Publications

This project set out to scientifically-tailor ''smart'' interfacial films and 3-D composite nanostructures to exhibit photochromic responses to specific, highly-localized chemical and/or mechanical stimuli, and to integrate them into optical microsystems. The project involved the design of functionalized chromophoric self-assembled materials that possessed intense and environmentally-sensitive optical properties (absorbance, fluorescence) enabling their use as detectors of specific stimuli and transducers when interfaced with optical probes. The conjugated polymer polydiacetylene (PDA) proved to be the most promising material in many respects, although it had some drawbacks concerning reversibility. Throughout his work we used multi-task scanning probes (AFM, NSOM), offering simultaneous optical and interfacial force capabilities, to actuate and characterize the PDA with localized and specific interactions for detailed characterization of physical mechanisms and parameters. In addition to forming high quality mono-, bi-, and tri-layers of PDA via Langmuir-Blodgett deposition, we were successful in using the diacetylene monomer precursor as a surfactant that directed the self-assembly of an ordered, mesostructured inorganic host matrix. Remarkably, the diacetylene was polymerized in the matrix, thus providing a PDA-silica composite. The inorganic matrix serves as a perm-selective barrier to chemical and biological agents and provides structural support for improved material durability in microsystems. Our original goal was to use the composite films as a direct interface with microscale devices as optical elements (e.g., intracavity mirrors, diffraction gratings), taking advantage of the very high sensitivity of device performance to real-time dielectric changes in the films. However, our optical physics colleagues (M. Crawford and S. Kemme) were unsuccessful in these efforts, mainly due to the poor optical quality of the composite films.

This report summarizes the development of sensor particles for remote detection of trace chemical analytes over broad areas, e.g residual trinitrotoluene from buried landmines or other unexploded ordnance (UXO). We also describe the potential of the sensor particle approach for the detection of chemical warfare (CW) agents. The primary goal of this work has been the development of sensor particles that incorporate sample preconcentration, analyte molecular recognition, chemical signal amplification, and fluorescence signal transduction within a ''grain of sand''. Two approaches for particle-based chemical-to-fluorescence signal transduction are described: (1) enzyme-amplified immunoassays using biocompatible inorganic encapsulants, and (2) oxidative quenching of a unique fluorescent polymer by TNT.

Abstract not provided.

Since the discovery of surfactant-templated silica by Mobil scientists in 1992, mesostructured silica has been synthesized in various forms including thin films, powders, particles, and fibers. In general, mesostructured silica has potential applications, such as in separation, catalysis, sensors, and fluidic microsystems. In respect to these potential applications, mesostructured silica in the form of thin films is perhaps one of the most promising candidates. The preparation of mesostructured silica films through preferential solvent evaporation-induced self-assembly (EISA) has recently received much attention in the laboratories. However, no amphiphile/silica films with reverse mesophases have ever been made through this EISA procedure. Furthermore, templates employed to date have been either surfactants or poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) triblock copolymers, such as pluronic P-123, both of which are water-soluble and alcohol-soluble. Due to their relatively low molecular weight, the templated silica films with mesoscopic order have been limited to relatively small characteristic length scales. In the present communication, the authors report a novel synthetic method to prepare mesostructured amphiphilic/silica films with regular and reverse mesophases of large characteristic length scales. This method involves evaporation-induced self-assembly (EISA) of amphiphilic polystyrene-block-poly(ethylene oxide) (PS-b-PEO) diblock copolymers. In the present study, the PS-b-PEO diblocks are denoted as, for example, PS(215)-b-PEO(100), showing that this particular sample contains 215 S repeat units and 100 EO repeat units. This PS(215)-b-PEO(100) diblock possesses high molecular weight and does not directly mix with water or alcohol. To the authors knowledge, no studies have reported the use of water-insoluble and alcohol-insoluble amphiphilic diblocks as structure-directing agents in the synthesis of mesostructured silica films through EISA. It is believed that the present system is the first to yield amphiphile/silica films with regular and reverse mesophases, as well as curved multi-bilayer mesostructures, through EISA. The ready formation of the diblock/silica films with multi-bilayer vesicular mesostructures is discussed.

