AbstractMicrofibrillated celluloses, liberated from macroscopic lignocellulosic fibers by mechanical means, are sub-fiber elements with lengths in the micron scale and diameters ranging from 10 to a few hundred nanometers. These materials have shown strong water interactions. This article describes an investigation and quantification of the ‘hard-to-remove (HR) water content’ in cellulose fibers and microfibrillated structures prepared from fully bleached softwood pulp (BSW). The fiber/fibril structure was altered by using an extended beating process (up to 300 minutes), and water interactions were determined with isothermal thermogravimetric analysis (TGA). Isothermal TGA is shown to be a convenient and insightful characterization method for fiber-water interactions for fibers and microfibrils at small sample size. In addition, scanning electron microscopic (SEM) images depict the differences between fibers and microfibrils with respect to beating time in the dried consolidated structures. Highly refined pulps with microfibrils were determined to have two critical drying points, i.e., two minima in the second derivative of weight versus time, not before reported in the literature. Also in this study, hard-to-remove (HR) water content is related to the area above the first derivative curve in the constant rate and falling rate drying zones. This measure of HR water correlates with a previous measurement method of HR water but is less ambiguous for materials that lack a constant drying rate zone. Blends of unbeaten fibers and microfibril containing samples were prepared and show potential as composite materials.