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Data from four samples of commercially available PET geogrids (made either of yarns or bars), which were measured by BAM or other institute, are analyzed to discuss the procedure and problems of determining the chemical reduction factor RFCH associated with a certain service life. Estimates from Arrhenius extrapolation usually have very large statistical errors. The level of confidence must therefore be specified. A reliable estimate requires data from immersion tests below the glass transition temperature of PET. To extrapolate the time of reductions for each reduction factor at such low temperatures, one has to know the functional form of the mechanical degradation curve. It is shown how the degradation curve of the tensile strength may be obtained by determining the relation between increase in concentration of carboxyl end group (CEG) and decrease in tensile strength. Therefore, experimental studies to determine the chemical reduction factor should be accompanied by the measurements of the CEG concentration and the intrinsic viscosity. Furthermore, such measurements allow a non-ambiguous determination of the molecular mass. Hydrolytic molecular degradation will proceed continuously even at 20 °C with half-life of the inverse of the CEG concentration of 40–100 y. Nevertheless, small chemical reduction factors at a lifetime of 100 y are obtained with high level of confidence for materials with low initial CEG concentration and high molecular mass. This is shown by pooling data from samples with comparable CEG concentration, molecular mass and above all comparable intrinsic relation between increase in CEG concentration and decrease in strength. Therefore, the recommendation of ISO TR 20432, Table 2, for chemical reduction factors seems to be applicable to PET geogrids with index properties well below the one specified by the technical report. Whether these index properties are actually a sufficient condition to have small chemical reduction factors even at a very long service life is still an open question. The determination of chemical reduction factor should be based on aging experiments, at least for products with index properties close to the limiting values for the following reasons. (1) Even so standards are available, results of different laboratories on absolute values of CEG concentration and number averaged molecular mass differ to a certain extent. (2) Other factors, like crystallization, affect the mechanical degradation significantly. (3) There is no universally applicable form of the mechanical degradation curve.
Copolyesters of glycolic acid combined with adipic acid and 1,4 butanediol were synthesized, their in vitro hydrolytic degradation was studied and correlated with their structure. The hydrolytic degradation of the copolyesters was directly related with the degree of crystallinity and the diameter of the crystallites. It was found that glycolate units disturb the ordering of the butylene adipate units, which results in a decrease of the crystallinity. By comparing the hydrolysis parameters of synthesized copolyesters with those of similar aliphatic copolyesters a hydrolysis mechanism was proposed. According to this mechanism, the degradation takes place not only by the loss of end units, but also through the removal of larger segments. MALDI-TOF MS data showed that the possibility of a copolyester macromolecule forming cyclic structures correlates with the arrangement of ester groups in the macromolecules and the structure of the linear segments.
The shape memory functionality of a segmented poly(ester urethane) and its hydrolytically aged specimens has been studied by cyclic thermo-mechanical measurements with an imposed strain of 100%. The shape memory effect was triggered by a melting transition in the soft segment phase. Aging was enforced by immersion in hot de-ionized water. In the course of the immersion the tensile properties (secant moduli, stress and strain at yield and break) were impaired by hydrolysis. Advanced specimen embrittlement finally led to rupture during the first thermo-mechanical cycle. This happened after 68 days of aging at 55 °C and correspondingly after 8 days at 80 °C. The residual strain after the first cycle, which was about 25%, increased significantly with aging time. Therefore, the total strain recoverability became ever smaller: aged specimens needed conditioning by at least two cycles for a full development of shape recoverability. Likewise the recovery force decreased continuously. Despite these degradation effects, it was observed that the shape fixity and the cycle-related shape recovery of appropriately conditioned specimens (number of cycles N > 2) remained on a constant high level (at round 100% and between 90% and 100%, respectively) throughout the whole aging period. These observations are discussed within the framework of a simplified model of the behavior of crystallizable shape memory polymers. The amorphous state of the polymer is described by the equation of the linear visco-elastic solid. As for the semi-crystalline state the material is assumed to react elastically with respect to deviations from the configuration, which was frozen up under constraint conditions. The curves of the dependence of the material behavior on aging time at 55 °C match perfectly those at 80 °C when the time axis is adjusted by a factor of 8.5, from which the apparent activation energy for hydrolytic aging in the amorphous state of 82 kJ mol-1 could be deduced.
In two hydrolytic degradation studies the tensile (mechanical) and functional (thermo-mechanical) properties of a hydrolysis-stabilized shape memory poly(ester urethane) and its non-stabilized analog were investigated. Hydrolytic degradation was enforced by specimen immersion in de-ionized water at 80 °C. Significant differences in the fundamental shape memory parameters were monitored as function of aging time for the stabilized and non-stabilized polymer. This included the ability to recover strain (shape recoverability) and stress (stress recoverability) on heating after shape programming. Hydrolysis-related mechanical and functional changes were correlated with morphological ones, detected by differential scanning calorimetry (DSC). The shape memory poly(ester urethane), which was protected by a carbodiimide-based hydrolysis stabilizer, revealed significantly improved resistance towards hydrolysis with respect to various mechanical and shape memory parameters.