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- Butchosa Robles, Núria, 1984-
(författare)
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Tailoring Cellulose Nanofibrils for Advanced Materials
- 2014
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Cellulose nanofibrils (CNFs) are nanoscale fibers of high aspect ratio that can be isolated from a wide variety of cellulosic sources, including wood and bacterial cellulose. With high strength despite of their low density, CNFs are a promising renewable building block for the preparation of nanostructured materials and composites. To fabricate CNF-based materials with improved inherent rheological and mechanical properties and additional new functionalities, it is essential to tailor the surface properties of individual CNFs. The surface structures control the interactions between CNFs and ultimately dictate the structure and macroscale properties of the bulk material. In this thesis we have demonstrated different approaches, ranging from non-covalent adsorption and covalent chemical modification to modification of cellulose biosynthesis, to tailor the structure and surface functionalities of CNFs for the fabrication of advanced materials. These materials possess enhanced properties such as water-redispersibility, water absorbency, dye adsorption capacity, antibacterial activity, and mechanical properties.In Paper I, CNFs were modified via the irreversible adsorption of carboxymethyl cellulose (CMC). The adsorption of small amounts of CMC onto the surface of CNFs prevented agglomeration and co-crystallization of the nanofibrils upon drying, and allowed the recovery of rheological and mechanical properties after redispersion of dried CNF samples.In Paper II, CNFs bearing permanent cationic charges were prepared through quaternization of wood pulp fibers followed by mechanical disintegration. The activation of the hydroxyl groups on pulp fibers by alkaline treatment was optimized prior to quaternization. This optimization resulted in individual CNFs with uniform width and tunable cationic charge densities. These cationic CNFs demonstrated ultrahigh water absorbency and high adsorption capacity for anionic dyes.In Paper III, via a similar approach as in Paper II, CNFs bearing polyethylene glycol (PEG) were prepared by covalently grafting PEG to carboxylated pulp fibers prior to mechanical disintegration. CNFs with a high surface chain density of PEG and a uniform width were oriented to produce macroscopic ribbons simply by mechanical stretching of the CNF hydrogel network before drying. The uniform grafted thin monolayer of PEG on the surface of individual CNFs prevented the agglomeration of CNFs and facilitated their alignment upon mechanical stretching, thus resulted in ribbons with ultrahigh tensile strength and modulus. These optically transparent ribbons also demonstrated interesting biaxial light scattering behavior.In Paper IV, bacterial cellulose (BC) was modified by the addition of chitin nanocrystals (ChNCs) into the growing culture medium of the bacteria Acetobacter aceti which secretes cellulose in the form of entangled nanofibers. This led to the in situ incorporation of ChNCs into the BC nanofibers network and resulted in BC/ChNC nanocomposites exhibiting bactericidal activity. Further, blending of BC nanofibers with ChNCs produced nanocomposite films with relatively lower tensile strength and modulus compared to the in situ cultivated ones. The bactericidal activity increased significantly with increasing amount of ChNCs for nanocomposites prepared by direct mixing of BC nanofibers and ChNCs.In Paper V, CNFs were isolated from suspension-cultured wild-type (WT) and cellulose-binding module (CBM) transformed tobacco BY-2 (Nicotiana tabacum L. cv bright yellow) cells. Results from strong sulfuric acid hydrolysis indicated that CNFs from transgenic cells overexpressing CBM consisted of longer cellulose nanocrystals compared to CNFs from WT cells. Nanopapers prepared from CNFs of transgenic cells demonstrated significantly enhanced toughness compared to CNFs of WT cells.
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| 2. |
- Mushi, Ngesa Ezekiel, 1979-
(författare)
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Chitin nanofibers, networks and composites : Preparation, structure and mechanical properties
- 2014
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Chitin is an important reinforcing component in load-bearing structures in many organisms such as insects and crustaceans (i.e. shrimps, lobsters, crabs etc.). It is of increasing interest for use in packaging materials as well as in biomedical applications. Furthermore, biological materials may inspire the development of new man-made material concepts. Chitinmolecules are crystallized in extended chain conformations to form nanoscale fibrils of about 3 nm in diameter. In the present study, novel materialshave been developed based on a new type of chitin nanofibers prepared from the lobster exoskeleton. Improved understanding about effects of chitin from crustaceans and chitin material preparation on structure is provided through Atomic Force Microscopy(AFM) (paper I&II), Scanning Transmission Electron Microscopy(STEM) (paper I&II), X-Ray Diffraction (XRD), Intrinsic Viscosity, solid state 13C Nuclear Magnetic Resonance (NMR) (paper II), Field Emission Scanning Electron Microscopy(FE-SEM) (paper I, II, III, IV & V), Ultraviolet-Visible Spectrophotometryand Dynamic Light Scattering (DLS) (paper III). The presence of protein was confirmed through colorimetric method(paper I & II). An interesting result from the thesis is the new features of chitin nanofiber including small diameter, high molar mass or nanofiber length,and high purity. The structure and composition of the nanofibers confirms this (paper I & II). Furthermore, the structure and properties of the corresponding materials confirm the uniqueness of the present nanofibers: chitin membrane (I & II), polymer matrix composites (III),and hydrogels (paper IV).Improved mechanical properties compared with typical data from the literature were confirmed for chitin nanofiber membranes in paper II, chitin-chitosan polymer matrix composites in paper III, and chitin hydrogel in paper IV. Mechanical tests included dynamic mechanical analysis and uniaxial tensile tests. Mechanical properties of chitin hydrogels were evaluated based onrheological and compression properties (paper IV). The values were the highest reported for this kind of chitin material. Furthermore, the relationships between materials structure and properties were analyzed. For membranes and polymer matrix nanocomposites, the degree of dispersion is an important parameter. For the hydrogels, the preparation procedure is very simple and has interesting practical potential.Chitin-binding characteristics of cuticular proteins areinteresting fornovel bio-inspired material development. In the present work(paper V), chitin nanofibers with newfeaturesincluding high surface area and low protein content were combined with resilin-like protein possessing the chitin-binding characteristics. Hydrated chitin-resilin nanocomposites with similar composition as in rubber-like insect cuticles were prepared. The main objective was to improve understanding on the role of chitin-binding domain on mechanical properties. Resilin is a rubber-like protein present in insects. The exon I (comprising 18 N-terminal elastic repeat units) together with or without the exon II (a typical cuticular chitin-binding domain) from the resilin gene CG15920 found in Drosophila melanogasterwere cloned and the encoded proteins were expressed as soluble products in Escherichia coli.Resilin-like protein with chitin-binding domain (designated as ResChBD) adsorbedin significant amount to chitin nanofiber surface andprotein-bound cuticle-like soft nanocomposites were formed. Although chitin bindingwas taking place only in proteinswith chitin-binding domain, the global mechanical behavior of the hydrated chitin-resilin nanocomposites was not so sensitive to this chitin-resilin interaction.In summary, chitin is an interesting material component with high potential as mechanical reinforcement in a variety of nanomaterials. The present study reports the genesisof novel chitin nanofibers and outlines the basic relationships between structure and properties for materials based on chitin. Future work should be directed towards both bio-inspired studies of the nanocomposite chitin structures in organisms, as well as the industrial applications of chitin waste from the food industry. Chitin nanofibers can strengthen the properties of materials, andprovide optical transparency as well as biological activities such as antimicrobial properties.
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