Tommy Hofmann

Capillary rise of water in hydrophilic nanopores.

We report on the capillary rise of water in three-dimensional networks of hydrophilic silica pores with 3.5 nm and 5 nm mean radii, respectively (porous Vycor monoliths). We find classical square root of time Lucas-Washburn laws for the imbibition dynamics over the entire capillary rise times of up to 16 h investigated. Provided we assume two preadsorbed strongly bound layers of water molecules resting at the silica walls, which corresponds to a negative velocity slip length of -0.5 nm for water flow in silica nanopores, we can describe the filling process by a retained fluidity and capillarity of water in the pore center. This anticipated partitioning in two dynamic components reflects the structural-thermodynamic partitioning in strongly silica bound water layers and capillary condensed water in the pore center which is documented by sorption isotherm measurements.

Nanoimprint-Induced Molecular Orientation in Semiconducting Polymer Nanostructures

The morphology and orientation of thin films of the polymer poly-3(hexylthiophene)-important parameters influencing electronic and photovoltaic device performance-have been significantly altered through nanoimprinting with 100 nm spaced grooves. Grazing-incidence small-angle X-ray scattering studies demonstrate the excellent fidelity of the pattern transfer, while wide-angle scattering convincingly shows an imprinting-induced π-π reorientation and polymer backbone alignment along the imprinted grooves. Surprisingly, temperature-dependent scattering measurements indicate that the imprinted induced orientation and alignment remain intact even at temperatures where the imprinted topographical features nearly vanish.

Morphology of air nanobubbles trapped at hydrophobic nanopatterned surfaces.

The details of air nanobubble trapping at the interface between water and a nanostructured hydrophobic silicon surface are investigated using X-ray scattering and contact angle measurements. Large-area silicon surfaces containing hexagonally packed, 20 nm wide hydrophobic cavities provide ideal model surfaces for studying the morphology of air nanobubbles trapped inside cavities and its dependence on the cavity depth. Transmission small-angle X-ray scattering measurements show stable trapping of air inside the cavities with a partial water penetration of 5-10 nm into the pores, independent of their large depth variation. This behavior is explained by consideration of capillary effects and the cavity geometry. For parabolic cavities, the liquid can reach a thermodynamically stable configuration-a nearly planar nanobubble meniscus-by partially penetrating into the pores. This microscopic information correlates very well with the macroscopic surface wetting behavior.

Elastic response of mesoporous silicon to capillary pressures in the pores

We study water adsorption-induced deformation of a monolithic, mesoporous silicon membrane traversed by independent channels of ∼8 nm diameter. We focus on the elastic constant associated with the Laplace pressure-induced deformation of the membrane upon capillary condensation, i.e., the pore-load modulus. We perform finite-element method (FEM) simulations of the adsorption-induced deformation of hexagonal and square lattices of cylindrical pores representing the membrane. We find that the pore-load modulus weakly depends on the geometrical arrangement of pores, and can be expressed as a function of porosity. We propose an analytical model which relates the pore-load modulus to the porosity and to the elastic properties of bulk silicon (Youngs modulus and Poissons ratio), and provides an excellent agreement with FEM results. We find good agreement between our experimental data and the predictions of the analytical model, with the Youngs modulus of the pore walls slightly lower than the bulk value. This...

Tuning the pore wall morphology of mesoporous silicon from branchy to smooth, tubular by chemical treatment

The effect of chemical treatment on physical and chemical properties, i.e., pore diameter, porosity, specific surface area, and chemical bonding of electrochemically formed mesoporous silicon were investigated by using of nitrogen sorption isotherm, scanning electron microscopy, and Fourier transform infrared spectroscopy. The adsorption isotherms measurements show the general behavior found for the porous materials, but at the same time, they exhibit clear differences following different chemical treatments of porous layer. It was clearly observed from Fourier transform infrared spectroscopy that the chemical environment of porous silicon wall changes significantly after chemical treatment. In scanning electron microscopy images, we see that the rough dendritic structure of the pore walls is modified to smooth tubular pore wall structure on chemical treatment. The changes in nanocrystalline porous silicon were also clearly observed by an asymmetric broadening and shift of the optical silicon phonons in R...

