含缩醛结构环氧树脂的固化行为及其碳纤维复合材料的制备与性能

郑波; 贾红丽; 颜春; 祝颖丹; 蒲浩; 刘东; 徐海兵; 刘小青; 代金月

doi:10.13801/j.cnki.fhclxb.20230918.003

含缩醛结构环氧树脂的固化行为及其碳纤维复合材料的制备与性能

doi: 10.13801/j.cnki.fhclxb.20230918.003

郑波^{1, 3},
贾红丽¹,
颜春^1, ,,
祝颖丹^1, ,,
蒲浩¹,
刘东¹,
徐海兵¹,
刘小青²,
代金月²

1.
中国科学院宁波材料技术与工程研究所　浙江省机器人与智能制造装备技术重点实验室，宁波 315201
2.
中国科学院宁波材料技术与工程研究所　材料技术研究所，宁波 315201
3.
宁波大学　材料科学与化学工程学院，宁波 315211

基金项目: 国家自然科学基金(U1909220)；宁波市科技创新2025重大专项(2023Z024；2022Z102)

详细信息

通讯作者:
颜春，博士，高级工程师，硕士生导师，研究方向为树脂基复合材料的制备及性能研究　E-mail: yanchun@nimte.ac.cn

祝颖丹，博士，研究员，博士生导师，研究方向为复合材料设计、制造和装备技术等基础研究与应用工作　E-mail: y.zhu@nimte.ac.cn

中图分类号: TB332
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出版历程
- 收稿日期: 2023-07-13
- 修回日期: 2023-08-20
- 录用日期: 2023-08-27
- 网络出版日期: 2023-09-19
- 刊出日期: 2024-05-15

Curing behavior of epoxy resin with acetal structure and preparation and properties ofits carbon fiber composites

ZHENG Bo^{1, 3},
JIA Hongli¹,
YAN Chun^{1
, ,},
ZHU Yingdan^{1
, ,},
PU Hao¹,
LIU Dong¹,
XU Haibing¹,
LIU Xiaoqing²,
DAI Jinyue²

1.
Zhejiang Provincial Key Laboratory of Robotics and Intelligent Manufacturing Equipment Technology, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, China
2.
Institute of Materials Technology, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, China
3.
School of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, China

Funds: National Natural Science Foundation of China (U1909220); Ningbo Key Projects of Science and Technology Innovation 2025 Plan (2023Z024; 2022Z102)

摘要

摘要: 针对含缩醛结构生物基环氧树脂体系的工艺性能开展研究，采用旋转流变仪和非等温DSC对缩醛环氧树脂体系的流变性能和固化行为进行了分析，确定了其注胶温度约为40℃。采用自催化模型结合n级模型的分段模型获得其固化动力学参数，分段模型拟合得到的曲线与实验曲线吻合较好，表明该模型在2.5~20 K/min的升温速率下能较好地描述含缩醛结构环氧树脂体系的固化反应过程。通过外推法确定了树脂体系的优化固化工艺条件，制备出的含缩醛结构环氧树脂的拉伸强度和弯曲强度分别为79 MPa和130 MPa。进一步研究了碳纤维与环氧树脂之间的界面粘结性能和力学性能，发现碳纤维/缩醛环氧树脂复合材料的界面剪切强度和力学性能与碳纤维/商用环氧树脂复合材料的基本相当，表明可降解的缩醛环氧树脂可以替代商用环氧树脂，具有广泛的应用前景。另外，碳纤维/缩醛环氧树脂复合材料具有较好的降解性能，回收碳纤维的单丝拉伸强度与原始碳纤维的相当，可以有效回收高质量的碳纤维。
- 环氧树脂 /
- 流变性能 /
- 固化动力学 /
- 固化模型 /
- 碳纤维复合材料 /
- 力学性能
Abstract: To investigate the forming process of bio-based epoxy resin system with acetal structure, the rheological properties and curing behavior of the epoxy resin system with acetal structure were studied by rotating rheometer and non-isothermal DSC. The glue injecting temperature is determined to be about 40℃. The curing kinetic parameters were obtained by the piecewise model combining the autocatalytic model and the n-order model. The fitting curves from the piecewise model are in good agreement with the experimental curves, indicating that the model can accurately describe the curing reaction process of epoxy resin system with acetal structure at the heating rates of 2.5-20 K/min. The curing procedure of the resin system was determined by an extrapolation method. The tensile strength and bending strength of the epoxy resin with acetal structure are 79 MPa and 130 MPa, respectively. It is found that the interfacial shear strength (IFSS) and interlaminar shear strength (ILSS) of carbon fiber/acetal epoxy resin composites are similar to those of carbon fiber/commercial epoxy resin composites, indicating that the interfacial bonding property between acetal epoxy resin and carbon fiber is similar to that of commercial epoxy resin. In addition, the tensile and flexural properties of the two composites are similar, indicating that the degradable acetal epoxy resin may replace the commercial epoxy resin and give potential competitive advantages over the applications. In addition, the carbon fiber/acetal epoxy resin composites have good degradation performance, and the single fiber tensile strength of the recovered carbon fiber is comparable to that of the original carbon fiber, indicating that high-quality carbon fiber can be effectively recycled.
- epoxy resin /
- rheological properties /
- curing kinetics /
- curing model /
- carbon fiber composites /
- mechanical properties

