喷雾-反溶剂结晶法制备掺杂铝粉的复合微球

doi:10.11949/0438-1157.20231397

化工学报 ›› 2024, Vol. 75 ›› Issue (4): 1724-1734.DOI: 10.11949/0438-1157.20231397

• 材料化学工程与纳米技术 • 上一篇下一篇

喷雾-反溶剂结晶法制备掺杂铝粉的复合微球

刘静¹(), 杨文博¹, 吕英迪²^,³, 陶胜洋¹()

^1.大连理工大学化学学院，精细化工国家重点实验室，智能材料化工前沿科学中心，大连市智能化学重点实验室，辽宁大连 116024
^2.西安近代化学研究所，陕西西安 710065
^3.西北工业大学化学与化工学院，陕西西安 710072

收稿日期:2023-12-31 修回日期:2024-01-28 出版日期:2024-04-25 发布日期:2024-06-06
通讯作者: 陶胜洋
作者简介:刘静（1999—），女，硕士研究生，liu224521@163.com
基金资助:
国家自然科学基金项目(22372025);中央高校基本科研业务费专项资金项目(DUT22LAB607);中国航空研究院1912项目

Spray-anti-solvent crystallization method for preparing doped aluminum powder composite microspheres

Jing LIU¹(), Wenbo YANG¹, Yingdi LYU²^,³, Shengyang TAO¹()

^1.School of Chemistry, State Key Laboratory of Fine Chemicals, Frontier Science Center for Smart Materials, Dalian Key Laboratory of Intelligent Chemistry, Dalian University of Technology, Dalian 116024, Liaoning, China
^2.Xi’an Modern Chemistry Research Institute, Xi’an 710065, Shaanxi, China
^3.School of Chemistry and Chemical Engineering, Northwestern Polytechnical University, Xi'an 710072, Shaanxi, China

Received:2023-12-31 Revised:2024-01-28 Online:2024-04-25 Published:2024-06-06
Contact: Shengyang TAO

摘要/Abstract

摘要：

纳米铝粉作为高能添加剂广泛应用于含能复合材料领域。然而，制备高球形度铝粉掺杂的复合微球却面临着一系列挑战。采用喷雾与反溶剂结晶相结合的方法，探索了一种制备纳米铝粉与有机分子形成复合功能微球的喷射-结晶途径。通过自主设计的内混三流式空气雾化喷嘴，将前驱液雾化成液滴，反溶剂接收浴接收后，溶剂与反溶剂发生快速的相互扩散和传质过程，含能分子模拟物蔗糖八乙酸酯（SOA）在液滴内部析出，将铝粉包裹在内，洗涤干燥后得到铝粉掺杂的复合微球。通过调控合适的雾化、溶剂与反溶剂、添加剂等条件，成功解决了干燥后复合微球球形度低、微球之间相互团聚等现象，最终制备出粒径分布窄、形貌均一、分散性较好、球形度和密实度较高的掺杂铝粉的微球复合材料。

关键词: 结晶, 聚合物添加剂, 掺杂, 蔗糖八乙酸酯, 纳米铝粉, 复合微球

Abstract:

Nano-aluminum powder is widely used in the field of energetic composite materials as a high-energy additive. However, the preparation of high sphericity aluminum powder doped composite microspheres is faced with a series of challenges. In this paper, a spray-crystallization method for the preparation of composite functional microspheres formed by nano-aluminum powder and organic molecules was explored by using the method of spray and anti-solvent crystallization. Through the self-designed internal mixing three-flow air atomization nozzle, the precursor liquid is atomized into liquid droplets. After receiving in the anti-solvent receiving bath, the solvent and anti-solvent rapidly mutual diffusion and mass transfer process occur. The energetic molecular simulation sucrose octaacetate (SOA) is precipitated in the droplet, the aluminum powder is wrapped in it, and the aluminum powder doped composite microspheres are obtained after washing and drying. In this paper, by adjusting suitable conditions such as atomization, solvent and anti-solvent, additives, etc., the phenomenon of low sphericity and agglomeration of the composite microspheres after drying was successfully solved. Finally, the doped aluminum powder microsphere composite material with narrow particle size distribution, uniform morphology, good dispersion, sphericity and high compactness was prepared.

Key words: crystallization, polymeric additives, doped, sucrose octaacetate, nano-aluminum, composite microspheres

中图分类号:

O 636.1

刘静, 杨文博, 吕英迪, 陶胜洋. 喷雾-反溶剂结晶法制备掺杂铝粉的复合微球[J]. 化工学报, 2024, 75(4): 1724-1734.

Jing LIU, Wenbo YANG, Yingdi LYU, Shengyang TAO. Spray-anti-solvent crystallization method for preparing doped aluminum powder composite microspheres[J]. CIESC Journal, 2024, 75(4): 1724-1734.

