ANPyO@PDA复合材料的制备、表征及热分解性能

张功震; 何志伟; 冉宪文; 程维; 汪扬文; 李志远; 张贺

doi:10.11858/gywlxb.20230697

ANPyO@PDA复合材料的制备、表征及热分解性能

doi: 10.11858/gywlxb.20230697

张功震^1,,
何志伟^1,*, ,,
冉宪文²,
程维¹,
汪扬文³,
李志远¹,
张贺¹

1.
安徽理工大学化学工程学院, 安徽淮南　232001
2.
国防科技大学理学院, 湖南长沙　410073
3.
安徽江南化工股份有限公司, 安徽合肥　230094

基金项目: 国家自然科学基金（51404006）

详细信息

作者简介:
张功震（1994－），男，硕士研究生，主要从事含能材料性能研究. E-mail：2241953568@qq.com

通讯作者:
何志伟（1979－），男，博士，副教授，主要从事含能材料及其配方性能研究. E-mail：751601138@qq.com

中图分类号: O342; TJ55
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出版历程
- 收稿日期: 2023-07-26
- 修回日期: 2023-08-09
- 网络出版日期: 2023-12-12
- 刊出日期: 2023-12-15

Preparation, Characterization and Thermal Decomposition Properties of ANPyO@PDA Composites

1.
School of Chemical Engineering, Anhui University of Science and Technology, Huainan 232001, Anhui, China
2.
National University of Defense Technology, Changsha 410073, Hunan, China
3.
Anhui Jiangnan Chemical Industry Co. LTD., Hefei 230094, Anhui, China

摘要

摘要: 为了提高2,6-二氨基-3,5-二硝基吡啶氧化物（ANPyO）的热稳定性，基于多巴胺氧化自聚合原理，采用原位聚合法将聚多巴胺（polydopamine，PDA）包覆在ANPyO晶体表面，通过调节反应时间，制备了不同包覆率的ANPyO@PDA核壳型复合材料。采用扫描电子显微镜、X射线衍射仪、傅里叶变换红外光谱仪、X射线光电子能谱仪对其形貌、晶体结构、分子结构和元素含量进行了表征，采用热重-差示扫描量热仪测试了ANPyO@PDA复合材料的热分解性能。结果表明：PDA在ANPyO表面形成均匀致密的涂层；PDA包覆后ANPyO晶体结构和分子结构没有发生改变；随着反应时间的增长，包覆率逐渐增加；PDA包覆3和9 h时，使得ANPyO的热分解峰值温度分别提高1.97和1.95 ℃，表观活化能分别增加25.04和139.33 kJ/mol，热爆炸临界温度分别提高23.12和20.04 ℃；ANPyO@PDA复合材料的热稳定性和热安全性高于ANPyO。
- 2,6-二氨基-3,5-二硝基吡啶氧化物（ANPyO） /
- 聚多巴胺（PDA） /
- 核壳结构 /
- 热稳定性 /
- 热安全性
Abstract: In order to improve the thermal stability of 2,6-diamino-3,5-dinitropyridine-1-oxide (ANPyO), polydopamine was coated on the surface of ANPyO crystal by in situ polymerization, based on the principle of dopamine oxidation self-polymerization. ANPyO@PDA core-shell composite materials with different coating rates were prepared by adjusting the reaction time. The morphology, crystal structure, molecular structure, and element content of ANPyO@PDA composites were characterized by scanning electron microscopy (SEM), X-ray diffractometer (XRD), Fourier transform infrared spectrometer (FT-IR) and X-ray photoelectron spectroscopy (XPS). The thermal decomposition performance of the ANPyO@PDA composites was also tested by thermogravimetry-differential scanning calorimetry (TG-DSC). The results show that PDA formed uniform and compact coating on the surface of the ANPyO, and the crystal and molecular structures of the ANPyO remained unchanged after the PDA coating. Additionally, the coating rate gradually increased with the growth of coating time. The thermal decomposition peak temperatures of the ANPyO were increased by 1.97 and 1.95 °C, respectively, as well as the apparent activation energy increased by 25.04 and 139.33 kJ/mol, and the critical temperatures of the thermal explosion were increased by 23.12 and 20.04 ℃ after PDA coating for 3 and 9 h, respectively. The thermal stability and thermal safety of the ANPyO@PDA composites are higher than that of the ANPyO.
- 2,6-diamino-3,5-dinitropyridine-1-oxide (ANPyO) /
- polydopamine (PDA) /
- core@shell structure /
- thermal stability /
- thermal safety

