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13.2: Crystalline and Amorphous Polymers

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    In ceramics or metals, a crystalline solid comprises repeating unit cells that contain each of the component atoms in the material. Each unit cell is composed of one or more molecular units. In a polymer this is not possible; the molecules are chains containing potentially millions of formula units. There is, however a repeating unit in a polymer - the monomer from which it was made. This must be the basis of both long and short-range order in a polymeric material.

    For example, a short section of linear poly(ethylene) looks like this:

    Schematic diagram of polymer chain

    However, the conformation of the bonds around each carbon atom can be represented schematically as follows:

    Diagram of Newman projections

    These diagrams are called Newman projections. The circle is a single C-H bond; and this diagram represents a projection along it. These two structures thus represent one half of the backbone continuing on either side of a C-C bond (trans), or both halves on the same side (gauche). Note that there are two possible gauche states, labelled gauche (-) and gauche (+).

    Whilst the trans conformation has a lower energy (since it's easier to position the hydrogen atoms on the carbon backbone further apart), an all-trans conformation would be a considerably more ordered structure than a random one - that is, it has a much lower entropy.

    Amorphous polymers are generally found in a random coil conformation and have a disordered chain structure. This is the most common structure of many polymers. Crystalline polymers are predominantly in the all-trans conformation, and the chains are arranged in lamellae, as below:

    Pre-folded lamellae Diagram showing polymer chains arranged in lamellae

    The polymer crystal is made up from one-dimensional chain-folded sequences, shown on the above left, where the repeat distance is given by the chain spacing. To the above right is shown a schematic arrangement of folded chains into a two-dimensional lamella.

    An amorphous polymer has the maximum entropy conformation (given by the Boltzmann distribution), and the chains are arrayed randomly throughout the material, making atomic positions quasi-random as in any other glassy material.

    As a result of the difference between the amorphous and crystalline arrangements of polymer chains, the X-ray diffraction patterns of the two phases are very different. The amorphous phase contains no long-range order, meaning that there are no regular crystalline planes to diffract X-rays. Thus the incident X-rays are scattered randomly and there are no sharp peaks in the diffraction pattern. In the crystalline phase, the repeating lamellar chains provide a regular structure, thus the diffraction pattern will contain sharp, prominent signature peaks, the position of which depends on the exact spacing between chains.

    As the degree of crystallinity of a polymer affects its properties, accurately determining it is important. X-ray diffraction can be used to determine the degree of crystallinity of a sample. Thermal analysis techniques such as differential scanning calorimetry (DSC) can also be used. The two determinations may not necessarily be in agreement, and the reasons for this are complex.

    This page titled 13.2: Crystalline and Amorphous Polymers is shared under a CC BY-NC-SA 2.0 license and was authored, remixed, and/or curated by Dissemination of IT for the Promotion of Materials Science (DoITPoMS) via source content that was edited to the style and standards of the LibreTexts platform; a detailed edit history is available upon request.

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