1. Introduction
It is a common engineering problem that chloride ions in marine environments penetrate through the concrete protective layer to rust rebars, which greatly jeopardizes their structural safety and durability. Coating rebars with protective shells (e.g., epoxy and galvanizing) is a common method to improve their ability to resist corrosion; However, the drawbacks, such as complex production process, poor anti-corrosion effect, and high costs, limits its application, especially in marine environment [
1,
2]. As one of the effective substitutes for rebars in marine engineering, GFRP bars are composed of continuous glass fiber and resin, featuring great corrosion resistance, high tensile strength, and light weight. Currently, GFRP bars have been widely used in coastal wave walls, barrier board, and marine loading platforms [
3]. Despite the advantage of corrosion resistance, GFRP bars cause microstructure damage and macro-mechanical property decline when used in a high alkali solution of concrete and seawater environment for a long time [
4,
5], which can be chiefly attributed to the damage of service environment to glass fiber, resin, and their interface phase [
6,
7]. Scholars usually place GFRP bars in different environments for accelerated aging test to explore the degradation law of long-term mechanical properties of GFRP bars. Alkali solution, saline solution, and neutral solution are commonly used to simulate the internal alkali environment of the concrete, the seawater environment, and the freshwater environment, respectively. The durability deterioration of GFRP bars in freeze-thaw and dry-wet cycling conditions was also investigated to estimate the environmental influences on GFRP reinforced concrete members. Manalo et al. [
8] pointed out that, under the same temperature conditions, the degradation speed of the ILSS of GFRP bars was alkaline solution, tap water, and saline solution, in order from fast to slow. The strength retention rate of GFRP bars in real concrete environments were higher than that in simulated concrete pore solution environment. Benmokrane [
9] put the GFRP bars based on polyester, vinyl-ester and epoxy resin in the alkali environment at 60 °C and tested them after accelerated aging for 5000 h, indicating that the physical and mechanical properties of GFRP bars of vinyl-ester and epoxy resin decreased less after accelerated aging, compared to GFRP bars of polyester resin. This phenomenon has been explained by Chen [
10], that when free OH
− and water molecules diffuse in GFRP bars, they will produce a chemical reaction with esters groups in resin matrix, resulting in degradation of GFRP bars. Among the three categories of resins commonly used in engineering, polyester resin with maximum ester groups embodies the most significant degradation effect. Koller et al. [
11] investigated the freeze-thaw resistance of GFRP bars ranging from −29 °C to 20 °C and indicated that freeze-thaw reduced the ultimate tensile strength of GFRP bars by no more than 10%.
In recent years, researchers have studied the durability of GFRP bars in the marine environment. Robert et al. [
12] simulated seawater by using salt solution with a concentration of 3%, and placed GFRP bars wrapped by concrete in the simulated seawater and tap water environment, respectively. It was found that the resin matrix of GFRP bars had a great impact on their durability. In view of offshore engineering exposed to the alternating action of seawater wet-dry environment, Al-Salloum et al. [
6] tested GFRP bars in 50 °C seawater with dry-wet cycle. They reported that after aging for 18 months, the tensile strength of GFRP bars lost 9.8%. Morales et al. [
13] used seawater instead of fresh water to produce concrete; that is, seawater concrete. They used seawater concrete to wrap the GFRP bars, and accelerated aging in seawater at 60 °C, based on an exponential degradation model. The retention rate of the tensile strength of GFRP bars was 72%. Khatibmasjedi et al. [
14] embedded GFRP bars in seawater concrete and immersed them in seawater at 60 °C. After 24 months of aging, the tensile strength decreased by 21–26%.
