Preparation and damage healing behavior of intrinsic self-repairing polymeric bonded explosives
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摘要: 为减轻高聚物粘结炸药(PBX)由于力、热等环境因素所产生的微裂纹等损伤对于其性能与使用寿命的影响，根据颗粒填充高分子复合材料的结构特性，设计合成了含DA键的本征型自修复高聚物粘结剂，以期实现PBX内部损伤的自主修复。研究结果表明，采用含可逆DA共价键的TAPE-DAPU为粘结剂，设计制备的PBX材料具有较强的损伤愈合能力，当损伤较轻时，该PBX的强度恢复率超过95%，对于较严重的贯穿性损伤，其修复效率也在65%以上。
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关键词:
- 复合材料 /
- 高聚物粘结炸药(PBX) /
- 损伤 /
- 自修复 /
- DA反应
Abstract: In order to reduce the influence of microcracks and other damages caused by environmental factors such as force and heat on the performance and service life of polymeric bonded explosives (PBX), an intrinsic self-repairing polymer binder containing DA bonds was designed and synthesized to realize autonomous healing of PBX internal damage according to the structural characteristic of particle filled polymer composites. The research results show that using TAPE-DAPU containing reversible DA covalent bonds as binder, the designed and prepared PBX material has good damage-healing ability. When the damage in PBX is slight, the strength recovery rate of the PBX exceeds 95%, while the repair efficiency is also above 65% for relatively severe penetrating damage.-
Key words:
- composite materials /
- polymeric bonded explosives (PBX) /
- damage /
- self-repairing /
- Diels-Alder reaction
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图 1 含DA键的自修复聚氨酯粘结剂的合成路线
Figure 1. Synthetic process of self-repairing PU binder containing DA bonds
图 2 TAPE-DAPU的FTIR图谱 (a) 与核磁氢谱 (b)
Figure 2. FTIR (a) and H-NMR (b) spectra of TAPE-DAPU
图 4 TAPE-DAPU划痕试样修复过程的光学图((a)不同加热温度；(b)120℃下加热不同时间)
Figure 4. Optic images of crack healing process of TAPE-DAPU ((a) At different temperatures; (b) At 120℃ with different time)
图 5 TAPE-DAPU试样多次划痕-修复后的拉伸曲线
Figure 5. Tensile curve of TAPE-DAPU after different self-healing cycles
图 6 平压头加载曲线及相应的应变云图
Figure 6. Loading curve and strain cloud map with plane-head clamp (((a), (a’)) 550 N; ((b), (b’)) 750 N)
图 7 弧形压头加载曲线及相应的应变云图
Figure 7. Loading curve and strain cloud map with arc-head clamp (((a), (a’)) Load to 950 N; ((b), (b’)) Load to form crack)
图 8 两种不同夹具加载后的PBX光学照片((a)平压头；(b)弧形压头)
Figure 8. Typical optic images of PBX after loading via two different clamps ((a) Plane-head; (b) Arc-head)
图 9 平压头夹具加载的PBX试样A1的修复前后的CT图像
Figure 9. CT images of PBX sample A1 loading with plane-head clamp((a) Damaged; (b) Healed)
图 10 弧形夹具预制的不同损伤PBX试样修复后CT图
Figure 10. CT images of healed PBX loading with arc-head clamp((a) Sample B2; (b) Sample C2; (c) Sample D2; (d) Sample D1)
表 1 三氨基三硝基苯(TATB)/含DA键的四氨基苯基乙烯基聚氨酯(TAPE-DAPU)的高聚物粘结炸药(PBX)的损伤预制与修复处理方式
Table 1. Damage prefabrication and healing methods of Triaminotrinitrobenzene(TATB)/ Tetrakis(4-aminophenyl)ethene polyurethane with Diels-Alder bonds (TAPE-DAPU) based polymer bonded explosive (PBX)
Sample Mode of damage-prefabrication Serial number Method of healing-treatment A Plane-head clamp, loading to 550 N A1 Heating at 125℃ for 1 h and keeping at 65℃ for 4 h A2 Heating at 125℃ for 2 h and keeping at 65℃ for 3 h B Arc-head clamp, loading to 950 N and keeping 100 s B1 Heating at 125℃ for 1 h and keeping at 65℃ for 4 h B2 Heating at 125℃ for 2 h and keeping at 65℃ for 3 h C Arc-head clamp, loading to 1000 N C1 Heating at 125℃ for 1 h and keeping at 65℃ for 4 h C2 Heating at 125℃ for 2 h and keeping at 65℃ for 3 h D Arc-head clamp, loading to form perforative crack D1 Heating at 125℃ for 1 h and keeping at 65℃ for 4 h D2 Heating at 125℃ for 2 h and keeping at 65℃ for 3 h 
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表 2 TATB-DAPU基PBX不同损伤修复试样的巴西性能
Table 2. Brazilian properties of TATB-DAPU based PBX after different damage-healing process
Sample Serial
numberBrazilian
strength/MPaElongation/% Original sample P0 6.45±0.15 1.173±0.020 A A1 6.28±0.11 0.857±0.015 A2 4.86±0.10 0.517±0.013 B B1 4.99±0.06 0.777±0.013 B2 4.79±0.09 0.627±0.014 C C1 4.78±0.09 0.617±0.016 C2 4.50±0.10 0.397±0.011 D D1 4.45±0.07 0.557±0.012 D2 4.25±0.09 0.635±0.011
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