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图 1 环氧树脂、稀释剂和固化剂的化学结构式

IPDA—Isophorone diamine

Figure 1. Chemical structure formula of epoxy resin, diluent and curing agent

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图 2 环氧树脂体系的化学流变性能：(a) 温度扫描曲线；(b) 时间扫描曲线

Figure 2. Chemical rheological properties of epoxy resin system: (a) Temperature sweep curves; (b) Time scan curves

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图 3 缩醛环氧树脂体系在不同升温速率下的DSC曲线

Figure 3. DSC curves of acetal epoxy resin system at different heating rates

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图 4 不同升温速率下的固化度(α)和温度(T)的关系

Figure 4. Relationship between curing degree (α) and temperature (T) at different heating rates

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图 5 (a) 0.2≤α≤0.8区间的$ \mathrm{ln}\left(\mathrm{d}\alpha/\mathrm{d}t\right) $与$ 1/T $的线性拟合曲线；(b) 活化能E_a随α的变化关系

Figure 5. (a) Linear fitting curves of ln(dα/dt) and 1/T within the range of 0.2≤α≤0.8; (b) Variations of activation energy (E_a) versus α

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图 6 Malek判定方程y(α)和z(α)随α的变化关系

Figure 6. Variations of Malek determination equation y(α) and z(α) versus α

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图 7 ln[(dα/dt)e^x]和ln[α^P (1−α)]的关系图

x—Reduced activation energy; P—Kinetic parameter ratio

Figure 7. Plots of ln[(dα/dt)e^x] and ln[α^P (1−α)]

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图 8 缩醛环氧树脂DSC曲线实验值与自催化模型计算值的对比

Figure 8. Comparison of DSC curves of acetal epoxy resin between experimental values and calculated values of autocatalytic model

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图 9 缩醛环氧树脂DSC曲线实验值与分段模型计算值的对比

Figure 9. Comparison of DSC curves of acetal epoxy resin between experimental values and calculated values of piecewise model

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图 10 固化放热峰特征温度与升温速率的线性拟合曲线

T_i—Initial temperature of the curing exothermic peak; T_P—Peak temperature of the curing exothermic peak; T_f—Final temperature of the curing exothermic peak

Figure 10. Linear fitting curves of characteristic curing temperatures and heating rates

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图 11 环氧树脂的TGA曲线(a)和DTG曲线(b)

