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Physics of Hard Spheres Experiment: Significant and Quantitative Findings Made

Direct examination of atomic interactions is difficult. One powerful approach to visualizing atomic interactions is to study near-index-matched colloidal dispersions of microscopic plastic spheres, which can be probed by visible light. Such spheres interact through hydrodynamic and Brownian forces, but they feel no direct force before an infinite repulsion at contact. Through the microgravity flight of the Physics of Hard Spheres Experiment (PHaSE), researchers have sought a more complete understanding of the entropically driven disorder-order transition in hard-sphere colloidal dispersions. The experiment was conceived by Professors Paul M. Chaikin and William B. Russel of Princeton University. Microgravity was required because, on Earth, index-matched colloidal dispersions often cannot be density matched, resulting in significant settling over the crystallization period. This settling makes them a poor model of the equilibrium atomic system, where the effect of gravity is truly negligible. For this purpose, a customized light-scattering instrument was designed, built, and flown by the NASA Glenn Research Center at Lewis Field on the space shuttle (shuttle missions STS 83 and STS 94). This instrument performed both static and dynamic light scattering, with sample oscillation for determining rheological properties. Scattered light from a 532- nm laser was recorded either by a 10-bit charge-coupled discharge (CCD) camera from a concentric screen covering angles of 0 to 60 or by sensitive avalanche photodiode detectors, which convert the photons into binary data from which two correlators compute autocorrelation functions. The sample cell was driven by a direct-current servomotor to allow sinusoidal oscillation for the measurement of rheological properties. Significant microgravity research findings include the observation of beautiful dendritic crystals, the crystallization of a "glassy phase" sample in microgravity that did not crystallize for over 1 year in 1g (Earth's gravity), and the emergence of face-centered-cubic (FCC) crystals late in the coarsening process (as small crystallites lost particles to the slow ripening of large crystallites). Significant quantitative findings from the microgravity experiments have been developed describing complex interactions among crystallites during the growth process, as concentration fields overlap in the surrounding disordered phase. Time-resolved Bragg scattering under microgravity captures one effect of these interactions quite conclusively for the sample at a volume fraction of 0.528. From the earliest time until the sample is almost fully crystalline, the size and overall crystallinity grow monotonically, but the number of crystallites per unit volume (number density) falls. Apparently nucleation is slower than the loss of crystallites because of the transfer of particles from small to large crystals. Thus, coarsening occurs simultaneously with growth, rather than following the completion of nucleation and growth as is generally assumed. In the same sample, an interesting signature appears in the apparent number density of crystallites and the volume fraction within the crystallites shortly before full crystallinity is reached. A brief upturn in both indicates the creation of more domains of the size of the average crystallite simultaneous with the compression of the crystallites. Only the emergence of dendritic arms offers a reasonable explanation. The arms would be "seen" by the light scattering as separate domains whose smaller radii of curvature would compress the interior phase. In fiscal year 1999, numerous papers, a doctoral dissertation, and the PHaSE final report were produced. Although this flight project has been completed, plans are in place for a follow-on colloid experiment by Chaikin and Russel that employs a light microscope within Glenn's Fluids and Combustion Facility on the International Space Station. PHaSE is providing us with a deeper understanding of the nure of phase transitions. The knowledge derived has added to the understanding of condensed matter. In addition, the burgeoning study of the dynamics of colloidal self-assembly may lead to the development of a range of photonic materials that control the desirable properties of light. Thus, applications of ordered colloidal structures include not only ultrastructure ceramics, but also photonic crystals and photothermal nanosecond light-switching devices. Industries dealing with semiconductors, electro-optics, ceramics, and composites stand to benefit from such advancements.

Doherty, Michael P.↗

Universal Features of the Fluid to Solid Transition for Attractive Colloidal Particles

Attractive colloidal particles can exhibit a fluid to solid phase transition if the magnitude of the attractive interaction is sufficiently large, if the volume fraction is sufficiently high, and if the applied stress is sufficiently small. The nature of this fluid to solid transition is similar for many different colloid systems, and for many different forms of interaction. The jamming phase transition captures the common features of these fluid to solid translations, by unifying the behavior as a function of the particle volume fraction, the energy of interparticle attractions, and the applied stress. This paper describes the applicability of the jamming state diagram, and highlights those regions where the fluid to solid transition is still poorly understood. It also presents new data for gelation of colloidal particles with an attractive depletion interaction, providing more insight into the origin of the fluid to solid transition.

