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Trans‐gauche concentration in crystalline polyethylene measured by the intensity of rocking mode vibrations of deuterated methylene groups

 

作者: D. H. Reneker,   J. Mazur,   J. P. Colson,   R. G. Snyder,  

 

期刊: Journal of Applied Physics  (AIP Available online 1980)
卷期: Volume 51, issue 10  

页码: 5080-5094

 

ISSN:0021-8979

 

年代: 1980

 

DOI:10.1063/1.327424

 

出版商: AIP

 

数据来源: AIP

 

摘要:

Polyethylene with a low concentration of deuterated methylene groups displays an infrared band in the frequency region 646–651 cm−1. This band is attributed to a rocking normal mode of a CD2group with one of the adjacent dihedral angles approximatelytransand the other approximatelygauche(tg). This mode vibrates at 620 cm−1when the dihedral angles adjacent to the CD2group are bothtrans(tt). In polyethylene crystalstgsequences can occur only in defects where constraints cause some of the dihedral angles to be approximatelytransorgauche. Calculations of the rocking mode vibrational frequencies of CD2groups in model chains which incorporate some of the typical defects showed that the bands were broadened but not completely disrupted by the distorted dihedral angles. Measurements of the relative intensities of the CD2rocking bands show an increase in the concentration oftgsequences consistent with the thermal generation of defects which may be involved in transport of the polymer chain through the crystal. Confidence in the particular values of the concentration ratio is limited by uncertainties in the determination of the base line for the infrared bands of interest. Quantitative measurements of the concentration ratiotg/(tg+tt), determined from the integrated band intensities, fall between limits set by reasonable independent estimates of the concentration of folds and point dislocations.

 

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