entry pressure drop, it does not take into account nonlinearities in the Bagley plot and is subject to errors in the extrapolation process. A more accurate method of PO determination is by direct measure- ment using an orifice die with effectively zero length [27]. The most common method is to use two dies, one long die (L:D = 16:1) and
one orifice die (L:D ≈ 0), carried out simultaneously in the case of
twin bore rheometers. From Fig. 6, die entry pressure drop can be
seen to increase with wall shear rate and molecular weight and decrease with increasing temperature.
Extensional viscosities and extensional strain rates were cal- culated using Eqs. (7) and (9), respectively and the relationship between these two parameters is shown in Fig. 9. Extensional vis- cosity was found to decrease with increase strain rate (i.e. tension thinning) at the rates examined, and increased with increasing molecular weight and decreasing melt temperature, in similar man- ner to that shown by shear viscosity. Extensional viscosities were observed to be a factor of between 260 and 2900 higher than shear viscosity, which is typical for polymer melts. Ratio of extensional to shear viscosity increased with increasing molecular weight and decreasing temperature, i.e. with increasing melt viscosity. The ratio between extensional viscosity and Newtonian shear viscos- ity is termed the Trouton ratio [28] and is 3:1 for Newtonian fluids. For non-Newtonian polymers at high strain rates, the ratio is sev- eral orders of magnitude greater, and provides an indication of the relative importance of extensional flow, which is highly dependent upon molecular structure.
An understanding of the relationships between shear and exten- sional flows with temperature, processing rate and molecular weight is a useful tool for process design, optimisation and trou- bleshooting. The characterisations carried out during these studies have shown that the flow behaviour of the HPC grades studied was typical of many thermoplastic polymers of relatively high molecu- lar weight, up to a certain processing rate. Above this critical rate or stress significant instabilities were generated, in particular for the two higher molecular weight HPC-SL and HPC-L grades at low tem- peratures. Two distinct instabilities were observed; the appearance of a surface roughness at high shear rates which was followed by the formation of a foamed extrudate core. The prior has been reported by many workers for polymers such as polyethylene, polypropy- lene, polystyrene and polybutadiene but formation of foam without [25] addition of additive has not been reported. It is important to understand the basic cause of this phenomenon, which is poten- tially advantageous to drug delivery system design, and is therefore the subject of ongoing research in our laboratories.