Preferred orientation of n-hexane crystallized in silicon nanochannels : A combined x-ray diffraction and sorption isotherm study

We present an x-ray diffraction study on n -hexane in tubular silicon channels of approximately 10 nm diameter both as a function of the filling fraction f of the channels and as a function of temperature. Upon cooling, confined n -hexane crystallizes in a triclinic phase typical of the bulk crystalline state. However, the anisotropic spatial confinement leads to a preferred orientation of the confined crystallites, where the 001 crystallographic direction coincides with the long axis of the channels. The magnitude of this preferred orientation increases with the filling fraction, which corroborates the assumption of a Bridgman-type crystallization process being responsible for the peculiar crystalline texture. This growth process predicts for a channel-like confinement an alignment of the fastest crystallization direction parallel to the long channel axis. It is expected to be increasingly effective with the length of solidifying liquid parcels and thus with increasing f . In fact, the fastest solidification front is expected to sweep over the full silicon nanochannel for f=1 , in agreement with our observation of a practically perfect texture for entirely filled nanochannels.

Melting and freezing of argon in a granular packing of linear mesopore arrays.

Freezing and melting of Ar condensed in a granular packing of template-grown arrays of linear mesopores (SBA-15, mean pore diameter 8 nm) has been studied by specific heat measurements C as a function of fractional filling of the pores. While interfacial melting leads to a single melting peak in C, homogeneous and heterogeneous freezing along with a delayering transition for partial fillings of the pores result in a complex freezing mechanism explainable only by a consideration of regular adsorption sites (in the cylindrical mesopores) and irregular adsorption sites (in niches of the rough external surfaces of the grains and at points of mutual contact of the powder grains). The tensile pressure release upon reaching bulk-liquid-vapor coexistence quantitatively accounts for an upward shift of the melting and freezing temperature observed while overfilling the mesopores.

Solid phases of spatially nanoconfined oxygen: A neutron scattering study

We present a comprehensive neutron scattering study on solid oxygen spatially confined in 12 nm wide alumina nanochannels. Elastic scattering experiments reveal a structural phase sequence known from bulk oxygen. With decreasing temperature cubic γ-, orthorhombic β- and monoclinic α-phases are unambiguously identified in confinement. Weak antiferromagnetic ordering is observed in the confined monoclinic α-phase. Rocking scans reveal that oxygen nanocrystals inside the tubular channels do not form an isotropic powder. Rather, they exhibit preferred orientations depending on thermal history and the very mechanisms, which guide the structural transitions.

Formation of Periodically Arranged Nanobubbles in Mesopores: Capillary Bridge Formation and Cavitation during Sorption and Solidification in an Hierarchical Porous SBA-15 Matrix

We report synchrotron-based small-angle X-ray scattering experiments on a template-grown porous silica matrix (Santa Barbara Amorphous-15) upon in situ sorption of fluorinated pentane C5F12 along with volumetric gas sorption isotherm measurements. Within the mean-field model of Saam and Cole for vapor condensation in cylindrical pores, a nitrogen and C5F12 sorption isotherm is well described by a bimodal pore radius distribution dominated by meso- and micropores with 3.4 and 1.6 nm mean radius, respectively. In the scattering experiments, two different periodicities become evident. One of them (d1 = 11.5 nm) reflects the next nearest neighbor distance in a 2D-hexagonal lattice of tubular mesopores. A second periodicity (d2 = 11.4 nm) found during in situ sorption and freezing experiments is traced back to a superstructure along the cylindrical mesopores. It is compatible with periodic pore corrugations found in electron tomograms of empty SBA-15 by Gommes et al. ( Chem. Mater. 2009, 21, 1311 - 1317). A Rayleigh-Plateau instability occurring at the cylindrical blockcopolymer micelles characteristic of the SBA-15 templating process quantitatively accounts for the superstructure and thus the spatial periodicity of the pore wall corrugation. The consequences of this peculiar morphological feature on the spatial arrangement of C5F12, in particular the formation of periodically arranged nanobubbles (or voids) upon adsorption, desorption, and freezing of liquids, are discussed in terms of capillary bridge formation and cavitation in tubular but periodically corrugated pores.

How do rod-like molecules freeze and arrange in mesopores?

We present an x-ray diffraction study on rod-like molecules, i.e. the normal alkanes C19H40 and C9H20 condensed in nanoporous Vycor glass. Temperature-dependent diffraction patterns elucidate how the structure and phase behaviour of these molecules are affected by the random substrate disorder and the geometric confinement. For the medium-length alkane C19H40 a quenching of the lamellar ordering is observed, whereas this geometric ordering principle survives in the case of the short-length C9H20, although in a modified fashion.