Cipelletti, L.↗

Colloidal characterization of silicon nitride and silicon carbide

The colloidal behavior of aqueous ceramic slips strongly affects the forming and sintering behavior and the ultimate mechanical strength of the final ceramic product. The colloidal behavior of these materials, which is dominated by electrical interactions between the particles, is complex due to the strong interaction of the solids with the processing fluids. A surface titration methodology, modified to account for this interaction, was developed and used to provide fundamental insights into the interfacial chemistry of these systems. Various powder pretreatment strategies were explored to differentiate between true surface chemistry and artifacts due to exposure history. The colloidal behavior of both silicon nitride and carbide is dominated by silanol groups on the powder surfaces. However, the colloid chemistry of silicon nitride is apparently influenced by an additional amine group. With the proper powder treatments, silicon nitride and carbide powder can be made to appear colloidally equivalent. The impact of these results on processing control will be discussed.

Feke, Donald L.↗

CHAP Enhances Versatility in Colloidal Probe Fabrication

A colloidal probe, comprising a colloidal particle attached to an atomic force microscope cantilever, is employed to measure directly interaction forces between the particle and a surface. It is possible to change or even destroy a particle while attaching it to a cantilever, thus limiting the types of systems to which the colloidal probe technique may be applied. Here we present the Controlled Heating and Alignment Platform (CHAP) for fabricating colloidal probes without altering the original characteristics of the attached particle. The CHAP applies heat directly to the atomic force microscope chip to rapidly and precisely control cantilever temperature. This minimizes particle heating and enables control over the viscosity of thermoplastic adhesive, to prevent it from contaminating the particle surface. 3D-printed components made the CHAP compatible with standard optical microscopes and streamlined the fabrication process while increasing the platform’s versatility. Using the CHAP with a thermoplastic wax adhesive, colloidal probes were fabricated using polystyrene and silica particles between 0.7 and 40 μm in diameter. We characterized the properties and interactions of the adhesive and particles, as well as the properties of the completed probes, to demonstrate the retention of particle features throughout fabrication. Pull-off tests with CHAP’s probes measured adhesive force values in the expected ranges and demonstrated that particles were firmly attached to the cantilevers.

Schmitz, Russell C.↗

The role of water in slip casting

Slips and casting are considered in terms of physical and colloidal chemistry. Casting slips are polydisperse suspensions of lyophobic particles in water, whose degree of coagulation is controlled by interaction of flocculating and deflocculating agents. Slip casting rate and viscosity are functions of temperature. Slip rheology and response to deflocculating agents varies significantly as the kinds and amounts of colloid modifiers change. Water is considered as a raw material. Various concepts of water/clay interactions and structures are discussed. Casting is a de-watering operation in which water moves from slip to cast to mold in response to a potential energy termed moisture stress. Drying is an evaporative process from a free water surface.

Mccauley, R. A.↗

Pumping Liquid Oxygen by Use of Pulsed Magnetic Fields

An effort is underway to develop a method of pumping small amounts of liquid oxygen by use of pulsed magnetic fields. This development is motivated by a desire to reduce corrosion and hazards of explosion and combustion by eliminating all moving pump parts in contact with the pumped oxygen. The method exploits the known paramagnetism of liquid oxygen. Since they both behave similarly, the existing theory of ferrofluids (liquids with colloidally suspended magnetic particles) is directly applicable to paramagnetic liquid oxygen. In general, the force density of the paramagnetic interaction is proportional to the magnetic susceptibility multiplied by the gradient of the square of the magnitude of the magnetic field. The local force is in the direction of intensifying magnetic field. In the case of liquid oxygen, the magnetic susceptibility is large enough that a strong magnetic-field gradient can lift the liquid in normal Earth gravitation.