图/表 13

图1 喷雾-反溶剂接收装置及喷嘴结构

Fig.1 Spray-antisolvent receiver and nozzle structure

图2 掺杂铝粉复合微球制备示意图

Fig.2 Schematic diagram of preparation of doped aluminum powder composite microspheres

表1 内混三流式空气雾化喷嘴雾化条件

Table 1 Atomization conditions of internal mixing three-stream air atomizing nozzle

序号	气压/mbar	液压/mbar	气液比	D₅₀/μm
1	1600	100	32	62.514
2	1700	100	34	60.144
3	1800	100	36	56.609
4	1900	100	38	54.237
5	2000	100	40	49.848
6	1800	90	40	50.781

图3 不同时刻收集液滴的光学显微照片

Fig.3 Optical images of the droplets at different time

图4 复合微球扫描电子显微镜图像

Fig.4 SEM image of composite microspheres

图5 反溶剂为石油醚、甲苯时液滴和复合微球表征

Fig.5 Characterization of droplets and composite microspheres with petroleum ether and toluene as antisolvent

图6 不同反溶剂接收的原始液滴的光学显微照片及粒径分布

Fig.6 Optical microscopy photos and particle size distribution of the original droplet received by different antisolvents

图7 复合微球扫描电子显微镜图像

Fig.7 SEM image of composite microspheres

图8 复合微球扫描电子显微镜图像

Fig.8 SEM of composite microspheres

图9 复合微球表面及断面扫描电子显微镜图及对应能谱

Fig.9 SEM images of surface and section and corresponding energy spectra of composite microspheres

