Polymer Testing 21 (2002) 313–317

www.elsevier.com/locate/polytest
Test Method
PVT testing of polymers under industrial processing
conditions
*
Sekhar Chakravorty
The Materials Centre, National Physical Laboratory, Teddington, Middlesex TW11 0LW, UK

Received 25 June 2001; accepted 8 August 2001

Abstract

The development of a PVT (Pressure–Volume–Temperature) equipment for measuring polymer properties at indus-
trial processing conditions is described. Results of rapid cooling (200°C/min) and high pressure (20–160 MPa) isobaric
temperature scan tests in HDPE and PP are presented. The development of a new test cell that allows PVT measurements
on thin samples (苲2 mm thick) has been reported with typical results from a commercial grade PP material. A new
generation of industrially relevant fast cooling PVT data on 10 widely used polymers have been collated on CD that
are aimed to benefit designers and engineers in the polymer processing sector. The database may also aid further
development of the commercial plastics processing software packages.  2002 Elsevier Science Ltd. All rights reserved.

1. Introduction components. Fig. 1 shows a typical 3-D mesh display of

Shrinkage, warpage and sink marks are important
problems of plastic injection moulded products. Ther-
mally induced volume shrinkage of the part during coo-
ling and thermal stresses produced during filling and
packing has been related to these defects [1]. For an
injection moulder to take on premium work requiring
tight tolerances with increased confidence and reduced
scrap rates, an improved understanding of the shrinkage
and warpage behaviour in plastic components may be
required. The ability to predict behaviour accurately can
be expected to provide the moulder with the benefits of
reduced cycle times, reduced time to market and reduced
scrap rates with consequent commercial benefits.
Commercial software packages, such as Moldflow/C-
Mold, are available which have the capability of pre-
dicting the shrinkage and warpage behaviour in plastic
* Tel.: +44-(0)20-8943-6919; fax: +44-(0)20-8943-6046.
E-mail address: sekhar.chakravorty@npl.co.uk (S.
Chakravorty).
a hubcap, on which volume shrinkage predictions were
made at slow and fast cooling rates (at 10°C/min and at
260°C/min). At slow cooling rate, the predicted shrink-
age was 苲1.2% in the central region as compared to
苲1.8% in the outer region, whereas at the fast cooling
rate, the predicted shrinkage at the centre was 苲5% as
compared to 苲3% in the outer region. A difference of
up to 400% in shrinkage distribution prediction value in
this component is obtained due to the cooling rate effect.
Accurate prediction is, therefore, only possible when
good quality credible data relevant to industrial pro-
cessing conditions are made available to the software
companies. This is also particularly true for a moulder
launching new products to ensure mould design is right
first time. In addition, it is also important to be able to
optimise processing conditions and to modify the choice
of polymer with ease each time requirements change.
Plastics processing, such as injection moulding, is a
rapid, high pressure process where both cooling rate and
pressure play critical roles for the final component
dimensions. The degree of crystallinity in semi-crystal-
line polymers depends on the rate of cooling, molecular
structure, shear and pressure history, presence of nucleat-
ing agents etc. Properties of semi-crystalline polymers
are particularly sensitive to the rate of cooling. Under