Youngquist, Robert↗

Crystalline Colloidal Arrays in Polymer Matrices

Crystalline Colloidal Arrays (CCA, also known as colloidal crystals), composed of aqueous or nonaqueous dispersions of self-assembled nanosized polymer colloidal spheres, are emerging toward the development of advanced optical devices for technological applications. The spontaneous self assembly of polymer spheres in a dielectric medium results from the electrostatic repulsive interaction between particles of uniform size and charge distribution. In a way similar to atomic crystals that diffract X-rays, CCA dispersions in thin quartz cells selectively and efficiently Bragg diffract the incident visible light. The reason for this diffraction is because the lattice (body or face centered cubic) spacing is on the order of the wavelength of visible light. Unlike the atomic crystals that diffract a fixed wavelength, colloidal crystals in principle, depending on the particle size, particle number and charge density, can diffract W, Vis or IR light. Therefore, the CCA dispersions can be used as laser filters. Besides, the diffraction intensity depends on the refractive index mismatch between polymer spheres and dielectric medium; therefore, it is possible to modulate incident light intensities by manipulating the index of either the spheres or the medium. Our interest in CCA is in the fabrication of all-optical devices such as optical switches, limiters, and spatial light modulators for optical signal processing. The two major requirements from a materials standpoint are the incorporation of suitable nonlinear optical materials (NLO) into polymer spheres which will allow us to alter the refractive index of the spheres by intense laser radiation, and preparation of solid CCA filters which can resist laser damage. The fabrication of solid composite filters not only has the advantage that the films are easier to handle, but also the arrays in solid films are more robust than in liquid media. In this paper, we report the photopolymerization process used to trap CCA in polymer matrices, the factors which affect the optical diffraction qualities of resulting polymer films, and methods to improve the efficiencies of solid optical filters. Before this, we also present the experimental demonstration, of controlling the optical diffraction intensities from aqueous CCA dispersions by varying the temperature, which establishes the feasibility of fabricating all-optical switching devices with nonlinear periodic array structures.

Sunkara, Hari B.↗

The concept of a facility for cosmic dust research on the International Space Station

A proposal for the development of a permanently operating facility for the experimental investigation of cosmic dust-related phenomena onboard the International Space Station (ISS) is presented. Potential applications for this facility are the convection-free nucleation of dust grains, studies of coagulation and aggregation phenomena in a microgravity environment, investigations of heat transport through, and dust emissions from, high-porosity cometary analogs, and experiments on the interaction of very fluffy dust grains with electromagnetic radiation and with low pressure gas flows. Possible extensions of such a facility are towards aerosol science and colloidal plasma research.

Blum, Juergen↗

Slippery Lubricant-Infused Silica Nanoparticulate Film Processing for Anti-Biofouling Applications

Microbial biofilm build-up in water distribution systems can pose a risk to human health and pipe material integrity. The impact is more devastating in space stations and to astronauts due to the isolation from necessary replacement parts and medical resources. As a result, there is a need for coatings to be implemented onto the inner region of the pipe to minimize the adherence and growth of biofilms. Lubricant-infused surfaces has been one such interesting material for anti-biofouling applications in which their slippery property promotes repellence to many liquids and thus prevents bacterial adherence. Textured and porous films are suitable substrate candidates to infuse and contain the lubricant. However, there is little investigation in utilizing a nanoporous thin film as the substrate material for lubricant infusion. A nanoporous film has high porosity within the structure which can promote greater lubricant infusion and retention. The implementation as a thin film structure aids to reduce material consumption and cost. In our study, we utilized a well-studied nanoporous thin film fabricated via layer-by-layer assembly of polycations and colloid silica and calcination for greater stability. The film was further functionalized to promote fluorinated groups upon the surface and pores of the film, which then could interact with a fluorinated lubricant. The pristine nanoporous film was characterized to determine its morphology, thickness, wettability, and porosity. The lubricant-infused film was then tested for its lubricant layer stability upon various washing conditions and its performance against bacterial biofilm adherence as a result of its slippery and thus anti-biofouling property.

biofilm↗

Biogeochemical Activity of Siderophilic Cyanobacteria: Implications for Paleobiogeochemistry

