Lifetime-encoded materials are particularly attractive as optical tags, however examples are rare and hindered in practical application by complex interrogation methods. Here, we demonstrate a design strategy towards multiplexed, lifetime-encoded tags via engineering intermetallic energy transfer in a family of heterometallic rare-earth metal-organic frameworks (MOFs). The MOFs are derived from a combination of a high-energy donor (Eu), a low-energy acceptor (Yb) and an optically inactive ion (Gd) with the 1,2,4,5 tetrakis(4-carboxyphenyl) benzene (TCPB) organic linker. Precise manipulation of the luminescence decay dynamics over a wide microsecond regime is achieved via control over metal distribution in these systems. Demonstration of this platform’s relevance as a tag is attained via a dynamic double encoding method that uses the braille alphabet, and by incorporation into photocurable inks patterned on glass and interrogated via digital high-speed imaging. This study reveals true orthogonality in encoding using independently variable lifetime and composition, and highlights the utility of this design strategy, combining facile synthesis and interrogation with complex optical properties.
The increasingly large payloads of Unmanned Aircraft Systems (UASs) are exponentially increasing the threat to the nuclear enterprise. Current mitigation using RF interference is effective, but not feasible for fully autonomous systems and is prohibited in many areas. A new approach to UAS threat mitigation is needed that does not create radio interference but is effective against any type of vehicle. At the present time there is no commercial counter-UAS system that directly assaults the mems gyros and accelerometers in the Inertial Measurement Unit on the aircraft. But lab testing has revealed resonances in some IMUs that make them susceptible to moderate amplitude acoustic monotones. Sandia's energetic materials facility has enabled a quick and thorough exploration of UAS vulnerability to directed acoustic energy by using intense acoustic impulses to destabilize or down a UAS. We have: 1) detonated/deflagrated explosive charges of various sizes; 2) accurately measured impulse pressure and pulse duration; 3) determined what magnitude of acoustic insult to the IMU disrupts flight and for how long and; 4) determined if the air blast/shock wave on aircraft/propellers disrupts flight.
The increasingly large payloads of Unmanned Aircraft Systems (UASs) are exponentially increasing the threat to the nuclear enterprise. Current mitigation using RF interference is effective, but not feasible for fully autonomous systems and is prohibited in many areas. A new approach to UAS threat mitigation is needed that does not create radio interference but is effective against any type of vehicle. At the present time there is no commercial counter-UAS system that directly assaults the mems gyros and accelerometers in the Inertial Measurement Unit on the aircraft. But lab testing has revealed resonances in some IMUs that make them susceptible to moderate amplitude acoustic monotones. Sandia's energetic materials facility has enabled a quick and thorough exploration of UAS vulnerability to directed acoustic energy by using intense acoustic impulses to destabilize or down a UAS. We have: 1) detonated/deflagrated explosive charges of various sizes; 2) accurately measured impulse pressure and pulse duration; 3) determined what magnitude of acoustic insult to the IMU disrupts flight and for how long and; 4) determined if the air blast/shock wave on aircraft/propellers disrupts flight.
In recent years a rich variety of emergent phenomena have been observed when suspensions of magnetic particles are subjected to alternating magnetic fields. These particle assemblies often exhibit vigorous dynamics due to the injection of energy from the field. These assemblies include surface and interface phenomena, such as highly organized, segmented "snakes" that can be induced to swim by structural symmetry breaking, and "asters" and "anti-asters," particle assemblies that can be manipulated to capture and transport cargo. In bulk suspensions of magnetic platelets subjected to multiaxial alternating fields, advection lattices and even vortex lattices have been created, and a variety of biomimetic dynamics-serpents, bees and amoebas-have been discovered in magnetic fluids suspended in an immiscible liquid. In this paper several new driven phases are presented, including flying chevrons, dense spinning clusters, filaments, and examples of phase coexistence in driven phases. These observations broaden the growing field of driven magnetic suspensions and present new challenges to those interested in simulating the dynamics of these complex systems.
The bearings used in energy storage flywheels dissipate a significant amount of energy and can fail catastrophically. Magnetic bearings would both reduce energy dissipation and increase flywheel reliability. The component of magnetic bearing that creates lift is a magnetically soft material embedded into a rebate cut into top of the inner annulus of the flywheel. Because the flywheels stretch about 1% as they spin up, this magnetic material must also stretch and be more compliant than the flywheel itself, so it does not part from the flywheel during spin up. At the same time, the material needs to be sufficiently stiff that it does not significantly deform in the rebate and must have a sufficiently large magnetic permeability and saturation magnetization to provide the required lift. It must also have high electrical resistivity to prevent heating due to eddy currents. In this paper we investigate whether adequately magnetic, mechanically stiff composites that have the tensile elasticity, high electrical resistivity, permeability and saturation magnetism required for flywheel lift magnet applications can be fabricated. We find the best composites are those comprised of bidisperse Fe particles in the resin G/Flex 650. The primary limiting factor of such materials is the fatigue resistance to tensile strain.
