‘D) Dynisco Polymer Test ‘THE CAPILLARY RHEOMETER: Applications in the Plastics Industry by Don DeLaney and Steve Houlston The conversion of thermoplastic materials from pellets info molded parts requires several process steps. No matter what the conversion process, be it injection molding blow molding, compression molding, calendering, or extrusion, the plastic is meted, forced to flow or deform, and then cooled to its final state as a solid or rubber. In all plastics conversion processes the flow characteristics are important in defining process parameters, For this reason, it is not surprising that the measurement of polymer melt flow has been considered a critical factor in determining the processabiliy ofthe polymer. “The preferred method for quantifying melt flow has been the mett flow index (MFI) oF ‘melt flow rate (MFR) test. In this test one determines the weight of polymer extruded in 10 minutes under standard eondiione of temperature, geometry, and forse. Th MFR. machine is inexpensive, and its simplicty of operation has made this test popular in the plastics industry, ‘The more complex capillary rheometer, which can measure the flow properties of a material over the ful range of rates, forces, geometries, and temperatures arising in Actual conversion processes, has often been relegated to the R & Dlabs. Frequent, a skilled professional has been required to operate such instruments In recent years, however, with the advent of more demanding molding and extrusion ‘applications, and the introduction of computer aided design and moid-fiow programs, the requirement for extensive theological data has increased dramatically. ‘At the same time, advances in automation and computer software have made the capilary rheometer more user friendly. In addition, there are now rheometers that, while stil more expensive than a MFR machine, are available at a moderate price. The capilary rheometer can now be used for solving day to day issues facing manufacturers and processors inthe polymer industry. ‘The capillary theometer is similar in construction to the MFR machine, with a temperature controlled barrel containing a piston, which forces melted polymer through a controlled dimension capillary. Whereas in the MFR machine the force used to extrude the polymer is produced by a fixed dead weight, inthe capilary rheometer itis generatedby a motor and screw or servoshydraulic system (See Fig, 1), allowing a variable force ‘and rate of extrusion, ‘The force (shear stress) required to produce polymer flow is measured either by a {oad cell on the piston or by a pressure transducer in the rheometer barrel. The rate of flow (shear rate) is determined from the pistons speed and geometry of the capllay die, Values of both the rate of polymer flow and the force needed to cause this fw are ‘combined to calculate the viscosity, or resistance to flow, from the relationship: Figure 1. The Capillary Rheometer Viscosity) = shear strss(x)/ shear rate (7) Since the viscosity is sensitive to temperature, control of the rheometer barrel temperature is critical to performance, and much effort goes into assuring a stable constant temperature during a testing ‘The capillary rheometer has all ofthe elements necessary to simulate the operation of machines used in plastics conversion processes. Early extruders and injection molding machines actualy used a ram rather than a secew. With the range of speeds avaiable in the capilary rheometer, It is able to simulate the rates at which polymer met is deformed in most conversion processes. It has become a valuable tool for the modeling ofthese processes and for the design of molds and dies, ‘The capillary cheometer is also be used to test the materials used in conversion processes to determine if they will mest the processing specifications, Since the temperature Is also controlled, iis possible to estabish the effects of the processing temperature on flow ofthe material “The viscosity ofa polymer is very sensitive to degradation or eross-tinking. Thus the capilary rheometer is frequenty used to predict resin thermal stability. The optimum ‘molding cycle or extrusion rate at a particular processing temperature can then be established from these measurements. Once the optimal processing properties havebeen established, the results can be used to ensure that all incoming materials are within specification. Some examples ofthese applications are given below. Grading polymers: The capillary rheometer may be used by both the resin manufacturer and the processor to assure that @ material complies with the flow tolerances set for that grade. A quality control graph of a polymer flow curve can be generated, with upper and lower critical viscosity limits over multiple decades of shear ‘ates being generated by running multiple tests on a standard material, ‘When a resin fis within this qualty curve over the entire range of shear rates tis in specification. Wen the resin fails to meet the specification, the curve may show that, for example, the resin is within the QC tolerances at low shear rates (where the MFR. test is run, but falls to qualify at high shear where the actual processing ofthe polymer takes place, (See Fig. 2.) This s clearly a valuable test for both manufacturers and