Vacuum-Induced Surface Freezing to Produce Monoliths of Aligned Porous Alumina.
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ABSTRACT: Vacuum-induced surface freezing has been used to produce uni-directional freezing of colloidal aluminum oxide dispersions. It leads to zones of different structure within the resulting sintered monoliths that are highly similar to those known for freeze casting using a cryogen cold source. A more-or-less dense surface layer and a cellular sub-surface region are formed, beneath which is a middle region of aligned lamellae and pores that stretches through most of the depth of the monolith. This is the case even at a volume fraction of dispersed phase as low as 0.032. A more-dense but still porous base layer is formed by accumulation of rejected nanoparticles preceding the freezing front and differs from previous reports in that no ice lenses are observed. X-ray micro-computed tomography reveals a uniform aligned pore structure vertically through the monolith. The pores close to the periphery are oriented radially or as chords, while the center region contains domains of parallel pores/lamellae. The domains are randomly oriented to one another, as already reported for regular freeze casting. This technique for directional freezing is convenient and easy to perform, but requires further refinement in that the temperature gradient and freezing rates remain yet to be measured. Also, control of the temperature gradient by varying chamber vacuum and shelf temperature needs to be evaluated.
Project description:Vacuum-induced surface freezing of colloidal alumina was used to produce membranes that have elongated, aligned channels and, hence, are tortuous in the direction perpendicular to ice crystal growth. The effective tortuosity of the membranes was measured by steady-state diffusion of a solute, methylene blue. The resulting diffusion profiles show an initial step-increase in amount of dye reaching the acceptor that is caused by capillarity drawing the donor solution through any non-wetted channels in the membrane. This is followed by a linear steady-state phase whose flux is proportional to dye concentration in the donor and inversely proportional to the colloid's volume fraction of dispersed phase. From the steady-state flux, the effective tortuosity, τ* = (α/τ)-1, was calculated. This is the reciprocal quotient of the reduced available area for diffusion within the membrane, α = A*/A, where A* is the available area and A is the cross-sectional area of the membrane, and the increased mean diffusional path length, i.e., tortuosity = L * / L , where L* is the mean path length and L is the membrane thickness. The values of τ* lie in the range of 2-38 and increase as the volume fraction of dispersed phase is larger. This latter effect indicates that τ* > 1 results, to a larger extent, from the reduced available diffusion area, α, than from the lengthened pathway, τ, in these aligned porous membranes.
Project description:Micro/nano-patterned alumina surfaces are important in a variety fields such as chemical/biotechnology, surface science, and microelectro-mechanical systems. However, for patterning alumina surfaces, it still remains a challenge to have a lithographic tool that has large flexibility in design layouts, structural reconfigurability, and a simple fabrication process. In this work, a new alumina-patterning platform that uses a photo-reconfigurable azobenzene-alumina composite as an imprinting material is presented. Under far-field irradiation, the azobenzene-alumina anisotropically flows in the direction parallel to the light polarization. Accordingly, an arbitrarily designed azobenzene-alumina composite by imprinting can be deterministically reconfigured by light polarization and irradiation time. The photo-reconfigured azobenzene-alumina is then converted to pure alumina through calcination in an air atmosphere, which provides thin crack-free alumina patterns with a high structural fidelity. The novel combination of photo-reconfigurable azobenzene moieties and an alumina precursor for imprinting the material provides large flexibility in designing and controlling geometric parameters of the alumina pattern, which potentially offers significant value in various micro/nanotechnology fields.
