University CrestOrganic/Inorganic Hybrid Nanocomposite ParticlesArmes Research Group
Current Location:  Research > Organic/Inorganic Hybrid Nanocomposite Particles
See Also
View All Our Publications
Search Our Publications
View All Our Presentations
Collaborations
Page Details
Designed by Peter Iddon
Maintained by Matt Rymaruk
This Page Last Modified:
  4 September 2005

In 1992 we discovered a simple route to conducting polymer-silica nanocomposite particles. Oxidative polymerisation of aniline or pyrrole in the presence of ultrafine (20 nm) silica particles at ambient temperature leads to the formation of 'raspberry'-shaped polyaniline-silica or polypyrrole-silica particles of 100-300 nm diameter. We have recently extended this serendipitous discovery to include vinyl polymer-silica nanocomposite particles [C. Barthet et al., Adv. Mater., 1999], using 4-vinylpyridine as an auxiliary comonomer (see schematic synthetic route below).

Formation of poly(4-vinylpyridine)-silica nanocomposite particles

Formation of poly(4-vinylpyridine)-silica nanocomposite particles

This EPSRC-funded project led to the development of an auxiliary-free protocol for these nanocomposite particles, which have potential applications in tough, transparent, scratch-resistant coatings [M.J. Percy and S. P. Armes, Langmuir, 2002]. Working with Prof. J. F. Watts' group at U. Surrey, we have examined the surface compositions of these new hybrid particles in some detail using x-ray photoelectron spectroscopy [M. J. Percy et al., J. Mater. Chem., 2002]. We have also collaborated with Dr. J. J. Titman's group at U. Nottingham to access solid-state NMR spectroscopy to probe the nature of the molecular interaction between the organic and inorganic phases [G. K. Agarwal et al., J. Phys. Chem. B, 2003]. In collaboration with Prof. F. Galembeck's group at the University of Campinas, Brazil, we have used electron energy loss spectroscopy to characterise the nanomorphologies of selected nanocomposite particles. Depending on the silica volume fraction and the surface composition, various particle morphologies have been identified, including 'raspberry', 'currant bun' and 'core-shell' particles.

More recently we have discovered [A. Schmid and S. P. Armes, Langmuir, 2005, in the press] that the surfactant-free polymerisation of styrene in the presence of ultrafine silica sols in methanol using AIBN at 60 °C leads to the formation of near-monodisperse, micrometer-sized polystyrene latex particles. Control experiments conducted in the absence of any silica sol always led to the macroscopic precipitation of amorphous polystyrene, thus confirming that the presence of the silica sol is essential for the formation of stable latexes. However, unlike the nanocomposite particles described above, these latexes typically contain less than 1 % silica by mass; the inorganic component is located almost exclusively at the latex surface, thus imparting colloid stability via a charge stabilisation mechanism.

