Application Note P0-001

Percent Crystallinity – XRD

PE (low density) film
Percent crystallinity of polymers is commonly determined via XRD (x-ray diffraction),
although DSC (differential scanning calorimetry) is also commonly used. XRD uses the
total x-ray scattering of both the crystalline and amorphous phases to determine the
crystallinity, and no external standard is needed. DSC uses the heat of crystallization
compared to the total heat given off by a certain weight of a polymer material to
determine the crystallinity (e.g. a standard is necessary). XRD provides a more
accurate result, and assuming all data collection and processing variables are
controlled, XRD provides very precise relative comparisons between samples.

When XRD is used to determine crystallinity of polymeric materials, the greatest

possible source of error is frequently related to the preferred orientation of the polymer.
Typical line or point source XRD instruments fail to observe large sections of the Debye
ring, and therefore essential peak intensity is missed and the relative intensities of the
crystalline peaks are misrepresented. Therefore, it is essential to use a 2-dimensional
detector, capturing the intensity variation around the Debye ring, as shown in figure 1
below. This 2D detector image shows the significant preferred orientation of the
orthorhombic polyethylene, and the hkl s of the reflections are shown on the figure.

Figure 1: 2D detector image of (101) and (200)

hkls showing preferred orientation.

Cell constants:
a: 7.4, b: 4.93, c: 2.534
α,  = 90
density of amorphous material: ~0.825 g/cc,
density of crystalline material: ~ 0.980 g/cc

When percent crystallinity is determined via XRD, the crystallinity is calculated by

dividing the total area of crystalline peaks by the total area under the diffraction curve
(crystalline plus amorphous peaks).

% Crystallinity = (total area of crystalline peaks) / (total area of all peaks)

Air scatter must be removed prior to profile fitting of peaks, and air scatter is typically
determined by running a “blank” (e.g. collecting a data pattern under identical conditions
without a sample in place) and subtracting that blank pattern from the pattern of the
sample under investigation. Compton’s scatter, which is inelastic (non-diffraction)
scattering, is typically approximated and removed since it is not related to the crystalline
or amorphous scatter. If air scatter and Compton’s scatter are not taken into account,
the reported percent crystallinity will be biased to lower calculated crystallinity.

It should also be noted that the exact locations of the amorphous and crystalline regions
are typically left to the judgment of the diffractionist. The refinement model should
account for all intensity in the pattern, and should account for all amorphous and
crystalline regions. Figure 2 shows the refinement and % crystallinity calculation for the
low density PE as calculated by the Topaz Rietveld Refinement software from Bruker.
Crystalline peak locations are labeled for clarity.

Figure 2: Peak locations and profile fitting for percent crystallinity

% crystallinity of low density PE

12,500
21.39479 29.86458 36.32292
12,000
23.75224 39.81042
11,500
43.03958
11,000
46.85
10,500
10,000
48.91667
9,500 52.79167
9,000 54.66458
8,500
8,000
7,500
7,000
6,500
6,000
5,500
5,000
4,500
4,000
3,500
3,000
2,500
2,000
1,500
1,000
500
0
-500
-1,000
-1,500

6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54 56 58 60 62 64 66

After peaks are assigned as crystalline or amorphous, the percent crystallinity is easily
calculated as shown in the equation above. In this case, three amorphous regions are
defined, at approximately 19, 42 and 58 in 2. The first amorphous peak, typically
located between 18 and 20 in 2, is occasionally referred to as “para”-crystalline in the
literature. Depending upon the FWHM (full width at half maximum) of this peak, this
scattering entity be displaying chain ordering in one or two crystallographic directions,
but has not developed well formed three dimensional crystallites. Therefore it may be
considered to be intermediate between amorphous and crystalline. If the diffractionist
chooses to define the peak as para-crystalline, the calculation for percent crystallinity
can be done by either excluding this peak from the calculation (e.g. it is not assined to
crystalline or amorphous intensity and is simply excluded), or it can be assigned as
crystalline intensity. For the purposes of this example, this leading peak of PE was
assigned as amorphous. The total percent crystallinity is calculated to be 53% as
shown in figure 3 below.

Figure 3: Topaz output for percent crystallinity calculations