Rheometrics

Density. Density of LLDPE is measured by flotation in density gradient columns according to ASTM D1505-85. The most often used Hquid system is 2-propanol—water, which provides a density range of 0.79—1.00 g/cm. This technique is simple but requires over 50 hours for a precise measurement. The correlation between density (d) and crystallinity (CR) is given hy Ijd = CRj + (1 — Ci ) / d, where the density of the crystalline phase, ify, is 1.00 g/cm and the density of the amorphous phase, is 0.852—0.862 g/cm. Ultrasonic methods (Tecrad Company) and soHd-state nmr methods (Auburn International, Rheometrics) have been developed for crystallinity and density measurements of LLDPE resins both in pelletized and granular forms. 

Fig. 29. Measurements of yield stress with a vane device and Rheometrics controlled stress rheometer. The torque required to cause yielding is between 1.88...

Eig. 34. Diagram of the Rheometric Melt Elongational Rheometer (RME) for elongational viscosity measurements on polymer melts. 

Dynamic Mechanical Thermal Analyzer (DMTA) c 10-" -2 X 10" 10 -10" Rheometric Scientific, Inc., Piscataway, N.J. 

The Rheometric Scientific RDA II dynamic analy2er is designed for characteri2ation of polymer melts and soHds in the form of rectangular bars. It makes computer-controUed measurements of dynamic shear viscosity, elastic modulus, loss modulus, tan 5, and linear thermal expansion coefficient over a temperature range of ambient to 600°C (—150°C optional) at frequencies 10 -500 rad/s. It is particularly useful for the characteri2ation of materials that experience considerable changes in properties because of thermal transitions or chemical reactions. 

Rheometric Scientific markets several devices designed for characterizing viscoelastic fluids. These instmments measure the response of a Hquid to sinusoidal oscillatory motion to determine dynamic viscosity as well as storage and loss moduH. The Rheometric Scientific line includes a fluids spectrometer (RFS-II), a dynamic spectrometer (RDS-7700 series II), and a mechanical spectrometer (RMS-800). The fluids spectrometer is designed for fairly low viscosity materials. The dynamic spectrometer can be used to test soHds, melts, and Hquids at frequencies from 10 to 500 rad/s and as a function of strain ampHtude and temperature. It is a stripped down version of the extremely versatile mechanical spectrometer, which is both a dynamic viscometer and a dynamic mechanical testing device. The RMS-800 can carry out measurements under rotational shear, oscillatory shear, torsional motion, and tension compression, as well as normal stress measurements. Step strain, creep, and creep recovery modes are also available. It is used on a wide range of materials, including adhesives, pastes, mbber, and plastics. 

Striking support of this contention is found in recent data of Castro (16) shown in Figure 14. In this experiment, the polymerization (60-156) has been carried out in a cone-and-plate viscometer (Rheometrics Mechanical Spectrometer) and viscosity of the reaction medium monitored continuously as a function of reaction time. As can be seen, the viscosity appears to become infinite at a reaction time corresponding to about 60% conversion. This suggests network formation, but the chemistry precludes non-linear polymerization. Also observed in the same conversion range is very striking transition of the reaction medium from clear to opaque. 

The products of the chemical degradation of PETP with triethylene tetramine and triethaneolamine can be used as epoxy resin hardeners, it is demonstrated. Products of PETP aminolysis with triethylene tetramine and aminoglycolysis with triethanolamine, were characterised using NMR and rheometric measurements. Characteristics of the crosslinking process for the system epoxy resin/ PETP/amine degradation product, and epoxy resin/TETA for comparison were investigated by DSC. Three classes of liquid epoxy resins based on bisphenol A, bisphenol F and epoxy novolak resins were used in the experiments. 16 refs. 

FIGURE 12.7 Monsanto rheometric curves of ethylene-propylene-diene monomer (EPDM) rubber-melamine fiber composites [64]. A, gum compound B, compound containing 30 phr melamine fiber but no dry bonding system and C, compound containing both dry bonding system and 30 phr melamine fiber. (From Rajeev, R.S., Bhowmick, A.K., De, S.K., Kao, G.J.P., and Bandyopadhyay, S., Polym. Compos., 23, 574, 2002. With permission.)... 

Any rheometric technique involves the simultaneous assessment of force, and deformation and/or rate as a function of temperature. Through the appropriate rheometrical equations, such basic measurements are converted into quantities of rheological interest, for instance, shear or extensional stress and rate in isothermal condition. The rheometrical equations are established by considering the test geometry and type of flow involved, with respect to several hypotheses dealing with the nature of the fluid and the boundary conditions the fluid is generally assumed to be homogeneous and incompressible, and ideal boundaries are considered, for instance, no wall slip. 

Rheometric Properties of Natural Rubber (NR) Mix Containing 10 pbr Fillers... 

Rheometric Results of Cryoground Rubber (CGR) Filled NR Vulcanizates... 

Mechanical rheometry requires a measurement of both stress and strain (or strain rate) and is thus usually performed in a simple rotating geometry configuration. Typical examples are the cone-and-plate and cylindrical Couette devices [1,14]. In stress-controlled rheometric measurements one applies a known stress and measures the deformational response of the material. In strain-controlled rheometry one applies a deformation flow and measures the stress. Stress-controlled rheometry requires the use of specialized torque transducers in conjunction with low friction air-bearing drive in which the control of torque and the measurement of strain is integrated. By contrast, strain-controlled rheometry is generally performed with a motor drive to rotate one surface of the cell and a separate torque transducer to measure the resultant torque on the other surface. 

All the viscoelastic measurements were carried out in the Rheometrics Dynamic Spectrometer RDS-770 at a frequency of 1Hz, a strain of 0.1%, and a temperature range of -140° to 140°C incremented every 2 degrees. The Texas Instrument Terminal Silent 700 was tapped to provide a hookup to an IBM 308X main frame computer located some miles away. The output of the Rheometrics unit was converted to a data file to be used in conjuc-tion with SAS (1). All statistical manipulations, software developments, and the necessary graphics that are reported here were carried out with the aid of SAS. 

Dynamic mechanical anlaysis (DMA) measurements were done on a Rheometrics RDS-7700 rheometer in torsional rectangular geometry mode using 60 x 12 x 3 mm samples at 0.05% strain and 1 Hz. Differential scanning calorimetry (DSC), thermomechanical analysis (TMA), and thermogravimetric analysis (TGA) were performed on a Perkin-Elmer 7000 thermal analysis system. 

Viscosity measurements were made using a Rheometrics System IV-dynamlc mechanical spectrometer. 

Thermal analysis, moisture uptake and dynamic mechanical analysis was also accomplished on cured specimens. Thermal analysis parameters used to study cured specimens are the same as those described earlier to test resins. The moisture uptake in cured specimens was monitored by immersing dogbone shaped specimens in 71 C distilled water until no further weight gain is observed. A dynamic mechanical scan of a torsion bar of cured resin was obtained using the Rheometrics spectrometer with a temperature scan rate of 2°C/minute in nitrogen at a frequency of 1.6Hz. The following sections describe the results obtained from tests run on the two different BCB resin systems. Unless otherwise noted all tests have been run as specified above. 

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