聚硅氧烷改性环氧树脂对玻璃纤维/酚醛复合材料高温残余强度的影响

李晨阳; 李书欣; 冀运东; 曹东风; 胡海晓; 陈震

doi:10.13801/j.cnki.fhclxb.20230301.001

聚硅氧烷改性环氧树脂对玻璃纤维/酚醛复合材料高温残余强度的影响

doi: 10.13801/j.cnki.fhclxb.20230301.001

李晨阳^1,,
李书欣^{2, 3, 4, 5},
冀运东^{1, 2, ,},
曹东风^{2, 4, 5},
胡海晓^{3, 4, 5},
陈震¹

1.
武汉理工大学　材料科学与工程学院，武汉 430070
2.
武汉理工大学　材料复合新技术国家重点实验室，武汉 430070
3.
武汉理工大学　新材料力学理论与应用湖北省重点实验室，武汉 430070
4.
先进能源科学与技术广东省实验室佛山分中心(佛山仙湖实验室)，佛山 528000
5.
武汉理工大学　先进材料制作装备与技术研究院，武汉 430070

基金项目: 国家自然科学基金(52273080)；先进能源科学与技术广东省实验室佛山分中心(佛山仙湖实验室)开放基金(XHT2020-002)；中央高校基本科研业务费专项资金(WUT2021IVA068；2020Ⅲ028GX；2021III015JC)

详细信息

通讯作者:
冀运东，博士，副教授，硕士生导师，研究方向为复合材料阻燃与残余强度　E-mail: jiyundong@whut.edu.cn

中图分类号: TB332
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出版历程
- 收稿日期: 2022-12-30
- 修回日期: 2023-02-24
- 录用日期: 2023-02-25
- 网络出版日期: 2023-03-01
- 刊出日期: 2023-12-01

Effect of polysiloxane modified epoxy on high temperature residual strength of glass fiber/phenolic composites

LI Chenyang^1
,,
LI Shuxin^{2, 3, 4, 5},
JI Yundong^{1, 2
, ,},
CAO Dongfeng^{2, 4, 5},
HU Haixiao^{3, 4, 5},
CHEN Zhen¹

1.
School of Materials Science and Engineering, Wuhan University of Technology, Wuhan 430070, China
2.
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China
3.
Hubei Key Laboratory of Theory and Application of Advanced Materials Mechanics, Wuhan University of Technology, Wuhan 430070, China
4.
Foshan Xianhu Laboratory of the Advanced Energy Science and Technology Guangdong Laboratory, Foshan 528000, China
5.
Institute of Advanced Materials and Manufacturing Technology, Wuhan University of Technology, Wuhan 430070, China

Funds: National Natural Science Foundation of China (52273080); Open Fund for Advanced Energy Science and Technology Guangdong Provincial Laboratory Foshan Branch (Foshan Xianhu Laboratory)(XHT2020-002); Special Funds for Basic Scientific Research Business Expenses of Central Universities (WUT2021IVA068; 2020Ⅲ028GX; 2021III015JC)

摘要

摘要: ASTM 3059-18标准将高温残余力学性能纳入树脂基复合材料阻燃指标，突破了复合材料传统化学阻燃概念，标志着结构阻燃概念得到了设计方的重视。本文将自制的聚硅氧烷改性环氧树脂(EP-Si)与酚醛树脂(PF)共混，并辅以无机粉料和玻璃纤维增强体，通过力学性能、热失重(TGA)、锥形量热(CCT)和扫描电镜(SEM)等测试方法，研究了EP-Si和无机粉料对玻璃纤维/酚醛复合材料高温残余强度的影响。实验结果表明：当EP-Si用量为40wt%，复合材料的常温及高温残余弯曲强度分别为384.4 MPa、53.3 MPa，相比PF复合材料提高了78.7%、85.1%；辅以适当比例无机粉料，高温残余弯曲强度最高可达85.1 MPa，相比PF复合材料提升了195.5%。高温处理后含硅PF复合材料厚度膨胀而PF复合材料厚度收缩；含硅PF复合材料的热解残留率更高，表层氧化降解更快，但内层生成CO含量低于PF复合材料；含硅树脂基体的无机热解产物保护了内层树脂和纤维，原位热解无机产物分布更均匀、与无机粉料相容性好及可能存在的共烧结作用进一步隔离了氧气侵入，提高了结构完整性和高温残余强度。
- 酚醛树脂 /
- 聚硅氧烷改性环氧树脂 /
- 高温残余强度 /
- 氧化降解 /
- 复合材料
Abstract: The ASTM 3059-18 standard incorporated high temperature residual mechanical properties into the flame retardant index of resin matrix composites, which broke through the traditional chemical flame retardant concept of composites, and marked that the concept of structural flame-retardant has been valued by the designer. In this work, the self-made polysiloxane modified epoxy resin (EP-Si) was blended with phenolic resin (PF), supplemented with inorganic powder and glass fiber reinforcement. The effects of polysiloxane modified epoxy resin and inorganic powder on the high temperature residual strength of glass fiber/phenolic composites were studied by means of mechanical properties, thermogravimetric analysis (TGA), cone calorimeter (CCT) and scanning electron microscope (SEM). The experimental results show that when the amount of EP-Si is 40wt%, the flexural strength and high temperature residual flexural strength of the composite is 384.4 MPa and 53.3 MPa, respectively, which is 78.7% and 85.1% higher than PF composite. With appropriate proportion of inorganic powder, the maximum residual flexural strength can reach 85.1 MPa, which is 195.5% higher than PF composite. After heat-treated, PF composite containing silicon expands along thickness, while PF composite shrinks along thickness. The pyrolysis residual rate of the PF composite containing silicon is higher and oxidative degradation of the surface layer is faster, but the content of CO generated in the inner layer is lower than that of PF composite. The inorganic pyrolysis product of resin matrix containing silicon protects inner layer resin and fibers. The distribution of the in-situ pyrolysis inorganic product is more uniform, the good compatibility with inorganic powder and possible co-sintering effect further isolates the oxygen intrusion, improves structural integrity and high temperature residual strength.
- phenolic resin /
- polysiloxane modified epoxy resin /
- high temperature residual strength /
- oxidative degradation /
- composite