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图 1 ANPyO (a) 和多巴胺(b)的分子结构

Figure 1. Molecular structure of ANPyO (a) and dopamine (b)

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图 2 ANPyO@PDA复合材料的制备

Figure 2. Preparation of ANPyO@PDA composites

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图 3 ANPyO和ANPyO@PDA复合材料的实物照片和SEM图像

Figure 3. Photos and SEM images of ANPyO and ANPyO@PDA composites

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图 4 ANPyO和ANPyO@PDA复合材料的XRD谱

Figure 4. XRD patterns of ANPyO and ANPyO@PDA composites

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图 5 ANPyO和ANPyO@PDA复合材料的FT-IR光谱

Figure 5. FT-IR spectra of ANPyO and ANPyO@PDA composites

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图 6 ANPyO、PDA和ANPyO@PDA复合材料的XPS光谱

Figure 6. XPS spectra of ANPyO, PDA and ANPyO@PDA composites

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图 7 ANPyO@PDA复合材料的TG曲线

Figure 7. TG curves of ANPyO@PDA composites

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图 8 ANPyO@PDA复合材料的TG-DTG曲线

Figure 8. TG-DTG curves of ANPyO@PDA composites

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图 9 ANPyO@PDA复合材料的DSC曲线

Figure 9. DSC curves of ANPyO@PDA composites

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图 10 ANPyO@PDA复合材料的动力学参数拟合结果

Figure 10. Fitting results of kinetic parameters of ANPyO@PDA composites

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表 1 ANPyO、PDA和ANPyO@PDA的表面元素组成

Table 1. Element content of ANPyO, PDA and ANPyO@PDA composites

Samples	w_C1s/%	w_N1s/%	w_O1s/%	Atomic ratio of N to C	ω/%
ANPyO	36.92	34.33	28.75	0.93
ANPyO@PDA-3h	42.00	29.41	28.59	0.70	14.33
ANPyO@PDA-6h	51.06	22.85	26.09	0.45	33.44
ANPyO@PDA-9h	58.57	12.14	29.29	0.21	64.63
PDA	70.82	7.65	21.53	0.11

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表 2 ANPyO和ANPyO@PDA复合材料的热分解动力学参数

Table 2. Thermal decomposition kinetic parameters of ANPyO and ANPyO@PDA composites

Samples	E_K/(kJ·mol⁻¹)	lgA_K/(kJ·mol⁻¹)	E_O/(kJ·mol⁻¹)
ANPyO	321.64	30.8	313.93
ANPyO@PDA-3h	346.44	28.7	339.33
ANPyO@PDA-9h	460.97	38.4	448.24

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表 3 ANPyO和ANPyO@PDA复合材料的热爆炸临界温度$T_{\mathrm{b}} $和自加速分解温度$T_{\mathrm{SADT}} $

Table 3. Critical temperatures of thermal explosion ($T_{\mathrm{b}} $) and self -accelerated decomposition temperature ($T_{\mathrm{SADT}} $) of ANPyO and ANPyO@PDA composites

Samples	T_b/K	T_SADT/K
ANPyO	611.69	602.02
ANPyO@PDA-3h	634.81	625.15
ANPyO@PDA-9h	631.73	624.53

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表 4 ANPyO@PDA复合材料的热力学参数

Table 4. Thermodynamic parameters of ANPyO@PDA composites

Samples	ΔH^≠/(kJ·mol⁻¹)	ΔS^≠/(J·mol⁻¹·K⁻¹)	ΔG^≠/(kJ·mol⁻¹)
ANPyO@PDA-3h	341.68	355.92	127.69
ANPyO@PDA-9h	455.91	540.80	126.89

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