Crystallization behavior characterization and analysis of CF/PEEK thermoplastic composites
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摘要: 为了深入了解热塑性复合材料在非等温热成型工艺下的晶体结构和组织演变规律，优化成型工艺参数并提高热塑性复合材料结构成型质量及其热学、力学性能，本文研究了碳纤维增强聚醚醚酮(CF/PEEK)热塑性复合材料在不同降温速率下的结晶行为。开展了不同冷却速率下CF/PEEK复合材料的DSC测试实验。基于Avrami方程、Ozawa方程和Mo方程描述了CF/PEEK复合材料的非等温结晶行为，计算了非等温结晶活化能并建立了结晶度演化动力学模型。此外，本文还使用光纤布拉格光栅(FBG)对CF/PEEK复合材料融凝过程进行了原位检测，结合结晶度演化模型分析了聚合物基体融凝过程中的应变变化机制。结果表明，CF/PEEK复合材料结晶度随冷却速率的增大而减小，对应的结晶时间也同样减少。经验证，本文建立的结晶度演化动力学模型能够有效分析任意冷却速率下CF/PEEK复合材料的结晶度演化过程，可以结合FBG应变检测分析CF/PEEK热塑性复合材料融凝过程中基体相变对特征应变的影响。
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关键词:
- CF/PEEK复合材料 /
- 非等温结晶行为 /
- 结晶动力学 /
- 光纤光栅传感技术 /
- 原位检测
Abstract: To gain a comprehensive understanding of the non-isothermal crystallization behavior of carbon fiber reinforced polyetheretherketone (CF/PEEK) composites, optimize process parameters, and enhance the structural forming quality and thermal and mechanical properties of thermoplastic composites, this study investigated the crystallization behavior of CF/PEEK thermoplastic composite materials under different cooling rates. Through conducting differential scanning calorimetry (DSC) experiments on CF/PEEK composite materials at various cooling rates, the non-isothermal crystallization behavior of CF/PEEK composite materials was analyzed using the Avrami, Ozawa, and Mo equations. The activation energy of non-isothermal crystallization was determined, and the crystallization kinetics model was developed. In addition, in-situ detection of the CF/PEEK composite material melting/crystallization process was carried out using fiber Bragg grating (FBG), and the strain variation mechanism during the polymer matrix melting/crystallization process was analyzed in conjunction with the crystallization kinetics model. The results indicate that the crystallinity of CF/PEEK composite materials decreases with increasing cooling rate, accompanied by a decrease in the corresponding crystallization time. It has been demonstrated that the established crystallinity crystallization kinetic model in this study effectively analyzes the crystallization process of CF/PEEK composite materials under different cooling rate. Additionally, it can be combined with fiber Bragg grating strain detection to analyze the influence of matrix phase transition on characteristic strain during the melting/crystallization process of CF/PEEK thermo-plastic composites. -
图 1 不同冷却速率下碳纤维增强聚醚醚酮(CF/PEEK)复合材料非等温熔融(a)/结晶过程(b)热流曲线图
Figure 1. Heat flow curves of non-isothermal melting (a)/crystallization (b) of carbon fiber reinforced polyetheretherketone (CF/PEEK) composites at different cooling rates
图 2 (a)嵌入光纤布拉格光栅(FBG)层压板横截面图；(b)嵌入FBG传感器示意图
Figure 2. (a) Cross section of laminate with embedded fiber Bragg grating FBG; (b) Diagram of laminate with embedded FBG
图 3 不同冷却速率下CF/PEEK复合材料二次升温熔融过程热流曲线图
Figure 3. Heat flow curves of CF/PEEK composites during reheating melting process at different cooling rates
图 4 CF/PEEK复合材料：(a)相对结晶度Xc(t)与温度关系曲线；(b)相对结晶度Xc(t)与时间关系曲线
Figure 4. CF/PEEK composites: (a) Relative crystallinity Xc(t)-temperature curves; (b) Relative crystallinity Xc(t)-time curves
