湿热老化对碳纤维增强复合材料力学和摩擦磨损性能的影响

田经纬; 齐肖; 郭瑞; 咸贵军

湿热老化对碳纤维增强复合材料力学和摩擦磨损性能的影响

田经纬^{1, 2},
齐肖³,
郭瑞^{1, 2},
咸贵军^{1, 2, ,}

1.
哈尔滨工业大学　结构工程灾变与控制教育部重点实验室, 哈尔滨 150090
2.
哈尔滨工业大学　土木工程学院, 哈尔滨 150090
3.
长三角碳纤维及复合材料技术创新中心, 常州 213126

基金项目: 国家重点研发计划(2022YFB3706501)

详细信息

通讯作者:
咸贵军，博士，教授，博士生导师，研究方向为土木工程纤维增强树脂复合材料与结构　E-mail: gjxian@hit.edu.cn

中图分类号: TB332
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- 被引次数: 0
出版历程
- 收稿日期: 2024-05-13
- 修回日期: 2024-06-11
- 录用日期: 2024-07-05
- 网络出版日期: 2024-07-19

Effect of hygrothermal aging on the mechanical and frictional wear properties of carbon fiber reinforced composites

TIAN Jingwei^{1, 2},
QI Xiao³,
GUO Rui^{1, 2},
XIAN Guijun^{1, 2
, ,}

1.
Key Lab of Structures Dynamic Behavior and Control, Harbin Institute of Technology, Ministry of Education, Harbin 150090, China
2.
School of Civil Engineering, Harbin Institute of Technology, Harbin 150090, China
3.
Yangtze River Delta Carbon Fiber and Composite Material Innovation Center, Changzhou 213126, China

Funds: National Key Research and Development Program of China (No. 2022YFB3706501)

摘要

摘要: 碳纤维增强复合材料(CFRP)具有轻质、高强、耐腐蚀、抗疲劳、耐磨损等优点，已经成为新型的先进海洋工程结构材料。本文研究了湿热老化对CFRP热/力学(拉伸、弯曲、短梁剪切性能)和摩擦磨损性能影响规律，结合微观形貌与结构分析，揭示CFRP在60 ℃蒸馏水浸泡长达90天力学和摩擦磨损性能退化机制。研究发现，湿热老化使得CFRP拉伸、弯曲和短梁剪切强度最大退化幅值为5.8%、13.0%和20.9%，归因于湿热老化过程水分子破坏了树脂高分子树脂链氢键和部分共价键，导致CFRP内部产生缺陷并丧失对纤维束横向约束，最终引起纤维/树脂界面脱粘。此外，湿热环境CFRP热力学和粘弹性行为呈现非线性变化规律，归因于积极的树脂后固化和消极的湿热老化耦合效应。与浸泡前相比，老化15、30、60和90天CFRP的平均摩擦系数依次降低了23.8%、35.0%、43.7%和53.8%，归因于扩散CFRP内部水分子摩擦过程中充当了摩擦润滑剂，缓解了CFRP/研磨球界面磨损程度；湿热老化90天CFRP的Ws和WSW较老化前增加了254.6%和114.9%，归因于与树脂基体形成新氢键的水分子处于结合水状态，导致树脂分子链间作用力减小及其内部微裂纹不断萌生，引发严重的疲劳磨损。
- 环氧树脂 /
- 碳纤维复合材料 /
- 湿热老化 /
- 力学性能 /
- 摩擦行为 /
- 磨损机制
Abstract: Carbon fiber reinforced composites (CFRP) have the advantages of light weight, high strength, corrosion resistance, fatigue resistance and wear resistance, and have become a new advanced structural materials for marine engineering. In this paper, the effects of hygrothermal aging on the thermal/mechanical (tensile, flexural and short-beam shear properties) and frictional wear properties of CFRP were investigated. Combined with the analysis of micro-morphology and structure, the degradation mechanisms of mechanical and frictional wear properties of CFRP immersed in the distilled water at 60℃ for up to 90 days were revealed. It was found that the maximum degradation amplitudes of CFRP tensile, flexural and short-beam shear strengths were 5.8%, 13.0%, and 20.9%, due to the destruction of hydrogen bonds and partial covalent bonds of polymer resin chains by water molecules during the hygrothermal aging process, which resulted in the defect creation and the lateral restraint loss of the fiber bundles within the CFRP, ultimately leading to the de-bonding of fiber/resin interfaces. In addition, the thermodynamic and viscoelastic behavior of CFRP in the hygrothermal environment exhibited a nonlinear change, attributing to the coupling effects of positive resin post-curing and negative hygrothermal aging. Compared with those before immersion, the average COFs of CFRP aged for 15, 30, 60, and 90 days decreased by 23.8%, 35.0%, 43.7% and 53.8%, respectively, which was attributed to the friction lubrication of water molecules inside the diffused CFRP acting as friction lubricants during friction, alleviating the wear of the CFRP/abrasive ball interface. The Ws and WSW of CFRP aged for 90 days increased by 254.6% and 114.9% compared with that before aging, which was attributed to the fact that the water molecules forming new hydrogen bonds with the resin matrix were in the bonded water state, reducing inter-chain force between resin molecules and the continuous growth of their internal micro-cracks, resulting in severe fatigue wear.
- Epoxy resin /
- Carbon fiber composites /
- Hygrothermal aging /
- Mechanical properties /
- Friction behavior /
- Wear mechanism

