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Many transparent plastic materials, rigid or not, turn opaque (white) when subjected to stress, deformations or when folded (if not rigid) . The effect seems to be irreversible.

What is the cause?

I would have guessed that some internal crystalline structure is broken, but plastic (like glasses) have no crystal structure, no?

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I would say that the reason for the white color is that by deformation you introduce a lot of small "cracks" into the material which scatter the incident light such that the deformed areas appear white. –  Philipp Aug 10 at 20:04
    
Not sure if this belongs on Chemistry.SE or Physics.SE. –  MSalters Aug 10 at 21:42
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@MSalters It's a perfect fit within our scope. –  Martin Aug 11 at 10:28

2 Answers 2

up vote 13 down vote accepted

The process of forming an opaque area when you apply stress to a polymer film is known as crazing.

Polymers are long chains and, when coated, often form tangled, amorphous, randomly aligned polymer regions. When stress is applied to the film, the stress can be relieved by the polymer chains aligning. In other words, energy introduced into the film by stressing it can be used to align some polymer chains.

Increasing the alignment in the stressed region means that the density of polymer in this region of the film will be different from the density in non-stressed regions. This difference in density will cause a difference in light reflection and scattering accounting for the different optical properties between these two regions.

Further, within the stressed area of the film, mechanical stresses are produced between areas that are more and areas that are less aligned. These stresses can be relieved through the formation of micro-cracks between the regions. These small cracks also result in different light reflecting and scattering properties of the film.

Finally, as the polymer chains align, they are more likely to crystallize. The formation of small crystallites within the stressed (aligned) region will also alter the light reflecting and scattering properties of the film. Often, upon heating or standing at room temperature (for a longer time) the optical changes may reverse as the thermal energy supplied will:

  1. cause the polymer structure to randomize back to its amorphous structure,
  2. allow the polymer to "flow" and fill the micro-cracks, and\or
  3. the crystallites can redissolve.

References: The following links provide more information about crazing and associated phenomena at different levels of complexity:

reference 1

reference 2

reference 3

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Thanks. Could you add some references? My first hits for "crazing" (eg Wikipedia) speak of something that looks different to me: formation of small cracks -visible as such. –  leonbloy Aug 11 at 11:55
    
Sure, I edited the post and added some references. –  ron Aug 11 at 13:53

@Philipp already mentioned microscopic cracks. This is called crazing. When a plastic is stretched, the extra space is filled randomly/irregularly. The gap between two polymer chains will grow, but most chains won't break. Also, if the material is already crystallized locally, the crystals will pull apart.

As the overall structure is non-crystalline, the cracks will have different sizes, and in particular quite a few will have sizes smaller than a micrometer - optical wavelengths, in other words. And with the variety in sizes, you don't get oen dominant color but a mixture of all colors which is of course white.

The other reason for the optical change is crystals forming. Again, these small crystals have different sizes around the wavelengths of visible light, so there's no dominant color from these either.

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@MSalters thanks for improving! it looks great now –  F'x Aug 11 at 20:28
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Well done! I appreciate very much, that you edited your post, this way the answers are more self relying and it helps a lot. –  Martin Aug 17 at 7:10

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