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

1944 ◽  
Vol 17 (3) ◽  
pp. 640-652
Author(s):  
S. D. Gehman ◽  
J. E. Field
Keyword(s):  
Molecular Structure ◽  
Physical Properties ◽  
X Ray Diffraction ◽  
Ray Method ◽  
Chain Molecules ◽  
X Ray ◽  
Rubberlike Material ◽  
Molecular Forces ◽  
Ray Patterns ◽  
Long Chain

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.

scholarly journals The structure of polychloroprene

1942 ◽  
Vol 180 (980) ◽  
pp. 100-107 ◽  
Keyword(s):  
Physical Properties ◽  
Crystalline Structure ◽  
Light Treatment ◽  
Unit Cell ◽  
Cross Linking ◽  
Chain Molecules ◽  
X Ray ◽  
Before And After ◽  
Ray Methods ◽  
Long Chain

Specimens of polychloroprene before and after light treatment have been examined by X -ray methods. There is no change in the crystalline structure, although there are differences in the physical properties ascribed to cross-linking of the long-chain molecules. The unit cell is possibly ortho­rhombic: a = 8·90 A , b = 4·70 A, c = 12·21 A, and contains four chloroprene (C 4 H 5 Cl) units.

Properties of Some Synthetic Rubbers

1943 ◽  
Vol 16 (4) ◽  
pp. 857-862
Author(s):  
L. B. Sebrell ◽  
R. P. Dinsmore
Keyword(s):  
Molecular Structure ◽  
Natural Rubber ◽  
Point Of View ◽  
General Point ◽  
Chain Molecules ◽  
X Ray ◽  
Synthetic Rubber ◽  
The Difference ◽  
Diffraction Patterns ◽  
Long Chain

Abstract X-RAY STRUCTURE OF SYNTHETIC RUBBER In presenting a series of x-ray diagrams of various types of synthetic rubber in comparison with natural rubber, in both the stretched and the unstretched condition, it is our purpose to bring out the fact that the molecular structure of synthetic rubbers is entirely different from that of natural rubber. It is proposed also to review briefly the theories which have been advanced, based on the x-ray analysis of rubber, to account for the elasticity of natural rubber, and to advance the possible reason for the difference shown by the x-ray diagrams of synthetic rubber. At the present time, from the most general point of view, the molecular structure of a rubberlike material is envisaged as a sort of brush-heap structure of entangled long chain molecules. x-Ray diffraction patterns show that, for some rubberlike materials, notable regularities of structure sometimes occur in the tangle of long-chain molecules. It is now realized that these regularities are not essential for rubberlike behavior. Nevertheless their observation and study is important because they afford a unique opportunity for studying the molecular structure of the chains and the molecular rearrangements which occur with the application of stress.

An X-Ray Investigation of Crystallinity in Rubber

1939 ◽  
Vol 12 (4) ◽  
pp. 706-718
Author(s):  
S. D. Gehman ◽  
J. E. Field
Keyword(s):  
Crystalline Structure ◽  
Polymeric Materials ◽  
The Other ◽  
X Ray Diffraction ◽  
Random Orientation ◽  
Chain Molecules ◽  
Micellar Structure ◽  
X Ray ◽  
Recent Developments ◽  
Long Chain

Abstract The crystalline structure which rubber exhibits under certain circumstances has come to be regarded as associated with a secondary or micellar structure of long chain molecules. The exact mechanism by which the localized ordered regions appear is a speculative subject in recent developments of the micellar theory of long chain polymeric materials. The views of various workers on this subject have been summarized by other authors. The crystalline structure of rubber displays varying degrees and types of orientation of the crystal units, depending on the conditions under which crystallization occurs. The amorphous x-ray diffraction pattern of unstretched rubber is shown in Figure 1, the unoriented crystalline diagram for frozen rubber in Figure 2. When crystallization is induced by stretching, the crystallites are aligned along the axis of stretching, giving the fiber diagrams of Figures 3 and 4. In this case there is random orientation of the other two axes of the crystallites. “Higher orientation,” in which all three axes of the crystallites are aligned, gives the diagram of Figure 15 and can be secured with suitable dimensions of the stretched piece.

