Hierarchically structured composites and porous materials

Thompson, Benjamin Robert

September 2017

Thesis or dissertation

© 2017 Benjamin Robert Thompson. All rights reserved. No part of this publication may be reproduced without the written permission of the copyright holder.

This thesis develops a hydrogel bead templating technique for the preparation of hierarchically structured composites and porous materials. This method involves using slurries of hydrogel beads with different size distributions as templates. Mixing hydrogel beads with a scaffolding material and then allowing the scaffold to harden, followed by drying of the composite leaves pores in the place of the hydrogel beads. These pores reflect the size and shape of the templates used and the porosity reflects the volume percentage of hydrogel bead slurry mixed with the scaffolding material. A viscous trapping technique has been developed which utilises the viscosity of methylcellulose to stop sedimentation of the scaffold particles during network formation. Both of these methods are attractive due to being cheap, non-toxic and they use food grade materials which allows their use in a multitude of applications.

Porous and hierarchically porous gypsum composites have been prepared using both hydrogel bead templating and viscous trapping techniques, or a combination of the two. The level of control over the final microstructure of the dried composites offered by these techniques allowed for a systematic investigation of their thermal and mechanical properties as a function of the pore size, porosity and hierarchical microstructure. It has been shown that the thermal conductivity decreases linearly with increasing porosity, however it was not dependent on the pore sizes that were investigated here. The mechanical properties, however, were significantly different. The porous composites produced with either small hydrogel beads (100 μm) or methylcellulose solution had approximately twice the compressional strength and Young’s modulus compared to the ones produced with large hydrogel beads (600 μm).

The sound insulating properties of porous and hierarchically porous gypsum composites have also been investigated. With increasing porosity, the sound transmission loss decreases, as expected. At constant porosity, it is shown that the composites with large pores perform significantly better than the ones with small pores in the frequency range of 75-2000 Hz. At higher frequencies (>2400 Hz) the composites with smaller pores begin to perform better. The material’s microstructure has been studied in an attempt to explain this effect.

The hydrogel templating technique can be used to prepare composite materials if the drying step is not performed. Hydrogel beads have been incorporated into a soap matrix. The dissolution rate of these composites as a function of hydrogel bead size and volume percentage of hydrogel beads incorporated within the soap matrix has been investigated. It has been shown that the dissolution rate can be increased by increasing the volume percentage of hydrogel beads used during composite preparation but it is independent on their size distribution. Finally, three methods of controlling the release rate of encapsulated species from these soap-hydrogel bead composites have been shown. The first method involved varying the size distribution of the hydrogel beads incorporated within the soap matrix. The second involved changing the concentration of the gelling polymer and the final method required co-encapsulation of an oppositely charged polyelectrolyte.

A binary hydrogel system has been developed and its rheological and thermal properties have been investigated. It consists of agar and methylcellulose and shows significantly improved rheological properties at high temperatures compared to agar alone. The storage modulus of the two component hydrogel shows a maximum at 55 °C which was explained by a sol-gel phase transition of methylcellulose, evidence of which was seen during differential scanning calorimetry measurements. After exposure of this binary hydrogel to high temperatures above the melting point of agar alone (> 120 °C), it maintains its structure. This suggests it could be used for high temperature templating or structuring of food products.

The melt-resistant binary hydrogel was used for the preparation of pancake-hydrogel composites using hydrogel bead templating. Mixing slurry of hydrogel beads of this composition with pancake batter, followed by preparation at high temperatures produced pancakes with hydrogel beads incorporated within. Bomb calorimetry measurements showed that the caloric density could be reduced by a controlled amount by varying the volume percentage of hydrogel beads used during preparation of the composites. This method could be applied to other food products such as biscuits, waffles and breakfast bars. Furthermore, there is scope for development of this method by the encapsulation of flavour enhancing or nutritionally beneficial ingredients within the hydrogel beads.

Department of Chemistry, The University of Hull
Paunov, Vesselin N.; Horozov, Tommy S.
Sponsor (Organisation)
Engineering and Physical Sciences Research Council; Unilever (Firm)
Qualification level
Qualification name
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