T_d5%—Onset degradation temperature; T_max—Maximum mass loss temperature

Figure 11. TGA (a) and DTG (b) curves of epoxy resins

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图 12 碳纤维(CF)/环氧树脂界面剪切强度(IFSS) (a)及脱粘后碳纤维表面形貌：(b) CF/商用环氧树脂；(c) CF/缩醛环氧树脂

Figure 12. Interfacial shear strength (IFSS) (a) of carbon fiber (CF)/epoxy resin and surface morphology of CF after debonding:(b) CF/commercial EP; (c) CF/acetal EP

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图 13 缩醛环氧树脂和商用环氧树脂复合材料的力学性能对比：(a)层间剪切强度(ILSS)；(b)拉伸强度与模量；(c)弯曲强度与模量

Figure 13. Comparison of mechanical properties of acetal epoxy resin and commercial epoxy resin composites: (a) Interlaminar shear strength (ILSS);(b) Tensile strength and modulus; (c) Flexural strength and modulus

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图 14 CF/商用环氧树脂(a)和CF/缩醛环氧树脂(b)的层间剪切破坏断裂面的SEM图像

Figure 14. SEM images of interlaminar shear fracture surface of CF/commercial EP composites (a) and CF/acetal EP composites (b)

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图 15 回收碳纤维的表面形貌(a)、原始碳纤维和回收碳纤维的拉曼光谱(b)及单丝拉伸应力-应变曲线(c)

Figure 15. Surface morphology of recycled CFs (a), Raman spectra (b) and representative tensile stress-strain curves of the virgin CF and recycled CF monofilaments (c)

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表 1 由DSC分析得到的α_p、α_M和$\alpha_{\mathrm{p}}^{\infty} $值

Table 1. Values of α_p, α_M and $\alpha_{\mathrm{p}}^{\infty} $ obtained by DSC

Heating rate/(K·min⁻¹)	α_p	α_M	$\alpha_{\mathrm{p}}^{\infty} $
2.5	0.43	0.036	0.92
5	0.46	0.041	0.92
10	0.47	0.042	0.93
15	0.49	0.031	0.92
20	0.51	0.047	0.89
Notes: α_p―Curing degree at the maximum values of heat flow; α_M―Curing degree at the maximum values of y(α); $\alpha_{\mathrm{p}}^{\infty} $―Curing degree at the maximum values of z(α).

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表 2 缩醛环氧树脂体系自催化模型固化动力学参数

Table 2. Curing kinetic parameters of autocatalytic model of acetal epoxy resin system

Heating rate/(K·min⁻¹)	E_a/(kJ·mol⁻¹)	lnA	m	n
2.5	66.19	16.31	0.049	1.33
5		16.34	0.057	1.34
10		16.30	0.059	1.36
15		16.26	0.044	1.36
20		16.19	0.064	1.28
Notes: E_a―Activation energy; A―Pre-exponential factor; m, n―Reaction orders.

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表 3 缩醛环氧树脂体系分段模型固化动力学参数

Table 3. Curing kinetic parameters for piecewise model of acetal epoxy resin system

Heating rate/(K·min⁻¹)	E_a/(kJ·mol⁻¹)	Autocatalytic model (α<0.825)			n-order model (α≥0.825)		Correlation index R²
Heating rate/(K·min⁻¹)	E_a/(kJ·mol⁻¹)	lnA	m	n	lnA	n	Correlation index R²
2.5	66.19	16.63	0.071	1.83	15.71	1.26	0.9925
5		16.62	0.071	1.83	15.95	1.42	0.9976
10		16.53	0.066	1.70	15.89	1.33	0.9995
15		16.48	0.087	1.65	15.91	1.34	0.9992
20		16.35	0.061	1.58	15.96	1.37	0.9997

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表 4 环氧树脂(EP)的力学性能

Table 4. Mechanical properties of epoxy resins (EP)

Sample	Tensile strength/ MPa	Tensile modulus/ GPa	Flexural strength/ MPa	Flexural modulus/ GPa
Acetal EP	79	2.5	130	2.8
Commercial EP	76	2.2	115	2.4

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