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Determination of molecular orientation by spectroscopic techniques

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Characterization of Polymers in the Solid State I: Part A: NMR and Other Spectroscopic Methods Part B: Mechanical Methods

Part of the book series: Advances in Polymer Science ((POLYMER,volume 66))

Abstract

The aim of this review article is to discuss the type of information which can be obtained concerning orientation in polymers by spectroscopic methods and to select examples which illustrate key problems in the area of polymer physics.

As a prelude to the discussion it is necessary to consider the definition of orientation in terms of the Euler angles, and the definition of an orientation distribution function in terms of an expansion of Legendre functions. These definitions set the scene for examining the information which can be obtained from different spectroscopic techniques. In this review, infra-red and Raman spectroscopy and nuclear magnetic resonance, will be considered.

Information on molecular orientation can be useful in two primary ways. First, it is possible to use the orientation functions or averages to gain an understanding of the mechanisms of plastic deformation. Secondly the orientation averages can provide a basis for understanding the influence of molecular orientation on physical properties, especially mechanical properties.

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Abbreviations

A:

Absorption

D:

Optical density

E:

Electric vector

fa :

Amorphous orientation average

fc :

Crystalline orientation average

I:

Nuclear spin number

Is :

Scattered intensity

I′:

Scattered intensity

IT :

Transmitted intensity

ki :

Imaginary part of complex principal refractive index

Δn:

Birefringence

ni :

Real part of complex principal refractive index

N:

Number of absorbing species per unit volume, Number of nuclei over which sum is taken

N′:

Number of random links per chain

N(ϑ, φ, ψ):

Distribution function of orientation for structural units

N′(β, γ):

Distribution function of orientation for spectroscopic effect studied

No :

Number of effective scatterers

p1mn :

Spherical harmonic function

P1mn :

Averages of p1mn

r:

Ratio of principal components of differential polarizability tensor

r j :

Direction in a structural unit

S:

Lattice sum

xcryst :

Crystalline fraction

xtrans :

Fraction of trans conformers

xi :

Rectangular coordinate axes in a structural unit

Xi :

Rectangular coordinate axes in the sample

Y e1m :

Generalised Legendre function

Z1mn :

Generalised Legendre function

αi :

Principal component of differential polarizability tensor

α ei :

Principal component of electronic polarizability tensor

β:

Polar angle defined with respect to a structural unit

γ:

Azimuthal angle defined with respect to a structural unit

λ:

Infra-red wavelength, Draw ratio

μ:

Transition dipole moment

μn :

Nuclear Magneton

ϱ(ϑ, φ):

Distribution function

Ï‘:

Euler angle

φ:

Euler angle

ψ:

Euler angle

φi :

Infra-red quantity

ξ:

Polar angle defined with respect to sample

η:

Azimuthal angle defined with respect to sample

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Authors and Affiliations

  1. Department of Physics University of Leeds, LS2 9JT, Leeds, UK

    I. M. Ward

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  1. I. M. Ward
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H. H. Kaush H. G. Zachman

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© 1985 Springer-Verlag

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Ward, I.M. (1985). Determination of molecular orientation by spectroscopic techniques. In: Kaush, H.H., Zachman, H.G. (eds) Characterization of Polymers in the Solid State I: Part A: NMR and Other Spectroscopic Methods Part B: Mechanical Methods. Advances in Polymer Science, vol 66. Springer, Berlin, Heidelberg. https://doi.org/10.1007/3-540-13779-3_18

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  • DOI: https://doi.org/10.1007/3-540-13779-3_18

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  • Print ISBN: 978-3-540-13779-5

  • Online ISBN: 978-3-540-39043-5

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