Nanomechanics of cellulose crystals and cellulose-based polymer composites

Cellulose-polymer composites have potential applications in aerospace and transportation areas where lightweight materials with high mechanical properties are needed. In addition, these economical and biodegradable composites have been shown to be useful as polymer electrolytes, packaging structures, optoelectronic devices, and medical implants such as wound dressing and bone scaffolds. In spite of the above mentioned advantages and potential applications, due to the difficulties associated with synthesis and processing techniques, application of cellulose crystals (micro and nano sized) for preparation of new composite systems is limited. Cellulose is hydrophilic and polar as opposed to most of common thermoplastics, which are non-polar. This results in complications in addition of cellulose crystals to polymer matrices, and as a result in achieving sufficient dispersion levels, which directly affects the mechanical properties of the composites. As in other composite materials, the properties of cellulose-polymer composites depend on the volume fraction and the properties of individual phases (the reinforcement and the polymer matrix), the dispersion quality of the reinforcement through the matrix and the interaction between CNCs themselves and CNC and the matrix (interphase). In order to develop economical cellulose-polymer composites with superior qualities, the properties of individual cellulose crystals, as well as the effect of dispersion of reinforcements and the interphase on the properties of the final composites should be understood. In this research, the mechanical properties of CNC polymer composites were characterized at the macro and nano scales. A direct correlation was made between: Dispersion quality and macro-mechanical properties Nanomechanical properties at the surface and tensile properties CNC diameter and interphase thickness Lastly, individual CNCs from different sources were characterized and for the first time size-scale effect on their nanomechanical properties were reported. Then the effect of CNC surface modification on the mechanical properties was studied and correlated to the crystalline structure of these materials.

SOLUTE-DERIVED THERMAL STABILITY OF NANOCRYSTALLINE ALUMINUM AND PROCESSING FACTOR INFLUENCE ON THE FORMATION OF AL6MN QUASICRYSTALS IN MELT-SPINNING

Thermal stability of nanograined metals can be difficult to attain due to the large driving force for grain growth that arises from the significant boundary area constituted by the nanostructure. Kinetic approaches for stabilization of the nanostructure effective at low homologous temperatures often fail at higher homologous temperatures. Thermodynamic approaches for thermal stabilization may offer higher temperature stability. In this research, modest alloying of aluminum with solute (1 at.% Sc, Yb, or Sr) was examined as a means to thermodynamically stabilize a bulk nanostructure at elevated temperatures. After using melt-spinning and ball-milling to create an extended solid-solution and nanostructure with average grain size on the order of 30-45 nm, 1 h annealing treatments at 673 K (0.72 Tm) , 773 K (0.83 Tm) , and 873 K (0.94 Tm) were applied. The alloys remain nanocrystalline (<100 nm) as measured by Warren-Averbach Fourier analysis of x-ray diffraction peaks and direct observation of TEM dark field micrographs, with the efficacy of stabilization: Sr>Yb>Sc. Disappearance of intermetallic phases in the Sr and Yb alloys in the x-ray diffraction spectra are observed to occur coincident with the stabilization after annealing, suggesting that precipitates dissolve and the boundaries are enriched with solute. Melt-spinning has also been shown to be an effective process to produce a class of ordered, but non-periodic crystals called quasicrystals. However, many of the factors related to the creation of the quasicrystals through melt-spinning are not optimized for specific chemistries and alloy systems. In a related but separate aspect of this research, meltspinning was utilized to create metastable quasicrystalline Al6Mn in an α-Al matrix through rapid solidification of Al-8Mn (by mol) and Al-10Mn (by mol) alloys. Wheel speed of the melt-spinning wheel and orifice diameter of the tube reservoir were varied to determine their effect on the resulting volume proportions of the resultant phases using integrated areas of collected x-ray diffraction spectra. The data were then used to extrapolate parameters for the Al-10Mn alloy which consistently produced Al6Mn quasicrystal with almost complete suppression of the equilibrium Al6Mn orthorhombic phase.