Liquids on Topologically Nanopatterned Surfaces

We report here surface x-ray scattering studies of the adsorption of simple hydrocarbon liquid films on nanostructured surfaces—silicon patterned by an array of nanocavities. Two different regimes, filling and growing, are observed for the wetting film evolution as a function of the chemical potential offset $\Delta \mu$ from the bulk liquid-vapor coexistence. The strong influence of geometrical effects is manifested by a $\Delta \mu$ dependence of liquid adsorption $\Gamma$ in the nanocavities that is stronger than the van der Waals behavior $\Gamma ~\Delta \mu -1/3$ for flat surfaces. The observed $\Delta \mu$ dependence is, however, much weaker than predicted for the infinitely deep parabolic cavities, suggesting that the finite-size effects contribute significantly to the observed adsorption behavior.Engineering and Applied Science

Capillary Filling of Anodized Alumina Nanopore Arrays

The filling behavior of a room temperature solvent, perfluoromethylcyclohexane, in approximately 20 nm nanoporous alumina membranes was investigated in situ with small angle x-ray scattering. Adsorption in the pores was controlled reversibly by varying the chemical potential between the sample and a liquid reservoir via a thermal offset, $\Delta$T. The system exhibited a pronounced hysteretic capillary filling transition as liquid was condensed into the nanopores. These results are compared with Kelvin-Cohan theory, with a modified Derjaguin approximation, as well as with predictions by Cole and Saam.Comment: 4 pages, 3 figures, pre-proof

Solvent Mediated Assembly of Nanoparticles Confined in Mesoporous Alumina

The controlled self-assembly of thiol stabilized gold nanocrystals in a mediating solvent and confined within mesoporous alumina was probed in situ with small angle x-ray scattering. The evolution of the self-assembly process was controlled reversibly via regulated changes in the amount of solvent condensed from an undersaturated vapor. Analysis indicated that the nanoparticles self-assembled into cylindrical monolayers within the porous template. Nanoparticle nearest-neighbor separation within the monolayer increased and the ordering decreased with the controlled addition of solvent. The process was reversible with the removal of solvent. Isotropic clusters of nanoparticles were also observed to form temporarily during desorption of the liquid solvent and disappeared upon complete removal of liquid. Measurements of the absorption and desorption of the solvent showed strong hysteresis upon thermal cycling. In addition, the capillary filling transition for the solvent in the nanoparticle-doped pores was shifted to larger chemical potential, relative to the liquid/vapor coexistence, by a factor of 4 as compared to the expected value for the same system without nanoparticles.Comment: 9 pages, 9 figures, appeared in Phys. Rev.

Composite Synthesis Methodology Development: Nanocrvstalline SiC and Ti3SiC2 Alloys for Reactory Materials – Outline of initial synthesis capabilities M4CT-13PN0405034

We have identified three initial preceramic polymers to help produce the SiC-based alloys for this project and have developed simple processing steps to make SiC-based alloy ceramics. The use of unfilled SMP-10 (Polycarbosilane) or SMP-877 (Methyl-Polycarbosilane) is not feasible due to the large mass losses that occur during pyrolysis. The pre-gelling steps below save time when those two polymers are filled with powders. The use of SL-MS30 provides us with a SiC-filled polymer that can be used to test out the CNT mats without further complications due to other powders

V1.6 Development of Advanced Manufacturing Technologies for Low Cost Hydrogen Storage Vessels

The goal of this project is to develop an innovative manufacturing process for Type IV high-pressure hydrogen storage vessels, with the intent to significantly lower manufacturing costs. Part of the development is to integrate the features of high precision AFP and commercial FW. Evaluation of an alternative fiber to replace a portion of the baseline fiber will help to reduce costs further

Hydrogen Tank Project Q2 Report - FY 11

Quarterly report that represents PNNL's results of HDPE, LDPE, and industrial polymer materials testing. ASTM D638 type 3 samples were subjected to a high pressure hydrogen environment between 3000 and 4000 PSI. These samples were tested using an instron load frame and were analyzed using a proprietary set of excel macros to determine trends in data. The development of an in-situ high pressure hydrogen tensile testing apparatus is discussed as is the stress modeling of the carbon fiber tank exterior

Capillary Wave Fluctuations and Intrinsic Widths of Coupled Fluid-Fluid Interfaces: An X-ray Scattering Study of a Wetting Film on Bulk Liquid

