Polymer Testing 21 (2002) 313317 www.elsevier.

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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 (PressureVolumeTemperature) equipment for measuring polymer properties at industrial processing conditions is described. Results of rapid cooling (200C/min) and high pressure (20160 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 (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 benet 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 Shrinkage, warpage and sink marks are important problems of plastic injection moulded products. Thermally induced volume shrinkage of the part during cooling and thermal stresses produced during lling and packing has been related to these defects [1]. For an injection moulder to take on premium work requiring tight tolerances with increased condence 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 benets of reduced cycle times, reduced time to market and reduced scrap rates with consequent commercial benets. Commercial software packages, such as Moldow/CMold, are available which have the capability of predicting 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).

components. Fig. 1 shows a typical 3-D mesh display of a hubcap, on which volume shrinkage predictions were made at slow and fast cooling rates (at 10C/min and at 260C/min). At slow cooling rate, the predicted shrinkage was 1.2% in the central region as compared to 1.8% in the outer region, whereas at the fast cooling rate, the predicted shrinkage at the centre was 5% as compared to 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 processing 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 rst 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 nal component dimensions. The degree of crystallinity in semi-crystalline polymers depends on the rate of cooling, molecular structure, shear and pressure history, presence of nucleating 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

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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 equilibrium state [5] or at slow (maximum 10C/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 rst time, at fast cooling rates (up to 300C/min), at high pressures (up to 250 MPa) and at high melt temperatures (up to 420C) with the measurement capability down to sub-zero temperatures (to 100C) on samples of thickness down to 2 mm in iso-baric and iso-thermal conditions, bringing the NPL PVT testing close to industrial polymer processing 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 20160 MPa and at a cooling rate of 200C/min (the temperature, in this case, was measured in the metal barrel, 1 mm away from the melt surface in a 7.8 mm diameter test cell). The isobaric cooling plots show the typical S shape at all given pressures 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 amorphous materials since the density would increase with crystallisation. In general, the onset of crystallisation greatly varies between about 250C to 120C in most polymers (150C to 120C in HDPE) due to differences in material types as well as applied pressures and moderately dependent on the cooling rates. Increasing pressure increases the onset temperature of crystallisation. The end of crystallisation in most polymers takes place between the temperatures 50C and 100C (50C70C in HDPE). The shrinkage due to melt compressibility is generally found to be 1020% in polymers (10% in HDPE) with the highest values obtained in TPE, PS, ABS and PVC. The

Fig. 1. 3-D mesh display of a hubcap from Moldow (diameter 410 mm, thickness 45 mm).

fast cooling rates, the transition to the crystalline phase occurs at lower temperatures [a downward shift of 100C 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 signicantly inuence shrinkage and warpage values. Several other factors such as visco-elastic behaviour of polymers, variable mould temperature prole due to non-uniform cooling, and molecular and bre 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 temperatures. It is, therefore, important to understand the pressure dependence of Tm, Tcrys and Tg from both practical (i.e. machine settings) and theoretical (i.e. free volume, compressibility effects) viewpoints [3]. Cooling rate plays a critical role in polymer processing because materials experience rapid cooling when transferring from the melt to the solid state [4]. Like pressure, cooling rates also inuence the parameters (Tcrys and Tg) but in this case, their positions are shifted to lower temperatures. Since most PressureVolumeTemperature (PVT) data on polymeric materials are only available under slow cooling rates (maximum 10C/min) which rarely occur in commercial injection moulding, there is

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

Fig. 3.

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

overall shrinkage in the test samples is found to vary between 2025% in all polymers including a change of 1015% 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 100C) from the melt temperature (see Fig. 2) at a constant cooling rate of up to 300C/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 beneting 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 annular samples (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

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conditions. This facility is expected to help the plastics industry to optimise processing parameters. A new generation of industrially relevant fast cooling PVT data on 10 widely used polymers is now available on CD, which could benet further development of the computer simulation software packages such as Moldow. 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.

Fig. 4. Test cell sealants for 2 mm thick annular sample (in the centre).

Acknowledgements The author would like to thank the members of the IAG on Measurement Methods Relating to the Processing 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 nanced by the United Kingdom Department of Trade and Industry.

thicker test samples would be drastically reduced in this case. Results of PVT tests on 2 mm thick samples of polypropylene (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 5% in shrinkage value (specic 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).

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, ANTEC93, 1993, p. 2182. [4] R.Y. Chang, C.H. Chen, K.S. Su, Polym. Eng. Sci. 36 (13) (1996) 1789.

3. Conclusions The NPL PVT equipment is the only one of its kind in the world that had been modied 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.

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[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.