Cellulose composite structures – by design

The aim of the work presented in this thesis was to investigate different mechanical and chemical pre-treatments which can dramatically change the properties of native cellulose and add alternative routes to structure formation. Ball milled cellulose, which had a reduced crystallinity, degree of polymerisation and degradation temperature, was rehydrated in excess water resulting in recrystallisation. Fully amorphous samples recrystallised to the more thermodynamically stable type II polymorphic crystal structure. Flash differential scanning calorimetry (DSC), which allows thermal transitions to be scanned at much higher rates than conventional DSC, was able to register a glass transition temperature for amorphous cellulose. The next stage of the study focussed on the production of freeze dried galactomannan foams. Cellulose fibres provided reinforcement to the foams. The level of reinforcement was related to fibre content, size, crystallinity and surface roughness. Microfibrillated cellulose (MFC) provided the greatest reinforcement due to its much higher surface area and fibrillated structure. Extrusion was found to be a useful alternative to homogenisation for the production of MFC and to create foams using alternative processing to the freeze drying routes. A novel molten salt hydrate, LiCl/urea/water, was found to swell native cellulose and reduce its crystallinity. A weak gel-like structure was formed at ambient temperature. Micro DSC results showed that this structure was melted out at 60oC but the process was reversible indicating hydrophilic to hydrophobic conformational changes on the surface of the cellulose fibres, although these were likely to be dependent on the celluloses having a low degree of polymerisation. In these solvent conditions starch granules were eroded from the outside rather than being swollen as has been found for some ionic liquids and underwent total dissolution in LiCl/urea/water. Fenugreek and xyloglucan, which are both highly branched, were found to increase in viscosity in LiCl/urea/water relative to water, possibly due to the breakage of all intramolecular associations whereas the viscosity of konjac which is predominantly unbranched did not change. Locust bean gum (LBG) had a lower viscosity in LiCl/urea/water compared to water due to the disruption of aggregates. Confocal microscopy showed that fenugreek and LBG are able to bind to cellulose in water, however, the conformational change of fenugreek in these solvent conditions inhibited it from binding to cellulose in LiCl/urea/water whereas conformational change allowed xyloglucan to bind to cellulose in LiCl/urea/water whilst it was unable to bind in water. Konjac did not bind to cellulose in either solvent system. The pre-treatments shown in this work will enable the creation of novel cellulose composites

Cellulose composite structures – by design

The aim of the work presented in this thesis was to investigate different mechanical and chemical pre-treatments which can dramatically change the properties of native cellulose and add alternative routes to structure formation. Ball milled cellulose, which had a reduced crystallinity, degree of polymerisation and degradation temperature, was rehydrated in excess water resulting in recrystallisation. Fully amorphous samples recrystallised to the more thermodynamically stable type II polymorphic crystal structure. Flash differential scanning calorimetry (DSC), which allows thermal transitions to be scanned at much higher rates than conventional DSC, was able to register a glass transition temperature for amorphous cellulose. The next stage of the study focussed on the production of freeze dried galactomannan foams. Cellulose fibres provided reinforcement to the foams. The level of reinforcement was related to fibre content, size, crystallinity and surface roughness. Microfibrillated cellulose (MFC) provided the greatest reinforcement due to its much higher surface area and fibrillated structure. Extrusion was found to be a useful alternative to homogenisation for the production of MFC and to create foams using alternative processing to the freeze drying routes. A novel molten salt hydrate, LiCl/urea/water, was found to swell native cellulose and reduce its crystallinity. A weak gel-like structure was formed at ambient temperature. Micro DSC results showed that this structure was melted out at 60oC but the process was reversible indicating hydrophilic to hydrophobic conformational changes on the surface of the cellulose fibres, although these were likely to be dependent on the celluloses having a low degree of polymerisation. In these solvent conditions starch granules were eroded from the outside rather than being swollen as has been found for some ionic liquids and underwent total dissolution in LiCl/urea/water. Fenugreek and xyloglucan, which are both highly branched, were found to increase in viscosity in LiCl/urea/water relative to water, possibly due to the breakage of all intramolecular associations whereas the viscosity of konjac which is predominantly unbranched did not change. Locust bean gum (LBG) had a lower viscosity in LiCl/urea/water compared to water due to the disruption of aggregates. Confocal microscopy showed that fenugreek and LBG are able to bind to cellulose in water, however, the conformational change of fenugreek in these solvent conditions inhibited it from binding to cellulose in LiCl/urea/water whereas conformational change allowed xyloglucan to bind to cellulose in LiCl/urea/water whilst it was unable to bind in water. Konjac did not bind to cellulose in either solvent system. The pre-treatments shown in this work will enable the creation of novel cellulose composites