An x-ray specular reflectivity (XR) and off-specular diffuse scattering (XDS) study of the coupled thermal capillary fluctuations and the intrinsic profiles of two interacting fluid-fluid interfaces is presented. The measurements are carried out on complete wetting films of perfluoromethylcyclohexane (PFMC) on the surface of bulk liquid eicosane (C20), as a function of film thickness 30<D<160 Å. In order to facilitate the analysis and interpretation of the data with minimal complexity, approximate methods for calculating scattering intensities are developed to take into account the subtleties of thermal diffuse scattering from layered liquid surfaces. With these methods, the calculations of XR/XDS intensities are reduced to a single numerical integration of simple functions in real space. In addition, an analytic expression is derived for small-angle XR that contains Debye-Waller-like factors with effective capillary roughness and takes into account the partial correlations of the two interfaces. The expression for the XR is quantitatively accurate so long as the reflection angle is small enough that the scattering from interfaces is distinguishable from bulk scattering. The results of the XR and XDS data analysis indicate that the capillary fluctuations at the two interfaces of the wetting films are partially correlated and their coupling is consistent with the van der Waals interactions. The relatively large intrinsic width (4∼6 Å) of the liquid-liquid interface observed for thicker films (D≳50 Å) is comparable to the value expected for the bulk liquid-liquid interface (D→∞), determined by either the radius of gyration (5.3 Å) or the bulk correlation length (4.8 Å) of the alkane C20. The intrinsic liquid-vapor interfacial width is sharper (∼2 Å) and remains essentially constant over the entire probed range of D.Engineering and Applied Science

Wetting of Liquid-Crystal Surfaces and Induced Smectic Layering at a Nematic-Liquid Interface: An X-ray Reflectivity Study

We report the results of a synchrotron x-ray reflectivity study of bulk liquid-crystal surfaces that are coated by thin wetting films of an immiscible liquid. The liquid-crystal subphase consisted of the nematic or isotropic phase of 4-octyl-4′-cyanobiphenyl (8CB), and the wetting film was formed by the fluorocarbon perfluoromethylcyclohexane (PFMC), a volatile liquid. The thickness of the wetting film was controlled by the temperature difference ΔTμ between the sample and a reservoir of bulk PFMC, contained within the sealed sample cell. Phase information on the interfacial electron density profiles has been extracted from the interference between the scattering from the PFMC-vapor interface and the surface-induced smectic order of the 8CB subphase. The liquid-crystal side of the nematic-liquid (8CB-PFMC) interface is characterized by a density oscillation whose period corresponds to the smectic layer spacing and whose amplitude decays exponentially toward the underlying nematic subphase. The decay length ξ of the smectic amplitude is independent of the PFMC film thickness but increases as the nematic–smectic-A transition temperature TNA is approached, in agreement with the longitudinal correlation length ξ∥∝(T−TNA)−0.7 for the smectic fluctuations in the bulk nematic. The results indicate that the homeotropic orientation of the 8CB molecules is preferred at the 8CB-PFMC interface and that the observed temperature dependence of the smectic layer growth is consistent with the critical adsorption mechanism. The observed ΔTμ dependence of the PFMC film thickness, L∝(ΔTμ)−1/3, implies that PFMC completely wets the 8CB surface and is dominated by the nonretarded dispersion interactions between hydro- and fluorocarbons. The complete wetting behavior of PFMC is nearly independent of the degree of interfacial smectic order in the subphase.Engineering and Applied Science

Wetting of Liquid-Crystal Surfaces and Induced Smectic Layering at a Nematic-Liquid Interface: An X-ray Reflectivity Study

We report the results of a synchrotron x-ray reflectivity study of bulk liquid-crystal surfaces that are coated by thin wetting films of an immiscible liquid. The liquid-crystal subphase consisted of the nematic or isotropic phase of 4-octyl-4′-cyanobiphenyl (8CB), and the wetting film was formed by the fluorocarbon perfluoromethylcyclohexane (PFMC), a volatile liquid. The thickness of the wetting film was controlled by the temperature difference ΔTμ between the sample and a reservoir of bulk PFMC, contained within the sealed sample cell. Phase information on the interfacial electron density profiles has been extracted from the interference between the scattering from the PFMC-vapor interface and the surface-induced smectic order of the 8CB subphase. The liquid-crystal side of the nematic-liquid (8CB-PFMC) interface is characterized by a density oscillation whose period corresponds to the smectic layer spacing and whose amplitude decays exponentially toward the underlying nematic subphase. The decay length ξ of the smectic amplitude is independent of the PFMC film thickness but increases as the nematic–smectic-A transition temperature TNA is approached, in agreement with the longitudinal correlation length ξ∥∝(T−TNA)−0.7 for the smectic fluctuations in the bulk nematic. The results indicate that the homeotropic orientation of the 8CB molecules is preferred at the 8CB-PFMC interface and that the observed temperature dependence of the smectic layer growth is consistent with the critical adsorption mechanism. The observed ΔTμ dependence of the PFMC film thickness, L∝(ΔTμ)−1/3, implies that PFMC completely wets the 8CB surface and is dominated by the nonretarded dispersion interactions between hydro- and fluorocarbons. The complete wetting behavior of PFMC is nearly independent of the degree of interfacial smectic order in the subphase.Engineering and Applied Science