Understanding the patterns of iron oxidation by cyanobacteria (CB) has tremendous importance for paleobiogeochemistry, since cyanobacteria are presumed to have been involved in the global oxidation of ferrous iron during the Precambrian (Cloud, 1973). B.K. Pierson (1999, 2000) first proposed to study iron deposition in iron-depositing hot springs (ID HS) as a model for Precambrian Fe(2+) oxidation. However, neither the iron-dependent physiology of individual species of CB inhabiting iron-depositing hot springs nor their interactions with minerals enriched with iron have been examined thoroughly. Such study could shed light on ancient iron turnover. Cyanobacterial species isolated from ID HS demonstrate elevated tolerance to colloidal Fe(3+) (= 1 mM), while a concentration of 0.4 mM proved toxic for mesophilic Synechocystis PCC 6803. Isolates from ID HS require 0.4-0.6 mM Fe3+ for maximal growth while the iron requirement for Synechocystis is approximately one order of magnitude lower. We have also demonstrated that thick polysaccharide sheaths around cells of CB isolated from ID HS serve as repositories for precipitated iron. The growth of the mesophilic cyanobacteria Phromidium aa in iron-saturated (0.6 mM) DH medium did not lead to iron precipitation on its filament surfaces. However, a 14.3 fil.2 culture, isolated from an ID HS and incubated under the same conditions, was covered with dense layer of precipitated iron. Our results, taken together with Pierson s data concerning the ability of Fe2+ to stimulate photosynthesis in natural CB mats in ID HS, suggest that CB inhabiting ID HS may constitute a new group of the extremophiles - siderophilic CB. Our recent experiments have revealed for the first time that CB isolates from ID HS are also capable of biodeterioration - the etching of minerals, in particular glasses enriched with Fe, Al, Ti, O, and Si. Thus, Precambrian siderophilic cyanobacteria and their predecessors could have been involved not only in iron deposition but also in the global release of elements. The ability of siderophilic CB to participate in iron turnover make them appropriate candidates for biotechnological processes.

Brown, Igor I.↗

Physics of Hard Sphere Experiment: Scattering, Rheology and Microscopy Study of Colloidal Particles

The Physics of Hard Sphere Experiment has two incarnations: the first as a scattering and rheology experiment on STS-83 and STS-94 and the second as a microscopy experiment to be performed in the future on LMM on the space station. Here we describe some of the quantitative and qualitative results from previous flights on the dynamics of crystallization in microgravity and especially the observed interaction of growing crystallites in the coexistance regime. To clarify rheological measurements we also present ground based experiments on the low shear rate viscosity and diffusion coefficient of several hard sphere experiments at high volume fraction. We also show how these experiments will be performed with confocal microscopy and laser tweezers in our lab and as preparation for the phAse II experiments on LMM. One of the main aims of the microscopy study will be the control of colloidal samples using an array of applied fields with an eye toward colloidal architectures. Temperature gradients, electric field gradients, laser tweezers and a variety of switchable imposed surface patterns are used toward this control.

Z D Cheng↗

Particle migration in suspensions by thermocapillary or electrophoretic motion

Two problems of similar mathematical structure are presented: the thermocapillary motion of bubbles and the electrophoresis of colloidal particles. For both problems, it is shown that in a cloud of n particles surrounded by an infinite expanse of fluid, the velocity of each sphere under creeping flow conditions is equal to the velocity of an isolated particle, unchanged by interactions between the particles. However, when the cloud fills a container, conservation of mass shows that this result cannot continue to hold, and the average translational velocity must be calculated subject to a constraint on the mass flux. It is concluded that the average thermocapillary or electrophoretic translational velocity of a particle in the cloud is related to the effective conductivity of the cloud over the whole range of particle volume fractions, provided that the particles are identical, non-conducting and, for the thermocapillary problem, inviscid.

Acrivos, A.↗

Topological Control of Polystyrene-Silica Core-Shell Microspheres

Controllable surface morphology is requisite across a gamut of processes, industries, and applications. The surface morphology of silica-coated polystyrene microspheres was controllably modified to enable generation of both smooth and bumpy, or raspberry-like, surfaces. Although smooth and raspberry-like silica shells on polystyrene templates have been demonstrated extensively, the method described here used readily available materials to produce radical changes in surface morphology from a single polystyrene template coated in silica through a facile sol-gel reaction processes. Silica shells were deposited via a sol-gel process (using tetraethyl orthosilicate as the silica precursor) onto 1 to 2 m diameter anionic polystyrene spheres, fabricated by emulsifier-free polymerization. By varying of the concentration of silica precursor and ammonium hydroxide catalyst and altering the electrostatic surface interactions via addition of a cationic polymeric brush, an array of surface topologies was generated. The resulting silica shells ranged from 100 to 200 nm in thickness, as measured by calcination of the polystyrene template. Empirical relations between reaction conditions and the resulting silica colloid diameter were utilized to understand the resultant silica shell topology. These results may serve as a guide to generate a versatile platform for research in the multitude of applications where polystyrene-silica core-shell particles are utilized.