Selected Publications
"Time-resolved small-angle x-ray scattering studies of polymer-silica nanocomposite formation and silica redistribution"
J. A. Balmer, O. O. Mykhaylyk, S. P. Armes*, J. P. A. Fairclough, A. J. Ryan, J. Gummel, M. W. Murray, K. A. Murray and N. S. J. Williams
Journal of the American Chemical Society 2011, 133, 826
Open PDF in this window | Open PDF in a new window
"Characterization of polymer-silica nanocomposite particles with core-shell morphologies using Monte Carlo simulations and small angle x-ray scattering"
J. A. Balmer, O. O. Mykhaylyk, A. Schmid, S. P. Armes, J. P. A. Fairclough and A. J. Ryan
Langmuir 2011, 27, 8075
Open PDF in this window | Open PDF in a new window
"A new highly efficient route to polymer-silica colloidal nanocomposite particles"
A. Schmid, J. Tonnar, S. P. Armes
Advanced Materials 2008, 20, 3331
Open PDF in this window | Open PDF in a new window
"Layer-by-Layer Formation of Smart Particle Coatings Using Oppositely Charged Block Copolymer Micelles"
S. Biggs, K. Sakai, T. Addison, A. Schmid, S. P. Armes, M. Vamvakaki, V. Btn, G. Webber
Advanced Materials 2007, 19, 247
Open PDF in this window | Open PDF in a new window
"Polystyrene-Silica Colloidal Nanocomposite Particles Prepared by Alcoholic Dispersion Polymerization"
A. Schmid, S. Fujii, S. P. Armes, C. A. P. Leite, F. Galembeck, H. Minami, N. Saito, M. Okubo
Chemistry of Materials 2007, 19, 2435
Open PDF in this window | Open PDF in a new window
"Cross-Linking of Cationic Block Copolymer Micelles by Silica Deposition"
J.-J. Yuan, O. O. Mykhaylyk, A. J. Ryan, S. P. Armes
Journal of the American Chemical Society 2007, 129, 1717
Open PDF in this window | Open PDF in a new window
"Surface ATRP of Hydrophilic Monomers from Ultrafine Aqueous Silica Sols Using Anionic Polyelectrolytic Macroinitiators"
C. D. Vo, A. Schmid, S. P. Armes., K. Sakai, S. Biggs
Langmuir 2007, 23, 408
Open PDF in this window | Open PDF in a new window
"Efficient synthesis of poly(2-vinylpyridine)-silica colloidal nanocomposite particles using a cationic azo initiator"
D. Dupin, A. Schmid, J. A. Balmer, S. P. Armes
Langmuir 2007, 23, 11812
Open PDF in this window | Open PDF in a new window
"Polystyrene-Silica Nanocomposite Particles via Alcoholic Dispersion Polymerization Using a Cationic Azo Initiator"
A. Schmid, S. Fujii and S. P. Armes
Langmuir 2006, 22, 4923
Open PDF in this window | Open PDF in a new window
"Effects of pH and Salt Concentration on Oil-in-Water Emulsions Stabilized Solely by Nanocomposite Microgel Particles"
B. P. Binks, R. Murakami, S. P. Armes and S. Fujii
Langmuir 2006, 22, 2050
Open PDF in this window | Open PDF in a new window
"Synthesis of micrometer-sized silica-stabilized polystyrene latex particles"
A. Schmid, S. Fujii and S. P. Armes
Langmuir 2005, 21, 8103
Open PDF in this window | Open PDF in a new window
"Synthesis of vinyl polymer-silica colloidal nanocomposites prepared using commercial alcoholic silica sols"
M. J. Percy, J. I. Amalvy, D. P. Randall, S. P. Armes, S. J. Greaves and J. F. Watts
Langmuir 2004, 20, 2184
Open PDF in this window | Open PDF in a new window
"Characterization of vinyl polymer/silica colloidal nanocomposites using solid state NMR spectroscopy: probing the interaction between the inorganic and organic phases on the molecular level"
G. K. Agarwal, J. Titman, M. J. Percy and S. P. Armes
Journal of Physical Chemistry B 2003, 107, 12497
Open PDF in this window | Open PDF in a new window
"Synthesis of vinyl polymer-silica colloidal nanocomposites via aqueous dispersion polymerization"
M. J. Percy, V. Michailidou, S. P. Armes, C. Perruchot, J. F. Watts, S. J. Greaves
Langmuir 2003, 19, 2072
Open PDF in this window | Open PDF in a new window
"Surface characterisation of vinyl polymer-silica colloidal nanocomposites using X-ray photoelectron spectroscopy"
M. J. Percy, J. I. Amalvy, C. Barthet, S. P. Armes, S. J. Greaves, J. F. Watts and H. Wiese
Journal of Materials Chemistry 2002, 12, 697
Open PDF in this window | Open PDF in a new window
"Surfactant-free synthesis of colloidal poly(methyl methacrylate)-silica nanocomposites in the absence of auxiliary comonomers"
M. J. Percy and S. P. Armes
Langmuir 2002, 18, 4562
Open PDF in this window | Open PDF in a new window
"Synthesis and characterization of novel film-forming vinyl polymer-silica colloidal nanocomposites"
J. I. Amalvy, M. J. Percy, S. P. Armes and H. Wiese
Langmuir 2001, 17, 4770
Open PDF in this window | Open PDF in a new window
"Synthesis and characterisation of vinyl polymer-silica colloidal nanocomposites"
M. J. Percy, C. Barthet, J. C. Lobb, M. A. Khan, S. F. Lascelles, M. Vamvakaki and S. P. Armes
Langmuir 2000, 16, 6913
Open PDF in this window | Open PDF in a new window
"Synthesis of novel polymer-silica colloidal nanocomposites via free-radical polymerisation of vinyl monomers"
C. Barthet, A. J. Hickey, D. B. Cairns and S. P. Armes
Advanced Materials 1999, 11, 408
Open PDF in this window | Open PDF in a new window

top of page