0142-9418/02/$ - see front matter  2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 1 4 2 - 9 4 1 8 ( 0 1 ) 0 0 0 8 9 - 7
314 S. Chakravorty / Polymer Testing 21 (2002) 313–317
Fig. 1. 3-D mesh display of a hubcap from Moldflow
(diameter 410 mm, thickness 4–5 mm).
fast cooling rates, the transition to the crystalline phase
occurs at lower temperatures [a downward shift of
苲100°C in transition temperature due to fast cooling in
a polyamide has been reported [2]]. The degree of
change from slow cooling rates to fast cooling rates
depends on the molecular structure, the degree to which
the material shrinks, and also due to the change in
material density. Changes induced by crystallisation, in
particular, have been found to significantly influence
shrinkage and warpage values. Several other factors such
as visco-elastic behaviour of polymers, variable mould
temperature profile due to non-uniform cooling, and mol-
ecular and fibre orientations, also contribute directly to
actual shrinkage and warpage values in moulded parts
[1].
Pressure is known to induce molecular order and shift
polymer melting points (Tm), crystallisation temperatures
(Tcrys) or glass transition temperatures (Tg) to higher tem-
peratures. It is, therefore, important to understand the
pressure dependence of Tm, Tcrys and Tg from both practi-
cal (i.e. machine settings) and theoretical (i.e. free vol-
ume, compressibility effects) viewpoints [3].
Cooling rate plays a critical role in polymer processing
because materials experience rapid cooling when trans-
ferring from the melt to the solid state [4]. Like pressure,
cooling rates also influence the parameters (Tcrys and Tg)
but in this case, their positions are shifted to lower tem-
peratures. Since most Pressure–Volume–Temperature
(PVT) data on polymeric materials are only available
under slow cooling rates (maximum 10°C/min) which
rarely occur in commercial injection moulding, there is
a need to introduce fast cooling rate effects into both
PVT measurements and modelling software.
2. Results and discussion
The demand for accurate and relevant data by the
designers, process engineers and software manufacturers
who evaluate the relationships between PVT behaviour
of polymers at high pressures and at high cooling rates
is increasing. Until recently most of the experimental
PVT data in the literature were reported either in equilib-
rium state [5] or at slow (maximum 10°C/min) cooling
rates ([4,6]) that are far from being the actual conditions
experienced during polymer processing. In addition, the
sample size has also not been given proper consideration
in the reported PVT results, hence, the data published
cannot be related directly to the actual component part
thickness.
In response to these measurement problems, the
National Physical Laboratory (NPL) in the UK has
developed a rapid cooling PVT equipment (jointly with
SWO/Haake GmbH) by incorporating a number of novel
technical features. The measurement of critical PVT
parameters is now possible, for the first time, at fast coo-
ling rates (up to 300°C/min), at high pressures (up to
250 MPa) and at high melt temperatures (up to 420°C)
with the measurement capability down to sub-zero tem-
peratures (to ⫺100°C) on samples of thickness down to
2 mm in iso-baric and iso-thermal conditions, bringing
the NPL PVT testing close to industrial polymer pro-
cessing conditions [7,8].
An example of the fast cooling PVT plots from a high
density polyethylene (HDPE) is shown in Fig. 2 under
a range of pressures between 20–160 MPa and at a coo-
ling rate of 200°C/min (the temperature, in this case, was
measured in the metal barrel, 苲1 mm away from the melt
surface in a 7.8 mm diameter test cell). The isobaric coo-
ling plots show the typical “S” shape at all given press-
ures indicating phase transition regions. These regions
(and hence, the shape), however, become sharper in slow
cooling tests where the crystallisation rate is relatively
slow (Fig. 3). Likewise, semi-crystalline polymers would
show phase transition regions more clearly than amorph-
ous materials since the density would increase with crys-
tallisation. In general, the onset of crystallisation greatly
varies between about 250°C to 120°C in most polymers
(150°C to 120°C in HDPE) due to differences in material
types as well as applied pressures and moderately depen-
dent on the cooling rates. Increasing pressure increases
the onset temperature of crystallisation. The end of crys-
tallisation in most polymers takes place between the tem-
peratures 50°C and 100°C (50°C–70°C in HDPE). The
shrinkage due to melt compressibility is generally found
to be 10–20% in polymers (苲10% in HDPE) with the
highest values obtained in TPE, PS, ABS and PVC. The
 S. Chakravorty / Polymer Testing 21 (2002) 313–317 315

Fig. 2. Fast controlled cooling PVT test results to sub-zero temperature: HDPE, cooling rate 200°C/min, sample thickness 3.9 mm,
isobaric temperature scan runs.

