Time-resolved small-angle neutron scattering study on guest-exchange processes in co-crystals of syndiotactic polystyrene

2014 ◽  
Vol 47 (1) ◽  
pp. 6-13 ◽  
Author(s):  
Fumitoshi Kaneko ◽  
Aurel Radulescu ◽  
Koichi Ute

Syndiotactic polystyrene (sPS) occupies a peculiar position among crystalline polymers: it forms co-crystals with many different kinds of chemical compounds, where the molecules are confined as guests in the regularly arranged cavities surrounded by the side phenyl groups. The guest molecules can be replaced smoothly by exposure to a vapour or a liquid of another compound, keeping the framework of the host polymer crystallites. It has been confirmed that the guest-exchange procedure is an effective way to incorporate a variety of chemical species into the crystalline region of syndiotactic polystyrene. In order to elucidate its characteristics, the guest-exchange process in co-crystals of syndiotactic polystyrene has been studied byin situtime-resolved small-angle neutron scattering measurements, exploiting the scattering length difference between fully protonated and deuterated isotopologues of guest compounds and employing fully deuterated syndiotactic polystyrene as the host matrix to avoid strong incoherent scattering. In this study, the guest-exchange process induced by exposure to the gas of small guest molecules was followed by monitoring of the reflections from crystalline lamellae. The lamellar reflections showed significant variations in intensity during the guest exchange, from which the diffusion coefficients of the guest molecules in the crystalline region could be evaluated.

2008 ◽  
Vol 77 (18) ◽  
Author(s):  
A. Wiedenmann ◽  
U. Keiderling ◽  
M. Meissner ◽  
D. Wallacher ◽  
R. Gähler ◽  
...  

1988 ◽  
Vol 132 ◽  
Author(s):  
J. A. Eastman ◽  
J. E. Epperson ◽  
H. Hahn ◽  
T. E. Klippert ◽  
A. Narayanasamy ◽  
...  

ABSTRACTNanophase titanium, prepared by the gas-condensation method both as aggregated powder and in lightly compacted discs, has been studied by conventional small angle neutron scattering, and by use of contrast variation methods. The contrast has been changed (a), isotopically, by means of deuterated/protonated solvents distilled into the specimen and (b) by progressive incremental oxidation of the Ti particles using fixed doses of low-pressure oxygen. It was shown that some evolution of the small angle pattern for lightly compacted nanophase Ti occurred over a period of several months at 300 K. Contrast matching by external solvent works well and has allowed the scattering lengths of oxidized and unoxidized specimens to be followed. The results imply that the scattering from metal and oxide can be separated under suitable conditions. The partial oxidation experiments indicate that there is both a fast and slow oxidation at 300 K. Also, during slow oxidation, high scattering length density scattering centers were formed whose number increased, but whose size remained the same at about 2 nm; these centers are tentatively assumed to be TiO2.


1994 ◽  
Vol 376 ◽  
Author(s):  
Rex P. Hjelm ◽  
Wesley Wampler ◽  
Michel Gerspacher

ABSTRACTAs part of our work on the structure of composite materials we have been exploring the use of small-angle neutron scattering using the method of contrast variation to dissect the component form, structure and distribution. This approach has resulted in a new look at very old problemreinforcement of elastomers by carbon black.Using this approach we studied an experimental high surface area (HSA) carbon black and a gel of "HSA-bound" rubber in cyclohexane/deuterocyclohexane mixtures. HSA in cyclohexane is found to be short rodlike particle aggregates. The aggregates have a shell-core structure with a high density graphitic outer shell and an inner core of lower density amorphous carbon. The core is continuous throughout the carbon black aggregate, making the aggregate a stiff, integral unit. Contrast variation of swollen composite gels shows that there are two length scales in the gel structure. Above 10 Å, scattering from carbon black predominates, and below 10 Å the scattering is from both carbon black and the elastomer. The HSA in the composite is completely embedded in polyisoprene. An estimate of the carbon black structure factor shows strong exclusion of neighboring aggregates, probably from excluded volume effects. The surface structure of the carbon black is unaltered by the interactions with elastomer and appears smooth over length scales above about 10 Å. These results show that contrast variation can provide information on composite structure that is not available by other means. This information relates to the reinforcement mechanism of elastomers by carbon blacks.


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