| 1. |
- Ankerfors, Mikael, 1978-
(författare)
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Microfibrillated cellulose: Energy-efficient preparation techniques and applications in paper
- 2015
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- This work describes three alternative processes for producing microfibrillated cellulose (MFC; also referred to as cellulose nanofibrils, CNF) in which bleached pulp fibres are first pretreated and then homogenized using a high-pressure homogenizer. In one process, fibre cell wall delamination was facilitated by a combined enzymatic and mechanical pretreatment. In the two other processes, cell wall delamination was facilitated by pretreatments that introduced anionically charged groups into the fibre wall, by means of either a carboxymethylation reaction or irreversibly attaching carboxymethylcellulose (CMC) to the fibres. All three processes are industrially feasible and enable energy-efficient production of MFC. Using these processes, MFC can be produced with an energy consumption of 500–2300 kWh/tonne. These materials have been characterized in various ways and it has been demonstrated that the produced MFCs are approximately 5–30 nm wide and up to several microns long.The MFCs were also evaluated in a number of applications in paper. The carboxymethylated MFC was used to prepare strong free-standing barrier films and to coat wood-containing papers to improve the surface strength and reduce the linting propensity of the papers. MFC, produced with an enzymatic pretreatment, was also produced at pilot scale and was studied in a pilot-scale paper making trial as a strength agent added at the wet-end for highly filled papers.
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| 2. |
- Bamba, Yu, et al.
(författare)
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Estimating the Strength of Single Chitin Nanofibrils via Sonication-Induced Fragmentation
- 2017
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Ingår i: Biomacromolecules. - : American Chemical Society (ACS). - 1525-7797 .- 1526-4602. ; 18:12, s. 4405-4410
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Tidskriftsartikel (refereegranskat)abstract
- We report the mechanical strength of native chitin nanofibrils. Highly crystalline alpha-chitiri nanofibrils Were purified from filaments produced by a microalgae Phaeocystis globosa, and two types of beta-chitin nariofibrils were purified from pens of a squid Loligo bleekeri and tubes of a tubeworm Lamellibrachia satsuma, with relatively low and high crystallinity, respectively. These chitin nanofibrils were fully dispersed in water. The strength of individualized nanofibrils was estimated using cavitation induced tensile fracture of nanoscale filaments in a liquid medium. Both types of beta-chitin nanofibrils exhibited similar strength values of approximately 3 GP; in contrast, the alpha-chitin nanofibrils exhibited a much lower strength value of 1.6 GPa. These strength estimates suggest that the tensile strength of chitin nanofibrils is governed by the molecular packing modes of chitin rather than their crystallinity.
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| 3. |
- Isogai, Akira, et al.
(författare)
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Preparation of cellulose nanofibers using green and sustainable chemistry
- 2018
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Ingår i: Current Opinion in Green and Sustainable Chemistry. - : Elsevier BV. - 2452-2236. ; 12, s. 15-21
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Forskningsöversikt (refereegranskat)abstract
- The development of green and sustainable routes to liberate crystalline cellulose microfibrils from plant cell walls is of utmost importance to enable development of the large-scale production of sustainable nanomaterials based on renewable resources. The catalytic oxidation of cellulose using 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO) under aqueous conditions at room temperature is a position-selective and efficient chemical modification. TEMPO-mediated oxidation of plant cellulose fibers, followed by gentle mechanical disintegration of the oxidized celluloses in water, results in the formation of TEMPO-oxidized cellulose nanofibers (TOCNs) with homogeneous widths (similar to 3 nm) and high aspect ratios. TOCNs are characteristic bio-based materials with high tensile strengths and elastic moduli. Sodium carboxylate groups are densely present on the crystalline TOCN surfaces and can undergo counterion exchange from sodium to other metal or alkylammonium ions under aqueous conditions. The hydrophilic/hydrophobic, stable/biodegradable, super deodorant, catalytic, and other functionalities of TOCNs can be controlled through counterion exchange.
