Viscosifying dicyclopentadiene monomer by prepolymerization and evaluation of its continuous carbon fiber composites
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摘要: 聚双环戊二烯(PDCPD)作为一种综合性能优异的热固性树脂，可与连续碳纤维进行复合，应用在工程领域上，以满足轻量化和节能环保需求。本文首先通过调节双环戊二烯单体(DCPD)与Grubbs 2代催化剂的质量比使其只聚合不交联，调节黏度以满足真空辅助灌注成型(VARI)工艺对树脂特性的要求。随后对碳纤维表面进行丙酮去浆处理，再与上述加入足量催化剂的预聚物进行复合。对比PDCPD复合材料与通用型环氧树脂复合材料的拉伸、弯曲、V型缺口剪切、层间I型以及II型断裂韧性、冲击和热力学性能，研究PDCPD复合材料在不同加载模式下的失效机制，探寻其在工程领域应用的关键点和方向。结果表明，去浆后碳纤维与PDCPD界面结合良好，PDCPD复合材料在强度上与环氧树脂相当，在抵抗变形能力上较弱，但是在遭受高于极限强度的载荷后，仍然具有一定程度的承载能力；从层间断裂韧性来看，PDCPD复合材料I型断裂韧性和II型断裂韧性分别相当于环氧树脂复合材料的406%和250%，具有优异的抵抗分层能力；对比两种复合材料抗冲击性能，3.2 mm的PDCPD复合材料层合板在40 J能量的冲击下，表面产生层合板勉强可见冲击损伤(BVID)，背面无明显纤维破裂现象，剩余冲击压缩强度比环氧树脂复合材料高34.7%。Abstract: Polydicyclopentadiene (PDCPD) as a thermosetting resin with excellent comprehensive performance, can be composited with continuous carbon fibers (CF), for the application of various engineering field to meet the requirements of lightweight, energy conservation and environmental protection. In this paper, firstly, the viscosity of the DCPD prepolymer could meet the demands of vacuum assisted resin infusion (VARI) molding process by adjusting the content of Grubbs 2 catalyst. Subsequently, the carbon fiber was subjected desizing treatment, and then compounded with the prepolymer added with sufficient catalyst. The tensile, flexural, V-notch shear, interlaminar fracture toughness, impact, and thermodynamic properties of PDCPD/CF composites were compared with thegeneral epoxy resin (EP)/CF composites, The failure mechanisms of PDCPD/CF composites under different loading modes were detected, and the key points and directions for their application in the engineering field were explored. The results show that the interface between the carbon fibers after desizing and PDCPD is well bonded, and the strength of PDCPD/CF composite is comparable to that of EP/CF composite. Although PDCPD/CF composite had weaker deformation resistance, they still had a certain degree of bearing capacity after being subjected to the ultimate loads. From the perspective of interlaminar fracture toughness, PDCPD/CF composites have excellent delamination resistance, with mode I and mode II fracture toughness equivalent to 406% and 250% of CF/EP composites, respectively. A barely visible impact damage (BVID) has formed on the top surface of a 3.2 mm-thickness PDCPD laminate after being subjected to a 40 J impact, while there is no significant fiber breakage on the bottom surface. The residual compression strength of PDCPD/CF composites is 34.7% higher than the EP/CF composite.
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图 1 (a) V型缺口剪切测试；(b) 冲击后压缩测试
Figure 1. (a) V-notch shear test; (b) Compression test after impact
图 2 含不同比例催化剂的DCPD单体溶液升温DSC曲线
Figure 2. DSC curves of DCPD monomer solution containing different contents of catalyst
图 3 不同含量催化剂的DCPD单体时间-黏度(η)曲线：(a) 60℃；(b) 70℃；(c) 80℃；(d) 不同温度下生成的预聚物在25℃的黏度
Figure 3. Viscosity (η) vs time curves of DCPD monomer with different contents of catalyst: (a) 60℃; (b) 70℃; (c) 80℃; (d) Viscosity of prepolymers with different temperatures at 25℃
图 5 预聚物、DCPD单体及聚双环戊二烯(PDCPD)的FTIR图谱 (a)及其1000~950 cm−1处的放大观察图 (b)
Figure 5. FTIR spectra (a) and enlarged observation at 1000~950 cm−1 (b) of prepolymer, DCPD monomer, and polydicyclopentadiene (PDCPD)
图 6 去浆后碳纤维性能表征：(a) 化学结构；(b) 元素分析；(c) 表面微观结构
Figure 6. Characterization of carbon fiber after desizing: (a) Chemical structure; (b) Elemental analysis; (c) Surface microstructures
图 8 PDCPD复合材料(PDCPD/CF)和环氧树脂复合材料(EP/CF)弯曲性能对比：(a) 荷载-位移曲线；(b) 弯曲强度对比；环氧树脂复合材料(c)和PDCPD复合材料(d)弯曲失效形貌
Figure 8. Comparison of flexural properties of PDCPD/CF and EP/CF: (a) Load-displacement curves; (b) Flexural strength comparison; Fracture morphologies of EP/CF (c) and PDCPD/CF (d)
CF—Carbon fiber; EP—Epoxy resin
图 9 PDCPD复合材料弯曲断裂面SEM图像