图10 PVP∶PEG=1∶1时复合微球热重分析

Fig.10 TGA of composite microspheres when PVP∶PEG=1∶1

图11 分析表征结果

Fig.11 Analysis and characterization results

图12 分子结构示意图

Fig.12 Schematic diagram of molecular structure

参考文献 33

1	胥会祥, 李兴文, 赵凤起, 等. 纳米金属粉在火炸药中应用进展[J]. 含能材料, 2011, 19(2): 232-239.
	Xu H X, Li X W, Zhao F Q, et al. Review on application of nano-metal powders in explosive and propellants[J]. Chinese Journal of Energetic Materials, 2011, 19(2): 232-239.
2	杨丰友, 彭泓铮, 黄开书, 等. 纳米金属粉及其复合物在火炸药中的研究应用进展[C]//(第六届)含能材料与钝感弹药技术学术研讨会. 成都, 2014.
	Yang F Y, Peng H Z, Huang K S, et al. The research and application progress of nano-metals and their compounds in propellant[C]// 6th Symposium on Energetic Materials and Insensitive Munitions. Chengdu, 2014.
3	袁志锋, 赵凤起, 张教强, 等. 纳米金属粉的制备、改性及其在推进剂中的应用[J]. 化学推进剂与高分子材料, 2017, 15(4): 7-14.
	Yuan Z F, Zhao F Q, Zhang J Q, et al. Preparation, modification of nanometer metal powder and its application in propellant[J]. Chemical Propellants & Polymeric Materials, 2017, 15(4): 7-14.
4	Huang K J, Tan C D. Preparation and exothermic characterization of dioctyl sebacate (DOS)-coated aluminum nanopowders[J]. Applied Mechanics and Materials, 2011, 79: 65-70.
5	Mathe V L, Varma V, Raut S, et al. Enhanced active aluminum content and thermal behaviour of nano-aluminum particles passivated during synthesis using thermal plasma route[J]. Applied Surface Science, 2016, 368: 16-26.
6	Yetter R A, Risha G A, Son S F. Metal particle combustion and nanotechnology[J]. Proceedings of the Combustion Institute, 2009, 32(2): 1819-1838.
7	严启龙, 刘林林. 含能材料前沿导论[M]. 北京: 科学出版社, 2022: 385.
	Yan Q L, Liu L L. Introduction to Frontier of Energetic Materials[M]. Beijing: Science Press, 2022: 385.
8	邱华, 齐暑华, 王劲, 等. 高纯度蔗糖八乙酸酯的制备研究[J]. 西北工业大学学报, 2009, 27(5): 736-741.
	Qiu H, Qi S H, Wang J, et al. Preparation of high purity sucrose octaacetate[J]. Journal of Northwestern Polytechnical University, 2009, 27(5): 736-741.
9	Zhou X Q, Zhang Q, Xu R, et al. A novel spherulitic self-assembly strategy for organic explosives: modifying the hydrogen bonds by polymeric additives in emulsion crystallization[J]. Crystal Growth & Design, 2018, 18(4): 2417-2423.
10	Jia S Z, Yang P, Gao Z G, et al. Recent progress in antisolvent crystallization[J]. CrystEngComm, 2022, 24(17): 3122-3135.
11	Liao D J, Li M J, Wang J C, et al. A review on the preparation and characterization methods of spherical explosive crystals[J]. Journal of Materials Research and Technology, 2023: 3098-3118.
12	Han R S, Chen J H, Zhang F, et al. Fabrication of microspherical hexanitrostilbene (HNS) with droplet microfluidic technology[J]. Powder Technology, 2021, 379: 184-190.
13	Chen S K, Ju X J, Wei J, et al. Controllable preparation of monodisperse chitosan microspheres based on microfluidic technology[J]. Journal of Chemical Education, 2023, 100(9): 3526-3532.
14	Sharma D, Murthy Z V P, Patel S R. Microfluidic antisolvent crystallization of lactose: effect of process parameters[J]. Waste and Biomass Valorization, 2023, 14(2): 645-653.
15	Kong L L, Chen R, Wang X Z, et al. Controlled co-precipitation of biocompatible colorant-loaded nanoparticles by microfluidics for natural color drinks[J]. Lab on a Chip, 2019, 19(12): 2089-2095.
16	Song N M, Yang L, Han J M, et al. Catalytic study on thermal decomposition of Cu-en/(AP, CL-20, RDX and HMX) composite microspheres prepared by spray drying[J]. New Journal of Chemistry, 2018, 42(23): 19062-19069.
17	Liu W J, Wu W D, Selomulya C, et al. Facile spray-drying assembly of uniform microencapsulates with tunable core-shell structures and controlled release properties[J]. Langmuir, 2011, 27(21): 12910-12915.
18	Zhou X Q, Shan J H, Chen D, et al. Tuning the crystal habits of organic explosives by antisolvent crystallization: the case study of 2, 6-dimaino-3, 5-dinitropyrazine-1-oxid (LLM-105)[J]. Crystals, 2019, 9(8): 392.
19	Kawashima Y, Okumura M, Takenaka H. Spherical crystallization: direct spherical agglomeration of salicylic acid crystals during crystallization[J]. Science, 1982, 216(4550): 1127-1128.
20	Zhang X X, Yang Z J, Nie F D, et al. Recent advances on the crystallization engineering of energetic materials[J]. Energetic Materials Frontiers, 2020, 1(3/4): 141-156.
21	艾吉文, 高智雪, 张丽, 等. 内混式空气雾化喷嘴雾化性能的实验及模拟研究[J]. 计算机与应用化学, 2019, 36(6): 645-651.
	Ai J W, Gao Z X, Zhang L, et al. Experimental and simulation study on atomization performance of internal mixing air atomizing nozzle[J]. Computers and Applied Chemistry, 2019, 36(6): 645-651.
22	刘丽艳, 杨静, 孔庆森, 等. 空气雾化喷嘴的液滴雾化性能实验研究[J]. 化学工业与工程, 2013, 30(3): 60-65.
	Liu L Y, Yang J, Kong Q S, et al. Experimental investigation on particle atomization performance of air atomizing nozzle[J]. Chemical Industry and Engineering, 2013, 30(3): 60-65.
23	Uusi-Penttilä M, Berglund K A. Spectroscopic monitoring of environmentally benign anti-solvent crystallization[J]. Journal of Crystal Growth, 1996, 166(1/2/3/4): 967-970.
24	Punmalee N, Wantha L, Flood A E. Antisolvent crystallization of polymorphs of L-histidine[J]. Chemical Engineering & Technology, 2018, 41(6): 1132-1138.
25	Erdemir D, Lee A Y, Myerson A S. Nucleation of crystals from solution: classical and two-step models[J]. Accounts of Chemical Research, 2009, 42(5): 621-629.
26	Thorat A A, Dalvi S V. Liquid antisolvent precipitation and stabilization of nanoparticles of poorly water soluble drugs in aqueous suspensions: recent developments and future perspective[J]. Chemical Engineering Journal, 2012, 181/182: 1-34.
27	Li C, Ding B J, Zhang L J, et al. 3D-printed continuous flow reactor for high yield synthesis of CH₃NH₃PbX₃ (X = Br, I) nanocrystals[J]. Journal of Materials Chemistry C, 2019, 7(30): 9167-9174.
28	Kim K J. Spherulitic crystallization of 3-nitro-1,2,4-triazol-5-one in water+N-methyl-2-pyrrolidone[J]. Journal of Crystal Growth, 2000, 208(1/2/3/4): 569-578.
29	Pant A, Nandi A K, Newale S P, et al. Preparation and characterization of ultrafine RDX[J]. Central European Journal of Energetic Materials, 2013, 10(3): 393-408.
30	Zhang C Y, Ji C L, Li H Z, et al. Occupancy model for predicting the crystal morphologies influenced by solvents and temperature, and its application to nitroamine explosives[J]. Crystal Growth & Design, 2013, 13(1): 282-290.
31	Shi N Q, Yao J, Wang X L. Effect of polymers and media type on extending the dissolution of amorphous pioglitazone and inhibiting the recrystallization from a supersaturated state[J]. Drug Development and Industrial Pharmacy, 2014, 40(8): 1112-1122.
32	Afrasiabi Garekani H, Sadeghi M S F. Dissolution of acetaminophen crystallised in the presence of polyvinylpyrrolidone[J]. Journal of Drug Delivery Science and Technology, 2004, 14(2): 141-146.
33	Pessina F, Schnell F, Spitzer D. Tunable continuous production of RDX from microns to nanoscale using polymeric additives[J]. Chemical Engineering Journal, 2016, 291: 12-19.

