纳米SiO<sub>2</sub>-硅烷协同改性对玄武岩纤维/环氧树脂复合材料力学性能及蠕变性能的影响

别依诺; 朱四荣; 贺攀; 陆士平

doi:10.13801/j.cnki.fhclxb.20210928.001

纳米SiO₂-硅烷协同改性对玄武岩纤维/环氧树脂复合材料力学性能及蠕变性能的影响

doi: 10.13801/j.cnki.fhclxb.20210928.001

1.
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
2.
四川航天拓鑫玄武岩实业有限公司，成都 610199
3.
上海富晨化工有限公司GB51160国家标准管理组，上海 200241

基金项目: 中央高校基本科研业务费专项资金(2018IB001)

详细信息

通讯作者:
朱四荣，博士，教授，博士生导师，研究方向为复合材料结构设计及复合材料长期力学性能研究　E-mail：zhusirong@whut.edu.cn

中图分类号: TB332
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出版历程
- 收稿日期: 2021-07-21
- 修回日期: 2021-08-28
- 录用日期: 2021-09-22
- 网络出版日期: 2021-09-28
- 刊出日期: 2022-08-31

Effect of nano-SiO₂ particles-silane synergistic modification on mechanical properties and creep properties of basalt fiber/epoxy composites

1.
Hubei Key Laboratory of Theory and Application of Advanced Materials Mechanics, Wuhan University of Technology, Wuhan 430070, China
2.
Sichuan Aerospace Tuoxin Basalt Industrial CO. LTD., Chengdu 610199, China
3.
GB51160 National Standards Management Group, Shanghai Fuchen Chemical CO. LTD., Shanghai 200241, China

摘要

摘要: 分别采用硅烷偶联剂和纳米SiO₂粒子-硅烷偶联剂对玄武岩纤维(BF)进行表面改性，通过缠绕成型工艺制备了玄武岩纤维/环氧树脂(BF/EP)复合材料。采用万能材料试验机测定了BF的拉伸性能和BF/EP复合材料的弯曲性能，借助FESEM观察了纤维表面及其复合材料弯曲断裂断口的形貌，自制三点弯曲蠕变测试装置测定了BF/EP复合材料2544 h的长期蠕变性能，采用万能材料试验机在不同应力水平下测定了BF/EP复合材料6000 s的短时蠕变性能，并分析了纤维表面改性对各项力学性能的影响。结果表明，在BF上浆剂中引入纳米SiO₂粒子后，纤维的拉伸性能、BF/EP复合材料的弯曲性能均得到有效改善。FESEM形貌显示BF的协同改性提高了纤维与树脂界面的粘结性能；2544 h的低应力长期蠕变实验及6000 s的不同应力水平短时蠕变实验中，均表现出蠕变柔量及其增长速率的显著降低；在20%、30%、40%及50%初始弯曲强度加载时的短时蠕变实验中，由蠕变曲线重合的应力值，可大致得到材料线性蠕变的应力阈值。使用Hooke-Kelvin-Kelvin (HKK)模型可有效描述BF/EP复合材料在低应力水平下的长期蠕变性能，由此可进行其蠕变性能指标的长期预测。
- 表面改性 /
- 纳米SiO₂ /
- 玄武岩纤维/环氧树脂复合材料 /
- 蠕变 /
- 应力水平
Abstract: Basalt fiber (BF) was modified by silane coupling agent and nano-SiO₂ particles-silane coupling agent, respectively. And the basalt fiber/epoxy (BF/EP) composites were prepared by winding process. The tensile properties of BF and the flexural properties of BF/EP composites were tested by universal material testing machine. The morphologies of BF surface and BF/EP composites flexural fracture were observed by FESEM. The long-term (2544 h) creep behaviors of BF/EP composites were tested by self-made three-point flexural creep test device. The short-term (6000 s) creep behaviors of BF/EP composites were tested by universal material testing machine at different stress levels. And the effect of fiber surface modification on the mechanical properties was analyzed. The results show that, with the introduction of nano-SiO₂ particles into BF sizing agent, the tensile properties of the fiber and the flexural properties of BF/EP are effectively improved. FESEM morphologies show that the synergistic modification of BF improves the bonding performance between the fiber and the resin. The creep compliance and its growth rate decrease significantly in the long-term creep tests with low stress for 2544 h and in the short-term creep tests with various stress levels for 6000 s. The stress threshold of linear creep of materials can be obtained from the coincidence curves of short-term creep tests at 20%, 30%, 40% and 50% stress levels. The Hooke-Kelvin-Kelvin (HKK) model can effectively describe the long-term creep performance of BF/EP composites at low stress level, so as to carry out the long-term prediction of its creep performance.
- surface modification /
- nano-SiO₂ particles /
- basalt fiber/epoxy composites /
- creep /
- stress levels