The ability to engineer ordered arrays of objects on multiple length scales has potential for applications such as microelectronics, sensors, wave guides, and photonic lattices with tunable band gaps. Since the invention of surfactant templated mesoporous sieves in 1992, great progress has been made in controlling different mesophases in the form of powders, particles, fibers, and films. To date, although there have been several reports of patterned mesostructures, materials prepared have been limited to metal oxides with no specific functionality. For many of the envisioned applications of hierarchical materials in micro-systems, sensors, waveguides, photonics, and electronics, it is necessary to define both form and function on several length scales. In addition, the patterning strategies utilized so far require hours or even days for completion. Such slow processes are inherently difficult to implement in commercial environments. The authors present a series of new methods of producing patterns within seconds. Combining sol-gel chemistry, Evaporation-Induced Self-Assembly (EISA), and rapid prototyping techniques like pen lithography, ink-jet printing, and dip-coating on micro-contact printed substrates, they form hierarchically organized silica structures that exhibit order and function on multiple scales: on the molecular scale, functional organic moieties are positioned on pore surfaces, on the mesoscale, mono-sized pores are organized into 1-, 2-, or 3-dimensional networks, providing size-selective accessibility from the gas or liquid phase, and on the macroscale, 2-dimensional arrays and fluidic or photonic systems may be defined. These rapid patterning techniques establish for the first time a link between computer-aided design and rapid processing of self-assembled nanostructures.

Abstract not provided.

Abstract not provided.

We report an evaporation-induced self-assembly procedure to prepare poly(bridged silsesquioxane) thin-film and particulate mesophases that incorporate organic moieties (1-3) into periodic, mesostructured frameworks as molecularly dispersed bridging ligands. Capacitance-voltage measurements along with a variety of structural characterization procedures were performed to begin to elucidate structure-property relationships of this new class of surfactant-templated mesophases. We observed a consistent trend of increasing modulus and hardness and decreasing dielectric constant with substitution of the bridged silsesquioxane (≡Si-(CH2)2-Si≡) for siloxane (≡Si-O-Si≡) in the framework. This preliminary evidence suggests that the introduction of integral organic groups into the frameworks of mesoporous materials can result in synergistic properties, promising an unprecedented ability to tune properties and function.

Using a micro-Contact Printing ({mu}-CP) technique, substrates are prepared with patterns of hydrophilic, hydroxyl-terminated SAMS and hydrophobic methyl-terminated SAMS. Beginning with a homogeneous solution of silica, surfactant, ethanol, water, and functional silane, preferential ethanol evaporation during dip-coating, causes water enrichment and selective de-wetting of the hydrophobic SAMS. Correspondingly, film deposition occurs exclusively on the patterned hydrophilic SAMS. In addition, by co-condensation of tetrafunctional silanes (Si(OR){sub 4}) with tri-functional organosilanes ((RO){sub 3}Si(CH{sub 2}){sub 3}NH{sub 2}), the authors have selectively derived the silica framework with functional amine NH{sub 2} groups. A pH sensitive, micro-fluidic system was formed by further conjugation reactions with pH sensitive dye molecules.

Living systems exhibit form and function on multiple length scales and at multiple locations. In order to mimic such natural structures, it is necessary to develop efficient strategies for assembling hierarchical materials. Conventional photolithography, although ubiquitous in the fabrication of microelectronics and microelectromechanical systems, is impractical for defining feature sizes below 0.1 micrometres and poorly suited to pattern chemical functionality. Recently, so-called 'soft' lithographic approaches have been combined with surfactant and particulate templating procedures to create materials with multiple levels of structural order. But the materials thus formed have been limited primarily to oxides with no specific functionality, and the associated processing times have ranged from hours to days. Here, using a self-assembling 'ink', we combine silica-surfactant self-assembly with three rapid printing procedures-pen lithography, ink-jet printing, and dip-coating of patterned self-assembled monolayers-to form functional, hierarchically organized structures in seconds. The rapid-prototyping procedures we describe are simple, employ readily available equipment, and provide a link between computer-aided design and self-assembled nanostructures. We expect that the ability to form arbitrary functional designs on arbitrary surfaces will be of practical importance for directly writing sensor arrays and fluidic or photonic systems.