图 5 CF/PEEK复合材料的非等温结晶过程中lg[−ln(1−Xc(t))]和lgt的Avrami图
Figure 5. Avrami plots of lg[−ln(1−Xc(t))] vs lgt of non-isothermal crystallization process of CF/PEEK composites
图 6 CF/PEEK复合材料的非等温结晶过程中lg[−ln(1−Xc(T))]和lgΦ的Ozawa图
Figure 6. Ozawa plots of lg[−ln(1−Xc(T))] vs lgΦ of non-isothermal crystallization process of CF/PEEK composites
图 7 CF/PEEK复合材料的非等温结晶过程中lgΦ和lgt的Mo图
Figure 7. Mo plots of lgΦ vs lgt of non-isothermal crystallization process of CF/PEEK composites
图 8 CF/PEEK复合材料的$\ln \left( \varPhi /T_{{\mathrm{p}}}^{2} \right) $-
1000 /Tp拟合曲线图Figure 8. $\ln \left( \varPhi /T_{{\mathrm{p}}}^{2} \right) $-
1000 /Tp fitting curve of CF/PEEK compositesΔE—Crystallization activation energy
图 9 CF/PEEK复合材料的t1/2 (a)、n1 (b)和To (c)随冷却速率的拟合结果
Figure 9. Fitting results of t1/2 (a)、n1 (b) and To (c) with cooling rates of CF/PEEK composites
图 10 CF/PEEK复合材料的DSC测试和模型预测结果对比
Figure 10. Comparison of CF/PEEK composites DSC test and model output results
图 11 CF/PEEK复合材料的温度、应变及相对结晶度曲线图：(a) 0°方向；(b) 90°方向；(c)纯PEEK树脂
Figure 11. Temperature, strain and relative crystallinity curves of CF/PEEK composites: (a) 0° direction; (b) 90° direction; (c) Pure PEEK resin
表 1 CF/PEEK复合材料不同冷却速率下的结晶参数
Table 1. Crystallization parameters of CF/PEEK composites at different cooling rates
Sample Φ/(℃·min−1) To/℃ Tp/℃ Te/℃ Tcc/℃ Tm/℃ tc/min Xc/% 1 5 315.5 302.8 279.5 173.2 337.7 7.2 23.1 2 10 311.0 299.4 268.9 173.0 340.1 4.2 20.8 3 15 308.4 294.4 262.6 172.8 338.9 3.1 20.1 4 20 301.5 283.9 243.2 169.2 337.6 2.9 19.8 Notes: Φ—Cooling rate; To—Crystallization initiation temperature; Tp—Peak crystallization temperature; Te—Crystallization end temperature; Tcc—Cold crystallization temperature; Tm—Melting point; tc—Crystallization time; Xc—Absolute crystallinity. 
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表 2 CF/PEEK复合材料不同冷却速率下的Avrami结晶参数
Table 2. Avrami crystallization parameters of CF/PEEK composites at different cooling rates
Cooling rate/(℃·min−1) n Zt 5 2.58 0.01 10 2.56 0.18 15 2.69 0.28 20 2.52 0.55 Notes: n—Exponents of Avrami's equation; Zt—Crystallization rate constant.
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表 3 CF/PEEK复合材料的Ozawa结晶参数
Table 3. Ozawa crystallization parameters of CF/PEEK composites
Temperature/℃ m K(T) 278 0.50 25.12 288 1.15 72.44 298 1.32 52.48 Notes: m—Exponents of Ozawa's equation; K(T)—Cooling function.
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表 4 CF/PEEK复合材料的Mo结晶参数
Table 4. Mo crystallization parameters of CF/PEEK composites
Xc(t)/% b F(T) 10 0.76 10.96 30 0.73 14.45 50 0.79 17.38 70 0.86 21.88 90 1.00 33.11 Notes: b—Exponents of Mo's equation; F(T)—Cooling rate value.
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表 5 CF/PEEK复合材料非等温结晶特征值
Table 5. Non-isothermal crystallization characteristics of CF/PEEK composites
Cooling rate/(℃·min−1) t1/2/min n1 To/℃ 5 2.60 2.33 315.53 10 1.50 2.68 311.01 15 1.20 2.95 308.38 20 0.98 2.60 301.52 Notes: t1/2—Half-crystallization time; n1—Previous exponent of Avrami equation; To—Crystallization initiation temperature.
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