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 MSA  Vol.7 No.1 , January 2016
Carbon-13 Solid State NMR Techniques to Evaluate the Morphology of PP/TiO2 Composites
Abstract: Solid state NMR was successfully used to determine the proton spin-lattice relaxation time in the rotating frame (T1ρH) for systems based on polypropylene (PP) and PP with titanium dioxide (TiO2) organically modified or unmodified incorporated, in order to understand the molecular behavior of these systems. These techniques were employed in the samples organically modified and unmodified TiO2 to investigate the effect of organic modification on the dispersion and distribution of the particles in the PP matrix. The results were analyzed in terms of the effect of the particles organic modified or not according to the intermolecular interaction in the composites. According to the T1ρH values, all composites showed at least two domains: the short values were related to the rigid part, which included the crystalline and amorphous phase constricted in it, while the longer times were attributed to the amorphous region, which had higher molecular mobility compared to the rigid region of the materials. The increase in the relaxation time parameter in the composites compared to the pure PP was associated to the strong interaction between titanium dioxide particles and the polymer chains. This effect was more pronounced for the systems containing organically modified TiO2. According to the results, it could be inferred that intermolecular interaction occurred in the CH2 and CH groups, being more intense with CH2 groups. Finally, the solid state NMR techniques were able to evaluate the molecular dynamics of those systems.
Keywords: NMR, PP, TiO2, Composites
Cite this paper: Soares, I. , Tavares, M. , Silva, A. and Feio, A. (2016) Carbon-13 Solid State NMR Techniques to Evaluate the Morphology of PP/TiO2 Composites. Materials Sciences and Applications, 7, 20-25. doi: 10.4236/msa.2016.71003.
References

[1]   Abragam, A. (1996) Principles of Nuclear Magnetism. Oxford Science Publications, Oxford.

[2]   Chandrakumar, N. and Subramanian, S. (1987) Modern Techniques in High-Resolution FT-NMR. Springer-Verlag, New York, 388.
http://dx.doi.org/10.1007/978-1-4612-4626-8

[3]   Gil, V.M.S. and Geraldes, C.F.G.C. (1987) Ressonancia Magnética Nuclear: Fundamentos, Métodos e Aplica??es. Funda??o Calouste Gulbenkian, Lisboa, 1012.

[4]   Slichter, C.P. (1990) Principles of Magnetic Resonance. Springer-Verlag, New York, 665.
http://dx.doi.org/10.1007/978-3-662-09441-9

[5]   Stejskal, E.O. and Memory, J.D. (1994) High Resolution NMR in the Solid State., New York, 189.

[6]   Bovey, F.A. and Mirau, P.A. (1996) NMR of Polymers. Academic Press.

[7]   Koenig, J.L. (1992) Spectroscopy of Polymer. American Chemical Society, Washington, 328.

[8]   Komoroski, R.A. (1986) High Resolution NMR Spectroscopy of Synthetic Polymers in Bulk. Methods in Stereochemical Analysis, 7, 379.

[9]   Lyerla, J.R. and Yannoni, C.S. (1983) High-Resolution Carbon-13 NMR of Polymers in the Solid State. IBM Journal of Research and Development, 27, 302-312.
http://dx.doi.org/10.1147/rd.274.0302

[10]   Schmidt-Rohr, K. and Spiess, H.W. (1994) Multidimensional Solid-State NMR and Polymers. 1st Edition, Vol. 1, Academic Press, London, 478.

[11]   Silvestri, R.L. and Koenig, J.L. (1993) Applications of Nuclear Magnetic Resonance Spectrometry to Solid Polymers. Analytica Chimica Acta, 283, 997-1005.
http://dx.doi.org/10.1016/0003-2670(93)80261-I

[12]   Berns, A.E. and Conte, P. (2011) Effect of Ramp Size and Sample Spinning Speed on CPMAS 13C NMR Spectra of Soil Organic Matter. Organic Geochemistry, 42, 926-935.
http://dx.doi.org/10.1016/j.orggeochem.2011.03.022

[13]   Silva, N.M., Tavares, M.I.B. and Stejskal, E.O. (2000) 13C-Detected 1H Spin Diffusion and 1H Relaxation Study of Multicomponent Polymer Blends. Macromolecules, 33, 115-119.

[14]   Tavares, M.I.B. (2000) NMR Molecular Dynamic Study of High Crystalline Polymers. Polymer Testing, 19, 899-904.
http://dx.doi.org/10.1016/S0142-9418(99)00060-4

[15]   Nogueira, M.C.J.A., Tavares, M.I.B. and Nogueira, J.S. (2004) 13C NMR Molecular Dynamic Investigation of Tropical Wood Angelin Pedra (Hymenolobium paetrum). Polymer, 45, 1217-1222.
http://dx.doi.org/10.1016/j.polymer.2003.12.031

[16]   Nogueira, R.F., Tavares, M.I.B. and San Gil, R.A.S. (2004) Carbon-13 Solid State NMR Study of Polypropylene/Clay Nanocomposite. Journal of Metastable and Nanocrystalline Materials, 22, 71-76.
http://dx.doi.org/10.4028/www.scientific.net/JMNM.22.71

[17]   Tavares, M.I.B, Nogueira, R.F., San Gil, R.A.S., Preto, M., Silva, E.O., Silva, M.B.R. and Miguez, E. (2007) Polypropylene-Clay Nanocomposite Structure Probed by H NMR Relaxometry. Polymer Testing, 26, 1100-1102.
http://dx.doi.org/10.1016/j.polymertesting.2007.07.012

[18]   Monteiro, M.S.S.B., Silva, E.O., Rodrigues, C.L., Cucinelli Neto, R.P. and Tavares, M.I.B. (2012) The Structure of Polycaprolactone-Clay Nanocomposites Investigated by 1H NMR Relaxometry. Journal of Nanoscience and Nanotechnology, 12, 7307-7313.
http://dx.doi.org/10.1166/jnn.2012.6431

[19]   Passos, A.A., Tavares, M.I.B., Cucinelli Neto, R.P., Moreira, L.A. and Ferreira, A.G. (2011) Preparation of EVA/Silica Nanocomposites Characterized with Solid State Nuclear Magnetic Resonance. Polímeros, 21, 98-102.
http://dx.doi.org/10.1590/S0104-14282011005000023

[20]   Olejniczak, S., Ka?mierski, S., Pallathadka, P.K. and Potrzebowski, M.J. (2007) A Review on Advances of High-Resolution Solid State NMR Spectroscopy in Structural Studies of Polymer/Clay Nanocomposites. Polimery, 52, 713-792.

[21]   Soares, I.L., Chimanowsky, J.P., Luetkmeyer, L., Silva, E.O., Souza, D.H.S. and Tavares, M.I.B. (2015) Evaluation of the Influence of Modified TiO2 Particles on Polypropylene Composites. Journal of Nanoscience and Nanotechnology, 15, 5723-5732.
http://dx.doi.org/10.1166/jnn.2015.10041

 
 
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