纳米ZIF-8@短碳纤维的制备及其对环氧复合材料阻燃、抑烟和力学性能的影响

杨宕莎; 王康琪; 朱妍妍; 李建根; 林健; 王新龙

doi:10.13801/j.cnki.fhclxb.20210616.005

纳米ZIF-8@短碳纤维的制备及其对环氧复合材料阻燃、抑烟和力学性能的影响

doi: 10.13801/j.cnki.fhclxb.20210616.005

南京理工大学　化学与化工学院，南京 210094

基金项目: 中国江苏省科技支撑计划(社会发展)(BE 2013714)；江苏省高等学校优先学术计划

详细信息

通讯作者:
王新龙，博士，教授，硕士生导师，研究方向为塑料改性与加工　E-mail：wxinlong323@163.com

中图分类号: TB332
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出版历程
- 收稿日期: 2021-04-13
- 修回日期: 2021-05-25
- 录用日期: 2021-06-05
- 网络出版日期: 2021-06-17
- 刊出日期: 2022-04-01

Preparation of nano ZIF-8@short carbon fibers and its effects on the flame retardancy, smoke suppression and mechanical properties of epoxy composites

School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, China

摘要

摘要: 通过原位生长的方法制备了ZIF-8@短碳纤维(SCFs)材料，将其与聚磷酸铵(APP)一起加入环氧树脂(EP)制备了阻燃性能和力学性能均有所提高的环氧树脂复合材料。通过氧指数测定仪、水平垂直燃烧测定仪、锥形量热仪及万能电子拉力机对ZIF-8@SCFs-APP/EP复合材料进行了阻燃与力学性能的测试。实验结果表明，与添加5wt%APP阻燃样品相比，当 ZIF-8@SCFs的添加量为1wt% (APP和ZIF-8@SCFs的质量比为4∶1)时，复合材料的极限氧指数从25.7%增加到28.1%，UL-94垂直燃烧试验达到V-1级、热释放率峰值(pHRR)和总烟雾量(TSP)明显降低；复合材料的抗张强度、弯曲强度、弹性模量和断裂伸长率分别提高了86%、81%、20%和75%，解决了无机阻燃填料的添加导致EP力学性能降低的问题，制备的阻燃复合材料具有实际应用价值。
- 环氧树脂 /
- 金属有机骨架 /
- 聚磷酸铵 /
- 短碳纤维 /
- 阻燃 /
- 力学性能
Abstract: The nano ZIF-8 on short carbon fibers (ZIF-8@SCFs) were prepared in situ growth. The composites were manufactured using ZIF-8@SCFs, ammonium polyphosphate (APP) and epoxy resin (EP) to improve the flame retardant and mechanical properties. Oxygen index tester, horizontal and vertical combustion tester, cone calorimeter and universal electronic tensile machine were used to investigate the flame retardant and mechanical properties of EP composite materials. The experimental results show that when the addition amount of ZIF-8@SCFs is 1wt% (the mass ratio of APP to ZIF-8@SCFs is 4∶1), the limiting oxygen index of the composite material increases from 25.7% to 28.1%, and UL-94 reaches V-1 level. The peak heat release rate (pHRR) and total smoke production (TSP) are reduced evidently compared with the sample with only 5wt% of APP. Besides, the tensile strength, flexural strength, elastic modulus and elongation at break of the composite material are increased by 86%, 81%, 20% and 75%, respectively, which solves the problem that the addition of inorganic flame-retardant destroys the mechanical properties of EP. The prepared composites could be applied in practice.
- epoxy resin /
- metal organic framework /
- ammonium polyphosphate /
- short carbon fiber /
- flame retardant /
- mechanical properties

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图 1 SCFs和ZIF-8@SCFs的SEM图像((a)~(c)) 及EDX图谱 (d)

Figure 1. SEM images ((a)-(c)) and EDX spectrum (d) of SCFs and ZIF-8@SCFs

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图 2 SCFs、ZIF-8和ZIF-8@SCFs的XRD图谱

Figure 2. XRD pattens of SCFs, ZIF-8 and ZIF-8@SCFs

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图 3 ZIF-8、SCFs和ZIF-8@SCFs的FTIR图谱

Figure 3. FTIR spectra of ZIF-8, SCFs and ZIF-8@SCFs

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图 4 ZIF-8@SCFs-聚磷酸铵(APP)/环氧树脂(EP)复合材料的极限氧指数(LOI)及UL-94垂直燃烧测试结果

Figure 4. Limiting oxygen index (LOI) and UL-94 vertical combustion test results of ZIF-8@SCFs- ammonium polyphosphate (APP)/ epoxy resin (EP) composites

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图 5 ZIF-8@SCFs-APP/EP复合材料的热释放率(HRR) (a)、总热释放(THR) (b)、质量损失率(MLR) (c)、总烟雾量(TSP) (d)、平均CO产量(AvCOY) (e) 和平均CO₂产量(AvCO₂Y) (f) 曲线

