Multiwalled carbon nanotubes grafted with polyhedral oligomeric silsesquioxane and its dispersion in poly(l-lactide) matrix

Abstract Multiwalled carbon nanotubes (MWNTs) were functionalized with polyhedral oligomeric silsesquioxane (POSS) via amide linkages. The oxidized MWNT (MWNT–COOH) was converted to the acyl chloride-functionalized MWNT (MWNT–COCl) by treating them with thionyl chloride (SOCl 2 ), and then MWNT–COCl was reacted with aminopropylisooctyl-POSS to prepare aminopropylisooctyl polyhedral oligomeric silsesquioxane modified MWNT (MWNT- g -POSS). Energy-filtering TEM, FTIR, and Raman spectroscopy revealed that the POSS was covalently attached to the MWNT and the weight gain due to the functionalization was determined by the thermogravimetric analyses (TGA). PLLA/MWNT and PLLA/MWNT- g -POSS composites with different MWNT loadings were first prepared by the simple solvent casting approach. A fine dispersion of MWNT- g -POSS throughout PLLA matrix was observed by SEM. Moreover, the composites were also prepared by using melt compounding under the different shearing speed of extruder via our custom-built high-shear extruder. A special feedback-type screw was used in this extruder to realize a high shearing flow field. Using this new technique, a uniform dispersion of the neat MWNTs in the PLLA matrix was found under higher screw rotation speed (≥1500 rpm) while poor dispersion was observed under low speed ( g -POSS composites without any aggregation was observed at full range of screw rotation speed. The fractured surface of the composites showed not only a uniform dispersion of MWNTs but also a strong interfacial adhesion with the matrix, as evidenced by the presence of many broken but strongly embedded MWNTs in the matrix in the absence of debonding of MWNTs from the matrix. Incorporation of MWNTs improved the mechanical properties.

[1]  Paul Calvert,et al.  Nanotube composites: A recipe for strength , 1999, Nature.

[2]  Robert H. Hauge,et al.  Poly(vinyl alcohol)/SWNT Composite Film , 2003 .

[3]  T. K. Chaki,et al.  Effect of processing parameters, applied pressure and temperature on the electrical resistivity of rubber-based conductive composites , 2002 .

[4]  S. Qian,et al.  Functionalization of multiwalled carbon nanotubes with polystyrene under atom transfer radical polymerization conditions , 2007 .

[5]  U. A. Handge,et al.  Deformation and orientation during shear and elongation of a polycarbonate/carbon nanotubes composite in the melt , 2007 .

[6]  Angel Rubio,et al.  Single‐Walled Carbon Nanotube–Polymer Composites: Strength and Weakness , 2000 .

[7]  Lawrence F. Allard,et al.  Functionalization of Carbon Nanotubes with Polystyrene , 2002 .

[8]  J. Coleman,et al.  Morphological and mechanical properties of carbon-nanotube-reinforced semicrystalline and amorphous polymer composites , 2002 .

[9]  J. Jang,et al.  A study on the effect of surface treatment of carbon nanotubes for liquid crystalline epoxide–carbon nanotube composites , 2003 .

[10]  M. Panhuis,et al.  A Microscopic and Spectroscopic Study of Interactions between Carbon Nanotubes and a Conjugated Polymer , 2002 .

[11]  Richard E. Smalley,et al.  Enhancement of adsorption inside of single-walled nanotubes: opening the entry ports , 2000 .

[12]  J. Lichtenhan,et al.  The incorporation of transition metals into polyhedral oligosilsesquioxane polymers , 1995 .

[13]  B. D. Agarwal,et al.  Analysis and Performance of Fiber Composites , 1980 .

[14]  Hua-ming Li,et al.  Functionalization of multiwalled carbon nanotubes with polyamide 6 by anionic ring-opening polymerization , 2007 .

[15]  D. Resasco,et al.  Polymer brushes on single-walled carbon nanotubes by atom transfer radical polymerization of n-butyl methacrylate. , 2004, Journal of the American Chemical Society.

[16]  S. Qian,et al.  Polymer-wrapped multiwalled carbon nanotubes synthesized via microwave-assisted in situ emulsion polymerization and their optical limiting properties , 2007 .

[17]  F. Feher,et al.  Syntheses of highly functionalized cube-octameric polyhedral oligosilsesquioxanes (R8Si8O12) , 1999 .

[18]  Eklund,et al.  Solution properties of single-walled carbon nanotubes , 1998, Science.

[19]  J. Lichtenhan,et al.  Linear Hybrid Polymer Building Blocks: Methacrylate-Functionalized Polyhedral Oligomeric Silsesquioxane Monomers and Polymers , 1995 .

