Technical Note

Measurement
MeasurementofofDegree
DegreeofofCrystallinitty
CrystallinittyofofPolymer
Polymerbyby
X-ray
X-rayDiffraction
DiffractionAnalysis
Analysis
Summary
The degree of the crystallinity of crystalline polymer is a structural parameter that has much to do with their
physical properties in general. An evaluation of the degree of crystallinity sometimes enables you to identify
the causes of insufficient rigidity, cracks, whitening and other defects.
The methods for measuring the degree of crystallinity include the density, thermal analysis, NMR and IR
methods.
An explanation will be given here of the method for measuring the degree of crystallinity by the X-ray
diffraction technique that makes it possible to make the measurement with the microcrystals 1mm or so in
diameter left in the solid state as they are.

Example of measurement by the wide angle X-ray diffraction method

In the X-ray diffraction analysis, a sample is irradiated by X-rays. From the diffraction information thus
obtained (wide angle X-ray diffraction patterns or wide angle X-ray diffraction profiles), the diffused regions
are divided into those derived from noncrystals and those derived from crystals. Then, the degree of
crystallinity is calculated as a ratio of crystal-derived scattering intensity to total scattering intensity

Decree of crystallinity (%)

= Crystal-derived scattering intensity
Crystal-derived scattering intensity + Noncrystal-derived scattering intensity

Normally, a multi-peak separation program is used to separate the crystal and noncrystal regions.
Further, the setting of the noncrystal region depends on a noncrystal model.

As a detailed method for analyzing the degree of crystallinity, there is a method described in the publication
of W. Ruland* to be followed that exclude incoherent scattering and take account of thermal oscillation and
disturbance in crystals. However, a short-cut version of this method is commonly used because there is
generally much demand for the evaluation of a relative degree of crystallinity and such short-cut version
provides an easy and quick method for making calculations with good reproducibility.
* W.Ruland, Acta Cryst.,14, 1180 (1961)

Example of measurement by the wide angle X-ray diffraction method

Diffraction intensity (relative intensity)

Sample: Polyethylene LLDPE

Crystal region
Crystallinity Xc 46

Noncrystal region

2angle()

Mitsui Chemical Analysis & Consulting Service, Inc.

E-mail: sod-mcanac@mitsuichemicals.com
http://www.mcanac.co.jp/

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