Figure 5. Heat release rate (HRR) (a), total heat release (THR) (b), mass loss rate (MLR) (c), total smoke production (TSP) (d), average CO production (AvCOY) (e) and average CO₂ production (AvCO₂Y) (f) of ZIF-8@SCFs-APP/EP composite materials

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图 6 EP (a)、5APP/EP (b)、0.3ZIF-8@SCFs-4.7APP/EP (c)、ZIF-8@SCFs-4APP/EP (d)和2ZIF-8@SCFs-3APP/EP (e) 的极限氧指数试验后残炭数码照片

Figure 6. Digital photo of residual carbon after limiting oxygen index test of EP (a), 5APP/EP (b), 0.3ZIF-8@SCFs-4.7APP/EP (c), ZIF-8@SCFs-4APP/EP (d) and 2ZIF-8@SCFs-3APP/EP (e)

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图 7 ZIF-8@SCFs-APP/EP复合材料在N₂中TGA(a)和TGA末端(b)曲线

Figure 7. TGA (a) and TGA end (b) curves of ZIF-8@SCFs-APP/EP composites in N₂

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图 8 EP((a₁)~(a₃))、5APP/EP ((b₁)~(b₃)) 和ZIF-8@SCFs-4APP/EP ((c₁)~(c₃))复合材料在锥形量热实验后的残炭照片及SEM图像

Figure 8. Carbon residue photos and SEM images of EP ((a₁)-(a₃)), 5APP/EP ((b₁)-(b₃)) and ZIF-8@SCFs-4APP/EP ((c₁)-(c₃)) after cone calorimetry test

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图 9 ZIF-8@SCFs-APP/EP复合材料残炭的FTIR图谱

Figure 9. FTIR spectra of carbon residue of ZIF-8@SCFs-APP/EP composites

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图 10 ZIF-8@SCFs-APP/EP复合材料残炭的拉曼光谱

Figure 10. Raman spectra of carbon residue of ZIF-8@SCFs-APP/EP composites

I_D/I_G—Intensity of D band/intensity of G band

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图 11 ZIF-8@SCFs-APP/EP复合材料残炭的XRD图谱

Figure 11. XRD pattarns of carbon residue of ZIF-8@SCFs-APP/EP composites

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图 12 90~710℃下5APP/EP (a)和ZIF-8@SCFs-4APP/EP (b)的热解气体三维红外图谱

Figure 12. 3D infrared spectra of pyrolysis gases of 5APP/EP (a) and ZIF-8@SCFs-4APP/EP (b) at 90-710℃

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图 13 ZIF-8@SCFs-APP/EP复合材料在310℃、340℃和690℃时气相产物的FTIR图谱

Figure 13. FTIR spectra of gas phase products of ZIF-8@SCFs-APP/EP composites at 310℃, 340℃ and 690℃

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图 14 ZIF-8@SCFs-APP/EP复合材料的弯曲强度、拉伸强度 (a) 及弹性模量和断裂伸长率 (b)

Figure 14. Tensile strength, flexural strength (a), elastic modulus and elongation at break (b) of ZIF-8@SCFs-APP/EP composites

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图 15 EP ((a₁)、(b₁))、5APP/EP ((a₂)、(b₂)) 和ZIF-8@SCFs-4APP/EP ((a₃)、(b₃)) 复合材料断面SEM图像

Figure 15. SEM images of EP ((a₁), (b₁)), 5APP/EP ((a₂), (b₂)) and ZIF-8@SCFs-4APP/EP ((a₃), (b₃))

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图 16 ZIF-8@SCFs-APP/EP复合材料的储能模量(a) 和损耗因子 (b)

Figure 16. Storage modulus (a) and loss factor (b) of ZIF-8@SCFs-APP/EP composites

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表 1 2-甲基咪唑锌盐(ZIF-8)@短碳纤维(SCFs)-聚磷酸铵(APP)/环氧树脂(EP)复合材料的组成配方

Table 1. Formulations of Zinc salt of 2-methylimidazole (ZIF-8)@short carbon fibers (SCFs)-ammonium polyphosphate (APP)/epoxy (EP) composites

Sample	EP/ wt%	APP/ wt%	ZIF-8@SCFs/ wt%
EP	100	0	0
5APP/EP	95	5	0
0.3ZIF-8@SCFs-4.7APP/EP	95	4.7	0.3
ZIF-8@SCFs-4APP/EP	95	4	1
2ZIF-8@SCFs-3APP/EP	95	3	2

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表 2 EP、5APP/EP和ZIF-8@SCFs-4APP/EP复合材料的锥形量热数据

Table 2. Cone calorimetric data of EP, 5APP/EP and ZIF-8@SCFs-4APP/EP composite materials

Sample	pHRR/(kW·m⁻²)	THR/(MJ·m⁻²)	AvMLR/(g·s⁻¹)	TSP/m²	AvCOY/%	AvCO₂Y/%
EP	989	265	0.11	57.30	0.05	1.43
5APP/EP	602	263	0.10	54.20	0.01	0.37
ZIF-8@SCFs-4APP/EP	422	225	0.07	45.70	0.01	0.27
Notes: pHRR—Peak heat release rate; AvMLR—Average mass loss rate.

下载: 导出CSV

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