[20]  Chin-San Wu,et al.  Study on the preparation and characterization of biodegradable polylactide/multi-walled carbon nanotubes nanocomposites , 2007 .

[21]  Gregory M. Glenn,et al.  Fiber-reinforced composites , 1988 .

[22]  R. Ruoff,et al.  Tensile loading of ropes of single wall carbon nanotubes and their mechanical properties , 2000, Physical review letters.

[23]  Eugene M. Terentjev,et al.  Dispersion rheology of carbon nanotubes in a polymer matrix , 2006 .

[24]  Linda S. Schadler,et al.  Surface modification of multiwalled carbon nanotubes: Toward the tailoring of the interface in polymer composites , 2003 .

[25]  M. Itkis,et al.  Chemistry of single-walled carbon nanotubes. , 2002, Accounts of chemical research.

[26]  P. Ajayan,et al.  Synthesis and Characterization of Thickness-Aligned Carbon Nanotube−Polymer Composite Films , 2005 .

[27]  P. Mather,et al.  Viscoelastic and morphological behavior of hybrid styryl-based polyhedral oligomeric silsesquioxane (POSS) copolymers , 1998 .

[28]  Yi Lin,et al.  Functionalized carbon nanotubes: properties and applications. , 2002, Accounts of chemical research.

[29]  Guangliang Chen,et al.  Controlled functionalization of multiwalled carbon nanotubes with various molecular-weight poly(L-lactic acid). , 2005, The journal of physical chemistry. B.

[30]  Joseph D. Lichtenhan,et al.  Polyhedral Oligomeric Silsesquioxanes: Building Blocks for Silsesquioxane-Based Polymers and Hybrid Materials , 1995 .

[31]  Joseph D. Lichtenhan,et al.  Hybrid organic-inorganic thermoplastics : Styryl-based polyhedral oligomeric silsesquioxane polymers , 1996 .

[32]  D. E. Hill,et al.  Characterization of Functionalized Single-Walled Carbon Nanotubes at Individual Nanotube-Thin Bundle Level , 2003 .

[33]  T. Ebbesen,et al.  Decoration of carbon nanotubes , 1996 .

[34]  J. Gilman,et al.  Thermolysis of Polyhedral Oligomeric Silsesquioxane (POSS) Macromers and POSS−Siloxane Copolymers , 1996 .

[35]  C. N. R. Rao,et al.  RAPID COMMUNICATION: The decoration of carbon nanotubes by metal nanoparticles , 1996 .

[36]  G. A. D. Briggs,et al.  Elastic and shear moduli of single-walled carbon nanotube ropes , 1999 .

[37]  F. J. García de abajo,et al.  Robust plasmon waveguides in strongly interacting nanowire arrays. , 2008, Nano letters.

[38]  Enrique V. Barrera,et al.  Key methods for developing single-wall nanotube composites , 2000 .

[39]  M. Terrones.  Science and Technology of the Twenty-First Century: Synthesis, Properties, and Applications of Carbon Nanotubes , 2003 .

[40]  S. Bachilo,et al.  Solubilization and Purification of Single-Wall Carbon Nanotubes in Water by in Situ Radical Polymerization of Sodium 4-Styrenesulfonate , 2004 .

[41]  Riichiro Saito,et al.  Characterizing carbon nanotube samples with resonance Raman scattering , 2003 .

[42]  J. Tour,et al.  Dispersion of Functionalized Carbon Nanotubes in Polystyrene , 2002 .

[43]  Rao,et al.  Polarized raman study of aligned multiwalled carbon nanotubes , 2000, Physical review letters.

[44]  Ya‐Ping Sun,et al.  Polymeric Carbon Nanocomposites from Carbon Nanotubes Functionalized with Matrix Polymer , 2003 .

[45]  J. Gilman,et al.  Low earth orbit resistant siloxane copolymers , 1996 .

[46]  Jason E. Riggs,et al.  Strong Luminescence of Solubilized Carbon Nanotubes , 2000 .

[47]  D. Colbert,et al.  Dissolution of Full-Length Single-Walled Carbon Nanotubes , 2001 .

[48]  R. Laine,et al.  Silsesquioxanes as synthetic platforms. II. Epoxy-functionalized inorganic-organic hybrid species , 1996 .

[49]  S. Horiuchi,et al.  Nanoscale Analysis of Polymer Interfaces by Energy-Filtering Transmission Electron Microscopy , 2005 .

[50]  Elizabeth C. Dickey,et al.  Load transfer and deformation mechanisms in carbon nanotube-polystyrene composites , 2000 .

[51]  Bin Zhao,et al.  Continuous spinning of a single-walled carbon nanotube-nylon composite fiber. , 2005, Journal of the American Chemical Society.