Herstellung und Charakterisierung von Nanocomposites aus thermoplastischen Elastomeren und funktionalisierten Kohlenstoff-Nanotubes mittels in situ Polykondensationsreaktion
Final Report Abstract
The effect of different functionalization processes based on oxidation and esterification of functional group with 1,4-butanediol (MWCNT-OH and SWCNT-OH) on the microstructure, thermo-oxidative stability and mechanical properties of PBT/PTMO nanocomposites was discussed. A remarkable improvement of mechanical properties was achieved by dispersing these functionalized CNTs in PBT/PTMO copolymers by insitu polycondensation process. On the other hand, the functional groups influenced significantly the process, due to reactions between the functional groups and the dimethyl terephthalate (DMT) and/or 1,4-butanediol (BD) during the esterification. Therefore, the properties of the polymeric matrix have been changed, due to possible changes in composition of the copolymer. In spite of that, the overall improvements due to the functionalized CNTs overcome these effects, since the nanocomposite still exhibited better mechanical properties than the neat PBT/PTMO polymer. In another process pristine multiwall carbon nanotubes and amino-functionalized carbon nanotubes have been treated with organic peroxides under mild conditions in order to attach functional groups (carboxylic or epoxy) at the CNT surface. These peroxidetreated MWCNTs did not affect the PBT/PTMO polycondensation process, as shown by TGA and DSC techniques. The peroxide-treated MWCNTs tend towards agglomeration during the polycondensation process. On the other hand the MWCNT-OH exhibited a very good dispersion. The stiffness of the nanocomposites containing peroxide-treated MWCNTs is not as high as for the nanocomposites containing MWCNT-OH or SWCNT- OH. On the other hand, the peroxide-treated MWCNT improved the elongation at break and at some extent the toughness. The treatment of CNTs with organic peroxides is a simple and even up-scalable functionalization process. Therefore, there is an obvious potential for this method. Since the organic peroxide groups used for the functionalization contain carboxylic (-COOH) and epoxy groups, the possibility of a post-functionalization with amines, like polyetheramines is plausible. One issue is also to avoid the extensive reaction between the functional groups of SWCNT-OH and MWCNT-OH with DMT and BD. A possible strategy would be the esterification of these carboxylic groups with BD and DMT prior to the in-situ polycondensation process. Therefore a short PBT chain could be grafted from the surface of the peroxide.treated CNTs. This would also ensure a better filler adhesion and even more significant improvement of mechanical properties. An even more promising approach is the development of nanocomposites based solely on PBT. This approach would avoid the impact of functional groups of MWCNT-OH or SWCNT-OH on the polymer matrix composition, since there would be no other polymeric component rather than PBT in the polymer nanocomposite.
Publications
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Polymer matrix nanocomposites based on carbon nanotubes, V conference „Carbon materials & Polymer Composites”, Ustron Jaszowiec, Poland
A. Szymczyk, M. Kwiatkowska, S. Paszkiewicz, G. Broza, Z. Roslaniec
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Deformation behaviour during cold drawing of nanocomposites based on single wall carbon nanotubes and poly (ether ester) copolymers. Polymer 48 (2007) pp.3286-3293
J. J. Hernández, M. C. García-Gutiérrez, A. Nogales, D. R. Rueda, A. Sanz, I. Šics, B. S. Hsiao, Z. Rosłaniec, G. Broza, T. A. Ezquerra
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Nanocomposite aus thermoplastischen Elastomeren PBT/PTMO und Carbon Nanotubes. 12. Problemseminar Polymermischungen, Gefüllte und verstärkte Polymerblends Nanoblends, Bad Lauchstädt, (2007)
G. Broza, K. Schulte
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The filler/matrix interface in MWCNT- reinforced poly (ether- ester) block copolymer nanocomposites. 15th World Forum on Advanced Materials, 15th Tutorial on Polymer Characterization, Buzios, Rio de Janeiro, Brazil (2007)
G. Broza, K. Schulte
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„X-ray microdiffraction and micro-Raman study on an injection moulding SWCNT-polymer nanocomposite” Composites Science and Technology 67 (2007) pp. 798-805
M. C.García-Gutiérrez, A. Nogales, D.R. Rueda, C. Domingo, J. V. García-Ramos, G. Broza, Z. Rosłaniec, K. Schulte, T. A. Ezquerra
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Development of nanocomposites with carbon nanotubes in a thermoplastic elastomer matrix. Carbon Structures & Devices Symposium NSTI Nanotech 11th Annual, Boston, USA (2008)
G. Broza, K. Schulte, Z. Rosłaniec
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Melt processing and Filler/Matrix Interphase in Carbon Nanotube Reinforced Poly (ether-ester) Thermoplastic Elastomer Polymer Engineering & Science 48 (2008) pp. 2033-2038
G. Broza, K. Schulte
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Potential of nanoscale carbon fibre reinforcements for high performance semi-crystalline polymers NSTI , Houston, USA, (2009)
G. Broza
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Development of nanocomposites with oxidized carbon nanotubes in a thermoplastic elastomer matrix. 4th Conference on Polymer Behavior – IUPAC, Lodz, Poland (2010)
A. Kopyniecka, G. Broza, L. A. S. A. Prado, Z. Roslaniec, K. Schulte
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Studies on morphology and interphase of poly(butylene terephthalate)/carbon nanotubes nanocomposites. Polymer Engineering and Science 50 (2010) pp.1571-1576
L. A. S. de A. Prado, M. Kwiatkowska, S.S. Funari, Z. Roslaniec, G. Broza, K. Schulte
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Synthesis, Properties, Functionalisation and Applications of Carbon Nanotubes: A State of the Art Review, Chemistry & Chemical Technology 4 (2010) pp. 35-45
G. Broza
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Thermoplastic elastomers with multi-walled carbon nanotubes: Influence of dispersion methods on morphology. Composites Science and Technology 70 (2010) pp. 1006-1010
G. Broza
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Impact of filler on the properties of thermoplastic (elastomers) / carbon nanotubes nanocomposites. Can we go any further? 2th Symposium on Frontiers in Polymer Science, Lyon, France (2011)
L. A. S. A. Prado, S. T. Buschhorn, G. Broza, K. Schulte
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Properties of thermoplastic (elastomer) carbon based nanocomposites. 11th Annual UNESCO / IUPAC Workshop and Conference on Functional Polymeric Materials & Composites, Stellenbosch, South Africa (2011)
K. Schulte, S. T. Buschhorn, G. Broza, L. A. S. A. Prado
