Performance optimization and deterioration mechanism of fiber reinforced epoxy/vinyl resin composite materials: A review
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摘要: 纤维增强聚合物(FRP)复合材料具有轻质高强、耐腐蚀、经济效益高的优势，在基础建设施设中表现出巨大潜力，但在复杂环境下长期服役后，FRP复合材料的力学性能下降超过50%，限制了其在工程中的应用。基于此，针对FRP复合材料各组分优化设计方法进行了总结，并分析了热氧、紫外线、腐蚀介质环境中FRP复合材料的长期性能演化规律；根据化学结构及微观形貌分析，阐述了FRP复合材料在复杂环境中的劣化机制，进一步归纳了其在复杂环境下的长期性能预测模型，可为保证FRP复合材料在复杂环境中的长期使用性能提供理论依据，促进其在实际工程中的应用。Abstract: Fiber reinforced polymer (FRP) composite has great potential in infrastructure construction due to the advantages of light weight and high strength, corrosion resistance and high economic benefit. However, the performance of FRP composite will decrease by more than 50% after long-term service in complex environment, which limits its application in engineering. In the paper, the enhancement methods of different FRP composites components are reviewed. The evolution law of FRP composites on long-term properties under thermal oxygen, ultraviolet and corrosive media environment are revealed, and the deterioration mechanism of FRP composites in complex environment is elucidated by the analysis of chemical structure and microstructure. In addition, the long-term performance prediction model of FRP composites under complex environments is summarized, which can provide theoretical basis for ensuring the long-term performance of FRP composites in complex environment and promote its application in practical engineering.
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图 1 纤维优化机制：(a) 化学刻蚀；(b) 偶联剂改性；(c) 偶联剂改性刻蚀纤维机制
Figure 1. Enhancements of fibers: (a) Chemical etching; (b) Modification of coupling agent; (c) Mechanism of etched fiber modified with coupling agent
图 3 树脂分子结构及相应性能：(a) 环氧树脂分子结构；(b) 乙烯基树脂分子结构
Figure 3. Corresponding performance of resin with molecular structure: (a) Molecular structure of epoxy resin; (b) Molecular structure of vinyl resin
图 4 改性纳米材料增强树脂机制： (a) 纳米材料表面改性；(b) 纳米材料改性树脂基体
Figure 4. Enhancement mechanism of resin improved by modified nanomaterials: (a) Modification on surface of nanomaterials; (b) Resin matrix modified with nanomaterials
图 9 碱溶液中FRP复合材料劣化机制：(a) 硅氧键反应过程；(b) 树脂降解机制
Figure 9. Deterioration mechanism of FRP composites in alkali solution: (a) Reaction of silicon-oxygen bond; (b) Degradation mechanism of resin
表 1 FRP复合材料力学性能特征预测模型
Table 1. Features of mechanical properties prediction models of FRP composites
Number Document Predicting value Prediction model Annotation 1 [63] Porosity of composites, $ {{P}}_{\text{s}} $ $ \alpha=\dfrac{29.92}{t+13}+\dfrac{0.75}{t+0.48}P_{\mathrm{s}}+0.12P_{\mathrm{s}}^2 $ $ \alpha $ is the ultrasonic attenuation coefficient; $ {t} $ is the thickness of the FRP composite. 2 [64] Strength of the composite at porosity $v $, $ {\sigma }_{{\mathrm{pre}}\left(v\right)} $ $ \sigma_{\rm{pre}} (v)=\sigma_{0(0)} \mathrm{e}^{-a_2 v}$ $ {\sigma }_{\text{0(0)}} $ is the strength of the composites when the porosity is 0; v is the porosity; b, a1, a2 are the coefficients, respectively. 3 [65] $ \sigma_{\text {pre }(v)}=\sigma_{0(0)}-\dfrac{1}{1-a_1+a_1 \mathrm{e}^{b v}} $ 4 [66] Tensile strength of the composite, $ {\sigma }_{\text{cu}} $ $ \sigma_{{\mathrm{c u}}}=C_{{\mathrm{o s}}} \eta_{{\mathrm{1 s}}} \varPhi_{\mathrm{f}} \sigma_{{\mathrm{fu}}}+\sigma_{{{\mathrm{mu}}}}\left(1-\varPhi_{\mathrm{f}}\right) $ $ {{C}}_{\text{os}} $ is the fiber orientation coefficient; $ {\eta }_{\text{1}\text{s}} $ is the fiber length effective factor; $ {\sigma}_{\text{mu}} $ is the tensile strength of resin matrix; $ {\varPhi}_{\text{f}} $ is the fiber volume fraction; σfu is the tensile strength of fibers. 5 [68] Elasticity modulus of FRP composites, $ {{E}}_{\text{a}} $ $ \dfrac{E_{\rm {a}}}{E_{\rm {m}}}=\dfrac{1+V_{\rm{f}}}{1-1.25 V_{\rm{f}}+4.3\left(E_{\rm{m}}/ E_{\rm{f}}\right) V_{\rm{f}}} $
$ \sigma_{\mathrm{c}}=\left(1-d_{\mathrm{c}}\right) E_{\mathrm{a}} \varepsilon_0$$ {{E}}_{\text{m}} $ is the elasticity modulus of resin matrix; $ {{E}}_{\text{f}} $ is the elasticity modulus of fibers; $ {{V}}_{\text{f}} $ is the volume fraction of fibers; $ \sigma_{\mathrm{c}} $ is the strength of composites; $ {d}_{{\mathrm{c}}} $ is the damage factor; $ {\varepsilon }_{0} $ is the strain of composites. 
