干法缠绕用预浸纱制备工艺优化及其性能

余木火; 王昊; 余许多; 戚亮亮; 张辉; 孙泽玉

doi:10.13801/j.cnki.fhclxb.20211213.001

干法缠绕用预浸纱制备工艺优化及其性能

doi: 10.13801/j.cnki.fhclxb.20211213.001

1.
东华大学　材料学院，上海市轻质结构复合材料重点实验室，上海市高性能纤维复合材料省部共建协同创新中心，上海 201620
2.
上海华渔新材料科技有限公司，上海 201610

基金项目: 上海市“科技创新行动计划”高新技术领域项目(19511106703；19511106601)；中央高校基本科研业务费专项资金(2232020G-12) ；国家新材料生产与应用示范平台建设项目(CLPT-2019-0016)

详细信息

通讯作者:
孙泽玉，博士，讲师，硕士生导师，研究方向为碳纤维复合材料低成本制造　E-mail: sunzeyu@dhu.edu.cn

中图分类号: TB332；V214.8
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出版历程
- 收稿日期: 2021-10-28
- 修回日期: 2021-11-23
- 录用日期: 2021-12-03
- 网络出版日期: 2021-12-13
- 刊出日期: 2022-12-01

Preparation process optimization and performance of pre-impregnated yarn for dry winding

1.
College of Materials Science and Engineering, Shanghai Key Laboratory of Lightweight Structural Composites, Shanghai High Performance Fiber Composite Materials Collaborative Innovation Center, Donghua University, Shanghai 201620, China
2.
Shanghai Huayu New Materials Tech. Inc, Shanghai 201610, China

摘要

摘要: 干法缠绕是缠绕成型工艺的重要分支，其缠绕过程含胶量均匀、缠绕效率高、环境污染小，更容易实现工业自动化生产。开发具有良好加工性能的预浸纱，对干法缠绕的推广应用具有重要意义。通过动态DSC和恒温DSC，结合流变测试，研究了所用环氧树脂体系固化特性，基于自催化模型建立树脂固化反应动力学方程，并与实测固化度对比验证。搭建预浸纱制备平台，采用改进热熔法制备干法缠绕用预浸纱，分析制备过程中不同固化度对预浸纱表面质量的影响。在此基础上通过响应面法分析不同工艺参数(纱架张力、收卷速率、烘道温度)对预浸纱含胶量的影响。结果表明：自催化模型与实验结果基本吻合，适用于干法缠绕预浸纱最佳固化度范围为5%~10%，对含胶量影响最大的因子是收卷速率，其次是放纱张力，烘道温度影响最小。综合考虑各工艺参数影响规律，获得优化的制备工艺参数：烘道温度为180℃，收卷速率为8 m/min，放纱张力为6 N，此时树脂含胶量为30.1wt%。NOL环拉伸强度可达2536.1 MPa，拉伸模量为162.3 GPa，层间剪切强度为57.3 MPa。
- 干法缠绕 /
- 预浸纱 /
- 热熔法 /
- 含胶量 /
- 固化动力学
Abstract: Dry winding is an important branch of the winding forming process. The winding process has uniform glue content, high winding efficiency, low environmental pollution and easier industrial automation production. The development of prepreg yarn with good processing properties is of great significance to the promotion and application of dry winding. Through dynamic DSC and constant temperature DSC, combined with the viscosity test, the curing characteristics of the epoxy resin system used were studied. Based on the autocatalytic model, the resin curing reaction kinetic equation was established and verified by comparison with the measured curing degree. A prepreg yarn preparation platform was set up, an improved hot-melt method to prepare dry winding prepreg yarn was adopted, and the influence of different curing degrees on the surface quality of prepreg yarn during the preparation process was analyzed. On this basis, the response surface method was used to analyze the influence of different process parameters (creel tension, winding speed, drying tunnel temperature) on the glue content of the prepreg yarn. The results show that the autocatalytic model is basically consistent with the experimental results, and the best curing range for dry winding prepreg yarn is 5%-10%. The factor that has the greatest influence on the glue content is the winding rate, followed by the unwinding tension. The temperature of the drying tunnel has the least influence. Considering the influence law of various process parameters, the optimized preparation process parameters are obtained: The temperature of the drying tunnel is 180℃, the winding speed is 8 m/min, the yarn unwinding tension is 6 N, and the resin mass fraction is 30.1wt% at this time. The tensile strength of the NOL ring can reach 2536.1 MPa, the tensile modulus is 162.3 GPa, and the interlaminar shear strength is 57.3 MPa.
- drying winding /
- prepreg yarn /
- hot-melt process /
- resin content /
- curing reaction kinetics

