熔盐法合成片状α-Al₂O₃中的作用[J]. 材料研究学报, 2008, 22(2): 205-208.
	ZHANG Qianying, ZHU Lihui, LIU Wei, et al. Influence of additives on the morphology control α-Al₂O₃ platelets synthesized in molten salt[J]. Chinese Journal of Materials Research, 2008, 22(2): 205-208.
36	王玲. 片状氧化铝制备与形成机理研究[D]. 武汉: 湖北工业大学, 2017.
	WANG Ling. The preparation and formation mechanism of flaky alumina[D]. Wuhan: Hubei University of Technology, 2017.

试验编号	熔盐比（摩尔比）	Na₃P₃O₉ 质量分数/%	TiO₂ 质量分数/%	煅烧温度 /℃
A-1	4	3	1	1200
A-2	4	3	2	1200
A-3	4	3	3	1200
A-4	4	3	5	1200
B-1	4	1	2	1200
B-2	4	2	2	1200
B-3	4	3	2	1200
B-4	4	4	2	1200
C-1	4	3	2	900
C-2	4	3	2	1100
C-3	4	3	2	1200
C-4	4	3	2	1300
D-1	2	3	2	1200
D-2	3	3	2	1200
D-3	4	3	2	1200
D-4	5	3	2	1200

试验编号	熔盐比（摩尔比）	Na₃P₃O₉ 质量分数/%	TiO₂ 质量分数/%	煅烧温度 /℃
A-1	4	3	1	1200
A-2	4	3	2	1200
A-3	4	3	3	1200
A-4	4	3	5	1200
B-1	4	1	2	1200
B-2	4	2	2	1200
B-3	4	3	2	1200
B-4	4	4	2	1200
C-1	4	3	2	900
C-2	4	3	2	1100
C-3	4	3	2	1200
C-4	4	3	2	1300
D-1	2	3	2	1200
D-2	3	3	2	1200
D-3	4	3	2	1200
D-4	5	3	2	1200

[1]	XIANG Shuo, LU Peng, SHI Weinian, YANG Xin, HE Yan, ZHU Liye, KONG Xiangwei. Controllable and large-scale preparation of two-dimensional WS₂ nanosheet and its tribological properties as lubricant additives in lithium grease [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4783-4790.
[2]	YANG Kailu, CHEN Mingxing, WANG Xinya, ZHANG Wei, XIAO Changfa. Research progress of preparation and modification of nanofiltration membrane for dye wastewater treatment [J]. Chemical Industry and Engineering Progress, 2023, 42(10): 5470-5486.
[3]	QIN Jian, LIU Tianxia, WANG Jian, LU Xing. Preparation and tribological properties of oleic acid modified graphene/molybdenum disulfide composite lubricating additives [J]. Chemical Industry and Engineering Progress, 2022, 41(9): 4973-4985.
[4]	ZHANG Saihui, LI Xiaoyang, GAO Hui, WANG Lili. Recent progress in additives in interfacial polymerization for the preparation of polyamide composite membrane [J]. Chemical Industry and Engineering Progress, 2022, 41(9): 4884-4894.
[5]	LI Yeqing, YANG Xingru, LIANG Zhuo, JIANG Hao, XU Quan, ZHOU Hongjun, FENG Lu. Impact of exogenous additives on hydrothermal dechlorination performance of polyvinyl chloride [J]. Chemical Industry and Engineering Progress, 2022, 41(5): 2706-2712.
[6]	FANG Yufei, DING Donghai, XIAO Guoqing, FU Pengcheng, ZHONG Xiaochuan, ZHU Xianfeng. Progress in academic and application researches on ceramic proppant [J]. Chemical Industry and Engineering Progress, 2022, 41(5): 2511-2525.
[7]	YANG Lining, ZHENG Donghao, WANG Lixin, YANG Guang. Bionic design and additive manufacturing of continuous carbon fiber reinforced resin matrix composites with dragonfly wing venation structure [J]. Chemical Industry and Engineering Progress, 2022, 41(11): 5961-5967.
[8]	HU Huakun, XUE Wendong, JIANG Peng, LI Yong. Research progress of safety additives for lithium ion batteries [J]. Chemical Industry and Engineering Progress, 2022, 41(10): 5441-5455.
[9]	LYU Penggang, LIU Tao, YE Hang, HUANG Xiaoliang, DUAN Hongchang, TAN Zhengguo. Advances in improving the performance of additives for increasing propylene production in FCC process [J]. Chemical Industry and Engineering Progress, 2022, 41(1): 210-220.
[10]	SU Weiyi, LIU Xing, HAO Qi, GUO Pan, HAO Hongxun, LI Chunli. Research progress in the effect of additives on the polymorphic crystallization of amino acids in solution [J]. Chemical Industry and Engineering Progress, 2021, 40(8): 4463-4472.
[11]	PAN Yi, XU Minglei, HOU Bing, GUO Qi, YANG Shuangchun, KANTOMA Daniel Bala. Research progress of temperature-sensitive polymer in oil and gas production [J]. Chemical Industry and Engineering Progress, 2021, 40(4): 2109-2119.
[12]	WANG Xiaoda, CHEN Yu, WANG Qinglian, HUANG Zhixian, YANG Chen, WANG Hongxing, QIU Ting. Review on etherification by reactive distillation [J]. Chemical Industry and Engineering Progress, 2021, 40(4): 1797-1811.
[13]	YANG Lining, WANG Jinye, ZHANG Yongdi, CHANG Hongjie, YANG Guang. Performance of continuous carbon fiber reinforced metal matrix composites formed by additive manufacturing [J]. Chemical Industry and Engineering Progress, 2021, 40(12): 6777-6784.
[14]	SUN Yue, LIU Lingling, LI Xinquan, PAN Jianfeng, LIU Jiabin. Research progress in mechanisms and effects of various additives used for preparing electrolytic copper foils [J]. Chemical Industry and Engineering Progress, 2021, 40(11): 5861-5874.
[15]	Yuehua LIU, Ju SHANGGUAN, Shoujun LIU, Song YANG, Wenguang DU. Nitrogen migration regarding the addition of iron-Ni composite additives during coal pyrolysis [J]. Chemical Industry and Engineering Progress, 2021, 40(1): 164-172.