爆轰法制备的纳米La<sub>2</sub>O<sub>3</sub>的表征与性能

朱群龙; 汪泉; 汪旭光; 李瑞; 涂唱畅; 杨锐; 朱文艳

doi:10.11858/gywlxb.20230643

爆轰法制备的纳米La₂O₃的表征与性能

doi: 10.11858/gywlxb.20230643

朱群龙^1,,
汪泉^{1, 2,*, ,},
汪旭光^{1, 3},
李瑞^{1, 2},
涂唱畅¹,
杨锐¹,
朱文艳¹

1.
安徽理工大学化学工程学院，安徽淮南　232001
2.
安徽省爆破器材与技术工程实验室，安徽淮南　232001
3.
北京矿冶研究总院，北京　102628

基金项目: 国家自然科学基金（11872002）；精细爆破国家重点实验室开放课题（PBSKL-2022-B-05）

详细信息

作者简介:
朱群龙（1995－），男，硕士研究生，主要从事爆炸合成新型材料研究. E-mail：2761368262@qq.com

通讯作者:
汪　泉（1980－），男，博士，教授，博士生导师，主要从事爆炸力学与爆炸安全研究.E-mail：wqaust@163.com

中图分类号: O521.1; TB34
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出版历程
- 收稿日期: 2023-04-19
- 修回日期: 2023-05-10
- 录用日期: 2023-05-17
- 网络出版日期: 2023-08-17
- 刊出日期: 2023-09-01

Characterization and Performance of Nano-La₂O₃ Prepared by Detonation Method

ZHU Qunlong^1
,,
WANG Quan^{1, 2,*
, ,},
WANG Xuguang^{1, 3},
LI Rui^{1, 2},
TU Changchang¹,
YANG Rui¹,
ZHU Wenyan¹

1.
School of Chemical Engineering, Anhui University of Science and Technology, Huainan 232001, Anhui, China
2.
Anhui Provincial Blasting Equipment and Technology Engineering Laboratory, Huainan 232001, Anhui, China
3.
Beijing General Research Institute of Mining & Metallurgy, Beijing 102628, China

摘要

摘要: 针对目前La₂O₃制备存在纯度低、烧结性差、分子间隙大等问题，发展纳米La₂O₃的新型制备方法显得尤为重要。以La(NO₃)₃·6H₂O作为镧源加入乳化炸药中，通过乳化炸药爆轰反应为La₂O₃的合成提供高温高压条件，采用爆轰法在0.5 kg TNT当量真空爆炸容器内制备稀土纳米La₂O₃粉末。爆轰产物提纯、煅烧后，通过X射线衍射、扫描电子显微镜、傅里叶变换红外光谱进行产物的物相、形貌、成分表征，采用紫外-可见光光谱、氮气吸附-脱附等温线、CO₂-程序升温脱附和O₂-程序升温脱附进行性能测定，结果表明：煅烧温度对La₂O₃粉体的结晶生长具有显著影响；在煅烧温度为800 ℃、煅烧时间为3 h的条件下成功制备出吸收紫外光、纯净且分散性较好的纳米La₂O₃粉末，其粒径在50～175 nm区间，晶体结构为六方晶系；纳米La₂O₃的比表面积为17.46 m²/g，孔道有序性较好，且孔径分布集中，具有较好的酸性气体吸附能力和氧迁移性能。爆轰法应用于纳米La₂O₃粉末制备，为纳米La₂O₃的工业化制备提供了一种新的参考方法。
- 乳化炸药 /
- 爆轰法 /
- 稀土 /
- 纳米La₂O₃ /
- 吸附
Abstract: It is very important that new preparation method of nano-lanthanum oxide is explored in view of the current problems of low purity, poor sinterability, and large molecular gaps. Detonation method was employed to prepare rare earth nano-La₂O₃ powder in this study. La(NO₃)₃·6H₂O was added to the emulsion explosive as a lanthanum source, and the high temperature and high pressure conditions for the synthesis of La₂O₃ were provided by the detonation reaction of the emulsion explosive in a 0.5 kg TNT equivalent vacuum explosion container. The physical phases, morphologies and ingredients of the purified and forged products were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FT-IR), and the powder performances were determined by ultraviolet-visible spectroscopy (UV-Vis), Brunauer Emmett Teller (BET), CO₂-temperature programmed desorption (CO₂-TPD) and O₂-temperature programmed desorption (O₂-TPD). The results show that the forging temperature has a significant effect on the crystalline growth of La₂O₃ powder. Nano-La₂O₃ powder with high ultraviolet light absorption, high purity and good dispersion was successfully produced at a forging temperature of 800 ℃ and a forging time of 3 h. The particle size is in the range of 50－175 nm, and the crystal has a hexagonal structure. The specific surface area of the nano-La₂O₃ is 17.46 m²/g, with a good pore order and concentrated pore size distribution. The nano-La₂O₃ has good adsorption of acid gas and oxygen migration performance. The detonation method applied to the preparation process of nano-La₂O₃ powder provides a new reference for the industrial preparation of nano-La₂O₃.
- emulsion explosive /
- detonation method /
- rare earth /
- nano-La₂O₃ /
- adsorption