HTML全文

图 1 预浸纱制备流程图

Figure 1. Schematic diagram of prepreg preparation facility

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图 2 预浸纱制备所用设备：(a) 收卷机；(b) 五辊牵引机；(c) 烘道；(d) 浸胶槽；(e) 放纱架

Figure 2. Equipment for prepreg preparation: (a) Winder; (b) Five-roller tractor; (c) Oven; (d) Dipping tank; (e) Carbon fiber creel

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图 3 HY230环氧树脂体系非等温DSC曲线

Figure 3. Isothermal DSC curves of HY230 epoxy resin mixture systems

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图 4 HY230环氧树脂体系在不同升温速率下的固化度$ \alpha $与时间$ t $的关系

Figure 4. Relationship between curing degree $ \alpha $ and curing time t of HY230 epoxy resin system at different heating rates

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图 5 HY230环氧树脂体系在不同升温速率下固化度$ \alpha $与温度T的关系

Figure 5. Relationship between curing degree $ \alpha $ and temperature T of HY230 epoxy resin system at different heating rates

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图 6 HY230环氧树脂体系Kissinger方程的线性回归图

Figure 6. Plot for determining the activation energy of the curing reaction by Kissinger equation of HY230 epoxy resin system

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图 7 HY230环氧树脂体系固化度-温度-时间三维关系图

Figure 7. Three-dimensional relationship diagram of curing degree-temperature-time of HY230 epoxy resin system

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图 8 不同升温速率下HY230环氧树脂体系固化速率模型拟合线与实验值对比

Figure 8. Comparison of the calculated reaction rate (lines) and experimental data (symbols) for the epoxy HY230

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图 9 HY230环氧树脂体系等温固化实验结果与自催化模型预测对比

Figure 9. Comparison of the autocatalytic model fitting curves and observed data for the isothermal curing of the epoxy HY230

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图 10 HY230环氧树脂体系黏度-温度曲线

Figure 10. Viscosity-temperature curve of HY230 epoxy resin system

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图 11 HY230环氧树脂体系凝胶时间与温度的关系

Figure 11. Relationship of gel time and temperature of HY230 epoxy resin system

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图 12 不同固化度环氧树脂黏度-温度曲线

Figure 12. Viscosity-temperature curves of resin system with different curing degree resin system

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图 13 T700/HY230预浸纱含胶量实验值与预测值对比

Figure 13. Comparison of the experimental and predicted values of resin content in T700/HY230 prepreg yarn

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图 14 T700/HY230预浸纱含胶量三维响应曲面图

Figure 14. Three-dimensional response surface of resin content in T700/HY230 prepreg yarn

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图 15 不同工艺参数所制备的T700/HY230预浸纱量化评价

Figure 15. Quantitative evaluation of T700/HY230 prepreg yarn prepared with different process parameters

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图 16 长度2000 m的自制T700/H230预浸纱

Figure 16. Actual picture of the T700/HY230 prepreg yarn with a length of 2000 m

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表 1 HY-230树脂不同升温速度下特征温度

Table 1. Parameters for the non-isothermal curing reaction thermogram of HY230

Heat rating β /(℃·min⁻¹)	T_onset /℃	T_P /℃	T_end /℃
5	123	162	199
10	129	185	214
15	141	189	227
20	149	197	235
Notes: T_onset—Temperature at onset point; T_P—Temperature at peak point; T_end—Temperature at end point.

