JOURNAL OF MATERIALS SCIENCE LETTERS 14 (1995) 1638-1640
Investigation of axial fibre stresses in transcrystalline regions of single-
fibre aramid/polypropylene composites using Raman spectroscopy
M. HEPPENSTALL-BUTLER, R. J. YOUNG
Manchester Materials Science Centre, UMIST/University of Manchester, Grosvenor Street, Manchester, M1 7HS,
UK
Transcrystallinity (TC) is a phenomenon that can
occur in a wide range of thermoplastic-matrix
polymer composites. Nucleated from reinforcing
fibres, this structure grows into the matrix and in
high volume fraction fibre-reinforced composites can
dominate the matrix morphology [1]. It is essential,
therefore, to understand the properties of both the
transcrystallinity and the interface between TC and
the nucleating fibres.
Despite all the literature produced on this subject,
the causes and effects of TC are not understood fully.
Transcrystalline regions are thought to have a higher
modulus than the spherulitic matrix [2], but their
effects on the interfacial adhesion are still unclear.
The different techniques used to characterize different
morphological types have yielded a selection of
results and views on how TC is caused and whether
or not it is useful for an improvement in composite
properties [1]. Investigating cotton cellulose in
isotactic polypropylene (iPP), Felix and Gatenholm
found an increase in interfacial shear stress (ISS)
with increasingly thick TC [3]. Yue and Cheung [4],
reported that nuclei adhering to glass fibres after pull-
out from iPP indicated that adhesion between fibre
and matrix was stronger at the point of nucleation
than in the outer lamellae of spherulites. From this
they deduced that the interfacial bond between a fibre
and TC would be stronger than that between fibre
and a spherulitic matrix. Folkes and Wong [5], found
that surface-treatment-nucleated transcrystallinity re-
duced the interfacial bond strength between glass
fibres and iPP. Others report, however, (e.g. Moon
[6]), that the effect of TC upon interfacial strength
varies with other matrix variables, or with fibre
volume fraction, but whatever the effect TC has upon
interfacial properties it is only minor [7-9]. There has
also been experimentation to determine the levels of
thermal residual stresses induced in the fibres due to
the presence of TC regions. Incardona et al. [10]
concluded that increasing the thickness of the
transcrystalline region lowers the residual thermal
stresses present in the fibre.
In this communication we present measurements of
the point-to-point thermal residual stress distributions
along Twaron fibres in various transcrystalline and
non-transcrystalline isotactic polypropylene (iPP)
matrix morphologies as measured using Raman
spectroscopy. This is the first time that such
measurements have been reported.
1638
The materials used were Twaron D1056 aramid
fibres, and SY6100 iPP, as described in references
[11-13] by Thomason and Van Rooyen. Long single-
fibres were placed between small slivers of iPP,
melted to 200 °C~ and pressed between glass slides to
reduce the thickness. After cooling, these samples
were placed in a Linkam THMS600 hot-stage
between glass cover slips in an argon atmosphere
and blank melted at 200°C for 5min before
receiving one of five thermal histories. Four of the
thermal histories involved a period of constant
temperature crystallization (T~), the fifth was fast-
cooled directly from the melt to room temperature at
-2.5 Ks -1. The constant temperature samples were
cooled at -10Kmin -1 to Tc=140°C, 135°C,
130°C, or 120°C for 300, 120, 70, or 10min,
respectively. Following this, they were then fast-
cooled at about -2.5 K s -1 to room temperature. The
thermal histories will be referred to as FC (fast
cooled), 140, 135, 130, or 120. The 135, 130, and
120 histories produce well-defined TC. The increas-
ing nucleation rate with decreasing T~ results in finer
TC with lower T~. The radii of spherulites and TC are
also affected, decreasing from -100gm in 135
samples to about -80~tm in 120 samples. FC
produces very fine TC of radius -20 girl. The 140
treatment produces a spherulitic matrix with no
transcrystallinity. The samples were 60 gm _+ 15 gm
thick, with fibres of diameter 11.7 gm _+ 0.4 gm
passing straight through the iPP films.
Raman spectroscopy can be used to measure the
axial stresses in the outer surface of aramid fibres.
The residual axial stress distribution along each
embedded fibre was measured using a series of
Raman spectra taken at intervals along the fibre in
the matrix. The Raman spectra were obtained as
follows. The 632.8 nm red line of a 15 mW helium-
neon laser was focused to a point about 5 gm
diameter on the fibre through a modified Olympus
optical microscope so that the polarized laser light
was oriented parallel to the axis of the fibre. The
scattered radiation from the fibre was passed through
a set of a collection optics to a SPEX 1000M
monochromator. The spectrum was collected using a
Wright Instruments Charge-Coupled Device (CCD)
camera cooled with liquid nitrogen [14]. Raman
spectra were taken along the fibre at 10, 20 or 50 gm
intervals from the region of fibre outside the matrix
through up to 2000 gm into the matrix. The region
0261-8028 © 1995 Chapman & Hall