Systematic Investigation on the Glass Transition Temperature of Binary and Ternary Sugar Mixtures and the Applicability of Gordon–Taylor and Couchman–Karasz Equation
Glass transition temperatures (<i>T<sub>g</sub></i>) of carbohydrate mixtures consisting of only one monomer and glycosidic binding type (aldohexose glucose, α1-4-glycosidic bonded) were studied by differential scanning calorimetry (DSC). The aim of this work was to systemati...
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2022-06-01
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author | Martin Schugmann Petra Foerst |
author_facet | Martin Schugmann Petra Foerst |
author_sort | Martin Schugmann |
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description | Glass transition temperatures (<i>T<sub>g</sub></i>) of carbohydrate mixtures consisting of only one monomer and glycosidic binding type (aldohexose glucose, α1-4-glycosidic bonded) were studied by differential scanning calorimetry (DSC). The aim of this work was to systematically assess the predictability of <i>T<sub>g</sub></i> of anhydrous binary and ternary sugar mixtures focusing on the components <i>T<sub>g</sub></i>, molecular chain length, and shape. Binary systems were investigated with glucose as a monosaccharide and its linear di-, tri-, tetra-, penta-, hexa-, and heptasaccharides. Additionally, the <i>T<sub>g</sub></i> of ternary carbohydrate systems prepared with different glucose/maltose/maltotriose mass fractions were studied to evaluate the behavior of more complex mixtures. An experimental method to prepare fully amorphized, anhydrous mixtures were developed which allows the analysis of mixtures with strongly different thermodynamic pure-component properties (<i>T<sub>g</sub></i>, melting temperature, and degradation). The mixtures’ <i>T<sub>g</sub></i> is systematically underestimated by means of the Couchman–Karasz model. A systematic, sigmoidal deviation behavior from the Gordon–Taylor model could be found, which we concluded is specific for the investigated glucopolymer mixtures. At low concentrations of small molecules, the model underestimates <i>T<sub>g</sub></i>, meeting the experimental values at about equimolarity, and overestimates <i>T<sub>g</sub></i> at higher concentrations. These deviations become more pronounced with increasing <i>T<sub>g</sub></i> differences and were explained by a polymer mixture-specific, nonlinear plasticizing/thermal volume expansion effect. |
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spelling | doaj.art-170031d74db1438ba1900e300f38d6fc2023-11-23T16:37:19ZengMDPI AGFoods2304-81582022-06-011112167910.3390/foods11121679Systematic Investigation on the Glass Transition Temperature of Binary and Ternary Sugar Mixtures and the Applicability of Gordon–Taylor and Couchman–Karasz EquationMartin Schugmann0Petra Foerst1Institute of Process Systems Engineering, Technical University of Munich, Gregor-Mendel-Straße 4, 85354 Freising, GermanyInstitute of Process Systems Engineering, Technical University of Munich, Gregor-Mendel-Straße 4, 85354 Freising, GermanyGlass transition temperatures (<i>T<sub>g</sub></i>) of carbohydrate mixtures consisting of only one monomer and glycosidic binding type (aldohexose glucose, α1-4-glycosidic bonded) were studied by differential scanning calorimetry (DSC). The aim of this work was to systematically assess the predictability of <i>T<sub>g</sub></i> of anhydrous binary and ternary sugar mixtures focusing on the components <i>T<sub>g</sub></i>, molecular chain length, and shape. Binary systems were investigated with glucose as a monosaccharide and its linear di-, tri-, tetra-, penta-, hexa-, and heptasaccharides. Additionally, the <i>T<sub>g</sub></i> of ternary carbohydrate systems prepared with different glucose/maltose/maltotriose mass fractions were studied to evaluate the behavior of more complex mixtures. An experimental method to prepare fully amorphized, anhydrous mixtures were developed which allows the analysis of mixtures with strongly different thermodynamic pure-component properties (<i>T<sub>g</sub></i>, melting temperature, and degradation). The mixtures’ <i>T<sub>g</sub></i> is systematically underestimated by means of the Couchman–Karasz model. A systematic, sigmoidal deviation behavior from the Gordon–Taylor model could be found, which we concluded is specific for the investigated glucopolymer mixtures. At low concentrations of small molecules, the model underestimates <i>T<sub>g</sub></i>, meeting the experimental values at about equimolarity, and overestimates <i>T<sub>g</sub></i> at higher concentrations. These deviations become more pronounced with increasing <i>T<sub>g</sub></i> differences and were explained by a polymer mixture-specific, nonlinear plasticizing/thermal volume expansion effect.https://www.mdpi.com/2304-8158/11/12/1679amorphous stateglass transitioncarbohydrate mixturessugar mixturesDSCamorphization |
spellingShingle | Martin Schugmann Petra Foerst Systematic Investigation on the Glass Transition Temperature of Binary and Ternary Sugar Mixtures and the Applicability of Gordon–Taylor and Couchman–Karasz Equation Foods amorphous state glass transition carbohydrate mixtures sugar mixtures DSC amorphization |
title | Systematic Investigation on the Glass Transition Temperature of Binary and Ternary Sugar Mixtures and the Applicability of Gordon–Taylor and Couchman–Karasz Equation |
title_full | Systematic Investigation on the Glass Transition Temperature of Binary and Ternary Sugar Mixtures and the Applicability of Gordon–Taylor and Couchman–Karasz Equation |
title_fullStr | Systematic Investigation on the Glass Transition Temperature of Binary and Ternary Sugar Mixtures and the Applicability of Gordon–Taylor and Couchman–Karasz Equation |
title_full_unstemmed | Systematic Investigation on the Glass Transition Temperature of Binary and Ternary Sugar Mixtures and the Applicability of Gordon–Taylor and Couchman–Karasz Equation |
title_short | Systematic Investigation on the Glass Transition Temperature of Binary and Ternary Sugar Mixtures and the Applicability of Gordon–Taylor and Couchman–Karasz Equation |
title_sort | systematic investigation on the glass transition temperature of binary and ternary sugar mixtures and the applicability of gordon taylor and couchman karasz equation |
topic | amorphous state glass transition carbohydrate mixtures sugar mixtures DSC amorphization |
url | https://www.mdpi.com/2304-8158/11/12/1679 |
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