The new two-layer protective coating developed for monuments constructed of limestone or marble was applied to highway cement and to tobermorite, a component of cement, and tested in batch dissolution tests. The goal was to determine the suitability of the protective coating in retarding the weathering rate of concrete construction. The two-layer coating consists of an inner layer of aminoethylaminopropylsilane (AEAPS) applied as a 25% solution in methanol and an outer layer of A2** sol-gel. In previous work, this product when applied to calcite powders, had resulted in a lowering of the rate of dissolution by a factor of ten and was shown through molecular modeling to bind strongly to the calcite surface, but not too strongly so as to accelerate dissolution. Batch dissolution tests at 22 C of coated and uncoated tobermorite (1.1 nm phase) and powdered cement from Gibson Blvd. in Albuquerque indicated that the coating exhibits some protective behavior, at least on short time scales. However, the data suggest that the outer layer of sol-gel dissolves in the high-pH environment of the closed system of cement plus water. Calculated binding configuration and energy of AEAPS to the tobermorite surface suggests that AEAPS is well-suited as the inner layer binder for protecting tobermorite.

Photosensitive films incorporating molecular photoacid generators compartmentalized within a silica-surfactant mesophase were prepared by an evaporation-induced self-assembly process. UV-exposure promoted localized acid-catalyzed siloxane condensation, enabling selective etching of unexposed regions, thereby serving as a resistless technique to prepare patterned mesoporous silica. The authors also demonstrated an optically-defined mesophase transformation (hexagonal {r_arrow} tetragonal) and patterning of refractive index and wetting behavior. Spatial control of structure and function on the macro- and mesoscales is of interest for sensor arrays, nano-reactors, photonic and fluidic devices, and low dielectric constant films. More importantly, it extends the capabilities of conventional lithography from spatially defining the presence or absence of film to spatial control of film structure and function.

Surface acoustic wave (SAW) sensors, which are sensitive to a variety of surface changes, have been widely used for chemical and physical sensing. The ability to control or compensate for the many surface forces has been instrumental in collecting valid data. In cases where it is not possible to neglect certain effects, such as frequency drift with temperature, methods such as the dual sensor technique have been utilized. This paper describes a novel use of a dual sensor technique, using two sensor materials, Quartz and GaAs, to separate out the contributions of mass and modulus of the frequency change during gas adsorption experiments. The large modulus change in the film calculated using this technique, and predicted by the Gassmann equation, provide a greater understanding of the challenges of SAW sensing.

We report a novel sol-gel dip-coating process to form dual-layer microporous silica membranes with improved membrane performance and reproducibility. First, we deposit a surfactant-templated silica (STS) intermediate layer on top of a commercial {gamma}-alumina support both to improve its ''surface finish'' and to prevent a subsequently deposited microporous overlayer from penetrating into the support. Second, membranes are processed under clean room conditions to avoid dust contamination and, third, membranes are vacuum-calcined to promote further pore shrinkage and impart surface hydrophobicity. The resulting asymmetric membrane exhibits a gradual change in pore diameter from 50{angstrom} ({gamma}-alumina support layer) to 10-12{angstrom} (STS intermediate layer), and then to 3-4{angstrom} (30nm thick, ultramicroporous silica top-layer). Compared to a single-layer process using only the microporous overlayer, the dual-layer process improves both flux and selectivity. For the industrially important problem of natural gas purification, the combined CO{sub 2} flux [(3{approx} 0.5) x 10{sup {minus}4} cm{sup 3}(STP)/(s{center_dot}cm{sup 2}{center_dot}cm-Hg)] and CO{sub 2}/CH{sub 4} separation factors [200{approx}600] are superior to all previously reported values for separation of a 50/50 (v/v) CO{sub 2}/CH{sub 4} gas mixture. In addition, the membrane selectively separated hydrogen from a simulated reformate from partial oxidation of methanol as evidenced by a high concentration of hydrogen recovery.

