No description available.

Thesis (Ph. D.)--Institute of Paper Chemistry, 1969. / Includes bibliographical references (p. 90-92).

Thesis (Ph. D.)--Institute of Paper Chemistry, 1970. / Includes bibliographical references (p. 85-88).

Thesis (M. S.)--Chemical Engineering, Georgia Institute of Technology, 2010. / Committee Chair: Banerjee Sujit; Committee Member: Deng Yulin; Committee Member: Haynes Danny. Part of the SMARTech Electronic Thesis and Dissertation Collection.

Solutions of cellulose esters with different concentrations in dimethylacetamide (DMAc) and with different types of substituents were studied in relation to their liquid crystalline (LC) solution behavior. Classical LC behavior was revealed for all solutions. Critical polymer concentration (V_p^c) is highest for cellulose acetate (CA) and lowest for cellulose acetate butyrate (CAB) with highest degree of butyration. This is opposite to the classical model by Flory which predicts an increase in V_p^c with decreasing aspect ratio (L/d). Fibers were spun from isotropic and anisotropic DMAc solutions of cellulose esters by dry jet/wet spinning process. The mechanical properties, orientation, and crystallinity of the fibers increased as spinning progressed from the isotropic to the anisotropic solution state. High butyryl content enhances both overall solubility and the formation of LC solutions at lower concentration, but it results in lower fiber properties. Unmodified cellulose (C) and cellulose hexanoate (CH) also exhibited LC behavior. The V_p^c value for CH was lower than that obtained for CAB with maximum degree of butyration. This indicates that bulky substituents may lower V_p^c values. The formation of high modulus (152 g/d) cellulose fibers from LC solutions is attributed to the air-gap that exists in the dry jet/wet spinning process. Presence of lithium chloride (LiCl) in the LC solutions of CAB exhibited ionic interactions. Mechano-sorptive creep behavior of the fibers spun from these solutions decreases in the presence of residual LiCl salt. Fibers from blends of CAB and of C with lignin (L) were spun from Lc solution. Morphological investigations demonstrate that CAB and L formed intimately mixed blends whereas C and L were partially mixed. The mechanical properties of the fibers with L increased due to good phase mixing of CAB and L molecules in the fiber matrix. / Ph. D.

Bio-basedcomposites are being increasingly used in applications where weight saving,and environmental friendliness is as important as structural performance. Obviously, bio-based materials have their limitations regarding durability and stability of the properties,but their potential in use for advanced applications can be expanded if they were functionalized and considered beyond their structural performance. Multifunctionalityincomposites can be achieved by modifyingeither of the composite constituents at different levelsso that they can perform energy-associated roles besides their structural reinforcement in the system. For the fibers, this can be done at the microscale by altering theirmicrostructure during spinning process or by applying functional coatings. As for the matrix, it is usually done by incorporating additives that can impart the required characteristics to the matrix. The nano-sized additives that mightbe considered for this objective are graphene and carbon nano-tubes. A big challenge with such materials is the difficulty to reachthe dispersionstate necessary for formation ofstable network to overcome the percolation threshold for conductivity. However, once the network is formed, the composite can have improved mechanical performance together with one or more of the added functionalities such as barrier capabilities,thermal and/or electrical conductivities or electromagnetic interference ability. Enormous work has been done to achieve the functionality incomposites produced with special care in laboratories. However, when it comes to mass production, it is both cost and energy inefficient to use tedious,complex methods for the manufacturing. Hence there is a need to investigate the potential of using scalable and industrial-relevant techniques and materials with acceptable compromise between cost and properties. The work presented in this thesis is performedwithin two projects aiming to achieve functional composites based on natural and man-made cellulosic fibers suitable for industrial upscaling. Conductive Regenerated Cellulose Fibers (RCFs) were produced by coating them with copper by electroless coating process using commercial materials. On the other hand, commercial masterbatches based on Graphene Nano-Platelets (GNPs) were used to produce wood polymer composites (WPC) with added multifunctionality by melt extrusion process. The process is one of the conventional methods used inpolymerproductionand needsno modifications for processingfunctional composites. Both materials together can be used to produce hybrid functional composites. The incorporation of the GNP into HDPE has resulted in improvement in the mechanical propertiesof polymer as well as composite reinforced with wood fibers. Stiffness has increased to a large extent while effect on the strength was less pronounced(>100% and 18% for stiffness and strength at 15%GNP loading). The enhancement of thermal conductivityat higher graphene loadingswas also observed. Moreover, time-dependent response of the polymer has also been affected and the addition of GNP has resulted in reduced viscoplastic strains and improved creep behavior. The copper-coated cellulose fibers showed a significant increasein electrical conductivity(<1Ω/50mm of coated samples) and a potential in use as sensor materials. However, these results come with the cost of reduction in mechanical properties of fibers (10% and 70% for tensile stiffness and strength, respectively) due to theeffect ofchemicals involved in the process.

No description available.

