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I am currently investigating the annealing of a polymer (Parylene-C). In my reading I have found that when the polymer is annealed, there is a decrease in thickness of the film which results from a decrease in d-spacing.

I don't have a background in polymer physics/chemistry and I was wondering if someone could explain why the d-spacing decreases as crystallinity increases?

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up vote 2 down vote accepted

Polymer chains pack together more densely when they're more crystalline simply because they line up with each other better. It's the same reason a ball of string has a higher density than a random tangle of string. has some info on this including examples of density for different crystallinities.

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