An X-Ray Method of Measuring Poisson's Ratio

1947 ◽  
Vol 157 (1) ◽  
pp. 52-55
Author(s):  
R. F. Hanstock ◽  
E. H. Lloyd
Keyword(s):  
Poisson’S Ratio ◽  
Diffraction Method ◽  
Poisson's Ratio ◽  
Original Position ◽  
X Ray Diffraction ◽  
Ray Method ◽  
Additional Advantage ◽  
X Ray ◽  
Crystallographic Planes ◽  
Ray Patterns

The paper describes the measurement of Poisson's ratio in metals by an X-ray diffraction method. The specimen, which is a small tensile test piece, is examined at various loads by a high-angle “back-reflection” X-ray technique. At any load (the value of which need not be known) X-ray patterns are obtained for various angular settings of the specimen relative to the incident X-ray beam, and, for each setting, the shift of the diffraction lines from their original position gives the strain in a direction normal to the reflecting crystallographic planes. The strains corresponding to various angular settings of the specimen, for any one load, give a linear graph when plotted against a simple function of the orientation of these crystallographic planes, and from this graph the value of Poisson's ratio is directly obtained. Experimental results are quoted for the aluminium alloy known as “Hiduminium RR.56”. The results obtained for various elastic loads are consistent within the experimental error, the resulting value of Poisson's ratio being 0·36. It is concluded that the method described is capable of an accuracy at least as good as that of the ordinary mechanical method, and that it has the additional advantage of providing values which apply to a single set of crystallographic planes in a polycrystalline metal.

Molecular Structure and Rubberlike Elasticity. II. The Stereochemistry of Chain Polymers

1942 ◽  
Vol 15 (4) ◽  
pp. 731-741
Author(s):  
C. W. Bunn
Keyword(s):  
Molecular Geometry ◽  
Sufficient Evidence ◽  
Zigzag Chain ◽  
X Ray Diffraction ◽  
Molecular Physics ◽  
Chain Molecules ◽  
X Ray ◽  
Gutta Percha ◽  
Extended Plane ◽  
Long Chain

Abstract In Part I of this work, the determination of the crystal structures of three long-chain polymers by interpretation of x-ray diffraction photographs was described. In all three crystals—β-gutta-percha, rubber and polychloroprene—themolecules have nonplanar zigzag chain forms and are asymmetric. It is now necessary to consider the bearing of the new knowledge of molecular geometry on the possibility of understanding rubber like properties in terms of molecular physics. It is widely believed that the flexibility, softness and other characteristic properties of rubberlike substances are in some way due to the flexibility of the molecules themselves. Long-chain molecules owe their potential flexibility to the swivelling of the chain units around the single bonds as axes, and it is therefore necessary to consider which bond positions are the most stable and what hindrances there are to rotation away from these positions. The present paper deals chiefly with the question of the most stable bond positions. The enquiry has interest, not only in relation to the problem of the origin of rubberlike properties, but also because it opens the way to a systematic consideration of chain types. There is already evidence that in many crystalline long-chain polymers, such as rubber hydrochloride, polyisobutylene, and some of the polyesters, the chains have not the fully extended plane zigzag form of polyethylene, but somewhat shortened (necessarily nonplanar) forms. It should be possible to discover what these forms are by interpretation of x-ray diffraction photographs, but the difficulties are in some cases formidable; some assistance in the form of guiding principles for the construction of possible chain types is desirable. It is the purpose of this paper to show that sufficient evidence already exists to suggest a general principle regulating bond positions in aliphatic molecules containing sequences of singly linked atoms. It will be called the principle of staggered bonds. In the three molecules whose structures were determined in Part I, every fourth chain bond is a double bond; the question of bond positions is less simple for such molecules than it is for those in which all the bonds are single. The latter will therefore be considered first.

