Nanoparticle Network Formation in Nanostructured and Disordered Block Copolymer Matrices

Incorporation of nanoparticles composed of surface-functionalized fumed silica (FS) or native colloidal silica (CS) into a nanostructured block copolymer yields hybrid nanocomposites whose mechanical properties can be tuned by nanoparticle concentration and surface chemistry. In this work, dynamic rheology is used to probe the frequency and thermal responses of nanocomposites composed of a symmetric poly(styrene-b-methyl methacrylate) (SM) diblock copolymer and varying in nanoparticle concentration and surface functionality. At sufficiently high loading levels, FS nanoparticle aggregates establish a load-bearing colloidal network within the copolymer matrix. Transmission electron microscopy images reveal the morphological characteristics of the nanocomposites under these conditions

Viscosity Measurement in a Lubricant Film Using an Ultrasonically Resonating Matching Layer

A novel ultrasonic viscometer intended for in-situ applications in lubricated components is presented. The concept is based on the reflection of a shear wave at a solid-liquid boundary that depends on the viscosity of the liquid and the acoustic properties of the solid. Very little ultrasound energy can propagate into the oil at a metal-oil interface because the acoustic mismatch is great, and this leads to large measurement errors. The method described in this paper overcomes this limitation by placing a thin intermediate matching layer between the metal and the lubricant. Results obtained with this technique are in excellent agreement with expected values from conventional viscometers when Newtonian mineral oils are analysed. When complex non-Newtonian mixtures are tested, the viscosity measurement is frequency dependent. At high ultrasonic frequencies, over 1 MHz, it is possible to shear only the base oil, while to obtain the viscosity of the mixture it is necessary to choose a lower excitation frequency to match the dispersed polymer relaxation time

DETERMINATION OF THE RELAXATION SPECTRUM FROM OSCILLATORY SHEAR DATA

In order to use either a linear or nonlinear model of viscoelasticity to calculate the stress response of a material to various deformations, it is usually necessary to have available an explicit equation for the linear relaxation modulus G(t). The most popular procedure is to use the data from a small-amplitude oscillatory shear experiment to determine the parameters of a generalized Maxwell model. However, this is an ill-posed problem and is not at all a straightforward curve-fitting operation. We compare three procedures for determining a set of relaxation times and discrete moduli that can then be used as empirical fitting parameters in fluid mechanics computations. These are linear regression, with and without regularization, and nonlinear regression. Nonlinear regression is found to give a good fit of the data with a minimum number of parameters

Assessing the practical utility of the hole-pressure method for the in-line rheological characterization of polymer melts

The most promising method capable of providing accurate measurements of the first and second normal-stress differences in shear flows at shear rates typical of polymer processing is the so-called hole-pressure method, but its use has not been as widespread as would be expected, namely due to the experimental difficulties associated with performing such experiments accurately. In this work, we use a small-scale modular slit die to assess the practical utility of the method for in-line monitoring of polymer melt flow. We provide a quantitative analysis of intrinsic error sources and use state-of-the-art data acquisition tools to minimize errors associated with pressure transducers. Our results demonstrate that the method can be used to accurately measure the viscosity and first normal-stress difference in melts but probably not the second normal-stress difference because the intrinsic errors are too high, even when the influence of all the potential error sources is minimized or eliminated.The authors acknowledge the financial support of the Center for Layered Polymeric Systems (NSF grant 0423914) and of the Foundation for Science and Technology, Portugal, through grants SFRH/BD/25311/2005, POCI/ EME/62461/2004, and PPCDT/EME/62461/200