Epoxies are often exposed to water due to rain and humid air environments. Epoxy yellows during its service time under these conditions, even when protected from UV radiation. The material’s color is not regained upon redrying, indicating irreversible aging mechanisms. Understanding what causes a discoloration is of importance for applications where the visual aspect of the material is significant. In this work, irreversible aging mechanisms and the cause of yellowing were identified. Experiments were performed using a combination of FT-NIR, ATR-FT-IR, EDX, HR-ICP-MS, pH measurements, optical microscopy, SEM, and DMTA. Such extensive material characterization and structured logic of investigation, provided the necessary evidence to investigate the long-term changes. No chain scission (hydrolysis or oxidation-induced) was present in the studied common DGEBA/HDDGE/IPDA/POPA epoxy, whilst it was found that thermo-oxidation and leaching occurred. Thermo-oxidation involved evolution of carbonyl groups in the polymeric carbon–carbon backbone, via nucleophilic radical attack and minor crosslinking of the HDDGE segments. Four probable reactive sites were identified, and respective reactions were proposed. Compounds involved in leaching were identified to be epichlorohydrin and inorganic impurities but were found to be unrelated to yellowing. Carbonyl formation in the epoxy backbone due to thermo-oxidation was the cause for the yellowing of the material.

Two different series of biobased polyethylene (BioPE) were used for the manufacturing of biocomposites, complemented with thermomechanical pulp (TMP) fibers. The intrinsic hydrophilic character of the TMP fibers was previously modified by grafting hydrophobic compounds (octyl gallate and lauryl gallate) by means of an enzymatic-assisted treatment. BioPE with low melt flow index (MFI) yielded filaments with low void fraction and relatively low thickness variation. The water absorption of the biocomposites was remarkably improved when the enzymatically-hydrophobized TMP fibers were used. Importantly, the 3D printing of BioPE was improved by adding 10% and 20% TMP fibers to the composition. Thus, 3D printable biocomposites with low water uptake can be manufactured by using fully biobased materials and environmentally-friendly processes.

Long-term creep properties and the effect of water are important for fiber reinforced polymer (FRP) composite materials used in offshore applications. Epoxies are often used as a matrix material in such composites. A typical design lifetime of offshore FRP structures is 25 or more years in direct contact with water leading to some deterioration of the material properties. Knowing and predicting the extent of the material property deterioration in water is of great interest for designers and users of the offshore FRP structures. It has been established that the time–temperature superposition principle (TTSP) is a useful tool for estimating changes in properties of polymer materials at long times or extreme temperatures. In this work, a time–temperature–plasticization superposition principle (TTPSP) is described and used for predicting the long-term creep behavior of an epoxy compound. The studied epoxy does not degrade chemically via hydrolysis or chain scission but is negatively affected by plasticization with water. The methodology enables prediction of the long-term viscoelastic behavior of amorphous polymers at temperatures below the glass transition (T_g) using short-term creep experimental data. The results also indicate that it is possible to estimate the creep behavior of the plasticized polymer based on the short-term creep data of the respective dry material and the difference between T_g values of dry polymer and plasticized polymer. The methodology is useful for accelerated testing and for predicting the time-dependent mechanical properties of a plasticized polymer below the glass transition temperature.

Monitoring water content and predicting the water-induced drop in strength of fiber-reinforced composites are of great importance for the oil and gas and marine industries. Fourier transform infrared (FTIR) spectroscopic methods are broadly available and often used for process and quality control in industrial applications. A benefit of using such spectroscopic methods over the conventional gravimetric analysis is the possibility to deduce the mass of an absolutely dry material and subsequently the true water content, which is an important indicator of water content-dependent properties. The objective of this study is to develop an efficient and detailed method for estimating the water content in epoxy resins and fiber-reinforced composites. In this study, Fourier transform near-infrared (FT-NIR) spectroscopy was applied to measure the water content of amine-epoxy neat resin. The method was developed and successfully extended to glass fiber-reinforced composite materials. Based on extensive measurements of neat resin and composite samples of varying water content and thickness, regression was performed, and the quantitative absorbance dependence on water content in the material was established. The mass of an absolutely dry resin was identified, and the true water content was obtained. The method was related to the Beer–Lambert law and explained in such terms. A detailed spectroscopic method for measuring water content in resins and fiber-reinforced composites was developed and described.

Glass fiber-reinforced composites are exposed to hydrolytic degradation in subsea and offshore applications. Fiber-matrix interphase degradation was observed after the matrix was fully saturated with water and typical water absorption tests according to ASTM D5229 were stopped. Due to water-induced dissolution, fiber-matrix interphase flaws were formed, which then lead to increased water uptake. Cutting sample plates from a larger laminate, where the fibers were running parallel to the 1.5 mm long short edge, allowed the hydrolytic degradation process to be studied. The analysis is based on a full mechanistic mass balance approach considering all the composite’s constituents: water uptake and leaching of the matrix, dissolution of the glass fibers, and dissolution of the composite interphase. These processes were modeled using a combination of Fickian diffusion and zero-order kinetics. For the composite laminate studied here with a saturated epoxy matrix, the fiber matrix interphase is predicted to be fully degraded after 22 to 30 years.

Swelling in fiber-reinforced composites is anisotropic. In this work, dealing with glass fiber epoxy composite immersed in distilled water, swelling coefficients are obtained in each direction experimentally. Swelling behaviour in the fiber direction was constrained by the non-swelling fibers and was close to null, while swelling in the transverse directions was found to occur freely—similar to the unconstrained polymer. An analytical method for predicting anisotropic swelling in composites from the swelling of the matrix polymer is reported in this work. The method has an advantage that it is simple to use in practice and requires only a swelling coefficient of the matrix polymer, elastic constants of the matrix and fibers, and a known fiber volume fraction of the composite. The method was validated using finite element analysis. Good agreement was obtained and is reported between experimental hygroscopic swelling data, analytical and numerical results for composite laminates, indicating the validity of this predictive approach.