In addition to the above-mentioned macro-mechanical properties of GFRP bars, researchers have utilized SEM, FTIR, and DSC to observe the effects on the microstructure damage [
8,
14], chemical composition change [
15], and T
g of GFRP bars [
16] caused by aging environments. The separation of fiber and resin of GFRP bars in seawater-contaminated concrete was reported by El-Hassan et al. [
7], especially at high temperature. Fergani et al. [
15] indicated that OH/CH was an effective index to reflect the degree of degradation of GFRP bars. Montaigu et al. [
16] analyzed T
g changes of GFRP in alkali environments at 60 °C by DSC test technology, indicating that after 183-day aging, the T
g of unsaturated resin-based GFRP decreased by approximately 6%.
Based on the decline of macro-mechanical properties and micro tests, researchers put forward durability models suitable for different environments based on Arrhenius equation. In the prediction model proposed by Bank et al. [
17], the linear relationship between the strength retention of fiber-reinforced-polymer (FRP) bars after aging and the logarithm of aging time appears in this model. Then, this model was applied by many researchers to predict the durability of FRP bars [
18,
19]. Some researchers used an exponential relationship to describe the relationship between the strength retention of FRP bars and aging time [
20,
21], and it is assumed that the degradation of mechanical properties of FRP bars caused the separation of the fiber and resin interface.
The purpose of this study was to attempt to analyze the durability of GFRP bars cured in natural seawater, artificial saline-alkali solution, and concrete environments. The effects of temperature (25, 40, and 60 °C) and aging time (15, 30, 60, 90, and 183 days) were investigated. Additionally, the study aimed to analyze the degradation law of mechanical properties of GFRP bars under different test conditions by ILSS, and to explain the degradation mechanism of GFRP bars by SEM, DSC, and FTIR. Ultimately, a prediction model of long-term mechanical properties of GFRP bars in seawater environment was proposed.
5. Long-Term Prediction Model of GFRP Bars
The conventional prediction models for long-term mechanical properties of GFRP bars are mostly based on Arrhenius equation [
21,
22]. According to Arrhenius’s theory, the relationships between strength, degradation rate, and temperature of GFRP bars is as follows [
26]:
where,
is degradation rate (1/time),
is degradation time, A is degradation constant,
is activation energy of materials,
is universal gas constant, and T is the temperature in Kelvin (K).
The conversion of Equation (4) are as follows:
The following three models are most used for predicting the long-term properties of GFRP bars:
where Y is strength retention; t is time; a, b and
are fitting parameters; and
is strength retention of FRP bars at infinite aging time.
It was noted that Model 1 proposed by Litherland et al. [
27] was used for predicting the durability of glass fiber concrete (GRC). Bank et al. [
17] employed Model 1 to analyze the long-term mechanical properties of FRP composites. Manalo et al. [
8] use this model to predict the relationship between the ILSS retention and aged time of GFRP bars in different environments. However, Model 1 also had the following limitations: (1) The model is fitted based on the experimental data without considering the degradation mechanism of materials; (2) The strength of FRP bars without aging is considered to be infinite in model 1, which is inconsistent with the fact; (3) The Arrhenius equation assumes that the degradation mechanism of materials does not change with temperature variation. However, the Arrhenius line obtained in many scholars’ studies [
18,
28] was not parallel, which violates the hypothesis. It was assumed in Model 2 and Model 3 that the main fracture mode of FRP bars proves to be the separation of fiber and resin interface, which is consistent with microscopic observation results [
14,
29]. Difference between the two models was whether the strength retention of materials becomes zero at infinite time. In other words, the strength retention of materials was considered to be zero in Model 2, while Model 3 assumes that the materials still retain some strength (
) at infinite time. It was proven that the
can exert a significant impact on accuracy of the model, and the values of
obtained by different researchers vary greatly [
24,
30]. Based on this, Model 2 was used in this study to establish the durability prediction model of GFRP bars in three environments.
In this paper, the long-term mechanical properties prediction model of GFRP bars in three accelerated aging environments (i.e., SA, SW, and SWC) was established in the following steps:
(1) The test data were fitted with Equation (8) to obtain fitting parameter (i.e.,
) and the fitting curve is shown in
Figure 9. Then,
and correlation coefficients obtained were listed in
Table 3.
