Interaction of poly(ethylene oxide) with fumed silica.
Interaction of poly(ethylene oxide) (PEO, 600 kDa) with fumed silica A-300 (SBET = 316 m2/g) was investigated under different conditions using adsorption, infrared (IR), thermal analysis (TG-DTA), AFM, and quantum chemical methods. The studied dried silica/PEO samples were also carbonized in a flow reactor at 773 K. The structural characteristics of fumed silica, PEO/silica, and pyrocarbon/fumed silica were investigated using nitrogen adsorption-desorption at 77.4 K. PEO adsorption isotherm depicts a high affinity of PEO to the fumed silica surface in aqueous medium. PEO adsorbed in the amount of 50 mg per gram of silica (PEO monolayer corresponds to CPEO approximately 190 mg/g) can disturb approximately 70% of isolated surface silanols. However, at the monolayer coverage, only 20% of oxygen atoms of PEO molecules take part in the hydrogen bonding with the surface silanols. An increase in the PEO amount adsorbed on fumed silica leads to a diminution of the specific surface area and contributions of micro- (pore radius R < 1 nm) and mesopores (1 < R < 25 nm) to the pore volume but contribution of macropores (R > 25 nm) increases with CPEO. Quantum chemical calculations of a complex of a PEO fragment with a tripple bond SiOH group of a silica cluster in the gas phase and with consideration for the solvent (water) effect show a reduction of interaction energy in the aqueous medium. However, the complex remains strong enough to provide durability of the PEO adsorption complexes on fumed silica; i.e., PEO/fumed silica nanocomposites could be stable in both gaseous and liquid media.
Institute of Surface Chemistry, 17 General Naumov Street, 03164 Kiev, Ukraine.
E F
EF
Voronin
V M
VM
Gun'ko
N V
NV
Guzenko
E M
EM
Pakhlov
L V
LV
Nosach
R
R
Leboda
J
J
Skubiszewska-Zieba
M L
ML
Malysheva
M V
MV
Borysenko
A A
AA
Chuiko
D000327:Adsorption; D008958:Models, Molecular; D011092:Polyethylene Glycols / Q000737:chemistry*; D012822:Silicon Dioxide / Q000737:chemistry*; D013499:Surface Properties; D013696:Temperature
D011092:Polyethylene Glycols; D012822:Silicon Dioxide