Understanding the influence of processing conditions on the extraction of rhamnogalacturonan-I “hairy” pectin from sugar beet pulp

Sugar beet pectin is rich in rhamnogalacturonan-I (RG-I) region, which is a potential source of prebiotics. RG-I pectin cannot be extracted the same way as commercial homogalacturan-rich pectin using hot acid. Therefore, this study has explored several alternative methods, including microwave-assisted extraction (MAE) and conventional- solvent extraction (CSE) at atmospheric pressure using different solvents, and microwave-assisted hydrothermal extraction (MAHE) under pressure using water. No conclusive differences in microwave and conventional heating were found with heating rate controlled. The optimum treatment times of both MAE and CSE at 90 °C atmospheric pressure and regardless of the solvents used were 120 min; however, MAHE at 130 °C under pressure can dramatically reduce the time to 10 min. Alcohol-insoluble solids (AIS) extracted using pH13 solvent by MAE had both the highest RG-I yield at 25.3% and purity at 260.2 mg/g AIS, followed by AIS extracts using water by MAHE with 7.5% and 166.7 mg/g AIS respectively

Enhancing natural product extraction and mass transfer using selective microwave heating

This study uses a combination of empirical observations and an analysis of mass transfer behaviour to yield new insights into the mechanism of microwave assisted extraction. Enhancements in extraction rate and yield were observed experimentally compared with conventional extraction at temperatures in excess of 50°C, however at lower temperatures there was no observable difference between the two processes. A step-change in extract yield between microwave and conventional processes was shown to be caused by selective heating. A temperature gradient of the order of 1oC is sufficient to reduce the water chemical potential within the cell structure, which changes the osmotic potential such that internal cell pressures can increase to the point where disruption occurs. This paper demonstrates the need to operate microwave extraction processes at a temperature that enables selective heating, and a newly-proposed mass transfer phenomenon that could have wider positive implications for extraction and leaching processes

New insights into the role of selective and volumetric heating during microwave extraction: investigation of the extraction of polyphenolic compounds from sea buckthorn leaves using microwave-assisted extraction and conventional solvent extraction

We report a direct comparison of microwave heating and conventional heating in solvent extraction by using exactly the same reaction conditions (including heating rate) in the extraction of polyphenols from dried sea buckthorn leaves. We have for the first time decoupled the effects of bulk heating rate and mixing regime from the fundamental microwave heating mechanism. We show that although microwave selective heating can increase the yield and quality of the polyphenols extracted, if the same bulk heating rate is applied there is no difference in treatment time and therefore theoretical energy requirements of the process. The first implication of these results for process intensification is that if microwave selective heating can be enhanced in scaled up processes through electromagnetic design, the extract yield and quality may be increased further. The second implication is that conventional extraction processes could be designed to provide the same heating rate and hence treatment time as microwave extraction, but any potential energy and space savings would have to be balanced against the increase in capital cost and complexity of the equipment. That said, the very small penetration depth of microwaves into ethanol/water solvent also poses design challenges in the scale up of microwave equipment

Design and characterisation of food grade powders and inks for microstructure control using 3D printing

Additive Manufacturing techniques have been previously applied to food materials with direct consumption in mind, as opposed to creating structural ingredients as shown in this study. First, semi-crystalline cellulose was mechanically treated by ball milling to render an amorphous powder, which has been characterised. Requirements for the subsequent recrystallization of this powder with a view to structuring have been determined through the control of moisture and thermal energy. Food inks based on xanthan gum have been formulated to enable successful jetting with a FujiFilm Dimatix ink jet printer. The polymer inks were subsequently jetted onto the amorphous cellulose powder to observe powder-binder interactions. Material combinations and parameters were optimised to produce cohesive geometric structures. The results of this study are promising when looking towards using these materials in a binder jetting additive manufacturing technique using designer particles and inks to create structures for use in food products