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The surface tensions of amine-, hydroxyl-, and methyl-terminated poly(dimethylsiloxane) (PDMS) oligomers with molecular weights ranging from 1000 to 75 000 are measured by pendant drop tensiometry. The surface tension increases with molecular weight for the methyl-terminated polymers, decreases with molecular weight for the amine-terminated polymers, and is nearly independent of molecular weight for the hydroxyl-terminated polymers. This behavior is attributed to differences in surface tension of the end groups and the repeat unit of the chain ( . -

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The depletion of alkylamine terminal groups at the vacuum-polymer interface is measured for a,@-difunctional poly(dimethylsi1oxane) oligomers by X-ray photoelectron spectroscopy. The driving force for this depletion is the high relative surface energy of the amine terminal groups compared to that of the low surface energy poly(dimethylsi1oxane) backbone. The degree of surface end group depletion, within the maximum sampling depth probed (ca. 7 nm), is found to be on the order of 40% for a 960 molecular weight oligomer and decreases slightly with an increase in the oligomer molecular weight. Angle-dependent measurements are applied to determine end-group concentration depth profiles. End-group depletion is largest at the shallowest sampling depths and decays rapidly toward the bulk. The decay profiles cannot be explained by simple monotonic decay functions, consistent with the expected effects of connectivity between the end groups and the chain backbone, but the data are insufficient to prove whether the profiles are oscillatory in nature, as expected from theoretical considerations.

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Soluble model segmented poly(urethane urea)s (PUU) with or without hard segment (HS) branching were utilized to explore the importance of hydrogen bonding and chain architecture in mediating the long-range connectivity of the HS phase. The HS content of all the PUU copolymers was 22 wt %, and the soft segment (MW 970 g/mol) was a heterofed random copolymer of 50:50 ethylene oxide:propylene oxide, which possesses a single terminal hydroxyl group (monol). An 80:20 isomeric mixture of 2,4-and 2,6-toluene diisocyanate, 4,4′,4′′-triphenylmethane triisocyanate and water were utilized during the chain extension step of the synthesis to incorporate HS branching. DSC and SAXS results on the final plaques indicated that the samples were still able to establish a microphase morphology even in the presence of the highest extent of HS branching utilized in the study. The tapping-mode AFM phase image of the PUU sample without HS branching exhibited the presence of long ribbonlike hard domains that percolated through the soft matrix. The long-range connectivity of the HS was increasingly disrupted with higher levels of HS branching. Accompanying such disruption was a systematic mechanical softening of the PUU samples. FT-IR indicated that incorporation of HS branching disrupted the hydrogen-bonded network within the hard phase. These results demonstrate the importance of hydrogen bonding and chain architecture in mediating the long-range connectivity and percolation of the HS and achieving dimensional stability.