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.

The Influence of Emulsifiers on the Crystal Properties of Tristearin and Trilaurin

1988 ◽  
Vol 3 (1) ◽  
pp. 19-22 ◽  
Author(s):  
J. Schlichter ◽  
I. Mayer ◽  
S. Sarig ◽  
N. Garti
Keyword(s):  
Crystal Structure ◽  
Melting Point ◽  
Diffraction Method ◽  
The Other ◽  
Sorbitan Monostearate ◽  
X Ray Diffraction ◽  
Sorbitan Monolaurate ◽  
X Ray ◽  
Crystal Properties ◽  
Long Chain

AbstractThe effect of solid emulsifiers, added at the level of 10%, on the lattice parameters of tristearin and trilaurin, has been studied by powder X-ray diffraction method. The presence of sorbitan monostearate and glycerol-l-stearate affects slightly the lattice constant a in tristearin; on the other hand, although sorbitan monostearate causes an increase in a of trilaurin, glycerol-l-stearate does not. The presence of sorbitan monolaurate and glycerol-l-laurate affect a of trilaurin similarly to the long chain emulsifiers.A correlation between the effect on a and the increase in melting point has been found.The presence of the emulsifier does not alter drastically the lattice dimensions of the fat. The slight dissimilarity in crystal structure between tristearin and trilaurin is confirmed by the diverse effects of the emulsifiers on the internal structure of the fat.

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.

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.

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 Electron Effect of Aromatic Group: Control Conformation of 2-Aromatic Cyclododecanone Derivatives

2020 ◽  
Vol 24 (10) ◽  
pp. 1139-1147
Author(s):  
Yang Mingyan ◽  
Wang Daoquan ◽  
Wang Mingan
Keyword(s):  
1H Nmr ◽  
13C Nmr ◽  
Nmr Spectra ◽  
Coupling Constants ◽  
The Other ◽  
Repulsive Interaction ◽  
X Ray Diffraction ◽  
X Ray ◽  
Electron Effect ◽  
Group Control

2-Phenylcyclododecanone and 2-cyclohexylcyclododecanone derivatives were synthesized and characterized by 1H NMR, 13C NMR, HR-ESI-MS and X-ray diffraction. Their preferred conformations were analyzed by the coupling constants in the 1H NMR spectra and X-ray diffraction, which showed the skeleton ring of these derivatives containing [3333]-2-one conformation, and the phenyl groups were located at the side-exo position of [3333]-2-one conformation due to the strong π-π repulsive interaction between the π- electron of benzene ring and π-electron of carbonyl group. The cyclohexyl groups were located at the corner-syn or the side-exo position of [3333]-2-one conformation depending on the hindrance of the other substituted groups. The π-π electron effect played a crucial role in efficiently controlling the preferred conformation of 2-aromatic cyclododecanone and the other 2-aromatic macrocyclic derivatives with the similar preferred square and rectangular conformations.

Study of the multiplet nature in shpol'skii effect: Host n-heptane crystalline structure by X-ray diffraction and guest coronene position by ESR

1977 ◽  
Vol 22 (2) ◽  
pp. 207-214 ◽  
Author(s):  
A.M. Merle ◽  
M. Lamotte ◽  
S. Risemberg ◽  
C. Hauw ◽  
J. Gaultier ◽  
...  
Keyword(s):  
Crystalline Structure ◽  
X Ray Diffraction ◽  
X Ray

PHASE TRANSITION IN LAYERED PEROVSKITE LIKE MANGANATE Ca3Mn2O7 UNDER HIGH PRESSURE

2001 ◽  
Vol 15 (18) ◽  
pp. 2491-2497 ◽  
Author(s):  
J. L. ZHU ◽  
L. C. CHEN ◽  
R. C. YU ◽  
F. Y. LI ◽  
J. LIU ◽  
...  
Keyword(s):  
Crystal Structure ◽  
High Pressure ◽  
Diamond Anvil Cell ◽  
The Other ◽  
Layered Perovskite ◽  
X Ray Diffraction ◽  
Two Phase ◽  
X Ray ◽  
Diamond Anvil

In situ high pressure energy dispersive X-ray diffraction measurements on layered perovskite-like manganate Ca 3 Mn 2 O 7 under pressures up to 35 GPa have been performed by using diamond anvil cell with synchrotron radiation. The results show that the structure of layered perovskite-like manganate Ca 3 Mn 2 O 7 is unstable under pressure due to the easy compression of NaCl-type blocks. The structure of Ca 3 Mn 2 O 7 underwent two phase transitions under pressures in the range of 0~35 GPa. One was at about 1.3 GPa with the crystal structure changing from tetragonal to orthorhombic. The other was at about 9.5 GPa with the crystal structure changing from orthorhombic back to another tetragonal.