processors. In contro! a i H a ll Figure 2. Quality Control with the Capillary Rheometer Thermal stability. Almost all polymers degrade if they are heated too hot or for too long. However, some materials wil continue to polymerize or will react to give cross- linking, which wll result in an increase the viscosity. If @ processor, in trying to reduce ‘yele time, raises the mett temperature, he may produce defective parts as a result of high flow from degradation of reduced flow due to cross-linking. Its important thatthe processor knows the thermal stablity of the material and the associated processing Tritatons, With the capillary cheometer the measurement of thermal stability is a straightforward test. The rheometer is set up measure viscosity at distinct time intervals, at a constant temperature and shear rete, over a set period of time. The stablity, at the set ‘temperature, can then be determined from whether the viscosity increases, decreases, or slays the same and how fast any change occur. “Tne rate of change can be obtained from the slope ofthe viscosity line. An exemple is given or PVC, which requires adequate stabilzation before it can be processed.! i ! | Figure 3. Thermal Stability of PVC Figure 3 shows the thermal stably test on one material st three different processing temperatures. In this case, the viscosity is. adequately stabilized at the lowest {tempersture, but there isan increase at higher temperatures, indicating that crosslinking is probably occurring, Temperature sensitivity: Not all meited polymers react to changes in temperature in the same way. Some resins, such as PMMA, show large changes in viscosity with small changes. in temperature while others, ike LDPE are relatively insensitve. This information is easily oblained trom the capillary rheometer by generating theology curves at several different possible processing temperatures. These data can then be Used to determine the relationships between temperature and viscosity at several shear rates. This information wil tel an injection molder by how much his molding cycle can be shortened, by raising temperature, before flashing occurs. LDPE will be much more forgiving than PMMA. The information is also valuable to the mald or die designer using ‘computer aided flow simulation programs. When used, along with the rheological profle, the temperature sensitivity of the polymer provides the information required to produce fan accurate flow model to be incorporated nto the mold filing or die flow design programs. Processing effects: Processing may have an effect onthe flow properties of a material ‘even when it meats all the requirements for a finished par. Figure 4 shows the viscosity change in PET before and after being molded. The third and lowest viscosity curve is for ‘material from a faled part containing recycle material ET is becoming very popular in the packaging industry, but is relatively expensive. ‘There is an interest in recycing material by adding it to the virgin resin to reduce costs Since the viscosity is a good indicator of the degree of degradation, the capillary ‘heometer is able to provide a measure ofthe quality of recycled material to be used in a process. It then can be used to obtain a measure of how the level of added scrap affects the processabilly and properties ofthe final product. Obviously too much recycle was used in the above example. This same procedure can also be applied to other engineering or commodity thermoplastics,vncoay (es oF co ‘ ‘shaarrae (i) Figure 4, Effect of Processing and Recycle on PET Process control optimisation: Rheological information can be a valuable tool in cffciently setting up production machines. When a new material is received for Introduction into a process, a series of capilary rheometer uns will provide a picture of the resin and is QC limits. Ths information ean then be comelated withthe processing Conditions established when the process is set up correctly. When the material fs within the QC limits, developed as shown earlier, the processor knows exactly how to set up the process. Ifthe flow curve falls outside ofthe limits, the ‘material can be returned or a new QC curve generated to correlate to the new machine Conditions. This process can be applied to different resins as well as diferent batches of the same resin. Eventually, the processor wil have a database that will alow the prediction for the machine set up from a quick rheological test. This wil save set up time {nd the cost ofthe resin used to start up the process. In conclusion, the capillary rheometer is a valuable, but under-utilized tool in the lobal plastics industry. In the past it has been viewed as an expensive and Sophisticated instrument, suited only for research labs and universes. However, now affordable systems are avalable and improvements in software have made It easy to perform analyses automatically. ‘The test results can be presented in an easily understandable form that may be dlcectly applied to the solution of practical problems experienced by the processor and ‘manufacturer. The reduction of problems with out of specification material, the faster ‘machine set-up time, and the improvements in qualty and process understanding wil provide an almost immediate payback,