Project description:A new method of surface modification is described for enabling the in situ formation of homogenous porous polymer monoliths (PPMs) within poly(dimethylsiloxane) (PDMS) microfluidic channels that uses 365 nm UV illumination for polymerization. Porous polymer monolith formation in PDMS can be challenging because PDMS readily absorbs the monomers and solvents, changing the final monolith morphology, and because PDMS absorbs oxygen, which inhibits free-radical polymerization. The new approach is based on sequentially absorbing a non-hydrogen-abstracting photoinitiator and the monomers methyl methacrylate and ethylene diacrylate within the walls of the microchannel, and then polymerizing the surface treatment polymer within the PDMS, entangled with it but not covalently bound. Four different monolith compositions were tested, all of which yielded monoliths that were securely anchored and could withstand pressures exceeding the bonding strength of PDMS (40 psi) without dislodging. One was a recipe that was optimized to give a larger average pore size, required for low back pressure. This monolith was used to concentrate and subsequently mechanical lyse B lymphocytes.
Project description:Anisotropy is a key factor regarding mechanical or transport properties and thus the functionality of porous materials. However, the ability to deliberately design the pore structure of hierarchically organized porous networks toward anisotropic features is limited. Here, we report two straightforward routes toward hierarchically structured porous carbon monoliths with an anisotropic alignment of the microstructure on the level of macro- and mesopores. One approach is based on nanocasting (NC) of carbon precursors into hierarchical and anisotropic silica hard templates. The second route, a direct synthesis approach based on soft templating (ST), makes use of the flexibility of hierarchically structured resorcinol-formaldehyde gels, which are compressed and simultaneously carbonized in the deformed state. We present structural data of both types of carbon monoliths obtained by electron microscopy, nitrogen adsorption analysis, and SAXS measurements. In addition, we demonstrate how the degree of anisotropy can easily be controlled via the ST route.
Project description:The preparation of porous carbon monoliths with a defined shape via template-assisted routes is reported. Monoliths made from porous concrete and zeolite were each used as the template. The porous concrete-derived carbon monoliths exhibited high gravimetric specific surface areas up to 2000 m²·g-1. The pore system comprised macro-, meso-, and micropores. These pores were hierarchically arranged. The pore system was created by the complex interplay of the actions of both the template and the activating agent as well. On the other hand, zeolite-made template shapes allowed for the preparation of microporous carbon monoliths with a high volumetric specific surface area. This feature could be beneficial if carbon monoliths must be integrated into technical systems under space-limited conditions.
Project description:A new rapid, very simple and one-step sol-gel strategy for the large-scale preparation of highly porous γ-Al₂O₃ is presented. The resulting mesoporous alumina materials feature high surface areas (400 m² g-1), large pore volumes (0.8 mL g-1) and the γ-Al₂O₃ phase is obtained at low temperature (500 °C). The main advantages and drawbacks of different preparations of mesoporous alumina materials exhibiting high specific surface areas and large pore volumes such as surfactant-nanostructured alumina, sol-gel methods and hierarchically macro-/mesoporous alumina monoliths have been analyzed and compared. The most reproducible synthesis of mesoporous alumina are given. Evaporation-Induced Self-Assembly (EISA) is the sole method to lead to nanostructured mesoporous alumina by direct templating, but it is a difficult method to scale-up. Alumina featuring macro- and mesoporosity in monolithic shape is a very promising material for in flow applications; an optimized synthesis is described.
Project description:This study deals with the fabrication of biodegradable porous materials from bacterial polyester, poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (P3HB3HHx), via thermally induced phase separation. P3HB3HHx monoliths with topological porous structure were prepared by dissolution of P3HB3HHx in dimethyl sulfoxide (DMSO) at 85 °C and subsequent quenching. The microstructure of the resulting P3HB3HHx monoliths was changed by the P3HB3HHx concentration of the polymer solution. Differential scanning calorimetry and polarized optical microscope analysis revealed that the P3HB3HHx monoliths crystallized during phase separation and the subsequent aging. The mechanical properties, such as compression modulus and stress, of the monoliths depended on the 3-hydroxyhexanoate content of P3HB3HHx. Furthermore, the P3HB3HHx monolith absorbed linseed oil in preference to water in a plant oil⁻water mixture. In combination with the biodegradable character of P3HB3HHx, the present study is expected to contribute to the development of bio-based materials.
