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

A fluorescence approach to investigate repartitioning of coalescing agents in acrylic polymer emulsions

Repartitioning of co-solvents between particles of latex emulsions was investigated by means of a fluorescence method based on the detection of the amount of co-solvent via the solvatochromic shift of the emission maximum of a fluorescent probe, copolymerized at a low concentration. Complete repartitioning of co-solvents between particles of latex materials with a low Tg (ca. 25 °C) occurred within minutes. For a hydrophilic latex with a Tg of 68 °C, equilibration was achieved within an hour. Repartitioning was faster for more hydrophobic co-solvents. For a hydrophobic latex of similar Tg, co-solvent repartitioning took place on the same time scale, but complete equilibration was not reached. Possibly, there is an additional slow component in the repartitioning, or the prolonged presence of co-solvent causes a structural change in the latex particles that affects the outcome of the experiment

Simple graphical method for inherent occupational health assessment

The concept of inherently safer design was introduced to design a fundamentally safer process so that hazards can be avoided or minimized rather than controlled or managed. The ideology has later been extended to the environmental, but not health criteria due to its complicated underlying principles. Even though health risk methods are already established, majority are for existing plants assessment. Early consideration of health aspect starting from process design stage however, has received much less attention. This paper introduces a simple graphical method to evaluate the inherent occupational health hazards of chemical processes during the R&D stage. A survey was conducted to identify the important health parameters for the graphical method development, involving nine world inherent safety and health experts. Based on their input, process mode, material volatility, operating pressure and chemical health hazard (toxicity and adverse effect) are the significant factors affecting inherent health hazards of chemical processes. The choice of parameters was bounded by the information availability at this stage. The method was applied on six routes to methyl methacrylate and ten routes to acetic acid. The parameters were plotted for each subprocess of the alternative routes. The ‘healthiest’ route was selected based on thorough hazards assessment across all the subprocesses. The first case study reveals the tertiary butyl alcohol as the ‘healthiest’ one as it poses relatively lower, or at least comparable hazards to the other routes due to exposure and health impacts. Meanwhile the acetic acid case study indicates ethanol oxide and ethyl oxide based routes as the inherently healthier as they operate at lower operating pressure besides posing comparable hazards level for the other three parameters, compared to the other routes. The case studies show that the inherent occupational health of a chemical process can already be evaluated easily in the R&D stage with the simple graphical method proposed