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Title: Structural studies of salt hydrates for heat-storage applications
Author: Clark, Rowan Elizabeth
ISNI:       0000 0004 7429 4849
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 2018
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Salt hydrates have the potential to be used in heat storage as both phase-change materials (PCMs) and thermochemical materials (TCMs). These materials offer advantages over traditional heat storage methods due to their high energy densities. However, both domestic and industrial applications require thousands of thermal cycles and there are often many issues that need to be overcome before these materials can be used reliably for heat storage. One of the major issues with using salt hydrates as PCMs is incongruency - the formation of anhydrous phases during melting. In this research, the mechanisms of the action of polymers to prevent incongruency in sodium acetate trihydrate have been investigated. A new polymorph of anhydrous sodium acetate, Form IV, was obtained in the presence of the polymer. This polymorph crystallises as long, blade-shaped crystals, thereby increasing the surface area to volume ratio. Indexing of the crystal faces revealed that every face had Na+ or the oxygen atoms of the acetate ion near or on the surface, as opposed to hydrophobic methyl groups found on the faces of the anhydrous salt grown without polymer. These two factors are believed to significantly increase the dissolution kinetics. This technique has the potential to be used for screening polymers to reformulate other salt hydrates that display incongruent behaviour. Eutectic compositions of NaCl and KCl with strontium hydroxide octahydrate were investigated as a potential means to prevent the incongruency of this PCM. However, degradation was observed with thermal cycling. Variable temperature PXRD studies discovered a new Sr(OH)2 hydrate when heating above 75 °C - Sr(OH)2. ⅓H2O. The recrystallisation of the octahydrate from the new phase was slow with incomplete conversion, explaining the degradation with continuous cycling. The effect of addition of NaCl and KCl to congruent barium hydroxide octahydrate was also investigated. On heating, a phase transition was observed, but the samples remained solid. Variable temperature PXRD investigations discovered that this was due to the formation of the salt hydrate, Ba(OH)Cl.2H2O. This hydrate melted at 110 °C, showing its potential as a high temperature PCM. The dehydration pathways of magnesium sulfate heptahydrate were investigated. In-situ PXRD studies showed that changing the heating rate changed the intermediates present during the dehydration. The fast dehydration rate saw both the known phases of trihydrate and 2.5 hydrate form as the dehydration product of the tetrahydrate. These both then dehydrated to the known dihydrate. This differed when the slower heating rate was used, as the trihydrate was the only product of dehydration from the tetrahydrate. The trihydrate then proceeded to dehydrate to a new phase. This was found to be a new polymorph of the dihydrate, β-MgSO4.2H2O. Dehydration of MgSO4.7H2O with 50 mol% NaCl was also performed. Loeweite, Na12Mg7(SO4)13.15H2O, a dication sulfate hydrate, was formed as the major intermediate. This mixture showed advantages over the pure MgSO4.7H2O as dehydration to the monohydrate took less time and occurred at a lower temperature. There were also three fewer intermediate phases before dehydration to the monohydrate. Suspension and encapsulation materials were used in order to overcome the major issue of agglomeration with magnesium sulfate. Liquid water was ruled out as a viable hydration medium. Apparatus was developed to test humidity cycling, which allowed the effects of dehydration time and temperature to be investigated, as well testing a range of different formulations.
Supervisor: Pulham, Colin ; Robertson, Neil Sponsor: Engineering and Physical Sciences Research Council (EPSRC)
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: salt hydrates ; phase-change materials ; thermochemical materials ; incongruency ; sodium acetate ; PCM ; phase transitions