Silica nanoparticles exhibiting hexagonal, cubic, and vesicular mesostructures have been prepared using aerosol assisted, self-assembled process. This process begins with homogennous aerosol droplets containing silica source, water, ethanol, and surfactant, in which surfactant concentration is far below the critical micelle concentration (cmc). Solvent evaporation enriches silica and surfactant inducing interfacial self-assembly confined to a spherical aerosol droplet and results in formation of completely solid, ordered spherical particles with stable hexagonal, cubic, or vesicular mesostructures.

Nanostructured particles exhibiting well-defined pore sizes and pore connectivities (1-, 2-, or 3-dimensional) are of interest for catalysis, chromatography, controlled release, low dielectric constant fillers, and custom-designed pigments and optical hosts. During the last several years considerable progress has been made on controlling the macroscopic forms of mesoporous silicas prepared by surfactant and block copolymer liquid crystalline templating procedures. Typically interfacial phenomena are used to control the macroscopic form (particles, fibers, or films), while self-assembly of amphiphilic surfactants or polymers is used to control the mesostructure. To date, although a variety of spherical or nearly-spherical particles have been prepared, their extent of order is limited as is the range of attainable mesostructures. They report a rapid, aerosol process that results in solid, completely ordered spherical particles with stable hexagonal, cubic, or vesicular mesostructures. The process relies on evaporation-induced interfacial self-assembly (EISA) confined to a spherical aerosol droplet. The process is simple and generalizable to a variety of materials combinations. Additionally, it can be modified to provide the first aerosol route to the formation of ordered mesostructured films.

Sol-gel matrices are promising host materials for potential chemical and biosensor applications. Previous studies have focused on modified sol-gel routes using alkoxides for encapsulation of enzymes. However the formation of alcohol as a byproduct during hydrolysis and condensation reactions poses limitations. We report the immobilization of glucose oxidase and peroxidase in silica prepared by an aqueous route which may provide a more favorable environment for the biomolecules. A two step aqueous sol-gel procedure using sodium silicate as the precursor was developed to encapsulate the enzymes and the dye precursor, o-dianisidine. Glucose oxidase catalyzes the oxidation of glucose to give gluconic acid and hydrogen peroxide. Peroxidase then catalyzes the reaction of the dye precursor with hydrogen peroxide to produce a colored product. The kinetics of the coupled enzymatic reactions were monitored by optical spectroscopy and compared to those occurring in tetramethyl orthosilicate (TMOS) derived silica matrices developed by Yamanaka. Enhanced kinetics in the aqueous silicate matrices were related to differences in the host microstructure as elucidated by microstructural comparisons of the corresponding aerogels.

Results appear to confirm the concept of surfactant-templating of thin film mesostructures. Final film pore structure depends on starting surfactant and water concentrations and process time scale (governed by evaporation rate). Surfactant ordering at substrate-film and film-vapor interfaces orients the porosity of adjoining films, leading to graded structures. SAW experiments show that depending on processing conditions, the porosity may be open or closed (restricted). Open porosity is monosized. Upon pyrolysis, lamellar structures collapse, while the hexagonal structures persist; when both hexagonal and lamellar structures are present, the hexagonal may serve to pillar the lamellar, avoiding its complete collapse. Thick lamellar films can be prepared because the surfactant mechanically decouples stress development in adjoining layers. Upon drying and heating, each individual layer can shrink due to continuing condensation reactions without accumulating stress. During surfactant pyrolysis, the layers coalesce to form a thick crack-free layer. Formation of closed porosity films is discussed.

