Biodegradable polymer-clay composites produced with functionalized Patagonian bentonite precursors

A. BIANCHI; L. D. JUNCIEL; G. ECHEVERRIA; I. TORRIANI

Santa Marta

Congreso; Latin American seminar of analysis by X-Ray techniques; 2012

BIODEGRADABLE POLYMER-CLAY COMPOSITES PRODUCED WITH PATAGONIAN BENTONITES A. E. Bianchi,1 L. Junciel.2  G. A. Echeverría,3  I. L. Torriani,4 P. Eisenberg,5 A. Botana,6 M. Mollo,7 R. M. Torres-Sanchez8 y G. Punte9   1-3, 9 IFLP (CCT- La Plata). Departamento de Física, Facultad de Ciencias Exactas Universidad Nacional de La Plata (UNLP) 115 y 49, 1900 La Plata Argentina. {bianchi@fisica.unlp.edu.ar, junciel@fisica.unlp.edu.ar, gualech@fisica.unlp.edu.ar, punte@fisica.unlp.edu.ar} 1-3 Facultad de Ingeniería, Universidad Nacional de La Plata1 y 47, 1900 La Plata Argentina. 4. Instituto de Física, Universidade Estadual de Campinas, Cidade Universitária, Campinas, Sao Paulo 13083-970, Brazil {torriani@ifi.unicamp.br} 5-7 National Institute of Industrial Technology, Centre of Technological Research for the Plastic Industry, Av. Gral.. Paz 5445 (1650), San Martin, Argentina. {mariana@inti.gob.ar, botana@inti.gob.ar, patsy@inti.gob.ar} 5-7 Institute of Research and Environmental Engineering (3iA), Universidad Nacional de Gral. San Martin, Belgrano 3563 (1650), San Martín, Argentina. 8 Centro de Tecnología de Recursos Minerales y Cerámica (CETMIC), CCT-La Plata Camino Centenario y 506, (1897), M.B. Gonnet, Argentina {rosats@cetmic.unlp.edu.ar}   Polymer composite films (PCF), based on semicrystalline biodegradable thermoplastic polyester, polycaprolactone (PCL), and a functionalized Patagonian bentonite were produced. The employed bentonite is predominately sodium montmorillonite (MMT), structural formula: [(Si3.89 Al0.11) (Al1.43 Fe0.26 Mg0.30)] M+0.41, cation exchange capacity (CEC): 174 meq/100g [1] and the organoclays had been prepared by addition of 1 and 2 CEC of hexadecyltrimethyl-ammonium (HDTMA) and octadecyl-trimethyl-ammonium  (ODTMA) to raw MMT diluted in deionized water and were fully characterized [2]. PCL/clay composites, with 5% of clay content in weight, were synthesized by melt intercalation in a Brabender Plasticorder mixing chamber at 100 °C, their thermal behavior of the was investigated by DSC. No difference was detected between melting point of PCL and those ones of the PCF, while a small decrease in the degree of crystallinity for PCF coming from 2 CEC loading organoclays could be perceived. SAXS and WAXS data analysis showed that organoclays expansion was not lost in the PCF. However, not all PCF present the same characteristics. PCL/ODTMA1 and PCL/ HDTMA2 keep the Bragg reflections observed in the WAXS region in the precursor organoclays and increase the proportion of clay expanded to d001= 40.8 and 39.3Å, respectively, as indicated by the noticeable Bragg peak in the SAXS region. On the other hand, in the other PCF lower intensity and much larger broadening of the (001) reflection in both WAXS and SAXS regions were observed. Bragg peaks in SAXS regions were located at 53.2 and 41,3 Å  and 53,7 and 33.2 Å and for PCL/ODTMA2 and PCL/ HDTMA1, respectively. Dielectric measurements showed that all the films present the maximum in the dielectric constant at the lowest frequency explored, 0.1 Hz, and a steady diminution as the frequency increases up to 1MHz. PCF showed a dielectric constant higher than that of the PCL film up to approximately 50Hz. In PCF containing organoclays with 1 and 2 CEC loading of HDTMA, the dielectric constant is about double of the value found in PCL film, difference reduces to about 18% at about 1kHz. The dielectric loss is also higher in PCF than in PCL for low frequencies. However, differences gradually decrease and PCF present values comparables to those of PCL within the frequency range 50 Hz to 1 MHz   Keywords: nanocomposites, SAXS, WAXS. Acknowledgements.  Ahtors thank financial support from LNLS, Brasil, UNLP and CONICET PIP 0985, Argentina.   [1] Magnoli. A. P. et al. (2008) Appl. Clay Sci. 40, 63?71. [2] Bianchi et al. ?ODTMA and HDTMA organomontymorillonites characterization: new insight by WAXS, SAXS and surface charge?. Sent for publication to Appl. Clay Sci.