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| 4. |
- Koso, Tetyana, et al.
(författare)
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2D Assignment and quantitative analysis of cellulose and oxidized celluloses using solution-state NMR spectroscopy
- 2020
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Ingår i: Cellulose. - : Springer Science and Business Media LLC. - 0969-0239 .- 1572-882X. ; 27:14, s. 7929-7953
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Tidskriftsartikel (refereegranskat)abstract
- The limited access to fast and facile general analytical methods for cellulosic and/or biocomposite materials currently stands as one of the main barriers for the progress of these disciplines. To that end, a diverse set of narrow analytical techniques are typically employed that often are time-consuming, costly, and/or not necessarily available on a daily basis for practitioners. Herein, we rigorously demonstrate a general quantitative NMR spectroscopic method for structural determination of crystalline cellulose samples. Our method relies on the use of a readily accessible ionic liquid electrolyte, tetrabutylphosphonium acetate ([P-4444][OAc]):DMSO-d(6), for the direct dissolution of biopolymeric samples. We utilize a series of model compounds and apply now classical (nitroxyl-radical and periodate) oxidation reactions to cellulose samples, to allow for accurate resonance assignment, using 2D NMR. Quantitative heteronuclear single quantum correlation (HSQC) was applied in the analysis of key samples to assess its applicability as a high-resolution technique for following cellulose surface modification. Quantitation using HSQC was possible, but only after applying T(2)correction to integral values. The comprehensive signal assignment of the diverse set of cellulosic species in this study constitutes a blueprint for the direct quantitative structural elucidation of crystalline lignocellulosic, in general, readily available solution-state NMR spectroscopy. [GRAPHICS] .
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| 5. |
- Li, Tian, et al.
(författare)
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Developing fibrillated cellulose as a sustainable technological material
- 2021
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Ingår i: Nature. - : Springer Nature. - 0028-0836 .- 1476-4687. ; 590:7844, s. 47-56
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Tidskriftsartikel (refereegranskat)abstract
- Cellulose is the most abundant biopolymer on Earth, found in trees, waste from agricultural crops and other biomass. The fibres that comprise cellulose can be broken down into building blocks, known as fibrillated cellulose, of varying, controllable dimensions that extend to the nanoscale. Fibrillated cellulose is harvested from renewable resources, so its sustainability potential combined with its other functional properties (mechanical, optical, thermal and fluidic, for example) gives this nanomaterial unique technological appeal. Here we explore the use of fibrillated cellulose in the fabrication of materials ranging from composites and macrofibres, to thin films, porous membranes and gels. We discuss research directions for the practical exploitation of these structures and the remaining challenges to overcome before fibrillated cellulose materials can reach their full potential. Finally, we highlight some key issues towards successful manufacturing scale-up of this family of materials. Opportunities for the application of fibrillated cellulose materials-which can be extracted from renewable resources-and broader manufacturing issues of scale-up, sustainability and synergy with the paper-making industry are discussed.
