The addition of carbon nanotubes (CNTs) to polymeric matrices or master batches has the potential to provide composites with novel properties. However, composites with a uniform dispersion of CNTs have proved to be difficult to manufacture, especially at an industrial scale. This paper reports on processing methods that overcome problems related to the control and reproducibility of dispersions. By using a high pressure homogenizer and a three-roll calendaring mill in combination, CNT reinforced epoxies were fabricated by mould casting with a well dispersed nanofiller content from 0.1 to 2 wt%. The influence of the nano-carbon reinforcements on toughness and electrical properties of the CNT/epoxies was studied. A substantial increase of all mechanical properties already appeared at the lowest CNT content of 0.1 wt%, but further raising the nanofiller concentration only led to moderate further changes. The most significant enhancement was obtained for fracture toughness, reaching up to 82%. The low percolation thresholds were confirmed by electrical conductivity measurements on the same composites yielding a threshold value of only about 0.01 wt%. As corroborated by a thorough microscopic analysis of the composites, mechanical and electrical enhancement points to the formation of an interconnected network of agglomerated CNTs.
Chemically modified cellulose micro-and nanofibrils were successfully used as paper strength additives. Three different kinds of cellulose nanofibrils (CNFs) were studied: carboxymethylated CNFs, periodate-oxidised carboxymethylated CNFs and dopamine-grafted carboxymethylated CNFs, all prepared from bleached chemical fibres of dissolving grade, and one microfibrillated cellulose from unbleached kraft fibres. In addition to mechanical characterization of the final paper sheets the fibril retention, sheet density and sheet morphology were also studied as a function of addition of the four different cellulose fibrils. In general, the cellulose fibrils, when used as additives, significantly increased the tensile strength, Young's modulus and strain-atbreak of the paper sheets. The effects of the different fibrils on these properties were compared and evaluated and used to analyse the underlying mechanisms behind the strengthening effect. The strengthenhancing effect was most pronounced for the periodate-oxidised CNFs when they were added together with polyvinyl amine (PVAm) or poly(dimethyldiallylammonium chloride) (pDADMAC). The addition of periodate-oxidised CNFs, with pDADMAC as retention aid, resulted in a 37% increase in tensile strength at a 2 wt% addition and an 89% increase at a 15 wt% addition (from 67 to 92 and 125 kNm/kg, respectively) compared to a reference with only pDADMAC. Wet-strong sheets with a wet tensile index of 30 kNm/kg were also obtained when periodate-oxidised CNFs and PVAm were combined. This significant increase in wet strength is suggested to be the result of a formation of cross-links between the aldehyde groups, introduced by the periodate oxidation, and hydroxyl groups on the lignocellulosic fibres and the primary amines of PVAm. Even though less significant, there was also an increase in wet tensile strength when pDADMAC was used together with periodate-oxidised fibrils which shows that the aldehyde groups are able to increase the wet strength without the presence of the primary amines of the PVAm. As an alternative method to strengthen the fibre network, carboxymethylated CNFs grafted with dopamine, by an ethyl dimethylaminopropyl carbodiimide coupling, were used as a strength additive. When used as an additive, these CNFs showed a strong propensity to form films on and around the fibres and Electronic supplementary material The online version of this article (doi:10.1007/s10570-017-1387-6) contains supplementary material, which is available to authorized users. Cellulose (2017) 24:3883-3899 DOI 10.1007/s10570-017-1387 significantly increased the mechanical properties of the sheets. Their addition resulted in an increase in the Younǵs modulus by 41%, from 5.1 to 7.2 GPa, and an increase in the tensile strength index of 98% (from 53 to 105 kNm/kg) with 5 wt% retained dopaminegrafted CNFs.
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