Melt mixed PCL/MWCNT composites prepared at different rotation speeds: Characterization of rheological, thermal, and electrical properties, molecular weight, MWCNT macrodispersion, and MWCNT length distribution

Composites of poly(caprolactone) (PCL) and 0.5 wt.% multiwalled carbon nanotubes (MWCNT) were prepared by melt-mixing in a conical twin-screw micro-compounder by varying the rotation speed between 25 and 400 rpm at constant mixing time and temperature. The state of dispersion analyzed by light microscopy was improved with increasing rotation speed but levels off starting at about 100 rpm. PCL molecular weight as well as crystallization and melting behavior did show only insignificant difference when varying the rotation speed. Concerning melt rheological properties, storage modulus G′ and complex viscosity η* at 0.1 rad/s increased up to a rotation speed of about 75 rpm illustrating improved dispersion. When further increasing the speed G′ and η* decreased which was attributed to more pronounced nanotube shortening as quantified by TEM measurements. Both effects - improved dispersion and nanotube shortening - are also reflected in the electrical resistivity values of compression molded samples which show a minimum of resistivity at the rotation speed of 75 rpm corresponding to a specific mechanical energy input of 0.47 kWh/kg. © 2013 Elsevier Ltd. All rights reserved

Influence of dry grinding in a ball mill on the length of multiwalled carbon nanotubes and their dispersion and percolation behaviour in melt mixed polycarbonate composites

Ball milling of carbon nanotubes (CNTs) in the dry state is a common way to produce tailored CNT materials for composite applications, especially to adjust nanotube lengths. For NanocylTM NC7000 nanotube material before and after milling for 5 and 10h the length distributions were quantified using TEM analysis, showing decreases of the mean length to 54% and 35%, respectively. With increasing ball milling time in addition a decrease of agglomerate size and an increase of packing density took place resulting in a worse dispersability in aqueous surfactant solutions. In melt mixed CNT/polycarbonate composites produced using masterbatch dilution step, the electrical properties, the nanotube length distribution after processing, and the nano- and macrodispersion of the nanotubes were studied. The slight increase in the electrical percolation threshold in the melt mixed composites with ball milling time of CNTs can be assigned to lower nanotube lengths as well as the worse dispersability of the ball milled nanotubes. After melt compounding, the mean CNT lengths were shortened to 31%, 50%, and 66% of the initial lengths of NC7000, NC7000-5h, and NC7000-10h, respectively. © 2011 Elsevier Ltd

Improvement of carbon nanotube dispersion in thermoplastic composites using a three roll mill at elevated temperatures

The paper reports the effect of using of a three roll mill as additional dispersion step after twin-screw melt extrusion of nanocomposites containing thermoplastic polymers and multiwalled carbon nanotubes. The three roll milling technology was adapted to elevated temperatures of up to 180 °C and examples are shown for its use in processing of different pre-compounded thermoplastic polymer composites based on polypropylene, polycaprolactone and ethylene-vinyl acetate. The aim is to enhance the state of dispersion achieved by the previous melt extrusion step. In particular, depending on the state of dispersion before three roll milling and the adapted conditions, like number of runs and gap sizes, a reduction of number and size of remaining primary nanotube agglomerates was found. This was studied using light microscopy. The resulting improvements in mechanical properties were assessed and could be attributed to the improved dispersion. In some cases agglomerate free samples could be achieved after the three roll milling process. © 2012 Elsevier Ltd

Characterization of the state of dispersion of carbon nanotubes in polymer nanocomposites

A practical overview of possibilities and limits to characterize the state of dispersion of carbon nanotubes (CNT) in polymer based nanocomposites is given. The most important and widely available methods are discussed with practical employment in mind. One focus is the quantitative characterization of the state of dispersion in solid samples using microscopy techniques such as optical microscopy or transmission electron microscopy. For dispersions of CNTs in aqueous media, solvents or monomers a sedimentation analysis is presented. This way dispersability and dispersion state of CNTs can be assessed. Indirect methods such as electrical conductivity measurements and rheological tests, dynamic differential scanning calorimetry and mechanical test are discussed. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Liquid sensing properties of melt processed polypropylene/poly(ε-caprolactone) blends containing multiwalled carbon nanotubes

The sensing properties of polypropylene (PP)/poly(epsilon-caprolactone) (PCL) blends containing multiwalled carbon nanotubes (MWNT) were studied in terms of their electrical resistance change in presence of liquids (solvents). The preparation of co-continuous blends based on the double percolation concept was done by melt mixing of electrically conductive PCL composites containing 3 wt.% MWNT and neat PP in ratios of 30:70, 40:60, and 50:50. The electrical resistance change of the PCL-MWNT composites and blends was monitored in a solvent immersion/drying cycle. Various solvents, such as n-hexane, ethanol, methanol, water, toluene, chloroform, and tetrahydrofuran were successfully detected, yielding different responses and reversibility of the resistance changes. PP and PCL were tested separately for solvent sorption using ethanol and n-hexane, both showing a low sorption of n-hexane. Ethanol sorption was large for PCL and almost absent for PP. The 50/50 blend composites with 3 wt.% MWNT in the PCL phase presented larger resistance changes for n-hexane, showing larger sensing ability for this solvent compared to PCL composites with 1 and 3 wt.% loadings. The opposite response was observed for immersion in ethanol where the PCL-MWNT composites showed larger changes than the blends. As the ratio of the conductive PCL phase over PP in the blend composition (i.e., the overall MWNT content) decreased, larger resistance changes were observed. The liquid sensing properties of compression-moulded disks and melt-drawn filaments were compared indicating higher responses for the disks.European Commission - Sixth Framework Programme for Research and Technological Development of the (NMP2-CT-2006-026626, INTELTEX Project