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| 6. |
- López Durán, Verónica, 1987-
(författare)
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Chemical Modification of Cellulose Fibres and Fibrils for Design of New Materials
- 2018
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Due to the growing interest in biobased materials in today’s society, where the need for a cyclic economy is obvious, there has been a huge increase in the interest for using cellulose due to its excellent mechanical and chemical properties. However, the properties of cellulose have to be modified and improved in order to satisfy advanced material applications where the cellulose properties can be tuned to fit the properties of other components in composite mixtures. This thesis explores the heterogeneous chemical modification of cellulose for improved material properties of cellulose-based materials and the use of cellulose fibres and fibrils in novel applications.In the first part of the work described in this thesis, a fundamental study was performed to clarify how the chemical composition and the fibre/fibril structure of the cellulose following chemical modification affect the material properties. The second part of the work was aimed at exploring the potential for using the chemically modified fibres/fibrils in novel material applications. Lignocellulosic fibres with different chemical compositions were modified by periodate oxidation and borohydride reduction, and it was found that the most important factor was the amount of holocellulose present in the fibres, since lignin-rich fibres were less reactive and less responsive to the treatments. Despite the lower reactivity of lignin-rich fibres, it was however possible to improve their mechanical properties and to achieve a significant increase in the compressive strength of papers prepared from modified unbleached kraft fibres.The chemical modifications were then expanded to nine different molecular structures and two different degrees of modification. Fibres modified at low degrees of modification were used to prepare handsheets, followed by mechanical and physical characterization. Highly modified fibres were also used to prepare cellulose nanofibrils (CNFs). It was found that the properties of handsheets and films prepared from modified fibres/fibrils are highly dependent on the chemical structure of the modified cellulose and, as an example, the ductility was greatly improved by converting secondary alcohols to primary alcohols. A detailed analysis of the modified fibres and fibrils also showed that, due to the heterogeneous chemical reaction used, the modified fibrils had a core-shell structure with a shell of modified cellulose with a lower crystalline order surrounding a core of crystalline cellulose. The results also showed that the chemical structure of the modified shell dramatically affects the interaction with moisture. Materials from fibrils containing covalent crosslinks have shown to be less sensitive to moisture at the cost of being more brittle. In a different application, modified CNFs were used as paper strength additives. Three differently modified CNFs were used: carboxymethylated CNFs, periodate-oxidised carboxymethylated CNFs and dopamine-grafted carboxymethylated CNFs. The properties of these CNFs were compared with that of a microfibrillated cellulose from unbleached kraft fibres. In general, a great improvement in the dry mechanical properties of handsheets was observed with the addition of the periodate-oxidised oxidised and dopamine-grafted modified fibrils, whereas only the periodate-oxidised carboxymethylated CNFs improved the wet strength.Finally, it was found that the chemically modified fibres could be used to prepare a novel low-density material with good mechanical strength, both wet and dry, and excellent shape recovery capacity in the wet state after mechanical compression. The fibre networks were produced by solvent exchange from water to acetone followed by air drying at room temperature. The properties of the fibre networks could also fairly easily be tuned in terms of porosity, density and strength.
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| 7. |
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| 8. |
- Sjöstedt, Anna
(författare)
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Preparation and characterization of nanoporous cellulose fibres and their use in new material concepts
- 2014
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The overall objective of the work in this thesis is to better utilize the non-collapsed structure of the delignified wood-fibre cell wall in the preparation of new types of materials.In order to utilize the fibres in new materials, it is crucial to have a well-defined starting material and to know how it reacts to certain treatments of the fibres. A new robust method for measuring the average pore size of water-swollen fibres-rich in cellulose is presented. This method is based on solid-state NMR, which measures the specific surface area [m2/g] of water-swollen samples, and the fibre saturation point (FSP) method, which measures the pore volume [water mass/solid mass] of a water swollen sample. These results can be combined since they are both recorded on water-swollen fibres in the presence of excess water and neither is based on any assumption of any particular pore geometry. Delignifed wood fibres (chemical pulp fibres) have an open fibrillar structure, with approximately 20 nm thick fibril aggregates arranged in a porous structure with a specific surface area of 150 m2/g. This open structure was preserved in the dry state by a liquid-exchange procedure followed by careful drying in argon gas. The dry structure had a specific surface area of 130 m2/g, which implies that the porous structure was preserved in the dry state.New fibre-basedmaterials were prepared by two different strategies.The first strategy was to utilize the open nanoporous fibre wall structure for the preparation of nanocomposites. The nanoporous structure was used as a scaffold, allowing monomers to impregnate the structure and to be in-situ polymerized inside the fibre wall pores. Poly(methyl methacrylate) (PMMA) and poly(butylacrylate) (PBA) were synthesized inside the dry nanoporous fibre wall structure, and an epoxy resin was cured in never-dried fibres oxidized to different degrees by TEMPO. The composites prepared thus have a mixture of fibril aggregates and a polymer matrix inside the fibre wall. The structure and performance of the composite materials were evaluated both by high resolution microscopy and mechanically. Characterization of the composite showed that the polymer matrix was successfully formed inside the fibre wall pores. The structural changes caused by oxidation were preserved and utilized for the composite with the epoxy matrix. By tailoring the supramolecular structure of fibres in their water-swollen state, it was hence indeed possible to control the mechanical performance of the nanostructured fibre composites.The secondbstrategy used to prepare composites was to improve the thermoplastic properties of paper by adding polylactic acid (PLA) latex during the preparation of fibrebsheets. By the addition of PLA-latex, it was possible to form double curved sheets with a nominal strain at break of 21%.