2D X-ray diffraction and molecular modelling of the crystalline structure of polyesters under uniaxial stress

2021 ◽  
pp. 096739112199822
Author(s):  
Ahmed I Abou-Kandil ◽  
Gerhard Goldbeck
Keyword(s):  
Crystalline Structure ◽  
Molecular Modelling ◽  
Three Dimensional ◽  
Uniaxial Stress ◽  
X Ray Diffraction ◽  
X Ray ◽  
Wide Range ◽  
Modelling Techniques ◽  
Diffraction Patterns

Studying the crystalline structure of uniaxially and biaxially drawn polyesters is of great importance due to their wide range of applications. In this study, we shed some light on the behaviour of PET and PEN under uniaxial stress using experimental and molecular modelling techniques. Comparing experiment with modelling provides insights into polymer crystallisation with extended chains. Experimental x-ray diffraction patterns are reproduced by means of models of chains sliding along the c-axis leading to some loss of three-dimensional order, i.e. moving away from the condition of perfect register of the fully extended chains in triclinic crystals of both PET and PEN. This will help us understand the mechanism of polymer crystallisation under uniaxial stress and the appearance of mesophases in some cases as discussed herein.

Studies Directed Towards the Total Synthesis of Anticapsin and Related Compounds. IV. Competitive Reaction of Amino and Carboxy Substituents in the Halohydrination of 2-Aminobicyclo[2.2.2]oct-5-ene-2-carboxylic Acid Derivatives

1994 ◽  
Vol 47 (12) ◽  
pp. 2221 ◽  
Author(s):  
MJ Crossley ◽  
SR Davies ◽  
TW Hambley
Keyword(s):  
Total Synthesis ◽  
The Other ◽  
X Ray Diffraction ◽  
Amino Groups ◽  
Competitive Reaction ◽  
Trimethylsilyl Group ◽  
X Ray ◽  
Tricyclic Compounds ◽  
Tricyclic Compound ◽  
Related Compounds

Bromohydrination of benzyl (1RS,2SR,4SR)-2-benzyloxycarbonylamino-1-trimethylsilyloxy-bicyclo[2.2.2]oct-5-ene-2-carboxylate (6a) and the (1RS,2RS,4SR)- diastereomer (6b) with N- bromoacetamide in aqueous dioxan has been investigated. These reactions are highly regio-and stereo-selective and give the corresponding bromohydrins (9a) and (9b), but in moderate to low yield. These bromohydrins have the necessary stereochemistry for conversion into anticapsin. The other products from the reaction are tricyclic compounds formed by capture of the anti- bromonium cation intermediates or resultant bromohydrins by interaction with the proximal protected carboxy and amino groups within the molecules. Thus the carbolactone (11) is formed from the endo -adduct (6a), and the carbonimidic acid derivative (12) and the cyclic urethane (13) are formed from the exo-adduct (6b). Cleavage of the trimethylsilyl group from the tricyclic compound (12) gives benzyl (1RS,2RS,3RS,7RS,8RS)-5-benzyloxy-2-bromo-8-hydroxy-4-oxa-6-azatricyclo[5.3.1.03,8]undec-5-ene-7-carboxylate(14), the structure of which was determined by X-ray diffraction methods and refined to a residual of 0.035 for 1549 independent observed reflections. The crystals of (14) are monoclinic, P21/c, a 12.954(3), b 6.197(3), c 26.784(7) Ǻ, β 95.33(2)°, Z 4. Reactions attempting to generate iodohydrins from the alkenes (6) were also highly regioselective and gave detrimethylsilylated iodo analogues of (11) and (13).

Sign in / Sign up

Export Citation Format

Share Document