Project description:The optimization of the air-solid contactor is critical to improve the efficiency of the direct air capture (DAC) process. To enable comparison of contactors and therefore a step toward optimization, two contactors are prepared in the form of pellets and wash-coated honeycomb monoliths. The desired amine functionalities are successfully incorporated onto these industrially relevant pellets by means of a procedure developed for powders, providing materials with a CO2 uptake not influenced by the morphology and the structure of the materials according to the sorption measurements. Furthermore, the amine functionalities are incorporated onto alumina wash-coated monoliths that provide a similar CO2 uptake compared to the pellets. Using breakthrough measurements, dry CO2 uptakes of 0.44 and 0.4 mmol gsorbent-1 are measured for pellets and for a monolith, respectively. NMR and IR studies of CO2 uptake show that the CO2 adsorbs mainly in the form of ammonium carbamate. Both contactors are characterized by estimated Toth isotherm parameters and linear driving force (LDF) coefficients to enable an initial comparison and provide information for further studies of the two contactors. LDF coefficients of 1.5 × 10-4 and of 1.2 × 10-3 s-1 are estimated for the pellets and for a monolith, respectively. In comparison to the pellets, the monolith therefore exhibits particularly promising results in terms of adsorption kinetics due to its hierarchical pore structure. This is reflected in the productivity of the adsorption step of 6.48 mol m-3 h-1 for the pellets compared to 7.56 mol m-3 h-1 for the monolith at a pressure drop approximately 1 order of magnitude lower, making the monoliths prime candidates to enhance the efficiency of DAC processes.
Project description:Three-dimensional anodic alumina templates (3D-AAO) are an astonishing framework with open highly ordered three-dimensional skeleton structures. Since these templates are architecturally different from conventional solids or porous templates, they teem with opportunities for engineering thermal properties. By establishing the mechanisms of heat transfer in these frameworks, we aim to create materials with tailored thermal properties. The effective thermal conductivity of an empty 3D-AAO membrane was measured. As the effective medium theory was not valid to extract the skeletal thermal conductivity of 3D-AAO, a simple 3D thermal conduction model was developed, based on a mixed series and parallel thermal resistor circuit, giving a skeletal thermal conductivity value of approximately 1.25 W·m-1·K-1, which matches the value of the ordinary AAO membranes prepared from the same acid solution. The effect of different filler materials as well as the variation of the number of transversal nanochannels and the length of the 3D-AAO membrane in the effective thermal conductivity of the composite was studied. Finally, the thermal conductivity of two 3D-AAO membranes filled with cobalt and bismuth telluride was also measured, which was in good agreement with the thermal model predictions. Therefore, this work proved this structure as a powerful approach to tailor thermal properties.
Project description:Scandium (Sc) is a high value Critical Material that is most commonly used in advanced alloys. Due to current and potential supply limitations, there has been an international effort to find new and improved ways to extract Sc from existing and novel resources. Solid-phase extraction (SPE) is one promising approach for Sc recovery, particularly for use with low-grade feedstocks. Here, unfunctionalized, powdered hierarchically porous silica monoliths from DPS Inc. (DPS) are used for Sc extraction in batch and semicontinuous flow systems at model conditions. The sorbent exhibits excellent mass transfer properties, much like the whole monoliths, which should permit Sc to be rapidly recovered from large volumes of feedstock. The Sc adsorption capacity of the material is ∼142.7 mg/g at pH 6, dropping to ∼12.0 mg/g at pH 3, and adsorption is furthermore highly selective for Sc compared with the other rare earth elements (REEs). Under semicontinuous flow conditions, recovery efficiency is limited by a kinetic process. The primary mechanism responsible for the system's slow approach to equilibrium is the Sc adsorption reaction kinetics rather than inter- or intraparticle diffusion. Overall, this unmodified hierarchically porous silica powder from DPS shows great promise for the selective extraction of Sc from various feedstocks.