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| 9. |
- Soeta, Hiroto, et al.
(författare)
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Low-Birefringent and Highly Tough Nanocellulose-Reinforced Cellulose Triacetate
- 2015
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Ingår i: ACS Applied Materials and Interfaces. - : American Chemical Society (ACS). - 1944-8244 .- 1944-8252. ; 7:20, s. 11041-11046
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Tidskriftsartikel (refereegranskat)abstract
- Improvement of the mechanical and thermal properties of cellulose triacetate (CTA) films is required without sacrificing their optical properties. Here, poly(ethylene glycol) (PEG)-grafted cellulose nanofibril/CTA nanocomposite films were fabricated by casting and drying methods. The cellulose nanofibrils were prepared by 2,2,6,6-tetramethylpiperidine-l-oxyl,(TEMPO)-mediated oxidation, and amine-terminated PEG chains were grafted onto the surfaces of the TEMPO-oxidized cellulose nanofibrils (TOCNs) by ionic bonds. Because of the nanosize effect of TOCNs with a uniform width of similar to 3 nm, the PEG-TOCN/CTA nanocomposite films had high transparency and low bitefringence. The grafted PEG chains enhanced the filler-matrix interactions and crystallization of matrix CTA molecules, resulting in the Young's modulus and toughness of CTA film being significantly improved by PEG-grafted TOCN addition. The coefficient of thermal expansion of the original CTA film was mostly preserved even with the addition of PEG-grafted TOCNs. These results suggest that PEG-TOCNs are applicable to the reinforcement for transparent optical films.
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| 10. |
- Soeta, Hiroto, et al.
(författare)
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Tailoring Nanocellulose-Cellulose Triacetate Interfaces by Varying the Surface Grafting Density of Poly(ethylene glycol)
- 2018
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Ingår i: ACS Omega. - : American Chemical Society (ACS). - 2470-1343. ; 3:9, s. 11883-11889
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Tidskriftsartikel (refereegranskat)abstract
- Careful design of the structures of interfaces between nanofillers and polymer matrices can significantly improve the mechanical and'thermal' properties of the overall nanocomposites. Here, we investigate]how the grafting density on the surface of nanocelluloses influences the properties of nanocellulose/cellulose triacetate (CTA) composites. 2,2,6,6 The surface of nanocellulose, which was preparedby tetramethylpiperidine-l-oxyl oxidation, was modified with long poly(ethylene glycol) (PEG) chains at different grafting_ densities. The PEG -grafted nanocelluloses were h omogene ously embedded in CTA matrices. The mechanical and thermal properties of the nanocomposites were characterized. Increasing the grafting density caused the soft PEG chains to form denser and thicker layers around the rigid nanocelluloses. The PEG layers were not completely miscible with the CTA matrix. This structure consfderably enhanced the energy dissipation by allowing sliding at the interface, which increased the toughness of the nanocomposites. The thermal and mechanical properties of the composites could be tailored by controlling the grafting density. These findings provide a deeper understanding about interfacial design for nanocellulose-based composite materials.
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