Using Dielectric Relaxation Spectroscopy to Characterize the Glass Transition Time of Polydextrose.

Dielectric relaxation spectroscopy was used to characterize the glass transition time, tg , of polydextrose, where the glass transition temperature, Tg , and water activity, aw (relative humidity), were held constant during polydextrose relaxation. The tg was determined from a shift in the peak frequency of the imaginary capacitance spectrum with time. It was found that when the peak frequency reaches 30 mHz, polydextrose undergoes glass transition. Glass transition time, tg , is the time for polydextrose to undergo glass transition at a specific Tg and aw . Results lead to a modified state diagram, where Tg is depressed with increasing aw . This curve forms a boundary: (a) below the boundary, polydextrose does not undergo glass transition and (b) above the boundary, polydextrose rapidly undergoes glass transition. As the boundary curve is specified by a tg value, it can assist in the selection of storage conditions. An important point on the boundary curve is at aw = 0, where Tg0 = 115 °C. The methodology can also be used to calculate the stress-relaxation viscosity of polydextrose as a function of Tg and aw , which is important when characterizing the flow properties of polydextrose initially in powder form.

Determining the critical relative humidity at which the glassy to rubbery transition occurs in polydextrose using an automatic water vapor sorption instrument.

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).