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The hydrolysis of thermoplastic poly(ester urethane) (PEU) is convoluted by its block copolymer phase structure and competing hydrolytic sensitivities of multiple functional groups. The exact pathways for water ingress, water interaction with the material and ultimately the kinetics and order of functional group hydrolysis remain to be refined. Additional diagnostics are needed to enable deeper insight and deconvolution of material changes. In combination with GPC results, a promising analytical technique – two-dimensional correlation spectroscopy (2D-COS) – has been reviewed and applied to analyze FTIR spectra of hydrolyzed PEUs aged under various conditions, such as exposure time, temperature, and relative humidity. 2D-COS allows the complex role of water with distinct intermediate steps to be established, plus it emphasizes the initial stages of PEU hydrolysis at more susceptible functional groups. As a complication for the raw material, ATR IR detected some talc on the surface of commercial PEU beads and pressed sheets thereof, which can interfere with water ingress and thereby retards PEU hydrolysis, particularly in its natural form or moderate aging at lower temperatures (e.g., below the melting point of PEU). As aging temperature increases above the melting temperature, even traces of water trapped inside the PEU are sufficient to initiate the hydrolysis, which then progresses strongly with increasing temperatures. Feedback from 2D-COS analysis confirms that PEU hydrolysis starts at esters in the soft-segments before those in the urethane linkage become susceptible. Only when the molecular weight of PEU is below a critical molar mass (M_c) will the hydrolysis occur in parallel in the hard-segments since protective morphological phase structures are then absent. The current observations demonstrate unexpected behavior that may result from 'unknown' additives in polymer degradation, the temporal and group-specific hydrolysis of PEU as a function of locally available water molecules, the order of reactivity of susceptible functional groups, and the importance of changes in molecular weight coupled with the phase structure of the polymer.

Parylene (poly-p-xylylene), and its family of halogenated variants, have a long history for application as protective coatings and dielectric barriers. Among them, Parylene-C is the most popular due to its high impermeability to moisture, resistance to corrosive environments, and its vapor deposition polymerization, which is self-initiated and unterminated creating an extremely pure polymer coating. Here, in order to apply these advantageous material characteristics in an environment containing ionizing radiation the effects of irradiation on the chemical stability of the polymer throughout the lifetime of the material needs to be further understood.

Generalized two-dimensional correlation spectroscopy (2D-COS) is a technique that has improved on traditional spectroscopic techniques by exposing samples to a variable amount of an external perturbation before they have been probed spectroscopically through IR, UV, Raman, etc. These perturbed signals are plotted over a second independent wavenumber axis and after mathematical manipulation, a dynamic spectrum is created that shows the synchronous and asynchronous spectra. The dynamic spectrum shows the way spectral changes in the material are correlated to each other, and a mechanism of material degradation can be proposed through a set of rules that Noda proposed. This technique is important to spectroscopic studies because of improved spectral resolution and the identification of complex or overlapping bands that cannot be distinguished in traditional analytical methods. This technique has been widely utilized since its inception, and has developed towards protein studies, as well as even wine chemistry, because of the advanced capabilities of band separation. Two-dimensional hetero-spectral correlation analysis has also been developed to find correlations in spectra with different spectroscopic probes. 2D-COS as an analytical technique has increasing avenues of expansion, and can be creatively used in many other fields in the future.