Observations on the X-Ray Structure of Rubber and the Size and Shape of Rubber Crystallites

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Abstract
In former times, we used to be painfully aware of the shortcomings and elastic imperfections of Hevea rubber. With its disappearance, we have come to think of it as having an ideal balance in physical properties for a rubberlike material which it has been difficult to approach with synthetic polymers. for this reason, it is still important to investigate the molecular structure of Hevea rubber and to try to understand the characteristics of this structure which are responsible for its physical properties. X-Ray diffraction methods can be applied to the problem of the molecular structure of Hevea rubber and a few synthetic rubbers, such as Butyl rubber and Neoprene, because crystallization occurs upon stretching. A detailed description of the x-ray diffraction results with rubber is available in a review article and need not be repeated here. It should be pointed out that the story obtained from the x-ray structure is not complete because there are important aspects of the structure which are not revealed by this means. It is not possible to measure directly the length of the chain molecules. The nature of the amorphous phase, such as the system of cross-linking of the long chain molecules on vulcanization, does not become evident in x-ray patterns. The physical properties of Hevea rubber must depend on a delicate balance of primary and secondary valence forces. The x-ray method does not permit any direct measurement of these forces but merely shows the geometrical arrangement which results from the molecular forces. Even with these limitations, much valuable information can be secured on the nature of the molecular rearrangements which occur upon stretching. Deductions can be drawn from the x-ray diffraction results regarding the form and spatial relationships of the long chain polymeric molecules and the manner in which they interact under stress. Correlations can then be looked for between the crystallization and the physical properties.

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