[1]	王宝凤, 王术高, 程芳琴. 固废基硫掺杂多孔炭材料制备及其对CO₂吸附性能研究进展[J]. 化工学报, 2024, 75(2): 395-411.
[2]	刘昌会, 肖桐, 刘庆祎, 耿龙, 赵佳腾. 多孔二氧化钛强化的相变材料储热机理研究[J]. 化工学报, 2024, 75(2): 706-714.
[3]	余留洋, 刘书博, 贾晟哲, 马航, 万邦隆, 苏琦雯, 王静康, 汤伟伟, 贺豫娟, 龚俊波. 电子级磷酸的纯化精制技术发展现状与研究进展[J]. 化工学报, 2024, 75(1): 1-19.
[4]	于宏鑫, 邵双全. 水结晶过程的分子动力学模拟分析[J]. 化工学报, 2023, 74(S1): 250-258.
[5]	傅予, 刘兴翀, 王瀚雨, 李海敏, 倪亚飞, 邹文静, 雷月, 彭永姗. F₃EACl修饰层对钙钛矿太阳能电池性能提升的研究[J]. 化工学报, 2023, 74(8): 3554-3563.
[6]	杨菲菲, 赵世熙, 周维, 倪中海. Sn掺杂的In₂O₃催化CO₂选择性加氢制甲醇[J]. 化工学报, 2023, 74(8): 3366-3374.
[7]	李凯旋, 谭伟, 张曼玉, 徐志豪, 王旭裕, 纪红兵. 富含零价钴活性位点的钴氮碳/活性炭设计及甲醛催化氧化应用研究[J]. 化工学报, 2023, 74(8): 3342-3352.
[8]	张琦钰, 高利军, 苏宇航, 马晓博, 王翊丞, 张亚婷, 胡超. 碳基催化材料在电化学还原二氧化碳中的研究进展[J]. 化工学报, 2023, 74(7): 2753-2772.
[9]	苏晓丹, 朱干宇, 李会泉, 郑光明, 孟子衡, 李防, 杨云瑞, 习本军, 崔玉. 湿法磷酸半水工艺考察与石膏结晶过程研究[J]. 化工学报, 2023, 74(4): 1805-1817.
[10]	苏伟怡, 丁佳慧, 李春利, 王洪海, 姜艳军. 酶促反应结晶研究进展[J]. 化工学报, 2023, 74(2): 617-629.
[11]	陈毓明, 历伟, 严翔, 王靖岱, 阳永荣. 初生态聚乙烯聚集态结构调控研究进展[J]. 化工学报, 2023, 74(2): 487-499.
[12]	周璇, 李孟亚, 孙杰, 岑振凯, 吕强三, 周立山, 王海涛, 韩丹丹, 龚俊波. 添加剂对氨基酸晶体生长的影响[J]. 化工学报, 2023, 74(2): 500-510.
[13]	杨小芹, 刘馨雨, 杨玉寒, 叶彦, 贾琼, 杨浩男, 秦志宏. 煤基泡沫炭复合F-TiO₂光催化降解苯酚[J]. 化工学报, 2023, 74(12): 4914-4925.
[14]	张博, 李壮壮, 赵丹, 钱翠珠, 王宝, 潘鹏举. 聚丙烯流延膜的制备与拉伸过程中的结构演变[J]. 化工学报, 2023, 74(12): 4997-5005.
[15]	周光正, 王学重, 周浩宇. 溶酶菌蛋白质结晶的多目标优化与模拟[J]. 化工学报, 2023, 74(10): 4191-4200.

喷雾-反溶剂结晶法制备掺杂铝粉的复合微球

Spray-anti-solvent crystallization method for preparing doped aluminum powder composite microspheres

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 13

参考文献 33

相关文章 15

编辑推荐

Metrics

本文评价