Preparation and Viscoelastic Properties of Composite Fibres Containing Cellulose Nanofibrils: Formation of a Coherent Fibrillar Network

Composite fibres with a matrix of poly(ethylene glycol) (PEG) and cellulose nanofibrils (CNF) as reinforcing elements were produced using a capillary viscometer. Two types of CNF were employed: one based on carboxymethylated pulp fibres and the other on TEMPO-oxidized pulp. Part of the latter nanofibrils was also grafted with PEG in order to improve the compatibility between the CNF and the PEG matrix. The nominal CNF-content was kept at 10 or 30 weight-%. The composite fibres were characterized by optical and scanning electron microscopy in addition to dynamic mechanical thermal analysis (DMTA). Evaluation of the storage modulus indicated a clear reinforcing effect of the CNF, more pronounced in the case of the grafted CNF and depending on the amount of CNF. An interesting feature observed during the DMTA-measurements was that the fibrils within the composite fibres appeared to forma rather coherent and load-bearing network which was evident even after removing of the PEG-phase (by melting). An analysis of the modulus of the composite fibres using a rather simple model indicated that the CNF were more efficient as reinforcing elements at lower concentrations which may be associated with a more pronounced aggregation as the volume fraction of CNF increased

Extrusion parameters for foaming of a beta-glucan concentrate

Plastics is a group of materials commonly encountered on a daily basis by many people. They have enabled rapid, low-cost manufacturing of products with complicated geometries and have contributed to the weight reduction of heavy components, especially when produced into a foamed structure. Despite the many advantages of plastics, some drawbacks such as the often fossil-based raw-material and the extensive littering of the material in nature, where it is not degraded for a very long time, needs to be dealt with. One way to address at least one of the issues could be to use polymers from nature instead of fossil-based ones. Here, a β-glucan concentrate originating from barley was investigated. The concentrate was processed into a foam by hot-melt extrusion, and the processing window was established. The effect of different blowing agents was also investigated. Water or a combination of water and sodium bicarbonate were used as blowing agents, the latter apparently giving a more uniform pore structure. The porous structure of the foamed materials was characterized mainly by using a combination of confocal laser scanning microscope and image analysis. The density of the samples was estimated and found to be in a similar range as some polyurethane foams. A set of 3D parameters were also quantified on two selected samples using X-ray microtomography in combination with image analysis, where it was indicated that the porous structure had a pre-determined direction, which followed the direction of the extrusion process

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

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

Rheological properties of elastomer-modified polypropylene and their influence on the formation of flow marks

A premium appearance is essential for many polymeric products and for this reason surface defects associated with the manufacturing process, e.g. injection molding, are detrimental. In this study, the interest is focussed on defects arising during injection molding of such elastomer-modified polymers that are often used in the automotive sector to produce interior and exterior components. In particular, defects denoted as "flow marks" or "tiger stripes" were investigated. These defects appear on the surface of the injection-molded components, especially if long flow lengths are involved and consist of alternating glossy and dull bands. Here an attempt was made to elucidate to what extent some important rheological properties of the polymer melts influence the generation of such flow marks. Hence, the flow properties, mainly in shear; of three different grades of elastomermodified polypropylene containing mineral fillers were correlated to their propensity for defect generation. In summary, it was noted that a higher melt elasticity, as reflected in pressure losses during flow through a capillary, the degree of die swell and to some extent the dynamic-mechanical behavior, leads to less severe flow marks or retards the formation of such defects. Elongational draw-down experiments also indicated a more stable flow in the case of the melt that exhibited the highest elasticity. Furthermore, subjecting the measured flow behavior to a Mooney analysis, the results obtained pointed to that wall-slip in itself is not a primary cause for the appearance of the type of flow marks studied here. \ua9 2010 Wiley Periodicals, Inc