Zane A. Grady↗

Metal colloids and semiconductor quantum dots: Linear and nonlinear optical properties

One aspect of this project involves a collaborative effort with the Solid State Division of ORNL. The thrust behind this research is to develop ion implantion for synthesizing novel materials (quantum dots wires and wells, and metal colloids) for applications in all optical switching devices, up conversion, and the synthesis of novel refractory materials. In general the host material is typically a glass such as optical grade silica. The ions of interest are Au, Ag, Cd, Se, In, P, Sb, Ga and As. An emphasis is placed on host guest interactions between the matrix and the implanted ion and how the matrix effects and implantation parameters can be used to obtain designer level optical devices tailored for specific applications. The specific materials of interest are: CdSe, CdTe, InAs, GaAs, InP, GaP, InSb, GaSb and InGaAs. A second aspect of this research program involves using porous glass (25-200 A) for fabricating materials of finite size. In this part of the program, we are particularly interested in characterizing the thermodynamic and optical properties of these non-composite materials. We also address how phase diagram of the confined material is altered by the interfacial properties between the confined material and the pore wall.

Henderson, D. O.↗

Nature of the Surface and Its Effect on Solid-state Interactions

An important aspect of the friction and wear of solids is the nature and the mechanical behavior of the surface films. A description of the mechanical, physical, and chemical behavior of surface films is achieved by an investigation of boundary lubrication. Two major points are demonstrated. First, the sliding of two solid surfaces under boundary lubricating conditions creates third bodies in the interface. Second, the nature and the evolution of the interface are dictated by the colloidal behavior of the products generated. To illustrate these two propositions, some recent work is presented.

Georges, J. M.↗

The Effects of Ground and Space Processing on the Properties of Organic, Polymeric, and Colloidal Materials

In recent years, a great deal of interest has been directed toward the use of organic materials in the development of high-efficiency optoelectronic and phototonic devices. There is a myriad of possibilities among organic materials which allow flexibility in the design of unique structures with a variety of functional groups. The use of nonlinear optical (NLO) organic materials as thin film wave-guides allows full exploitation of their desirable qualifies by permitting long interaction lengths and large susceptibilities allowing modest power input. There are several methods in use to prepare thin films such as Langmuir-Blodgett (LB) and self-assembly techniques, vapor deposition, growth from sheared solution or melt, and melt growth between glass plates. Organic-based materials have many features that make them desirable for use in optical devices, such as high second-and third-order nonlinearity, flexibility of molecular design, and damage resistance to optical radiation. However, their use in devices has been hindered by processing difficulties for crystals and thin films. We discuss the potential role of microgravity processing of a few organic and polymeric materials. It is of interest to note how materials with second-and third-order NLO behavior may be improved in a diffusion-limited environment and ways in which convection may be detrimental to these materials. We focus our discussion on third-order materials for all-optical switching, and second-order materials for frequency conversion and electrooptics. The goal of minimizing optical loss obviously depends on processing methods. For solution-based processes, such as solution crystal growth and solution photopolymerization, it is well known that thermal and solutal density gradients can initiate buoyancy-driven convection. Resultant fluid flows can affect transport of material to and from growth interfaces and become manifest in the morphology and homogeneity of the growing film or crystal. Likewise, buoyancy-driven convection can hinder production of defect-free, high-quality crystals or films during crystal and film growth by vapor deposition.

Frazier, Donald O.↗

Surface Plasmon Resonance Evaluation of Colloidal Metal Aerogel Filters

We have fabricated aerogels containing gold, silver, and platinum nanoparticles for gas catalysis applications. By applying the concept of an average or effective dielectric constant to the heterogeneous interlayer surrounding each particle, we extend the technique of immersion spectroscopy to porous or heterogeneous media. Specifically, we apply the predominant effective medium theories for the determination of the average fractional composition of each component in this inhomogeneous layer. Hence, the surface area of metal available for catalytic gas reaction is determined. The technique is satisfactory for statistically random metal particle distributions but needs further modification for aggregated or surfactant modified systems. Additionally, the kinetics suggest that collective particle interactions in coagulated clusters are perturbed during silica gelation resulting in a change in the aggregate geometry.

Smith, David D.↗