X-Ray Diffraction Patterns of Crystalline Sol Rubber Prepared from Ethereal Solution

1939 ◽  
Vol 12 (3) ◽  
pp. 482-484
Author(s):  
George L. Clark ◽  
Siegfried T. Gross ◽  
W. Harold Smith
Keyword(s):  
Sol Gel ◽  
Crystalline Material ◽  
X Rays ◽  
X Ray Diffraction ◽  
Experimental Procedure ◽  
Chain Molecules ◽  
X Ray ◽  
Measurement And Analysis ◽  
Diffraction Patterns ◽  
Long Chain

Abstract In a previous publication there was reproduced an x-ray diffraction pattern of crystals obtained from a solution, cooled to temperatures between −40° and −50° C, of an ether-gel fraction of rubber from Hevea brasiliensis. Measurements of three strong interferences indicated that the crystals were similar to those of stretched gel rubber and of frozen sol, gel and total rubber. Although many attempts were made at that time, unsatisfactory diffraction patterns were obtained with crystalline ether-sol rubber. The interferences were faint and not suitable for accurate measurement and analysis. Since the crystalline material is bulky and some specimens are more compact than others, it seemed possible that the average number of cell diameters was too small to permit sharp definition, and that more material was required for the examination by x-rays. However, it is not certain that lack of definition was caused by insufficient crystalline rubber. The possibility that parts of the long-chain molecules become crystalline and that parts remain amorphous is not excluded, and might be its cause. Additional work with crystalline sol rubber, using a slightly different experimental procedure and more material than in earlier experiments, finally resulted in a satisfactory pattern.

The Preparation, Physical Properties, and Structure of Oxotetrachloroaquorhenium(VI), ReOCl4(OH2)

1972 ◽  
Vol 50 (12) ◽  
pp. 1811-1818 ◽  
Author(s):  
P. W. Frais ◽  
C. J. L. Lock
Keyword(s):  
Molecular Structure ◽  
Infrared Spectroscopy ◽  
Physical Properties ◽  
Single Crystal ◽  
Least Squares ◽  
Intensity Data ◽  
X Ray Diffraction ◽  
Full Matrix ◽  
X Ray ◽  
First Time

Oxotetrachloroaquorhenium(VI), ReOCl4•H2O, has been prepared and characterized for the first time by analysis, infrared spectroscopy and single crystal X-ray diffraction. The crystals were orthorhombic, a = 10.834(8), b = 11.089(8), c = 5.517(4) Å, Pn21a, Z = 4. Intensity data were recorded by integrating film methods and measured with a Joyce–Loebl microdensitometer, and 624 observable of the 704 measured independent reflections were given non-zero weight in the final cycle of full matrix least-squares refinement where R1 = 0.0572 and R2 = 0.0687. The molecular structure is based on a very distorted octahedron with a strongly bonded oxo-group (Re—O, 1.63(2) Å) trans (177(2)°) to a weakly bonded aquo-group (Re—O, 2.27 (2) Å). The Re—Cl distances do not differ significantly (2.29(1) Å av). The chlorine atoms are bent away from the oxo-group (angles vary from (94–102°(1)).

Microstructure and Physical Properties of Clay-Polymer Composites

2000 ◽  
Vol 628 ◽  
Author(s):  
T.N. Blanton ◽  
D. Majumdar ◽  
S.M. Melpolder
Keyword(s):  
Composite Materials ◽  
Physical Properties ◽  
Polymer Composites ◽  
Basal Plane ◽  
X Ray Diffraction ◽  
X Ray ◽  
Layered Clay

ABSTRACTClay-polymer nanoparticulate composite materials are evaluated by the X-ray diffraction technique. The basal plane spacing provided information about the degree of intercalation and exfoliation of the 2: 1 layered clay structure. Both intercalation and exfoliation are controlled by the identity of the polymer and the clay:polymer ratio.

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