J. Synchrotron Rad. (1997). 4, 223-227
Investigation of the Variation in Orientation and Crystallinity
in Poly(ethylene terephthalate) Containers Using Microfocus
X-ray Diffraction
C. Martin, a A. Mahendrasingam, a W. Fuller, ~ J. L. Harvie, b D. J. Blundell, c
J. Whitehead, c R. J. Oldman, c C. Riekel a and P. Engstr6m a
aDepartment of Physics, Keele University, Keele, Staffordshire ST5 5BG, UK,
blCI Polyesters, PO Box 90, Wilton, Middlesbrough, Cleveland TS90 8JE, UK,
clCI Wilton Research and Technology Centre, PO Box 90, Wilton, Middlesbrough,
Cleveland TS90 8JE, UK, and dESRF, BP 220, F-38043 Grenoble CEDEX, France.
E-mail: pha40 @ keele, ac. uk
(Received 6 February 1997;accepted20 March 1997)
The microfocus X-ray beamline at the European Synchrotron Radiation Facility has been used
to investigate the variation in molecular orientation and crystallinity in the wall of a container
fabricated from poly(ethylene terephthalate). Two-dimensional wide-angle X-ray scattering patterns
were recorded and displayed in real time as the specimen was tracked across the incident X-ray
beam enabling the measurement of textural changes to be made with a spatial resolution of ,~ 2 lam.
Keywords: PET; X-ray diffraction; microfocus; orientation; crystallinity; wide-angle scattering;
CCD detectors.
223
1. Introduction
We have recently reported the use of microfocus instru-
mentation on beamline ID13 at the European Synchrotron
Radiation Facility to investigate the variation in poly-
mer orientation and crystallinity in spherulites of the
optically active thermoplastic homopolymer poly-D-(-)-
3-hydroxybutyrate (Mahendrasingam et al., 1995). In these
studies the diameter of the X-ray beam at the specimen was
~101am and this spatial resolution was sufficient to show
that the crystallites in the specimen were systematically
oriented so that the a axis in each crystallite was oriented
parallel to a radius of the spherulite but with the degree
of orientation and crystallinity decreasing towards the
centre of the spherulite. Using similar techniques, local
variations in polymer chain orientation have been described
in injection-moulded liquid-crystalline polymers (Dreher,
Zachmann, Riekel & Engstrrm, 1995).
Physical properties, such as strength and gas-transport
properties, of artefacts fabricated from poly(ethylene
terephthalate) (PET) depend on the degree of polymer
orientation and crystallinity and its variation in the artefact.
In an effort to improve the efficiency and quality control
in the processing of bulk polymers in the manufacture
of products such as containers from PET (which have
a high performance specification), we have undertaken a
preliminary study of the dependence of polymer orientation
and crystallinity on fabrication conditions. This report
describes experiments where the microscopic variation of
these characteristics is studied with a resolution of ,~ 2 lxm
within the wall of such a container.
© 1997 International Union of Crystallography
Printed in Great Britain - all rights reserved
The manufacture of PET containers involves first the
injection moulding of an unoriented amorphous preform
followed by blowing the preform into a cold shaped mould
to form the container. Often this process is carried out via
a two-stage route in which the preform is first cooled to
room temperature and is then subsequently reheated for
the blowing stage. However, the container used for this
investigation was formed by the alternate one-stage route
where the hot preform is moved to a conditioning zone in
order to cool to the blowing temperature before moving
to the blowing zone. In both these manufacturing routes
there is a significant variation in the temperature profile
through the wall of the preform at the moment of extension
in the blowing zone. During blowing, the inner surface of
the preform is cooled by the expansion of the compressed
air used for inflation, the outer surface is cooled by contact
with the (relatively) cold mould whilst the internal thermal
energy is raised by strain heating. In addition, the contour
shape of the container and the complex blowing process
itself produces considerable variation in wall thickness and
direction of stretching at different positions in the container.
The polymer therefore experiences a wide variation in draw
temperature, draw ratio and draw direction at different
positions of the container and at different depths in the wall,
resulting in a wide variation of orientation and crystallinity
in the local polymer structure. In order to understand the
mechanical properties of the container it is necessary to
be able to characterize how this structure can vary. One
of the main difficulties of this characterization, and the
reason for undertaking this investigation, is the difficulty of
probing variations in structure through the container wall
Journal of Synchrotron Radiation
ISSN 0909-0495 © 1997