Rheology Testing of Polymers and the Determination of Properties Using Rotational Rheometers and Cap
Topics Covered
Background Factors That Affect the Rheology of Polymers Melt Viscosity and Its Temperature Dependence Die Swell or Extrudate Swell Melt Elasticity Concentration of Additives Characterising Flow Behaviour Rotational Rheometers Capabilities of Modern Rotational Rheometers Flow Curves Creep Tests Stress Relaxation Small Amplitude Sinusoidal Oscillatory Testing How Viscoelastic Characterisation has Solved Real Processing Problems Variability of Tube and Pipe Gauges in Extrusion Processes Reducing Inconsistent Fibre Spinning Properties Capillary Extrusion Rheometers Determination of Die Swell Applications of Capillary Rheometers Extensional Properties Capillary Rheometers and Processing Behaviour Melt Fracture Differences between Calculated Rheological Properties and Practice Conclusion
Background
Rheology is the science of studying the flow and deformation of materials rooted in the laws of elasticity and viscosity proposed by Hooke and Newton in the late 17th Century. Thermoplastic polymer melts are widely used in many modern industrial processes to manufacture a multitude of objects. Polymers are used because they are relatively cheap to form into complex shapes in the molten state and therefore, we need to understand how they flow when being processed.
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Rheology Testing of Polymers and the Determination of Properties Using Rotational Rheometers and Cap
Melt Elasticity
Melt elasticity can also have profound implications for many other polymer processes such as: Blow Moulding where the wall thickness of the blown component depends on the degree of swell that has taken place during the extrusion process prior to the mould being closed. Vacuum Forming or Thermoforming where the polymer must maintain a degree of elasticity to prevent the material sagging before it is pulled by vacuum over the cold forming die. If the material does not have sufficient elasticity it is likely to come into contact with the chilled die before the vacuum or pressure is applied.
Concentration of Additives
Polymer processing properties also depend on the concentration of lubricants, plasticisers, fillers and other components in the compound being processed. From this brief introduction one can appreciate that proper characterisation of polymer melt flow behaviour is likely to require sophisticated and versatile instrumentation.
Rotational Rheometers
These instruments normally require a small specimen of the material to be tested in the form of disk typical dimensions being 25mm diameter and 1mm thick. The sample is placed between a pair of parallel plates or upper cone and lower plate whose temperature can be maintained by an external heating device such as a blown gas oven or electrical heating of the plates.
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Rheology Testing of Polymers and the Determination of Properties Using Rotational Rheometers and Cap
Flow Rates Creep Tests Stress Relaxation Small amplitude sinusoidal Oscillatory Testing
Flow Curves
Flow curves to measure the shear viscosity versus shear rate or shear stress. At sufficiently low shear rates a constant value for the viscosity will be attained. This so called zero shear viscosity has been shown to depend on the average molecular weight of the polymer and the length of the plateau (how high a rate before the viscosity decreases) is known to reflect the width of the molecular weight distibution. Software packages are available to determine the average molecular weight and molecular weight distribution from such data.
Figure 1. Flow curve for LDPE at 190C showing low shear rate plateau for viscosity. The magnitude of the zero shear viscosity is determined by the average molecular weight of the polymer.
Creep Tests
Creep tests (application of constant stress for a defined period of time) allow an alternative means of determining the zero shear viscosity. When combined with recovery testing (removal of the stress) these tests enable the amount of elasticity in the sample to be measured because a material will with elasticity will recoil and attempt to recover its original shape.
Figure 2. Creep (Blue) & Recovery (Red) Curve Polypropylene at 190C allow zero shear viscosity to be determined and equilibrium recoverable compliance.
Stress Relaxation
Stress Relaxation tests apply an instantaneous deformation (strain) to the sample and record the time dependent decay of stress with time. The rate of decay of the stress depends on the viscoelasticity of the polymer at the test
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Rheology Testing of Polymers and the Determination of Properties Using Rotational Rheometers and Cap
temperature. The data is often displayed as relaxation modulus versus time. Integration of the modulus versus time function is an often forgotten but rapid means of determining the zero shear viscosity and hence average molecular weight. Differentiation of the modulus/time function produces the continuous relaxation time distribution curve. This rather complex function in principle contains information relating to the molecular weight distribution of the polymer.