The material properties of fibre networks and fibre reinforced composites are strongly influenced by fibre-fibre interactions. Stress transfer between load bearing elements in such materials is often dictated by the nature of the fibre-fibre interface. Inter-fibre bonding is solely responsible for internal cohesion in paper, because all stresses transferred between fibres operate through fibre-fibre bonds. . The future development of cellulosic fibre materials will require an improved understanding of the fibre-fibre interface. Fluorescence resonance energy transfer (FRET) was proposed as a new tool for the study of fibre interfaces. A protocol for covalent linkage of fluorophores to natural and regenerated cellulosic fibres was developed and the absorptive and emissive properties of these dyes were characterized. The fluorescent response of these dyed fibres in paper sheets was studied using steady-state fluorescence spectroscopy. Fluorescence micrographs of fibre crossings on glass slides were analyzed using the FRETN correction algorithm. Energy transfer from coumarin dyed fibres to fluorescein dyed fibres at the interface was observed. The FRETN surfaces for spruce and viscose rayon fibre crossings were distinctly different. The FRET microscopy method was able to detect statistically significant differences in spruce fibre interface development when fibre fraction and wet pressing were varied. The coalescence of natural cellulosic fibre interfaces during drying was also observed with the technique. Polysaccharide films were employed as model systems for the natural and regenerated cellulose fibre interfaces. It was found that pressing cellulose films did not result in significantly increased FRETN either due to resistance to deformation or the inability to participate in interdiffusion. Conversely, xylan films demonstrated a drastic increase in the FRETN signal with increased wet pressing. These results support the previously observed differences between regenerated cellulose fibres and natural wood fibres. The results of the FRETN analysis of the polysaccharide film model systems suggest that lower molecular weight amorphous carbohydrates are likely to be significant contributors to fibre interface development.

Cellulose is a biodegradable, renewable, flexible, inexpensive, biopolymer which is abundantly present in nature. In spite of these inherent advantages, cellulose fibers cannot be used directly in a number of potential industrial applications because of their hydrophilic nature; a surface modification is often required to alter the surface properties of cellulose. This thesis work reports a fabrication method that results in superhydrophobic properties (contact angle (CA) > 150°) on cellulose (paper) surfaces. Superhydrophobicity was obtained by domain-selective etching of amorphous portions of the cellulose fiber in an oxygen plasma, and by subsequently coating the etched surface with a thin fluorocarbon film deposited via plasma enhanced chemical vapor deposition from a pentafluoroethane precursor. Two forms of superhydrophobicity with vastly different degrees of adhesion were obtained by varying the plasma treatment conditions, in particular the duration of oxygen etching: "roll-off" (contact angle (CA): 166.7° ± 0.9° and CA hysteresis: 3.4° ± 0.1°) and "sticky" (CA: 153.4° ± 4.7° and CA hysteresis: 149.8±5.8°) superhydrophobicity. The CA hysteresis could be tuned between the two extremes by adjusting the oxygen etching time to control the formation of nano-scale features on the cellulose fibers. The effects of fiber types (soft vs. hard wood) and paper making parameters on fabricating superhydrophobic paper were also investigated. There were no significant differences in the formation of the nano-scale features created via oxygen etching on paper substrates obtained from different fiber types and paper making parameters. Because "roll-off" superhydrophobicity is primarily determined by the nano-scale roughness, this property is therefore not significantly affected by the fiber types or paper making parameters. While the fiber type does not affect "roll-off" or "sticky" superhydrophobicity, paper making process parameters affect the structure of the paper web on the micro-scale and thus lead to variations in "sticky" superhydrophobicity. Superhydrophobic paper substrates were patterned with high surface energy ink deposited using a commercial desktop printer. The patterns could be used to manipulate the drag and extensional adhesion of water drops on the substrates. Classic 'drag' and 'extensional' adhesion expressions were used to model the behavior of water drops on basic dot and line patterns of variable dimensions. A fundamental understanding of the adhesive forces of water drops as a function of pattern shape and size was thus obtained. Based on this knowledge, patterned paper substrates were then designed and fabricated to perform simple unit operations, such as storage, transfer, mixing and merging of water drops. These basic functionalities were combined in the design of a simple two-dimensional lab-on-paper (LOP) device. Further studies of more complicated pattern shapes led to the generation of patterns that allowed directional mobility and tunable adhesion of water drops. These developments are critical for designing novel components for two-dimensional LOP devices such as flow paths, gates/diodes, junctions and drop size filters.

A new method for enhancing rates of enzymatic hydrolysis for cellulosic fiber is presented. By adding a cationic polyelectrolyte to a cellulase/cellulose hydrolytic system, the polyelectrolyte binds to the cellulase and fiber forming flocs. The cellulase is bound by a patching mechanism. By using this technique, the rate of enzymatic hydrolysis can be enhanced. This thesis covered observations made about the cellulase/cationic polyelectrolyte/fiber interactions. A mechanism was proposed based on the experimental results.