title: Determining the critical relative humidity at which the glassy to rubbery transition occurs in polydextrose using an automatic water vapor sorption instrument.
abstract: Similar to an increase in temperature at constant moisture content, water vapor sorption by an amorphous glassy material at constant temperature causes the material to transition into the rubbery state. However, comparatively little research has investigated the measurement of the critical relative humidity (RHc) at which the glass transition occurs at constant temperature. Thus, the central objective of this study was to investigate the relationship between the glass transition temperature (Tg), determined using thermal methods, and the RHc obtained using an automatic water vapor sorption instrument. Dynamic dewpoint isotherms were obtained for amorphous polydextrose from 15 to 40 °C. RHc was determined using an optimized 2nd-derivative method; however, 2 simpler RHc determination methods were also tested as a secondary objective. No statistical difference was found between the 3 RHc methods. Differential scanning calorimetry (DSC) Tg values were determined using polydextrose equilibrated from 11.3% to 57.6% RH. Both standard DSC and modulated DSC (MDSC) methods were employed, since some of the polydextrose thermograms exhibited a physical aging peak. Thus, a tertiary objective was to compare Tg values obtained using 3 different methods (DSC first scan, DSC rescan, and MDSC), to determine which method(s) yielded the most accurate Tg values. In general, onset and midpoint DSC first scan and MDSC Tg values were similar, whereas onset and midpoint DSC rescan values were different. State diagrams of RHc and experimental temperature and Tg and %RH were compared. These state diagrams, though obtained via very different methods, showed relatively good agreement, confirming our hypothesis that water vapor sorption isotherms can be used to directly detect the glassy to rubbery transition. Practical Application: The food polymer science (FPS) approach, pioneered by Slade and Levine, is being successfully applied in the food industry for understanding, improving, and developing food processes and products. However, despite its extreme usefulness, the Tg, a key element of the FPS approach, remains a challenging parameter to routinely measure in amorphous food materials, especially complex materials. This research demonstrates that RHc values, obtained at constant temperature using an automatic water vapor sorption instrument, can be used to detect the glassy to rubbery transition and are similar to the Tg values obtained at constant %RH, especially considering the very different approaches of these 2 methods--a transition from surface adsorption to bulk absorption (water vapor sorption) versus a step change in the heat capacity (DSC thermal method).
authors.affiliation: Dept. of Pharmaceutical Sciences, Univ. of Kentucky, 789 S. Limestone, KY 40536-0596, USA.
authors.forename: Xiaoda
authors.initials: X
authors.lastname: Yuan
authors.forename: Brady P
authors.initials: BP
authors.lastname: Carter
authors.forename: Shelly J
authors.initials: SJ
authors.lastname: Schmidt
mesh_terms: D000042:Absorption; D000327:Adsorption; D002152:Calorimetry, Differential Scanning / Q000379:methods; D055598:Chemical Phenomena; D004043:Dietary Fiber / Q000008:administration & dosage / Q000032:analysis*; D005524:Food Technology; D005527:Food, Fortified / Q000032:analysis; D005936:Glucans / Q000737:chemistry*; D008956:Models, Chemical; D044367:Phase Transition; D012212:Rheology; D013227:Steam; D013696:Temperature; D044366:Transition Temperature; D014867:Water / Q000032:analysis*
chemical_list: D004043:Dietary Fiber; D005936:Glucans; D013227:Steam; D014867:Water; C033375:polydextrose