Figure 3. Stress relaxation data LDPE at 190C. The relaxation time distribution curve includes information about the molecular weight distribution of the polymer.
Figure 4. Frequency Sweep for Polypropylene at 190C. The Cross-Over Point is determined by the average molecular weight and molecular weight distribution.
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Rheology Testing of Polymers and the Determination of Properties Using Rotational Rheometers and Cap
scope of this short article, but the following examples are included to illustrate how viscoelastic characterisation of polymers has solved real processing problems:
Figure 5. Frequency Sweep data for two HDPE pipes. The sample with higher elastic modulus produced the larger gauge pipe.
Figure 6. Complex Viscosity as a function of frequency for good and bad PP Fibre samples. Note that no discernable difference is evident.
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Rheology Testing of Polymers and the Determination of Properties Using Rotational Rheometers and Cap
Figure 7. Storage Modulus as a function of frequency for good and bad PP Fibre samples. The bad sample had more elasticity causing inconsistent fibre diameter.
Extensional Properties
Figures 8 & 9 show both shear and extensional data, which illustrates an important and often neglected point: Two polymers may have almost identical shear flow behaviour, but may exhibit considerably different extensional properties. As noted previously, many polymer processes (fibre spinning, blow moulding) are essentially extensional processes and so determination of extensional viscosity is more important than measuring shear viscosity.
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Rheology Testing of Polymers and the Determination of Properties Using Rotational Rheometers and Cap
Figure 8. Shear viscosity versus shear rate. The data for the two rubbers is indistinguishable.
Figure 9. Extensional viscosity versus extension rate for the same materials shown in figure 8. There are clear differences in the extensional.
Melt Fracture
Flow instability or melt fracture is generally the result of tensile stress when the melt flows from a large cross-section to a smaller one. If the tensile stress becomes large enough, the melt fractures. The effect of melt fracture becomes less noticeable as the length of die is increased and as the die temperature is increased. Increasing die length damps out the effect of the cross-section change at the entrance of the die and increasing temperature reduces the viscosity and also the stress at the same shear rate. In a capillary rheometer a region of melt fracture is revealed as a regular oscillation of the melt pressure signal as shown below. The melt effectively fractures and then reforms with the effect that adjacent elements have experienced different extensional histories and so will swell differently upon exiting the die.
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Rheology Testing of Polymers and the Determination of Properties Using Rotational Rheometers and Cap
Figure 10. Evidence of Melt Fracture is shown by the oscillating pressure signal. The material is Polypropylene measured at 190C.
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Rheology Testing of Polymers and the Determination of Properties Using Rotational Rheometers and Cap
Figure 11. Rheograms for HDPE at 200C. The line of constant stress reveals evidence of Wall Slip.
Figure 12. Slip velocity versus shear rate for HDPE at 200C. Slip velocity is calculated by Mooneys method.
Conclusion
Polymer melt rheology is a complex subject that requires careful experiment design in order to obtain the information needed to meet an investigators requirements. Rotational rheometers are the preferred choice when the requirement is to obtain information concerning the molecular structure and how this affects processing characteristics. In particular, the ability to easily extract information about the average molecular weight and molecular weight distribution via measurement of the viscoelastic properties makes the rotational rheometer a powerful tool. The capillary rheometer extends the shear rate range attainable in the laboratory beyond that available in a rotational instrument and allows the flow properties to be measured under typical processing conditions. In addition, the ability to readily determine both the shear and extensional properties under real life conditions provide the polymer producer and processor with information that is vital to the successful use of a polymer melt. Finally, the capillary rheometer enables processing problems to be investigated in a controlled environment without the need to stop. Source: A Rheological Viewpoint of Thermoplastic Melts, Application Note by Malvern Instruments. For more information on this source please visit Malvern Instruments Ltd (UK) or Malvern Instruments (USA).
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Rheology Testing of Polymers and the Determination of Properties Using Rotational Rheometers and Cap
Date Added: Apr 13, 2005
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measurement in a single system allowing the generation of information important in determining dispersion stability and understanding and controlling the behavior of nanoparticles in dispersion. Malvern rheometers have applications in testing the bulk properties of materials, for example to demonstrate whether or not materials are suitably stabilized. Properties that the Zetasizer Nano can determine include: Particle size Dispersion stability Zeta potential Rheological properties
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