Steven C. Roth

Electric‐field‐induced phase changes in poly(vinylidene fluoride)

The antipolar crystal form of poly(vinylidene fluoride) can be made piezoelectric and pyroelecric by the temporary application of electric fields in excess of 1 MV/cm at room temperature. Infrared and x‐ray diffraction data reveal that the polarization occurs in two stages. At fields near 1 MV/cm, a phase transition to a polar form II occurs with presumably no change in chain conformation. Fields near 5 MV/cm cause a change in conformation to produce form I. Our results indicate that at least a portion of the residual polarization occurs within the crystal phase of the polymer.

Hysteresis measurements of remanent polarization and coercive field in polymers

An experimental method is described which allows estimation of remanent polarization and coercive field without assuming functional forms for the capacitive and electrical resistance terms. The method can be used to measure polarization in specimens with voltage‐dependent conductivity (often arising from the presence of ions in the specimens), voltage‐dependent capacitance, and significant amounts of space charge. It consists of: (1) performing bipolar current/voltage hysteresis loops to allow a steady state of remanent polarization and space charge to build up in the specimen, and (2) following a bipolar loop with two or more unipolar loops in which the polarization changes in the first unipolar loop. Both sinusoidal and linear time‐dependent applied voltages may be used. Automatic data processing of hysteresis loops is described for cases in which specimen behavior may be considered to be ideal.

Experimental Evidence of Rotating Stall in a Pump-Turbine at Off-Design Conditions in Generating Mode

An experimental investigation of the rotating stall in reduced scale model of a low specific speed radial pump-turbine at runaway and turbine brake conditions in generating mode is achieved. Measurements of wall pressure in the stator are performed along with high-speed flow visualizations in the vaneless gap with the help of air bubbles injection. When starting from the best efficiency point (BEP) and increasing the impeller speed, a significant increase of the pressure fluctuations is observed mainly in the wicket gates channels. The spectral analysis shows a rise of a low frequency component (about 70% of the impeller rotational frequency) at runaway, which further increases as the zero discharge condition is approached. Analysis of the instantaneous pressure peripheral distribution in the vaneless gap reveals one stall cell rotating with the impeller at sub-synchronous speed. High-speed movies reveal a quite uniform flow pattern in the guide vanes channels at the normal operating range, whereas at runaway the flow is highly disturbed by the rotating stall passage. The situation is even more critical at very low positive discharge, where backflow and vortices in the guide vanes channels develop during the stall cell passage. A specific image processing technique is applied to reconstruct the rotating stall evolution in the entire guide vanes circumference for a low positive discharge operating point. The findings of this study suggest that one stall cell rotates with the impeller at sub-synchronous velocity in the vaneless gap between the impeller and the guide vanes. It is the result of rotating flow separations developed in several consecutive impeller channels which lead to their blockage.

Method of Evaluating the Thermal Stability of the Pyroelectric Properties of Polyvinylidene Fluoride Effects of Poling Temperature and Field

The ac pyroelectric response of a number of differently poled polyvinylidene fluoride films has been measured while the temperature was varied at a constant rate ∼5 °C/min from room temperature to near the melting temperature. The response first increases with increasing temperature, which is attributed to an increase of the thermal expansion coefficient and eventually decreases due to melting and/or loss of electric dipole orientation. The details of the temperature dependence are influenced in a reproducible manner by the poling variables, especially the poling temperature. The measurement is therefore proposed as a way of evaluating the effect of processing variables on the thermal stability of the piezoelectric and pyroelectric properties.

Temperature Dependence of Fluorescent Probes for Applications to Polymer Materials Processing

We have examined the temperature dependence of fluorescence spectra from dyes that can be used as molecular probes during polymer processing. The dyes, perylene and benzoxazolyl stilbene, are in a class of dyes called band definition dyes, so called because their fluorescence spectra contain distinct intensity peaks at characteristic wavelengths. The dyes were chosen for this study because they are soluble at dopant levels of concentration in organic polymers at elevated temperatures and they survive without degradation at polymer processing temperatures up to 300 °C. Changes induced in the fluorescence spectra over a range of typical processing temperatures were examined using statistical techniques that establish correlations between fluorescence intensity, wavelength, and temperature. The derived correlations are the basis for temperature calibrations that can be applied to process monitoring. A phenomenological model that assumes temperature dependence for both nonradiative and radiative decay modes is developed. A fit of the model parameters to the fluorescence spectra yielded activation energies for the temperature dependence of fluorescence decay rates.

