Chemical Modification of Cellulose Nanocrystals: Creating a Novel Toolbox Utilising the Overlooked Sulphate Surface Groups

The move towards a bio-based economy has created an increasing demand for renewable, sustainably produced materials. For future generations, it is crucial to develop economically, socially and environmentally sustainable materials and processes. Cellulose, as the main component in plant biomass, has been an integral part of society since the dawn of age and still continues to provide new possibilities. The complex hierarchical structure of lignocellulosic materials makes it possible to liberate nano-sized cellulose particles with extraordinary and versatile properties, such as large surface area, transparency and excellent mechanical properties. However, the hydrophilic nature of nanocellulose can cause issues in certain applications, and in other instances it may be desirable to introduce additional properties to the CNCs. This can be achieved by functionalising the nanocellulose surface through chemical modification.This thesis presents a novel approach to chemical modification of cellulose nanocrystals, by utilising the sulphate half-ester groups that decorate their surface. Cellulose nanocrystals produced by sulphuric acid hydrolysis were functionalised with dialkylamines through a ring-opening reaction with azetidinium salts, as well as through conjugation with dialkyl alkylchloride and dialkyl cyclocarbonate. The impact on thermal and rheological properties of the functionalised CNCs was evaluated and they were also incorporated as reinforcing elements in bio-based composites. The functionalisation had a significant impact on the thermal stability, improving it by around 100\ua0\ub0C. The functionalised CNCs also exhibited a significantly higher viscosity compared to unmodified CNCs and were prone to network formation at considerably lower solid contents. The conjugation protocol was improved by a more robust synthesis path for the dialkylamine reagents and by shifting from using organic solvents to water, to facilitate scale-up. Incorporation of CNCs into a polymeric matrix resulted in a near three-fold increase in stiffness, depending on matrix, modification and processing techniques used. The modifications also created a stronger interphase between the CNCs and the matrix

Melt Processing of Ethylene-Acrylic Acid Copolymer Composites Reinforced with Nanocellulose

To investigate the impact of process design factors such as number of passes, screw design and screw type, a poly(ethylene-co-acrylic acid) and a masterbatch containing 40 vol% nanocellulose were compounded using a twin-screw extruder with two different screw configurations. The 20 vol% composite pellets obtained, containing nanocellulose of different morphologies, cellulose nanofibrils and cellulose nanocrystals, were re-extruded several times to study the effect of re-extrusion. The compounded pellets were extruded into films using a single-screw extruder. These films contained aggregates of the nanocellulose material, which was reduced in size upon re-extrusion leading to an improvement in properties of the composites. With the best combination of process factors, the Young\u27s modulus and stress at break of the composites increased by factors of 10 and 1.6, respectively. The presence of a strong network of the cellulosic entities was observed qualitatively using melt rheology upon re-extrusion. Re-extrusion had a negligible effect on the crystallinity of the composites. POLYM. ENG. SCI., 2020. (c) 2020 The Authors. Polymer Engineering & Science published by Wiley Periodicals, Inc. on behalf of Society of Plastics Engineers

Water-assisted extrusion and injection moulding of composites with surface-grafted cellulose nanocrystals – An upscaling study

The large-scale surface modification of cellulose nanocrystals (CNC) was carried out to produce CNC-containing composites, in a scale of 3 kg, using industrial-scale melt processing techniques such as twin-screw extrusion and injection moulding. Two different polymer matrices, ethylene-acrylic acid copolymer (EAA) and low-density polyethylene (LDPE), were reinforced with 10 wt% unmodified cellulose nanocrystals (CNC) or surface-treated CNC, where a 2-hydroxyproyl-N-diallyl group had been grafted onto the sulphate half-ester groups on the CNC surfaces. This was achieved by mixing an aqueous CNC dispersion and the polymer pellets directly in the twin-screw extruder followed by a second dry compounding step prior to shaping by injection moulding. The injection-moulded materials were characterized with respect to their mechanical properties and thermal stability. The addition of 10 wt % CNC resulted in all cases in an increase in the yield strength and stiffness by 50–100%, most significantly for the EAA based composites. There were indications of the presence of a stable interphase and a percolating network in the EAA-based materials, according to dynamic-mechanical measurements. A reduction in thermal stability was observed for the melt-processed samples containing diallyl-modified CNC and discoloration in the EAA based samples