Fig. 3. Slow cooling PVT test results in HDPE. Cooling rate 5°C/min, sample thickness 3.9 mm, isobaric runs.

overall shrinkage in the test samples is found to vary
between 20–25% in all polymers including a change of
10–15% in value due to crystallisation.
In order to assess the correct shrinkage values in the
specimen, it was necessary to ensure that the entire sample
becomes solid in rapid cooling tests before the test is over.
This led to further development of the NPL equipment,
which enabled it to operate under sub-zero temperatures
(i.e. down to ⫺100°C) from the melt temperature (see Fig.
2) at a constant cooling rate of up to 300°C/min and at
pressures between 30 and 250 MPa. This particular
improvement is also expected to indicate the extent of any
temperature gradient present in the rapidly cooled test
samples, thus benefiting the PVT measurement from better
understanding of the morphology and related shrinkage
behaviour in polymeric materials [9,10].
A new design of the test cell based on piston/cylinder
type geometry (Fig. 4) has been developed at NPL which
enables PVT measurements to be carried out on thin annu-
lar samples (苲2 mm thick). The PVT data thus generated
would be closer to typical component part thickness. It is
also expected that any temperature gradient present in the
316 S. Chakravorty / Polymer Testing 21 (2002) 313–317
Fig. 4. Test cell sealants for 2 mm thick annular sample (in
the centre).
thicker test samples would be drastically reduced in this
case. Results of PVT tests on 2 mm thick samples of poly-
propylene (PP) at 400 bar pressure are shown in Fig. 5
at various cooling rates using the newly developed test
cell. The typical “S” shape of the isobaric cooling plots
indicate the onset and the end of crystallisation regions in
this material and show a maximum difference of 苲5% in
shrinkage value (specific volume) compared to the data
obtained from similar PVT tests on 3.9 mm thick samples
in a 7.8 mm diameter test cell (Fig. 5).
3. Conclusions
The NPL PVT equipment is the only one of its kind in
the world that had been modified to make measurements
of critical PVT parameters close to injection moulding
Fig. 5. PVT test results in 2 mm annular and 7.8 mm diameter cells, polypropylene, 400 bar pressure, isobaric runs.
conditions. This facility is expected to help the plastics
industry to optimise processing parameters. A new gener-
ation of industrially relevant fast cooling PVT data on 10
widely used polymers is now available on CD, which
could benefit further development of the computer simul-
ation software packages such as Moldflow. Engineers and
designers in the polymer processing sector may gain better
understanding of the shrinkage and warpage behaviour in
their products from these new industrial PVT data.
Acknowledgements
The author would like to thank the members of the
IAG on “Measurement Methods Relating to the Pro-
cessing of Plastics” for their kind support and advice and
to the following staff members of NPL for their help and
useful discussions: C.S. Brown, P. Alder, L. Sharma and
C. Hobbs. The work reported here was carried out under
the EID “Measurements for Processability of Materials
(MPM) Programme” financed by the United Kingdom
Department of Trade and Industry.
References
[1] R.Y. Chang, B.D. Tsaur, Polym. Eng. Sci. 35 (15)
(1995) 1222.
[2] M. Mahishi, C-Mold News 10 (4) (1998) 4.
[3] S. Yang, M. Ke, ANTEC’93, 1993, p. 2182.
[4] R.Y. Chang, C.H. Chen, K.S. Su, Polym. Eng. Sci. 36 (13)
(1996) 1789.
 S. Chakravorty / Polymer Testing 21 (2002) 313–317 317

[5] P. Zoller, D. Walsh, Standard PVT Data for Polymers,
Technomic Co, 1995.
[6] S. Chakravorty, C.S. Brown, NPL report DMM (D)262,
June 1995.
[7] C.B. Hobbs, C.S. Brown, NPL report CMMT (A)163,
February 1999.
[8] S. Chakravorty, NPL report CMMT (A)244, December
1999.
[9] S. Chakravorty, Plastics and Adhesives News newsletter,
issue 6, NPL, 2000.
[10] S. Chakravorty, Plastics and Adhesives News newsletter,
issue 7, NPL, 2001.