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Composites in 25 kg batches were compounded of cellulose nanocrystals (CNC) and thermomechanical pulp (TMP) and shaped into caps at industrial facilities on a pilot-plant scale. Some of the material was also injection molded into plaques to compare the effect of laboratory-scale and pilot-scale compounding of poly(ethylene-co-acrylic acid) (EAA7) and poly(caprolactone) composites reinforced with 10 wt% CNC and TMP. The materials compounded under laboratory-scale conditions showed a different morphology, improved mechanical properties, and a higher viscosity, than the materials compounded on a pilot-scale. In some cases, the rheological properties of the melts indicated the presence of a relatively strong percolating cellulosic network, and the interphase region between the cellulose and the matrix appears to be important for the mechanical performance of the composites. After the compounding on a pilot scale, both the length and width of the pulp fibers was reduced. The TMP provided better reinforcement than the CNC possibly due to the higher aspect ratio.

Composite materials based on an ethylene-acrylic acid (EAA) copolymer and 20 wt% cellulose fibers were compounded by two runs in a twin-screw extruder. The composite material with cellulose fibers (CF) and a reference of unfilled EAA were injection molded into plaques using three different temperature profiles with end zone temperatures of 170°C, 200°C, and 230°C. The injection molded samples were then characterized in terms of their mechanical properties, thermal properties, appearance (color and gloss), and surface topography. The higher processing temperatures resulted in a clear discoloration of the composites, but there was no deterioration in the mechanical performance. The addition of cellulose typically gave a tensile modulus three times higher than that of the unfilled EAA, but the strength and strain at rupture were reduced when fibers were added. The processing temperature had no significant influence on the mechanical properties of the composites. Gloss measurements revealed negligible differences between the samples molded at the different melt temperatures but the surface smoothness was somewhat higher when the melt temperature was increased. In general, addition of the cellulose to the EAA reduced the gloss level and the surface smoothness. POLYM. ENG. SCI., 2019. © 2019 Society of Plastics Engineers.

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 °C). Composites containing surface-modified or unmodified CNC (0.1, 1.0 and 10 wt%) 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 wt% 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.

Cellulose nanocrystals (CNC) were surface modified by grafting azetidinium salts onto the sulphate ester groups on the cellulosic surfaces. The modified CNC were characterized using NMR, FTIR spectroscopy, conductometric titration and measurement of the ζ-potential. Thermal gravimetrical analysis revealed that the onset temperature for the thermal degradation was shifted upwards by almost 100 °C as a result of the surface grafting. The rheological properties of dispersions based on unmodified and modified CNC were evaluated in detail. Two solids contents were studied; 0.65 and 1.3 wt%. In general, the grafting of the salts significantly increased the shear viscosity at a given shear rate as well as the storage and loss moduli of the dispersions. The CNC concentration at the gel point (network formation) decreased in a corresponding manner when the nanocellulosic particles were surface modified. This may be associated with pronounced hydrophobic attractive interactions between the grafted substituents.

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.

Aiming at better understanding the ageing behaviour of cellulose composites, the accelerated thermo-oxidative ageing of polyethylene reinforced with two types of wood-based cellulose fibres was studied. Materials were prepared by extrusion mixing of either un-stabilized or stabilized polyethylene reinforced with 5 and 20 vol % cellulose content. The materials were extruded into strips and then aged at 90°C in circulating air. The effect of accelerated ageing up to 31 days was assessed by oxidation induction time and mechanical properties in tension. The results indicated that the added cellulose fibres did not increase the degradation of the composites during this ageing. Reinforcement with 20 % cellulose fibre having a 28 % lignin content together with 0.005 % Irganox 1010 antioxidant resulted in a remarkable improvement in the resistance against accelerated thermo-oxidation, compared to the pure polyethylene with added antioxidant. The findings of increased lifetime of LDPE by addition of wood-based reinforcement is of great interest, since the durability aspect is crucial to understand and predict before usage in commercial applications and especially as structural composites.