X-Ray Diffraction Analysis of Polymers

Jia Liu

Executive Summary

The objective of this experiment is to understand the principle of X-Ray Diffraction (XRD)
and its application in characterizing polymer samples. In this experiment we compare the
XRD pattern of two nylon 66 samples with different cooling methods so as to discuss the
crystalline conditions and parameters.

Introduction

Have a knowledge of crystal structure is a prerequisite to understand phenomena such as

plastic deformation, alloy formation, and phase transformation. XRD method is a powerful
tool for investigating orderly arrangements of atoms or molecules through the interaction
of electromagnetic radiation to give interference effects with structures comparable in size
to the wavelength of the radiation.[1] X-rays are produced in an x-ray tube consisting of
two metal electrodes enclosed in a vacuum chamber. Electrons are produced by heating a
tungsten filament cathode. The cathode is at a high negative potential, and the electrons
are accelerated toward the anode, which is normally at ground potential. The electrons,
which have a very high velocity, collide with the water-cooled anode. The loss of energy of
the electrons due to the impact with the metal anode is manifested as X-rays. Actually
only less than 1% of the electron beam is converted to x-rays; the majority is dissipated as
heat in the water-cooled metal anode. The components of an X-ray Diffract meter include
the X-ray source (in this experiment, Cu-K,  = 1.542 A), the specimen (Nylon66 films by
compression molding), the optics and the detector. By considering crystals as reflection
gratings for X-rays, Bragg derived his equation: λ=2 d sinθ ,Where λ is the X-ray
wavelength, θ is the angle between the X-ray beam and these atomic planes.[2] Besides,
Scherrer derived an expression for broadening of X-ray diffraction peaks due only to small
crystallite sizes: D=Kλ/(Bcosθ),where λ is the wavelength of the X-ray used, θ is the Bragg
angle, B is the average crystallite size measured in a direction perpendicular to the
surface of the specimen, and K is a constant.[2]

Experiment Procedure

The samples prepared are two nylon 66 films endured different cooling process: slowly
cooled (3C /min) and quench. The instrument was set Voltage: 30 kV, Current30 mA and
Power 0.9 kW with Cu-K radiation in the 2θ angle range of 5∘ to 35∘. The samples are
tested one after another following the operation manual.

Analysis and Discussion

1
 20000

17500

15000
Slowly cooled down
12500
Intensity

10000
Quenched
7500 (amorphous)

5000

2500

0 5 10 15 20 25 30 35 40 45

Diffraction angle(2)

Figure1. X-Ray diffraction Pattern of slowly cooled and quenched nylon 66

TABLE.1 Indexing the Diffraction Pattern of nylon66 (slowly cooled)

Peak 2θ θ θ B B d D %
(radians) (radians) (Å) (Å) Crystallinity
d1 20.24 10.12 0.1761 0.79 0.0137 4.39 1.76 18.24
d2 23.72 11.86 0.2064 1.32 0.0230 3.75 1.06

Calculations:
1. d-pacing: d=λ/ (2sinθ), for Cu-Kα, λ=1.542Å
2. Crystallinity:
%Crystallinity =Ic /(Ic+Ia)* 100
Where Ic =Intensity of Amorphous region=113920.857
Ia =Intensity of Crystalline region=25412.453
3. Crystallite size: D=Kλ/ (Bcosθ)
Where K=0.89, λ=1.542Å, B is the Breadth of the peak at half height (in crystal region), θ
is Bragg’s angle in radians.

For slowly cooled nylon 66, the pattern consists of two peaks which combined together.
The peak intensity is plotted on the ordinate and the measured diffraction angle, 2θ, along
the abscissa. Each peak, in the diffraction pattern corresponds to X-ray diffracted from a
specific set of planes in the specimen, and these peaks are of different heights. The
intensity is proportional to the number of X-ray photons of a particular energy that have
been counted by the detector for each angle 2θ. The intensities of the reflections depend
on several factors, including structure factor, incident intensity, slit width, and values of
current and voltage. The position of the peak depends on the crystal structure of the

2
materials as well as the wavelength of the X-rays. The difference between slowly cooled
nylon 66 and quenched nylon 66 is by rapidly quenching it from the melt phase, it can be
made almost amorphous; then, by annealing the polymer at a temperature above the
recrystallization temperature, the crystallinity will recover. [1]As amorphous polymers do
not contain any crystalline regions, “crystalline” polymers generally are only semi
crystalline, so we can calculate the crystallinity by integrating the total area of the curve
(both crystalline and amorphous) and the halo parts (the amorphous) as shown in table 1.

Conclusions

X-ray diffraction is an effective method to study the polymer crystal properties; it can tell
kinds of lattice and show details of crystal structures. According to this experiment, we get
to know the D-spacing, crystal size and crystallinity from the diffraction pattern. The longer
the cooling time is, the bigger the crystal size is. Both crystallinity and crystal Size follow
the same trend: Quench < Slowly cooled

Reference

[1] C.Suryanarayana, M. Grant Norton. X-Ray Diffraction – A practical Approach. Plenum

Press, 1998
[2] B.D.Cullity, Elements of X-Ray Diffraction. Addison-Wesley Publishing Company, Inc,
1967
[3] L.H.Sperling, Introduction to Physical Polymer Science. John Wiley& Sons, Inc. 2006