Fluorescence anisotropy sensor and its application to polymer processing and characterization

An optical sensor containing polarizing optical components has been constructed to monitor fluorescence anisotropy during polymer processing and to carry out remote sensing of polymer products doped with fluorescent dyes. The sensor is a compact unit that is used to polarize incident excitation light as well as to analyze the polarization of generated fluorescent light. Optical fibers are used to carry light between the sensor head and the light source and detecting equipment. The anisotropy measurement yields information about the orientation of a fluorescent dye molecule that has been doped into polymer matrix. Fluorescent dyes that have geometrical asymmetry in their molecular structure are used. Experiments are described for which the sensor is positioned in line during extrusion, during specimen extension, and where the sensor is used to carry out area scans of films and sheets. Measurements were made on polyethylene, polyethylene terephthalate, and polybutadiene resins that contained a low concentra...

High-speed flow visualization in a pump-turbine under off-design operating conditions

The flow hydrodynamics in a low specific speed radial pump-turbine reduced scale model is experimentally investigated under off-design operating conditions in generating mode. Wall pressure measurements, in the stator, synchronized with high-speed flow visualizations in the vaneless space between the impeller and the guide vanes using air bubbles injection are performed. When starting from the best efficiency point and increasing the runner speed, a significant increase of the pressure fluctuations is observed mainly in channels between wicket gates. The spectral analysis shows a rise of one stall cell, rotating with about 70% of the impeller frequency, at runaway, which further increases as the zero discharge condition is approached. Then a specific image processing technique is detailed and applied to create a synthetic instantaneous view of the flow pattern on the entire guide vanes circumference for an operating point in turbine-brake mode, where backflow and vortices accompany the stall passage.

In-line dielectric monitoring during extrusion of filled polymers

Real-time monitoring of the dielectric properties of polymer melts and filled polymer melts has been carried out during extrusion. The measurements are obtained using a dielectric cell that is placed directly in line with the extruder machine. The dielectric cell consists of interdigitating electrodes that are deposited on the inside of a ceramic ring that is electrically insulated and temperature controlled to the set point of extrusion. As the processed resin passes through the ring, its permittivity and conductivity are measured. The spatial sensitivity of the cell was determined experimentally and was biased to the resin flowing near the electrodes. Using the spatial sensitivity function, we examined the time profile of the transition from one composition to another during extrusion. We demonstrate the operation of the cell during the processing of polystyrene filled with aluminum oxide and calcium carbonate and of polyethylene-ethyl vinyl acetate copolymer filled with montmorillonite clay.

A dielectric slit die for in-line monitoring of polymer compounding

The dielectric slit die is an instrument that is designed to measure electrical, rheological, ultrasonics, optical, and other properties of a flowing liquid. In one application, it is connected to the exit of an extruder, pump or mixing machine that passes liquefied material such as molten plastic, solvents, slurries, colloidal suspensions, and foodstuffs into the sensing region of the slit-shaped die. Dielectric sensing is the primary element of the slit die, but in addition to the dielectric sensor, the die contains other sensing devices such as pressure, optical fiber, and ultrasonic sensors that simultaneously yield an array of materials property data. The slit die has a flexible design that permits interchangeability among sensors and sensor positions. The design also allows for the placement of additional sensors and instrumentation ports that expand the potential data package obtained. To demonstrate sensor operation, we present data from the extrusion and compounding of a polymer/clay nanocomposit...

Thermal Expansion Coefficients of Low-K Dielectric Films From Fourier Analysis of X-Ray Reflectivity

We determine the thermal expansion coefficient of a fluorinated poly(arylene ether) low-k dielectric film using Fourier analysis of x-ray reflectivity data. The approach is similar to that used in Fourier analysis of x-ray absorption fine structure. The analysis compares two similar samples, or the same sample as an external parameter is varied, and determines the change in film thickness. The analysis process is very accurate and depends on no assumed model. We determine a thermal expansion coefficient of 55±9×10−6 K−1 using this approach.