Hydrolytic aging of polycarbonate. I. Physical aspects

The hydrolytic aging of an unstabilized industrial sample of polycarbonate was studied at 40, 70, 80, and 90°C, 100% RH. The water absorption characteristics show that, at equilibrium, the polymer absorbs about 0.04 mol water per ester group and that the equilibrium is reached after about 10–40 h exposure, i.e., far before irreversible changes of physical properties are observed. Differential scanning calorimetry reveals the combined effects of hydrolytic chain scission and physical aging on glass transition temperature. Investigations on tensile yield properties showed that hydrolytic chain scission leads to a significant decrease of the apparent Eyring's activation volume. These observations strongly support the hypothesis that there are preexisting or hydrolysis-induced defects responsible for an heterogeneous distribution of chain scissions that would be concentrated into localized microdomains. © 1995 John Wiley & Sons, Inc.     

Humid aging of polyetherimide. I. Water sorption characteristics

The sorption and desorption kinetics of water into polyetherimide (ULTEM 1000) were studied at various temperatures ranging from 20 to 100°C. The water equilibrium concentration increases slightly with temperature from 1.39% (by weight) at 20°C to 1.50% at 100°C. The solubility coefficient, S, calculated from these data, and the water vapor pressure decrease with temperature. The calculated heat of dissolution H_s is close to −43 kJ mol⁻¹, which explains the low effect of temperature on the equilibrium concentration. The diffusion coefficient, D, varies from about 1.10⁻¹² m² · s⁻¹ at 20°C to about 16.10⁻¹² m² · s⁻¹ at 100°C. The apparent activation energy of diffusion, E_D, and the heat of dissolution, H_s, of water in the polymer have opposite values (respectively, +43 and −42 kJ · mol⁻¹). From this observation and a comparison of these data with water diffusion characteristics in other glassy polar polymers, it is hypothesized that the transport rate of water is kinetically controlled by the dissociation of water–polymer complexes. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1439–1444, 2000     

Water sorption characteristics in moderately hydrophilic polymers,Part 1: Effect of polar groups concentration and temperature in water sorption in aromatic polysulfones

The water equilibrium concentration has been determined for three aromatic polysulfones differentiated essentially by the sulfone concentration, in the 0–0.9 activity range, at temperatures of 50, 60, and 70°C, using a dynamic vapor sorption apparatus. In all the cases, Henry's law was obeyed. The corresponding solubility S and heat of dissolution H_s were determined and their relationships with structure were investigated. The fact that S increases nonlinearly with the sulfone concentration and that H_s is also an increasing function of the latter leads one to abandon classical approaches to polymer–water interactions and propose a model in which water is doubly bonded. Then, S depends on the distribution of distances between polar groups, characterized by a function P(r) and H_s depends on both P(r) and the hydrogen bond potential U(r). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Hydrolytic aging of polysiloxane networks modeling the glass fiber epoxy-amine interphase

It has previously been shown that polycondensates of trialkoxysilanes (AlkO)₃SiR could chemically simulate coupling agent layers located at the interphase of amine-crosslinked epoxy/glass fiber composites (1) and that a humid environment modifies the degree of condensation of the network. Although it is generally believed that water will inevitably hydrolyze the polysiloxane structure and destroy the interphase (2), the authors have demonstrated that the siloxane links of the network evolve toward an equilibrium state. This state depends on the chemical structure of the organic chain that can react with the matrix. For example, in the case of aminopropyltriethoxysilane, the siloxane equilibrium concentration is low enough to allow total hydrolysis of the polymer. Conversely, propylsilane network stability could be explained by a very high siloxane equilibrium concentration. In this article, one of the previously studied systems has been selected: GPS (glycidylpropylsilane), in which the coupling function is an epoxide group (glycidyl). In an epoxy/glass fiber composite, this group is expected to react with an amine group belonging to the epoxy network. Aniline has been used here to model the GPS-epoxy network bonding. This reaction modifies the chemical nature of the organic chain branched on the silicon and then potentially displaces the siloxane equilibrium. A gravimetric method, size exclusion chromatography (SEC), Fourier transform infrared spectroscopy (FTIR), ²⁹Si nuclear magnetic resonance (NMR), and ¹³C NMR have been used. The results are that, when exposed to hot water, the GPS and the GPS-aniline networks evolve contradictorily. Although GPS tends to hydrolysis, GPS-aniline tends to condensation. This article analyzes the compatibility of the different behaviors with the simple kinetic model reported in a previous paper (1) and the importance of this phenomenon concerning the aging of the glass/matrix interphase of composite materials.     

Hydrolytic aging of polycarbonate. II. Hydrolysis kinetics,effect of static stresses

Plaques of bisphenol A polycarbonate (PC) were exposed to a water-saturated atmosphere at temperatures ranging from 40 to 90°C for up to 7 months. Certain samples were exposed under tensile load at 60 and 90°C, 100% RH with stresses ranging from 3.7 to 8.7 MPa. The PC molecular weight was determined by steric exclusion chromatography, and the kinetic parameters for hydrolytic chain scission were determined. It appears clearly that in the presence of tensile stresses, the hydrolysis rate is increased (at both temperatures under study) by a factor of about 10. The stress effect cannot be represented by the Eyring-Zhurkov relationship because the activation volume appears as an increasing function of the temperature and a decreasing function of time. Some possible causes of the observed stress effects are discussed © 1995 John Wiley & Sons, Inc.     

Water sorption in amorphous poly(ethylene terephthalate)

The water sorption characteristics of poly(ethylene terephthalate) (PET) amorphous samples of 250 μm thickness have been studied at various temperatures in a saturated atmosphere. Concerning diffusivity, one can distinguish the following two domains characterized by distinct values of the activation energy: E_D ≈ 36 kJ mol⁻¹ at T > 100°C, and E_D ≈ 42 kJ mol⁻¹ at T < 60°C, with a relatively wide (60–100°C) intermediary domain linked to the glass transition of the polymer. The crystallization of this latter occurs in the time scale of diffusion above 80°C but doesn't change the Fickian character of sorption curves. The equilibrium concentration m_∞ is an increasing function of temperature, but the solubility coefficient S decreases sharply with this latter, with the apparent enthalpy of dissolution ΔH_s being of the order of −28 kJ mol⁻¹ at T < 80°C and −45 kJ mol⁻¹ at T > 80°C. Density measurements in the wet and dry states suggest that water is almost entirely dissolved in the amorphous matrix at T < 80°C but forms partially a separated phase at T > 80°C. Microvoiding can be attributed to crystallization-induced demixing. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1131–1137, 1999