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图 1 BF表面形貌

Figure 1. Surface morphologies of BF

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图 2 玄武岩纤维/环氧树脂 (BF/EP) 复合材料弯曲断口形貌

Figure 2. Flexural fracture morphologies of basalt fiber/epoxy (BF/EP) composites

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图 3 BF/EP复合材料弯曲应力-弯曲应变曲线

Figure 3. Flexural stress-flexural strain curves of BF/EP composites

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图 4 BF/EP复合材料蠕变柔量随时间的变化曲线

Figure 4. Curves of creep compliance of BF/EP composites vs. time

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图 5 不同应力水平下BF/EP复合材料蠕变柔量随时间的变化曲线

Figure 5. Curves of creep compliance of BF/EP composites at different stress levels vs. time

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图 6 各应力水平下BF/EP复合材料蠕变柔量增量随时间的变化曲线

Figure 6. Curves of creep compliance increment of BF/EP composites at different stress levels vs. time

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图 7 Hooke-Kelvin-Kelvin(HKK)蠕变模型

Figure 7. Hooke-Kelvin-Kelvin (HKK) creep model

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图 8 HKK模型拟合BF/EP复合材料蠕变柔量随时间的变化曲线

Figure 8. Curves of creep compliance of BF/EP composites vs. time fitted by HKK model

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表 1 纳米SiO₂-硅烷偶联剂KH-560协同改性玄武岩纤维(BF)正交试验因素水平表

Table 1. Orthogonal test factor and level table of basalt fiber (BF) modified by nano-SiO₂-silane coupling agent KH-560

Level	Factor
Level	Nano-SiO₂ dispersion (A)	Lubricant (B)	KH-560 (C)
1	0	0	0
2	1.5	0.4	0.5
3	5	1	1

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表 2 BF丝束强度正交试验分析

Table 2. Orthogonal test analysis of BF bundle strength

Test	Column
Test	1A	2B	3C	P/(N·(10⁻⁶kg·m⁻¹)⁻¹)
1	1	1	1	0.49
2	1	2	2	0.59
3	1	3	3	0.60
4	2	1	2	0.63
5	2	2	3	0.64
6	2	3	1	0.61
7	3	1	3	0.57
8	3	2	1	0.59
9	3	3	2	0.62
k₁	0.560	0.563	0.563
k₂	0.627	0.607	0.613
k₃	0.593	0.610	0.603
Range	0.067	0.047	0.050
Optimum schem	A2	B3	C2
Notes: P−Tensile strength of BF bundle; k_i−Average of level i.

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表 3 BF及其浸胶纱的拉伸性能

Table 3. Tensile properties of BF and its resin-impregnated yarn

Sample	P/(N·(10⁻⁶kg·m⁻¹)⁻¹)	σ_t/MPa	E_t/GPa
KH-560-BF	0.57	2722.8	89.1
SiO₂-KH-560-BF	0.66	2859.6	91.7
Notes: KH-560-BF—BF modified by KH-560; SiO₂-KH-560-BF—BF modified by nano-SiO₂ particles-KH-560; σ_t—Tensile strength of BF resin-impregnated yarn; E_t—Tensile modulus of BF resin-impregnated yarn.

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表 4 BF/EP复合材料弯曲性能

Table 4. Flexural properties of BF/EP composites

Sample	σ_f/MPa	E_f/GPa
KH-560-BF/EP	837.5	26.6
SiO₂-KH-560-BE/EP	1165.5	34.2
Notes: KH-560-BF/EP—BF/EP made of BF modified by KH-560; SiO₂-KH-560-BF/EP—BF/EP made of BF modified by nano-SiO₂ particles; σ_f-Flexural strength; E_f-Flexural modulus.

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表 5 HKK模型拟合参数

Table 5. Fitting parameters of HKK model

Sample	E₀/GPa	E₁/GPa	E₂/GPa	η₁/(GPa·h)	η₂/(GPa·h)	R²
KH-560-BF/EP	30.18	350.82	1381.22	200466.79	4417.78	0.99
SiO₂-KH-560-BF/EP	43.11	881.41	2155.41	404318.58	5889.18	0.99
Notes: E_i—Elastic modulus of each spring model (i=0, 1, 2); η_i—Viscosity coefficient of each Kelvin model (i=1, 2); R²—Goodness of fit.

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表 6 BF/EP复合材料蠕变柔量计算值与实验值对比 (2544 h)

Table 6. Comparison of calculated and experimental values of creep compliance of BF/EP composites (2544 h)

Sample	C_t/(10⁻¹¹Pa⁻¹)	C_c/(10⁻¹¹Pa⁻¹)	Deviations/%
KH-560-BF/EP	3.73	3.67	−1.70
SiO₂-KH-560-BF/EP	2.51	2.48	−1.19
Notes: C_t—Experimental value of creep compliance; C_c—Calculated value of creep compliance.

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