(2) Substitute
into the Equation (8), making the strength retention 60%, 70%, 80%, and 90%, respectively. Then, the Arrhenius straight-line was fitted, as is shown in
Figure 10, and the straight-line slope and correlation coefficient were listed in
Table 4.
It was seen that the correlation coefficients (R2) of the regression equation in Equation (6) were not less than 0.95, showing an accurate fitting; The obtained from high to low was from SW, SWC, and SA environments, which indicated that the strength degradation of GFRP bars in SW environment required more activation energy, which is consistent with the test results.
(3) The Arrhenius equation was used to obtain the time-shift factor (TSF) under different aging conditions.
TSF was introduced to compare the time that GFRP bars can reach the same degradation rate at different temperatures. If the strength degradation rates of GFRP bars maintain k in the aging environment at temperature T
1 and T
2, the required time relationship was analyzed as follows, according to Equation (4):
By using Equation (12) and taking the average temperature of 12.3 °C offshore in the Yellow Sea area of China as an example, the TSF at different temperatures under three environments are listed in
Table 5.
By using the data and test results in
Table 5, the master curve of the long-term mechanical model of GFRP bars in offshore area of Yellow Sea of China (annual average temperature is 12.3 °C) was established, as shown in
Figure 11, and the parameters of regression equation are listed in
Table 6.
It was seen that the master curves matched well with the measured ILSS retention with correlation coefficients larger than 0.9 and can be used to predict the strength retention of GFRP bars serving in three environments (i.e., SA, SW, and SWC) tested in this study.
6. Conclusions
This paper explored the mechanical degradation law and mechanism of GFRP bars in different aging environments. The research results are as follows:
1. Under the same conditions, the strength degradation rate of GFRP bars was the fastest in SA environment, followed by SWC and then SW. It was seen that strong alkali environments (i.e., SA and SWC environments) caused serious damage to GFRP bars. The main reason is that the OH− radical reacts with SiO2 to degrade the glass fiber. The concrete in SWC environment had a certain protective effect, leading to less damage.
2. Under the three environments, the degradation rate of ILSS of GFRP bars mounts with the increase of temperature. The main reason for this phenomenon was that temperature increase could accelerate the hydrolysis reaction rate of GFRP bars. In the early stage of aging, water molecules quickly diffused to the GFRP bars, weakening the interfacial bonding ability of the resin and fiber, resulting in a significant decrease in ILSS. In the later stage of aging, as the GFRP bars become saturated, the rate of decrease in material strength slows down. Therefore, the strength degradation rate in the early stage was faster than that in the later stage.
3. The microstructures of the samples after accelerated aging for 183 days in three environments were observed. It was observed from the cross-sectional view that the sample fiber and resin were separated in varying degrees after aging in SA and SWC environments. This phenomenon was caused by different expansion degrees of resin matrix after water absorption, and the seepage pressure will also destroy the interface phase. Moreover, the resin produced a few holes, demonstrating that the resin eroded in the aging environment, but the overall properties were not affected much. It was seen in the longitudinal section micrograph that the fiber surface of samples was significantly damaged after aging in SA and SWC environments, and that samples in SW environment bear a little light aging damage.
4. DSC was applied to test Tg of GFRP bars aged in three environments at 60 °C for 183 days. Compared with Tg of ordinary samples, Tg of GFRP bars decreased by 1.7%, 7.8%, and 7.0%, respectively, in three environments. Thus, it indicated that the resin caused an irreversible reaction, which was consistent with the observation results of SEM. FTIR was used to test the infrared spectra of GFRP bars that were unconditioned and aged at 60 °C in three environments for 183 days. It was seen that the hydrolysis degree of GFRP bars was the most conspicuous in SA environment, followed by SWC, with the weakest in SW environment, which is consistent with the degradation law of mechanical properties, observation results of SEM, and analysis results of Tg changes.
5. The master curve of long-term mechanical model of GFRP bars in the Yellow Sea area of China was established, which can predict the strength retention of GFRP bars serving in three environments.