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表 2 HY230环氧树脂体系多重线性回归参数

Table 2. Multiple linear regression parameters of HY230 epoxy resin system

Heat rating/(℃·min⁻¹)	m	n	lnA
5	1.03	0.09	14.01
10	0.95	0.05	14.14
15	0.74	0.10	14.40
20	0.84	0.06	14.48

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表 3 HY230环氧树脂适用期

Table 3. HY230 epoxy resin pot life

Temperature/℃	Gel time/h	Shelf life/d
−18	8383.9	174.6
0	1257.8	26.2
25	131.9	2.7

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表 4 不同固化度预浸纱制备实验方案

Table 4. Preparation experiment plan of prepregs with different curing degrees

Curing degree /%	Pulling speed /(m·min⁻¹)	Temperature /℃
0	2	0
5	0.5	130
10	2	170
15	0.5	150
20	1	170
25	0.5	160

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表 5 不同固化度预浸纱表面情况

Table 5. Surface quality of prepregs with different curing degrees

Curing degree /%	Wetness index	Glutinosity
0	Serious	Low
5	Slightly moist	Slightly adhesive
10	Moderate	Moderate
15	Slightly dry	Relatively adhesive
20	Relatively drier	Seriously adhesive
25	Tow curing	Not sticky

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表 6 预浸纱制备工艺参数

Table 6. Process parameters of prepreg yarn preparation

Parameter	Payoff tension/N	Pulling speed/ (m·min⁻¹)	Temperature/ ℃
Range	4-12	2-8	140-180

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表 7 预浸纱制备工艺Box-Behnken实验设计因素与水平

Table 7. Levels of factors by Box-Behnken design of prepreg yarn preparation

Code	Factor	Level
Code	Factor	−1	0	1
A	Payoff tension/N	4	8	12
B	Pulling speed/(m·min⁻¹)	2	5	8
C	Temperature/℃	140	160	180
Notes: −1—Code of minimum value of process parameter range; 0—Code of middle value of process parameter range; 1—Code of maximum value of process parameter range.

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表 8 预浸纱制备工艺Box-Behnken实验结果

Table 8. Results of Box-Behnken experiment for prepreg yarn preparation

Number	Payoff tension/N	Pulling speed/ (m·min⁻¹)	Tempera-ture/℃	Resin content/%
1	0	0	0	30.62
2	1	0	1	27.77
3	0	0	0	32.08
4	−1	0	1	30.97
5	−1	0	−1	32.46
6	1	1	0	31.71
7	0	0	0	31.58
8	1	0	−1	30.92
9	1	−1	0	27.58
10	0	−1	1	27.10
11	0	0	0	30.75
12	0	1	−1	32.85
13	0	−1	−1	27.26
14	0	0	0	31.00
15	0	1	1	31.33
16	−1	1	0	33.98
17	−1	−1	0	29.73

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表 9 T700/HY230含胶量模型方差分析

Table 9. Variance analysis of regression equation of T700/HY230 prepreg yarn

Source	Sum of squares	D_f	Mean square	F- value	P- value	Signifi- cance
Model	63.70	9	7.08	17.29	0.0005	**
A	10.49	1	10.49	25.63	0.0015	**
B	41.41	1	41.41	101.17	<0.0001	***
C	4.99	1	4.99	12.20	0.0101	*
AB	0.0036	1	0.0036	0.0087	0.9279	-
AC	0.69	1	0.69	1.68	0.2356	-
BC	0.46	1	0.46	1.13	0.3231	-
A²	0.20	1	0.20	0.50	0.5041	-
B²	1.92	1	1.92	4.69	0.0669	-
C²	3.38	1	3.38	8.25	0.0239	*
Residual	2.86	7	0.41	-	-	-
Lack of fit	1.37	3	0.46	1.22	0.4118	-
Pure error	1.50	4	0.37	-	-	-
Cor total	66.56	16	-	-	-	-
Notes: D_f—Degree freedom; F-value—Ratio of the mean square to the residual term; P-value—Influence degree value of each factor; *—Significant in [−∞, 0.0001]; —Significant in [0.0001, 0.01]; *—Significant in [0.01, 0.05].

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表 10 T700/H230预浸纱NOL环力学性能测试结果

Table 10. Interlaminar shear strength and tensile strength of T700/HY230 prepreg yarn NOL rings

Parameter	Resin content/ wt%	Ring shear strength/ GPa	Tensile strength/ MPa	Tensile modulus/ GPa
Average value	30.1	57.3	2536.1	162.3
Standard deviation	0.9	4.3	76.6	41.1

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