We have studied the different driving forces behind syneresis in MTES/TEOS gels by aging them in different H{sub 2}O/EtOH pore fluids. We show using shrinkage, density, contact angle, and N{sub 2} sorption measurements, the influence of gel/solvent interactions on the microstructural evolution during drying. Competing effects of syneresis (that occurs during aging) and drying shrinkage resulted in the overall linear shrinkage of the organically modified gels to be constant at {approximately}50%. Increasing the hydrophobicity of the gels caused the driving force for syneresis to change from primarily condensation reactions to a combination of condensation and solid/liquid interfacial energy. In addition the condensation driven shrinkage was observed to be irreversible, whereas the interfacial free energy driven shrinkage was observed to be partially reversible. Nitrogen sorption experiments show that xerogels with the same overall extent of shrinkage can have vastly different microstructures due to the effects of microphase separation.

Polymer-based routes to ceramic oxides take advantage of precursor chemistry and structure to produce materials with a range of pore sizes. Polymer precursor routes to non-oxide ceramics offer products with superior thermal and chemical stability in many cases. Polymethylsilane (PMS), a versatile cross linked SiC precursor, [(MeHSi){sub x}(MeSi){sub y}], was synthesized using published procedures to yield fluid precursors with a low (20--40%) degree of cross linking. Unique, highly cross linked (60--70%), solid polymers were produced under reaction conditions which carefully conserve the volatile monomer. These two polymers were converted to SiC to determine the relative importance of the various contributions to porosity, and to assess the role of precursor structure on porosity development in non-oxides. Initial results indicate that precursor structure has little effect on porosity. The development of the porosity appears to be dominated by high temperature thermochemistry and/or microstructural changes.

Polymeric silica sols, were deposited on commercial {gamma}-alumina supports to prepare gas separation membranes. Optimization of the sol fractal dimension and radius of gyration and minimization of condensation rate led to formation of a discrete film with pores of molecular dimensions. Two coatings of this sol (A2{sup **}) led to a membrane with ideal separation factor of 7 for helium versus nitrogen after calcination to 400C (helium permeance 0.002 cm{sup 3}/cm{sup 2}-s-cm Hg). Partial sintering of these membranes resulted in a further reduction in pore size or narrowing of pore size distribution as evidenced by larger separation factors e.g. 9 for helium versus nitrogen (helium permeance 0.0028 cm{sup 3}/cm{sup 2}-s-cm Hg) with only one A2{sup **} coating. Single gas measurements also showed high ideal separation factors for helium versus methane, propylene, sulfur hexafluoride and carbon dioxide. The deposited A2{sup **} membrane was reacted with titanium isopropoxide (Ti(O i-Pr){sub 4}) to improve both its thermal and chemical stability and modify its pore size. This reaction led to an increase in the membrane selectivity to >300 for He versus N{sub 2} below to 120C, and CO{sub 2} versus CH{sub 4}, when measured below 200C. A2{sup **} was also used as a host matrix for preparing imogolite composite membranes that showed molecular sieving behavior.

A percolation model is developed which accounts for most known features of the process of porous glass membrane preparation by selective dissolution of multi-component glasses. The model is founded within tile framework of the classical percolation theory, wherein the components of a glass are represented by random sites on a suitable lattice. Computer simulation is used to mirror the generation of a porous structure during the dissolution process, reproducing many of the features associated with the phenomenon. Simulation results evaluate the effect of the initial composition of the glass on the kinetics of the leaching process as well as the morphology of the generated porous structure. The percolation model establishes the porous structure as a percolating cluster of unreachable constituents in the glass. The simulation algorithm incorporates removal of both, the accessible leachable components in the glass as well as the independent clusters of unreachable components not attached to the percolating cluster. The dissolution process thus becomes limited by the conventional site percolation thresholds of the unreachable components (which restricts the formation of the porous network), as well as the leachable components (which restricts the accessibility of the solvating medium into the glass). The simulation results delineate the range of compositional variations for successful porous glass preparation and predict the variation of porosity, surface area, dissolution rates and effluent composition with initial composition and time. Results compared well with experimental studies and improved upon similar models attempted in die past.

