Mesoscopically ordered, transparent silica-surfactant monoliths have been p
repared using amphiphilic triblock poly(ethylene oxide)-poly(propylene oxid
e)-poly(ethylene oxide) (PEO - PPO - PEO) copolymer species to organize pol
ymerizing silica networks. The block copolymer acts as a structure-directin
g agent, as the aqueous silica cations partition within the hydrophilic reg
ions of the self-assembled system and associate preferentially with the PEO
blocks. Subsequent polymerization of the silica precursor species under st
rongly acidic conditions (pH similar to 1) produces a densely cross-linked
silica network that may be mesoscopically organized by the block copolymer
species into composites with characteristic ordering length scales of >10 n
m. When this is accompanied by slow evaporation of the aqueous solvent, suc
h composite mesostructures can be formed into transparent and crack-free mo
noliths (e.g., 2.5 cm diameter x 3 mm thick). Distributions and dynamics of
the PEO and PPO copolymer blocks within the silica matrix were investigate
d in situ using Si-29{H-1} and C-13{H-1} two-dimensional solid-state hetero
nuclear correlation NMR techniques and H-1 NMR relaxation measurements, Mes
ostructural ordering was determined by X-ray diffraction and transmission e
lectron microscopy. The degree of microphase separation and the resulting m
esostructure of bulk samples were found to depend strongly upon the concent
ration of block copolymer, with higher concentrations producing higher degr
ees of order.