Hydrothermal aging of an epoxy-anhydride network has been studied by means of gravimetric analysis, Fourier transform infrared spectroscopy (FTIR) and modulated differential scanning calorimetry (MDSC). The long-term aging results revealed a fourth stage mechanism in which an initial short diffusional period is followed by the hydrolysis of the ester groups. Degraded materials showed two values of glass transition temperature suggesting a heterogeneous process. Hydrolysis undergoes in preferential sites due to the catalytic effect of the carboxyl acids formed during the chemical degradation. Domains with low crosslinking density and high mobility are formed. At long degradation time, samples presented a unique glass transition temperature around 50°C. The lixiviation of low molecular weight species formed by the hydrolytic scissions was confirmed by FTIR and pH variations.

Halloysite nanotubes (HNTs) have attracted a technologic and scientific attention as reinforcements of epoxy-based nanocomposites. However, their reported interaction with epoxy matrices is varied and the controlled dispersion of HNTs is still a challenge. In this work, we study the effect of chemical reactions taking place in the dispersion process of halloysite and their possible influence in the composite's properties. HNTs' surface was modified through an alkaline treatment and by grafting two aminosilanes with different chain lengths and functionality numbers. Evidence of homopolymerization and degradation reactions was found, depending on the surface treatment. The rheological study indicated that an interconnected network can be achieved in epoxy/HNTs blends depending on the surface chemical characteristics of the nanofillers and the blending method. The better dispersion was accomplished when ultrasonicating with the aid of a solvent. Nevertheless, the mechanical properties of the nanocomposites are not warranted by selecting a dispersion method.During the last decade, scientists and engineers have discovered and developed a large range of exciting new applications for these unique, cheap, and abundantly available naturally occurring clays. 17,18 Regarding the production of reinforced polymers, one key factor needed to obtain a composite material that successfully fulfill the required service life performance, is to control nanofiller dispersion and nanofiller/matrix interaction. Due to their lower number of surface hydroxyl groups, it is expected that HNTs will disperse better than other silicates such as montmorillonite and kaolinite. It is reported that HNTs can be dispersed quite uniformly by a direct melt-blending Additional Supporting Information may be found in the online version of this article.

Epoxy–anhydride‐based polymers are commonly used as a matrix in pipeline systems exposed to water during their in‐service life. Water absorption at moderate temperatures and/or at long exposure times could lead to irreversible hydrolysis reaction decreasing considerably the polymer overall performance. A strategy to enhance the barrier properties of epoxy resins is to add nanofillers to traditional matrices. In this work, we added bentonite and chemically modified bentonite to this purpose. Water absorption of the resulting materials at three different temperatures (22°C, 80°C, and 93°C) was studied, and simultaneously, the evolution during the immersion tests of glass transition temperature and flexural modulus was recorded. Long‐term gravimetric results showed that composites with chemically modified bentonite produce a delay on the hydrolysis of epoxy–anhydride matrix, which is a relevant result, because of the tough application and uses of the system, from the technological point of view. Copyright © 2016 John Wiley & Sons, Ltd.