Very highly porous (aerogel) silica films with refractive index in the range 1.006--1.05 (equivalent porosity 98.5--88%) were prepared by an ambient-pressure process. It was shown earlier using in situ ellipsometric imaging that the high porosity of these films was mainly attributable to the dilation or `springback` of the film during the final stage of drying. This finding was irrefutably reconfirmed by visually observing a `springback` of >500% using environmental scanning electron microscopy (ESEM). Ellipsometry and ESEM also established the near cent per cent reversibility of aerogel film deformation during solvent intake and drying. Film thickness profile measurements (near the drying line) for the aerogel, xerogel and pure solvent cases are presented from imaging ellipsometry. The thickness of these films (crack-free) were controlled in the range 0.1-3.5 {mu}m independent of refractive index.

The pore size r{sub p} in a gel is determined by the extent of shrinkage of the gel network during drying. Shrinkage is driven by the collapse of the gel network in response to the capillary pressure P{sub c} exerted by the pore fluid. The extent of shrinkage depends on the balance between the capillary pressure P{sub c} in the pore fluid and the bulk modulus K{sub p} of the gel. The hydraulic pore radius, r{sub H} = 2V{sub p}/S{sub a}, where V{sub p} is the pore volume and S{sub a} is the apparent N{sub 2} BET surface area, is often used to characterize the pore size of a gel. A series of acid catalyzed silica gels dried in pore fluids with different {gamma}{sub lv}, showed that there is a limit to the minimum apparent r{sub H} obtainable in a gel, and when the volume fraction of porosity {phi} {le} 0.37, r{sub H} becomes constant and {approximately}0.8 nm. In contrast, experimental data show that the true pore size r{sub p} of gels continues to decrease when {phi} {le} 0.37. Analysis of their adsorption isotherms show that while r{sub H} apparently stays constant: (a) the BET C constant continues to increase, (b) the width and average of their pore size distributions continue to decrease, and (c) as shrinkage continues the gels eventually become non-porous to N{sub 2} at 77K but are still porous to CO{sub 2} at 273K. This paper reviews these results and addresses micropore formation in silica gels with the goal of determining how P{sub c} influences the final r{sub p}, and why r{sub p} and r{sub H} diverge when {phi} {le} 0.37.

We have used several sol-gel strategies to prepare supported inorganic membranes by a process that combines the features of slip-casting and dip-coating. To be viable the deposited membranes must exhibit both high flux and high selectivity. For porous membranes these requirements are met by extremely thin, defect-free porous films exhibiting a narrow size distribution of very small pores. This paper considers the use of polymeric silica and hybrid-organosilyl precursor sols in the context of the underlying physics and chemistry of the membrane deposition process. Since the average membrane pore size is ultimately established by the collapse of the gel network upon drying, it is necessary to promote polymer interpenetration and collapse during membrane deposition in order to achieve the very small pore sizes necessary for molecular sieving. For polymeric sols, this is accomplished using rather weakly branched polymers characterized by fractal dimension D < 1.5 under deposition conditions in which the silica condensation rate is minimized. By analogy to organic polymer sols and gels, we believe that the breadth of the pore size distribution can be influenced by the occurrence of micro-phase separation during membrane deposition. Minimization of the condensation rate not only fosters polymer collapse but should inhibit phase separation, leading to a narrower pore size distribution. The formation of microporosity through collapse of the gel network requires that small pores are achieved at the expense of membrane porosity. Incorporation of organic template ligands within a dense silica matrix followed by their removal allows us to independently control pore size and pore volume through the size and volume fraction of the organic template. Such strategies can be used to create microporous films with large volume fraction porosities.