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图 1 0.5 kg TNT当量真空爆炸容器

Figure 1. 0.5 kg TNT equivalent vacuum explosion vessel

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图 2 不同La₂O₃样品的XRD谱

Figure 2. XRD patterns of different La₂O₃ samples

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图 3 不同La₂O₃样品的SEM图像

Figure 3. Scanning electron microscopic images of different La₂O₃ samples

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图 4 不同La₂O₃样品的FT-IR谱

Figure 4. FT-IR spectra of different La₂O₃ samples

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图 5 (a) 不同La₂O₃粉体的UV-Vis漫反射吸收光谱和(b) 样品3的(αhv)²-能量变换关系

Figure 5. (a) UV-Vis diffuse reflection absorption spectra of different La₂O₃ powdersand (b) (αhv)²-Energy transformation diagram of sample 3

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图 6 不同La₂O₃样品的N₂吸附-脱附等温线和相应的孔径分布曲线

Figure 6. N₂ adsorption-desorption isotherms and corresponding pore size distribution curves of different La₂O₃ samples

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图 7 La₂O₃的CO₂-TPD (a) 和O₂-TPD (b)

Figure 7. CO₂-TPD (a) and O₂-TPD (b) profiles of La₂O₃

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表 1 专用乳化炸药配方设计

Table 1. Formulation design of specialised emulsified explosive

No.	Mass fraction/%					Oxygen balance
No.	NH₄NO₃	La(NO₃)₃·6H₂O	H₂O	Emulsifiers	Composite wax	Oxygen balance
1	81	5	8	2	4	−0.0061
2	76	10	8	2	4	0.0024
3	71	15	8	2	4	0.0109
4	66	20	8	2	4	0.0194

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表 2 专用乳化炸药爆炸的实验结果

Table 2. Pre-experimental results of specialized emulsion explosives

No.	Explosive transmission ability	Average burst speed/(cm·s⁻¹)
1	Full explosion	4015.1
2	Full explosion	4247.9
3	Full explosion	4513.5
4	Explosion rejection

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表 3 混合炸药及爆轰产物的热化学参数^[19]

Table 3. Thermochemical parameters of composite explosives and detonation products^[19]

Molecular formula	M/(g·mol⁻¹)	ΔH_m/(kJ·mol⁻¹)	Molecular formula	M/(g·mol⁻¹)	ΔH_m/(kJ·mol⁻¹)
NH₄NO₃	80	−353.5	H₂O(l)	18	−286.1
La(NO₃)₃·6H₂O	433	−3887.3	H₂O(g)	18	−241.8
C₁₈H₃₈	254	−558.0	CO₂	44	−393.5
C₂₄H₄₄O₆	428	−1333.9	CO	28	−110.5
La₂O₃	172	−1089.9	N₂	28	0

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表 4 不同热处理温度下纳米La₂O₃表面的性能参数

Table 4. Performance parameters of nano-La₂O₃ surfaces under different heat treatment temperatures

Sample	S_BET/(m²·g⁻¹)	V_pore/(cm³·g⁻¹)	Pore diameter/nm
1	16.5194	0.124929	27.7599
2	17.4581	0.146736	31.0622
3	16.9762	0.103253	32.9184

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