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图 1 环氧树脂基体及其对应的两种固化剂

Figure 1. Epoxy resin matrix and its corresponding two curing agents

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图 2 真空灌注成型工艺示意图

Figure 2. Vacuum perfusion molding process diagram

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图 3 湿热老化90天前后CFRP形貌分析：(a) 老化前表面形貌；(b) 老化后表面形貌；(c) 老化后拉伸断口；(d) 老化后弯曲断口；(e) 老化后低倍数下短梁剪切断口；(f) 老化后高倍数下短梁剪切断口

Figure 3. Morphology analysis of CFRP before and after 90 days of hygrothermal aging: (a) surface morphology before aging; (b) surface morphology after aging; (c) tensile fracture after aging; (d) bending fracture after aging; (e) short beam shear fracture at low magnification after aging; (f) short beam shear fracture at high magnification after aging

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图 4 环氧树脂基体与CFRP在60℃湿热老化工况下的傅里叶红外光谱

Figure 4. Fourier transform infrared spectroscopy of epoxy resin matrix and CFRP under hygrothermal aging condition at 60℃

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图 5 湿热老化对CFRP摩擦磨损性能的影响：(a) COFs；(b) Ws和WSW

Figure 5. Effect of hygrothermal aging on friction and wear properties of CFRP: (a) COFs; (b) Ws and WSW

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图 6 湿热老化对CFRP表面及其研磨球微观形貌影响：(a) 0天；(b) 15天；(c) 30天；(d) 60天；(e) 90天

Figure 6. Effect of hygrothermal aging on CFRP surface and grinding ball micro-morphologies: (a) 0 day; (b) 15 days; (c) 30 days; (d) 60 days; (e) 90 day

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图 7 湿热老化对CFRP磨损轨迹微观形貌影响：(a) 0天；(b) 15天；(c) 30天；(d) 60天；(e) 90天

Figure 7. Effect of hygrothermal aging on micro-morphologies of CFRP wear trajectory: (a) 0 day; (b) 15 days; (c) 30 days; (d) 60 days; (e) 90 days

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表 1 碳纤维增强复合材料(CFRP)及其环氧树脂基体力学性能

Table 1. Mechanical properties of carbon fiber reinforced composite (CFRP) and epoxy resin matrix

Formula		Strength/MPa	Modulus/GPa	Maximum strain/%
Tensile properties	Resin matrix	63.91(±1.87)	3.66(±0.11)	3.78(±0.11)
Tensile properties	CFRP	1330.45(±62.24)	103.32(±3.09)	1.29(±0.08)
Bending properties	Resin matrix	115.30(±3.79)	3.26(±0.22)	4.34(±0.12)
Bending properties	CFRP	1224.15(±51.74)	80.41(±1.70)	1.47(±0.03)
Shear properties of short beams	CFRP	80.41(±3.32)	/	/
Notes: The preparation and testing methods of the epoxy resin system can be found in Reference [22]。

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表 2 湿热老化对CFRP力学性能的影响

Table 2. Effect of hygrothermal aging on the CFRP mechanical properties

Formula	Immersion time	Tensile strength/MPa	Bending strength/MPa	Shear strength/MPa
CFRP	0 day	1330.45(±62.24)	1224.15(±51.74)	82.41(±3.32)
	15 days	1323.35(±52.48)	1188.65(±65.35)	76.63(±2.15)
	30 days	1307.83(±48.24)	1167.84(±57.48)	74.38(±1.56)
	45 days	1291.87(±53.27)	1129.89(±68.32)	71.32(±0.87)
	60 days	1301.18(±62.92)	1143.36(±42.54)	70.36(±4.42)
	75 days	1273.24(±29.67)	1101.74(±39.65)	66.90(±3.42)
	90 days	1252.63(±43.15)	1065.01(±52.25)	65.13(±3.90)
FC₅F(F：Flax；C₅：Carbon of 5 lays；))/CFRP-70℃ (Water solution)^[36]	/	FC₅F	CFRP	/
	0 day	626.32(±46.12)	634.56(±63.28)	/
	14 days	423.35(±35.45)	523.18(±48.17)
	28 days	384.26(±39.12)	489.32(±54.78)
	56 days	368.34(±58.85)	465.25(±89.12)
CFRP-70℃ Under 80% RH^[37]	0 day	/	785.34(±68.41)	/
	14 days		736.15(±75.24)
	28 days		683.15(±59.24)
	56 days		632.89(±65.24)

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表 3 60℃湿热老化工况下浸泡时间对CFRP热力学性能的影响

Table 3. Effect of immersion time on CFRP thermodynamic properties under hygrothermal aging condition at 60℃

Immersion time	T_g/℃	Storage modulus/MPa	Loss modulus/MPa	Loss factor
0 day	136.80 (±2.01)	38536	9071	0.2354
15 days	129.93 (±1.59)	35216	7906	0.2245
30 days	122.56 (±1.26)	32326	6582	0.2036
45 days	118.25 (±2.06)	30457	5991	0.1967
60 days	117.69 (±0.95)	28456	5620	0.1975
75 days	120.25 (±1.26)	29574	5445	0.1841
90 days	116.49 (±0.68)	25740	4438	0.1724
Notes: T_g stands for glass transition temperature.

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表 4 FTIR光谱中环氧树脂和CFRP特征吸收谱带所对应的化学基团

Table 4. The chemical groups corresponding to the characteristic absorption bands of epoxy resin and CFRP in FTIR spectra

Wavenumber/cm⁻¹	Corresponding chemical group	Reference number
3400	O—H stretching vibration	[35]
2930	C—H stretching vibration	[33]
1612	C=C stretching vibration (olefin)	[33]
1509	C=C (arene)	[35]
1244	C—O—Φ nonsymmetric stretching vibration	[33]
1041	C—O—Φ symmetrical stretching vibration	[39]
827	C—H (benzene)	[35]

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