화학공학소재연구정보센터
Langmuir, Vol.26, No.12, 10158-10164, 2010
Mesoporous Hydrogels: Revealing Reversible Porosity by Cryoporometry, X-ray Scattering, and Gas Adsorption
Mesoporous poly(2-hydroxyethyl methacrylate-co-ethylene glycol dimethacrylate) networks, with cross-linker contents ranging from 100 to 5 mol %, were prepared using a hard-templating approach. The imbibition of the silica pellets with a monomer/cross-linker mixture resulted in mesoporous gels with a pore size of similar to 10 nm, which corresponds well with the average size of the fumed silica particles (10-11 nm). The highly cross-linked materials showed permanent surface areas of up to 230 m(2) g(-1) and porosities up to similar to 33 vol %. The porosity of the hydrogels was investigated in both dry and water-saturated state by nitrogen sorption, cryoporometry, and small-angle X-ray scattering (SAXS). It is only polymeric materials that contain 50 mol % or more of the cross-linker that showed a significant porosity after evaporative drying. Freeze-drying is able to preserve the porosity also for hydrogels of intermediate cross-linker content, but the pores of the materials of low cross-linker content collapses completely upon solvent removal. The observed critical cross-linker ratio for pore stability compared favorably with a simple estimate of the critical cross-linker density needed to make the material sufficiently stiff to withstand the Laplace pressure during solvent removal. Analysis of the hydrogels in the water swollen state revealed that gels having cross-linker contents down to 5 mol % still possessed mesoporosity. The pores got less defined at very low cross-linker contents, while their size was rather constant at intermediate to high cross-linking densities. Closed pores could be reopened upon swelling, which suggests that the observed pore collapse upon drying may be at least partly reversible.