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图 1 试样升温曲线

Figure 1. Heating curve of samples

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图 2 高温处理后环氧树脂(EP)、酚醛树脂(PF)、EP(40)/PF、聚硅氧烷改性环氧树脂(EP-Si)和EP-Si(40)/PF复合材料试样的宏观形貌

Figure 2. Macroscopic morphology of epoxy resin (EP), phenolic resin (PF), EP(40)/PF, self-made polysiloxane modified epoxy resin (EP-Si) and EP-Si(40)/PF composite samples after high temperature treatment

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图 3 EP、EP-Si、EP(40)/PF、PF和EP-Si(x)/PF复合材料试样常温及高温残余弯曲强度

Figure 3. Flexural strength and high temperature residual flexural strength of EP, EP-Si, EP(40)/PF, PF and EP-Si(x)/PF composite samples

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图 4 PF、EP(40)/PF和EP-Si(40)/PF树脂TGA (a) 和DTG (b) 曲线

Figure 4. TGA (a) and DTG (b) curves of PF, EP(40)/PF and EP-Si(40)/PF resin

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图 5 PF和EP-Si(40)/PF复合材料试样锥形量热仪总耗氧量 (a) 和氧含量 (b) 曲线

Figure 5. Cone calorimeter total oxygen consumed (a) and oxygen content (b) curves of PF and EP-Si(40)/PF composite samples

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图 6 PF和EP-Si(40)/PF复合材料试样锥形量热仪CO (a) 和CO₂(b) 含量曲线

Figure 6. Cone calorimeter CO (a) and CO₂ (b) content curves of PF and EP-Si(40)/PF composite samples

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图 7 EP-Si(40)/PF和PF试样热解层和热影响层两相结构模型

Figure 7. Two-phase structure model of pyrolysis layer and heat-affected layer of EP-Si(40)/PF and PF samples

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图 8 热处理后复合材料试样断面SEM图像

Figure 8. SEM images of composite sample section after heat treatment

Powder is composed of kaolin, flyash and silica; Mass ratio is 20:10:1

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表 1 EP(40)/PF和EP-Si(x)/PF的命名

Table 1. Naming of EP(40)/PF and EP-Si(x)/PF

Sample	Mass ratio of EP (Total mass of resin matrix is 100)	Mass ratio of EP-Si (Total mass of resin matrix is 100)
EP(40)/PF	40	—
EP-Si(10)/PF	—	10
EP-Si(20)/PF	—	20
EP-Si(30)/PF	—	30
EP-Si(40)/PF	—	40
EP-Si(50)/PF	—	50

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表 2 粉料成分及含量对复合材料弯曲强度的影响

Table 2. Effect of powder composition and content on flexural strength of composite

Kaolin/wt%	Flyash /wt%	Silica /wt%	EP-Si /wt%	PF /wt%	Resin residual rate/%	Residual flexural strength/MPa	Flexural strength /MPa
0	0	0	0	100	21.8	28.8	215.1
10	20	0	0	100	30.8	34.4	177.3
10	20	1	0	100	31.5	37.1	150.0
10	20	5	0	100	29.7	36.3	120.8
0	0	0	40	60	23.6	53.3	384.4
10	20	0	40	60	33.0	74.7	340.3
10	20	1	40	60	37.0	85.1	330.8
10	20	5	40	60	36.6	80.6	310.3

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表 3 PF、EP(40)/PF和EP-Si(40)/PF树脂热重分析数据

Table 3. Thermogravimetric analysis data of PF, EP(40)/PF and EP-Si(40)/PF resin

Atmosphere	Sample	T_−5%/℃	T_max1/℃	T_max2/℃	R₈₀₀/%
Air	PF	297.5	—	623.0	1.5
	EP(40)/PF	244.8	410.7	591.0	1.4
	EP-Si(40)/PF	277.5	412.5	633.5	8.2
Notes: T_−5%—Thermal degradation temperature at 5wt% mass loss; T_max1 and T_max2—Maximum thermal degradation temperature in the first and second stage; R₈₀₀—Pyrolysis residue rate at 800℃.

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表 4 EP-Si(40)/PF试样断面热解残留物表面元素原子分数

Table 4. Surface element atomic percentages of pyrolysis residue of EP-Si(40)/PF sample cross section

Sample	C/at%	O/at%	Si/at%
1	81.06	18.75	0.19
2	72.69	26.10	1.21
Notes: Sample 1—EP-Si(40)/PF composite at room temperature; Sample 2—EP-Si(40)/PF composite after heat treatment.

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