Figure 9. SEM images of fracture surfaces of PDCPD/CF composite after three points bending
图 10 PDCPD复合材料和环氧树脂复合材料拉伸性能对比：(a) 应力-应变曲线；(b) 拉伸强度和模量对比；环氧树脂复合材料(c)和PDCPD复合材料(d)的拉伸断面SEM图像
Figure 10. Comparison of tensile properties of PDCPD/CF and EP/CF: (a) Stress-strain curves; (b) Tensile strength and modulus comparison; Fracture morphologies of EP/CF (c) and PDCPD/CF (d)
图 11 PDCPD复合材料和环氧树脂复合材料V型缺口剪切性能对比：(a) 荷载-位移曲线；(b) V型缺口剪切强度对比；环氧树脂复合材料(c) 和PDCPD复合材料 (d) 的V型缺口剪切失效图
Figure 11. Comparison of V-notch shear properties of PDCPD/CF and EP/CF: (a) Load-displacement curves; (b) V-notch shear strength comparison; V-notch shear failure diagram of EP/CF (c) and PDCPD/CF (d)
图 12 PDCPD复合材料和环氧树脂复合材料I型断裂韧性GIC对比：(a) 荷载-位移曲线；(b) R曲线；(c) 模式I能量释放率GIC性能对比
Figure 12. Comparison of mode I fracture toughness GIC of PDCPD/CF and EP/CF: (a) Load-displacement curves; (b) R curves; (c) Mode I energy release rate values GIC comparison
图 13 环氧树脂复合材料 (a) 和PDCPD复合材料 (b) 的I型断裂失效表面
Figure 13. SEM images of mode I fracture surfaces of EP/CF (a) and PDCPD/CF
图 14 两种复合材料II型断裂韧性分析：(a) 荷载-位移曲线；(b) 模式二能量释放率GIIC性能对比
Figure 14. Mode II fracture toughness of EP/CF and PDCPD/CF: (a) Load-displacement curves; (b) Mode II energy release rate values GIIC comparison
图 15 EP/CF (a)和PDCPD/CF (b)的II型断裂失效表面SEM图像
Figure 15. SEM images of mode II fracture surface of EP/CF (a) and PDCPD/CF (b)
图 16 两种复合材料冲击性能：(a) 荷载-位移曲线；(b) 能量吸收-时间曲线；环氧树脂复合材料(c)和PDCPD复合材料(d)冲击后表面形貌；环氧树脂复合材料(e)和PDCPD复合材料(f)冲击后背面形貌
Figure 16. Impact properties of EP/CF andPDCPD/CF: (a) Load-displacement curves; (b) Energy absorption-time curve; Top surface morphologies of EP/CF (c) and PDCPD/CF (d) after impact; Bottom surface morphologies of EP/CF (e) and PDCPD/CF (f) after impact
BVID—Barely visible impact damages
图 17 两种复合材料冲击后压缩性能：(a) 荷载-位移曲线；(b) 压缩强度对比；环氧树脂复合材料 (c) 和PDCPD复合材料 (d) 压缩侧面失效形貌
Figure 17. Compression properties of composites after impact: (a) Load-displacement curves; (b) Compression strength comparison; Failure morphologies of EP/CF (c) and PDCPD/CF (d) after compress
图 18 树脂及其复合材料动态热力学性能：(a) 树脂储能模量；(b) 复合材料储能模量；(c) 损耗因子tanδ-温度曲线
Figure 18. Dynamic thermodynamic properties of resin and its composite: Storage modulus for resin (a) and its composites (b); (c) Loss factor tanδ vs temperature curves
图 19 环氧树脂复合材料和PDCPD复合材料综合性能评价
Figure 19. Comprehensive performance evaluation of EP/CF and PDCPD/CF
表 1 预聚物的配方设计
Table 1. Formulation design of prepolymer
Formulation number Mass ratio of DCPD monomer to GC2 1 1∶1×10−5 2 1∶2×10−5 3 1∶3×10−5 4 1∶4×10−5 5 1∶5×10−5 Notes: DCPD—Dicyclopentadiene; GC2—Grubbs 2 catalyst. 
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表 2 复合材料各项性能测试参数
Table 2. Technical details for the performed composites tests
Test Test speed Layers Nominal sample dimensions/mm3 Three point bending 1 mm/min 16 120×13×3.2 Tension 2 mm/min 12 250×25×2.4 V-notched rail shear 2 mm/min 12 76×56×2.4, groove depth is 12.7 mm and groove angle is 90℃ Double cantilever beam 1 mm/min 20 150×25×4, pre-crack length is 75 mm End notched flexure 2 mm/min 20 150×25×4, pre-crack length is 45 mm Compression after impact 1.25 mm/min for compression rate 16 150×100×3.2 Dynamic mechanical properties 1 Hz, heating rate of 5℃/min 10 60×12×2
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表 3 预聚物全固化后力学性能对比
Table 3. Comparison of mechanical properties of prepolymers after full curing
Resin system Tensile strength/MPa Elongation at break/% Tensile modulus/GPa Flexural strength/MPa Fracture toughness/(MPa·m1/2) PDCPD without prepolymerzation
53.9±2.7 8.2±0.6 1.52±0.09 82.1±4.4 2.56±0.12 No.2 prepolymer 53.7±2.4 8.2±0.5 1.55±0.08 84.3±5.6 2.59±0.18 No.3 prepolymer 52.6±1.9 8.0±0.5 1.48±0.08 83.7±3.9 2.48±0.15 No.4 prepolymer 54.2±2.1 8.1±0.7 1.55±0.1 82.4±4.7 2.50±0.09 No.5 prepolymer 53.8±1.8 8.0±0.6 1.51±0.12 83.6±4.7 2.55±0.13 Epoxy resin 74.9±3.1 3.9±0.2 2.45±0.1 123.4±5.5 0.68±0.03
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