Determining the Shear Relaxation Modulus and Constitutive Models for Polyurea and Polyurea-Based Composite Materials from Dynamic Mechanical Testing Data

Polyurea and polyurea-based composite materials are widely used due to their excellent mechanical properties. In order to facilitate large-scale computational studies for this group of materials, a robust and standard method is needed to extract their viscoelastic constitutive parameters. In this study, frequency-domain master curves which cover a wide range of frequencies are developed using the data of dynamic mechanical analysis through time-temperature superposition (TTS). The quality of the master curves is assessed both by Kramers-Kronig relations and by comparing with the ultrasonic wave testing data. Then the time-domain relaxation modulus is obtained by the high-resolution Prony series approximated from the relaxation spectrum. To reduce computational cost, 4 to 8-term Prony series are then fitted from the time-domain relaxation modulus for a limited frequency range of interest. Both the high and low-resolution Prony series are converted back to frequency domain to compare with the master curves developed by TTS and show good agreements. This method is not limited to polyurea and polyurea-based composites and it can be applied to other similar polymer systems as well

Exploration of new multivariate spectral calibration algorithms.

A variety of multivariate calibration algorithms for quantitative spectral analyses were investigated and compared, and new algorithms were developed in the course of this Laboratory Directed Research and Development project. We were able to demonstrate the ability of the hybrid classical least squares/partial least squares (CLSIPLS) calibration algorithms to maintain calibrations in the presence of spectrometer drift and to transfer calibrations between spectrometers from the same or different manufacturers. These methods were found to be as good or better in prediction ability as the commonly used partial least squares (PLS) method. We also present the theory for an entirely new class of algorithms labeled augmented classical least squares (ACLS) methods. New factor selection methods are developed and described for the ACLS algorithms. These factor selection methods are demonstrated using near-infrared spectra collected from a system of dilute aqueous solutions. The ACLS algorithm is also shown to provide improved ease of use and better prediction ability than PLS when transferring calibrations between near-infrared calibrations from the same manufacturer. Finally, simulations incorporating either ideal or realistic errors in the spectra were used to compare the prediction abilities of the new ACLS algorithm with that of PLS. We found that in the presence of realistic errors with non-uniform spectral error variance across spectral channels or with spectral errors correlated between frequency channels, ACLS methods generally out-performed the more commonly used PLS method. These results demonstrate the need for realistic error structure in simulations when the prediction abilities of various algorithms are compared. The combination of equal or superior prediction ability and the ease of use of the ACLS algorithms make the new ACLS methods the preferred algorithms to use for multivariate spectral calibrations

Design and optimisation of organic Rankine cycles for waste heat recovery in marine applications using the principles of natural selection

Power cycles using alternative working fluids are currently receiving significant attention. Selection of working fluid among many candidates is a key topic and guidelines have been presented. A general problem is that the selection is based on numerous criteria, such as thermodynamic performance, boundary conditions, hazard levels and environmental concerns. A generally applicable methodology, based on the principles of natural selection, is presented and used to determine the optimum working fluid, boiler pressure and Rankine cycle process layout for scenarios related to marine engine heat recovery. Included in the solution domain are 109 fluids in sub and supercritical processes, and the process is adapted to the properties of the individual fluid. The efficiency losses caused by imposing process constraints are investigated to help propose a suitable process layout. Hydrocarbon dry type fluids in recuperated processes produced the highest efficiencies, while wet and isentropic fluids were superior in non-recuperated processes. The results suggested that at design point, the requirements of process simplicity, low operating pressure and low hazard resulted in cumulative reductions in cycle efficiency. Furthermore, the results indicated that non-flammable fluids were able to produce near optimum efficiency in recuperated high pressure processes

Optimal design of water treatment processes

Predicted water shortages assign water treatment a leading role in improving water resources management. One of the main challenges associated with the processes remains early stage design of techno-economically optimised purification. This work addresses the current gap by undertaking a whole-system approach of flowsheet synthesis for the production of water at desired purity at minimum overall cost. The optimisation problem was formulated as a mixed-integer non-linear programming model. Two case studies were presented which incorporated the most common commercial technologies and the major pollution indicators, such as chemical oxygen demand, dissolved organic carbon, total suspended solids and total dissolved solids. The results were analysed and compared to existing guidelines in order to examine the applicability of the proposed approach

Interactions of bile salts with a dietary fibre, methylcellulose, and impact on lipolysis

Methylcellulose (MC) has a demonstrated capacity to reduce fat absorption, hypothetically through bile salt (BS) activity inhibition. We investigated MC cholesterol-lowering mechanism, and compared the influence of two BS, sodium taurocholate (NaTC) and sodium taurodeoxycholate (NaTDC), which differ slightly by their architecture and exhibit contrasting functions during lipolysis. BS/MC bulk interactions were investigated by rheology, and BS behaviour at the MC/water interface studied with surface pressure and ellipsometry measurements. In vitro lipolysis studies were performed to evaluate the effect of BS on MC-stabilised emulsion droplets microstructure, with confocal microscopy, and free fatty acids release, with the pH-stat method. Our results demonstrate that BS structure dictates their interactions with MC, which, in turn, impact lipolysis. Compared to NaTC, NaTDC alters MC viscoelasticity more significantly, which may correlate with its weaker ability to promote lipolysis, and desorbs from the interface at lower concentrations, which may explain its higher propensity to destabilise emulsions