Composition and structure of cell wall ulvans recovered from Ulva spp. along the Swedish west coast

The cell wall polysaccharide ulvan was isolated from two species of the seaweed Ulva collected along the Swedish west coast. Acidic extraction was benchmarked against hot water extraction with enzymatic purification and against commercial ulvan. Extracted ulvan contained 11–18 % g/g of ash, some protein (up to 1.3 % g N/g) but minimal colored impurities. The ulvans had high molecular weights (660,000–760,000 g/mol) and were composed of 77–79 % g/g carbohydrates, mainly rhamnose, xylose, glucose, glucuronic acid, and iduronic acid. The extraction protocol and the ulvan source strongly impact the molecular weight and the chemical composition. Acidic extraction caused almost complete desulfation of the isolated ulvan while the other method preserved a significant degree of SO3 substituents. Elemental analysis of ash remaining after thermal degradation showed presence of common mineral elements such as Na, Ca, Mg, Al, and K, but none of the heavy metals Pb, Hg, or As

Composites with surface-grafted cellulose nanocrystals (CNC)

Hydroxyazetidinium salts were used to surface-modify cellulose nanocrystals (CNC) by grafting the salts onto the sulphate ester groups on the CNC surfaces. The grafting was confirmed by ζ-potential measurements and by the thermal degradation behaviour of the modified CNC. The thermal stability (onset of degradation) of the CNC was improved by the surface modification (almost 100\ua0\ub0C). Composites containing surface-modified or unmodified CNC (0.1, 1.0 and 10\ua0wt%) with an ethylene-based copolymer as matrix were produced by compression moulding. The thermal stability of the composites was not, however, markedly improved by the surface grafting onto the CNC. It is suggested that this is due to a degrafting mechanism, associated with the alkaline character of the system, taking place at high temperatures. Model experiments indicated, however, that this did not occur at the conditions under which the composites were produced. Furthermore, in the case of a reference based on pH-neutralised polymeric system and modified CNC, an upward shift in the onset of thermal degradation of the composite was observed. The addition of the CNC to the polymer matrix had a strong influence of the mechanical performance. For example, the tensile modulus increased approximately three times for some systems when adding 10\ua0wt% CNC. The surface grafting of the hydroxyazetidinium salts appeared mainly to affect, in a positive sense, the yield behaviour and ductility of the composites. The results of the mechanical testing are discussed in terms of interactions between the grafted units and the matrix material and between the grafted groups

Composites with surface-grafted cellulose nanocrystals (CNC)

Hydroxyazetidinium salts were used to surface-modify cellulose nanocrystals (CNC) by grafting the salts onto the sulphate ester groups on the CNC surfaces. The grafting was confirmed by ζ-potential measurements and by the thermal degradation behaviour of the modified CNC. The thermal stability (onset of degradation) of the CNC was improved by the surface modification (almost 100\ua0\ub0C). Composites containing surface-modified or unmodified CNC (0.1, 1.0 and 10\ua0wt%) with an ethylene-based copolymer as matrix were produced by compression moulding. The thermal stability of the composites was not, however, markedly improved by the surface grafting onto the CNC. It is suggested that this is due to a degrafting mechanism, associated with the alkaline character of the system, taking place at high temperatures. Model experiments indicated, however, that this did not occur at the conditions under which the composites were produced. Furthermore, in the case of a reference based on pH-neutralised polymeric system and modified CNC, an upward shift in the onset of thermal degradation of the composite was observed. The addition of the CNC to the polymer matrix had a strong influence of the mechanical performance. For example, the tensile modulus increased approximately three times for some systems when adding 10\ua0wt% CNC. The surface grafting of the hydroxyazetidinium salts appeared mainly to affect, in a positive sense, the yield behaviour and ductility of the composites. The results of the mechanical testing are discussed in terms of interactions between the grafted units and the matrix material and between the grafted groups