Gudrun Reichenauer

Deformation of porous carbons upon adsorption.

N2 and CO2 sorption measurements with in situ dilatometry implemented in a commercial volumetric sorption instrument were performed at 77 and 273 K, respectively. The resolution of the linear deformation was about ±0.2 μm. To separate effects due to microporosity, external surface area and mesopores synthetic porous carbons (xerogels) with different external surface areas and microporosities were applied as a model system. The experimental data show that the relative length change of the monolithic carbon xerogels investigated passes different stages during ad- and desorption, which are connected to micropore-, multilayer- and mesopore-sorption. The length change observed in the range of micropore and surface adsorption was found to be nonmonotonic and to take negative as well as positive values, with the maximum swelling observed being on the order of 4‰. With respect to the length change, the micropore structure seems to have the most significant impact on the overall length change, while the external surface is only of minor importance. Quantiative analysis of the deformation according to the models of Bangham and Scherer for the length change in the range of multilayer- and mesopore-adsorption allows extracting the macrosopic as well as the skeletal Youngs modulus.

In Situ Modification of the Silica Backbone leading to Highly Porous Monolithic Hybrid Organic–Inorganic Materials via Ambient Pressure Drying

We report the synthesis of monolithic porous hybrid organic-inorganic materials based on tetraethoxysilane (TEOS) and a bifunctional precursor synthesized from 3-aminopropyltriethoxysilane (APTES) and 3-glycidoxypropyltrimethoxysilane (GLYMO) via base catalysis. To compensate for the slower hydrolysis and condensation rate of the organically modified silane in basic media, it was prehydrolysed prior to adding it to the silane solution. This process leads to a lower shrinkage and stable monoliths with densities as low as 200 kg/m(3). Analysis of the samples supports the assumption that the porous monolithic materials derived via ambient pressure drying of the gels consist of a network of homogeneous hybrid primary particles. These particles are larger than their inorganic counterparts in classical silica gels and therefore the capillary forces while drying the gels at ambient pressure are reduced. This leads to less shrinkage and thus lower densities of the materials derived via ambient pressure drying. An inorganic xerogel with the same low density can be achieved by a subsequent oxidation step that decomposes the organic moieties.

Setting Directions: Anisotropy in Hierarchically Organized Porous Silica

Structural hierarchy, porosity, and isotropy/anisotropy are highly relevant factors for mechanical properties and thereby the functionality of porous materials. However, even though anisotropic and hierarchically organized, porous materials are well known in nature, such as bone or wood, producing the synthetic counterparts in the laboratory is difficult. We report for the first time a straightforward combination of sol-gel processing and shear-induced alignment to create hierarchical silica monoliths exhibiting anisotropy on the levels of both, meso- and macropores. The resulting material consists of an anisotropic macroporous network of struts comprising 2D hexagonally organized cylindrical mesopores. While the anisotropy of the mesopores is an inherent feature of the pores formed by liquid crystal templating, the anisotropy of the macropores is induced by shearing of the network. Scanning electron microscopy and small-angle X-ray scattering show that the majority of network forming struts is oriented towards the shearing direction; a quantitative analysis of scattering data confirms that roughly 40% of the strut volume exhibits a preferred orientation. The anisotropy of the materials macroporosity is also reflected in its mechanical properties; i.e., the Youngs modulus differs by nearly a factor of 2 between the directions of shear application and perpendicular to it. Unexpectedly, the adsorption-induced strain of the material exhibits little to no anisotropy.

Impact of thermal coupling effects on the effective thermal conductivity of aerogels

Nanoporous aerogels are excellent thermal insulation materials with thermal conductivities down to about 0.012u2009Wu2009m−1u2009K−1 at ambient conditions. So far, it was assumed that the total thermal conductivity of aerogels can be described by a simple superposition of the different individual heat transport contributions. However, recent investigations reveal that thermal coupling effects can result in a gas pressure dependent contribution that may be up to three times higher than expected from just a gas phase thermal conductivity, which is predicted by the Knudsen equation at given porosity and pore size. In this study, we use data from previous publications covering a gas pressure range from 10−5 to 10u2009MPa and analyze systematically the impact of pore size as well as solid phase and gas phase thermal conductivity on the coupling effect. The goal is to evaluate the data with respect to practical implications for aerogels in general. This means using the gas pressure dependence of the thermal conductivity of aerogels to determine their average pore size as well as allowing for a targeted optimization of aerogel-based insulations for applications at given gas pressure and temperature.Graphical Abstract