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表 2 FRP复合材料长期性能预测模型
Table 2. Features of long-term performance prediction models of FRP composites
Number Document Predicting value Prediction model Annotation 1 [72] Tensile strength retention rate, $ \mathit{{Y}} $ $ Y =100\left(1-\dfrac{\sqrt{2 D_0 C_t}}{r_0}\right)^2 $
$ \dfrac{M_t}{M_{\infty}} =1-\exp \left[7.3\left(\dfrac{D_0 t}{h^2}\right)^{0.75}\right]$$ {D}_{0} $ is the diffusion coefficient; $ {{C}}_{{t}} $ is the ion concentration of solution; $ {{r}}_{\text{0}} $ is the radius of the composites; $ {{M}}_{{t}} $ is the hygroscopicity of the FRP composites at time t; $ {{M}}_{\text{∞}} $is the saturated hygroscopicity; $ {h} $ is the thickness of material. 2 [74] Alculated diffusion coefficients after long-term aging, $ {D}_{{\mathrm{{\mathrm{c}}}}} $ $ {D}_{{\mathrm{c}}}={D}_{0}{{\mathrm{e}}}^{-\dfrac{{E}_{{\mathrm{a}}}}{RT}} $ $ {{E}}_{\text{a}} $ is the activation energy; $ {R} $ is the universal gas constant; $ {T} $ is the absolute temperature. 3 [75] Deterioration rate, K $K = A{\rm{exp}}\left( {\dfrac{{ - {E_{\rm{a}}}}}{{RT}}} \right) $ A is a constant. 4 [76] Temperature time-shift factor, $ \mathrm{TSF} $ $ \mathrm{TSF}=\exp\left[\dfrac{E_{\mathrm{a}}}{R}\left(\dfrac{1}{T_0}-\dfrac{1}{T_1}\right)\right] $ $ {{T}}_{\text{0}} $, $ {{T}}_{\text{1}} $ are the ambient temperature, respectively. 5 [77] Temperature-corrected time-shift factor, η $\eta=\dfrac{12}{\sum_1^{12} \exp \left[{E_{\mathrm{a}}}/{{R}}\left({1}/{T_{{\mathrm{A T}}}}-{1}/{T_{{\mathrm{M T}}}}\right)\right]}$ $ {{T}}_{\text{AT}} $ is the average annual temperature; $ {{T}}_{\text{MT}} $ is the average monthly temperature. 6 [76] Design value of tensile strength, $ {f}_{{\rm{ftd}}} $ $ {\mathrm{E R F}}=1-\beta\left[\varDelta_1-\rho \lg \left(\dfrac{{\mathrm{D L}}}{\alpha \cdot {\mathrm{T S F}} \cdot \eta}\right)\right]$
$ {{f}}_{\text{ftd}}\text{=}{{f}}_{\text{ftd}}\text{}{{\mathrm{ERF}}} $$ {{\mathrm{ERF}}} $ is the environmental factor; $ \beta $ is the correction factor of FRP composites; $ \alpha $is the correction factor of normal FRP composite; $ \varDelta _{\text{1}} $the strength decay rate of composites after one year exposure; $ \rho $is the slope of the linear regression of Arrhenius' formula; DL is design life in years. 7 [78] Strength retention rate, Yt ${Y_t} = (100 - {Y_\infty }){\rm{exp}}\left( {\dfrac{{ - t}}{\tau }} \right) + Y $ t is the exposure time; $ \tau $ is the fitting parameter; Y∞ is the strength retention of the composite when the exposure time is infinity.
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