Roos, Y.H., Jouppila, K. & Zielasko, B. Journal of Thermal Analysis (1996) 47: 1437. doi:10.1007/BF01992838
An exotherm, observed in differential scanning calorimetry (DSC) scans of amorphous food materials above their glass transition temperature,Tg, may occur due to sugar crystallization, nonenzymatic browning, or both. In the present study, this exothermal phenomenon in initially anhydrous skim milk and lactose-hydrolyzed skim milk was considered to occur due to browning during isothermal holding at various temperatures above the initialTg. The nonenzymatic, Maillard browning reaction produces water that in amorphous foods, may plasticize the material and reduceTg. The assumption was that quantification of formation of water from theTg depression, which should not be observed as a result of crystallization under anhydrous conditions, can be used to determine kinetics of the nonenzymatic browning reaction. The formation of water was found to be substantial, and the amount formed could be quantified from theTg measured after isothermal treatment at various temperatures using DSC. The rate of water formation followed zero-order kinetics, and its temperature dependence well aboveTg was Arrhenius-type. Although water plasticization of the material occurred during the reaction, and there was a dynamic change in the temperature differenceT−Tg, the browning reaction was probably diffusioncontrolled in anhydrous skim milk in the vicinity of theTg of lactose. This could be observed from a significant increase in activation energy. The kinetics and temperature dependence of the Maillard reaction in skim milk and lactose-hydrolyzed skim milk were of similar type well above the initialTg. The difference in temperature dependence in theTg region of lactose, but above that of lactose-hydrolyzed skim milk, became significant, as the rate in skim milk, but not in lactose-hydrolyzed skim milk, became diffusion-controlled. The results showed that rates of diffusion-controlled reactions may follow the Williams-Landel-Ferry (WLF) equation, as kinetic restrictions become apparent within amorphous materials in reactions exhibiting high rates at the same temperature under non-diffusion-controlled conditions.
browning crystallization glass transition kinetics milk powder water