We have recently reported that two classes of time-dependent triaxial magnetic fields can induce vorticity in magnetic particle suspensions. The first class-symmetry-breaking fields-is comprised of two ac components and one dc component. The second class-rational triad fields-is comprised of three ac components. In both cases deterministic vorticity occurs when the ratios of the field frequencies form rational numbers. A strange aspect of these fields is that they produce fluid vorticity without generally having a circulating field vector, such as would occur in a rotating field. It has been shown, however, that the symmetry of the field trajectory, considered jointly with that of the converse field, allows vorticity to occur around one particular field axis. This axis might be any of the field components, and is determined by the relative frequencies of the field components. However, the symmetry theories give absolutely no insight into why vorticity should occur. In this paper we propose a particle-based model of vorticity in these driven fluids. This model proposes that particles form volatile chains that follow, but lag behind, the dynamic field vector. This model is consistent with the predictions of symmetry theory and gives reasonable agreement with previously reported torque density measurements for a variety of triaxial fields.
We report on the thermodynamic properties of binary compound mixtures of model groups II-VI semiconductors. We use the recently introduced Stillinger-Weber Hamiltonian to model binary mixtures of CdTe and CdSe. We use molecular dynamics simulations to calculate the volume and enthalpy of mixing as a function of mole fraction. The lattice parameter of the mixture closely follows Vegard's law: a linear relation. This implies that the excess volume is a cubic function of mole fraction. A connection is made with hard sphere models of mixed fcc and zincblende structures. The potential energy exhibits a positive deviation from ideal soluton behaviour; the excess enthalpy is nearly independent of temperatures studied (300 and 533 K) and is well described by a simple cubic function of the mole fraction. Using a regular solution approach (combining non-ideal behaviour for the enthalpy with ideal solution behaviour for the entropy of mixing), we arrive at the Gibbs free energy of the mixture. The Gibbs free energy results indicate that the CdTe and CdSe mixtures exhibit phase separation. The upper consolute temperature is found to be 335 K. Finally, we provide the surface energy as a function of composition. It roughly follows ideal solution theory, but with a negative deviation (negative excess surface energy). This indicates that alloying increases the stability, even for nano-particles.
It has recently been reported that two types of triaxial electric or magnetic fields can drive vorticity in dielectric or magnetic particle suspensions, respectively. The first type - symmetry-breaking rational fields - consists of three mutually orthogonal fields, two alternating and one dc, and the second type - rational triads - consists of three mutually orthogonal alternating fields. In each case it can be shown through experiment and theory that the fluid vorticity vector is parallel to one of the three field components. For any given set of field frequencies this axis is invariant, but the sign and magnitude of the vorticity (at constant field strength) can be controlled by the phase angles of the alternating components and, at least for some symmetry-breaking rational fields, the direction of the dc field. In short, the locus of possible vorticity vectors is a 1-d set that is symmetric about zero and is along a field direction. In this paper we show that continuous, 3-d control of the vorticity vector is possible by progressively transitioning the field symmetry by applying a dc bias along one of the principal axes. Such biased rational triads are a combination of symmetry-breaking rational fields and rational triads. A surprising aspect of these transitions is that the locus of possible vorticity vectors for any given field bias is extremely complex, encompassing all three spatial dimensions. As a result, the evolution of a vorticity vector as the dc bias is increased is complex, with large components occurring along unexpected directions. More remarkable are the elaborate vorticity vector orbits that occur when one or more of the field frequencies are detuned. These orbits provide the basis for highly effective mixing strategies wherein the vorticity axis periodically explores a range of orientations and magnitudes.
Reliable methods for tin whisker mitigation are needed for applications that utilize tin-plated commercial components. Tin can grow whiskers that can lead to electrical shorting, possibly causing critical systems to fail catastrophically. The mechanisms of tin whisker growth are unclear and this makes prediction of the lifetimes of critical components uncertain. The development of robust methods for tin whisker mitigation is currently the best approach to eliminating the risk of shorting. Current mitigation methods are based on unfilled polymer coatings that are not impenetrable to tin whiskers. In this paper we report tin whisker mitigation results for several filled polymer coatings. The whisker-penetration resistance of the coatings was evaluated at elevated temperature and high humidity and under temperature cycling conditions. The composite coatings comprised Ni and MgF2-coated Al/Ni/Al platelets in epoxy resin or silicone rubber. In addition to improved whisker mitigation, these platelet composites have enhanced thermal conductivity and dielectric constant compared with unfilled polymers.
II-VI quantum dots, such as CdSe and CdTe, are attractive as downconversion materials for solid-state lighting, because of their narrow linewidth, tunable emission. However, for these materials to have acceptable quantum yields (QYs) requires that they be coated with a II-VI shell material whose valence band offset serves to confine the hole to the core. Confinement prevents the hole from accessing surface traps that lead to nonradiative decay of the exciton. Examples of such hole-confined core/shell QDs include CdTe/CdSe and CdSe/CdS. Unfortunately, the shell can also cause problems due to lattice mismatch, which ranges from 4-6% for systems of interest. This lattice mismatch can create significant interface energies at the heterojunction and places the core under radial compression and the shell under tangential tension. At elevated temperatures (~240°C) interfacial diffusion can relax these stresses, as can surface reconstruction, which can expose the core, creating hole traps. But such high temperatures favor the hexagonal Wurtzite structure, which has lower QY than the cubic zinc blende structure, which can be synthesized at lower temperatures, ~140°C. In the absence of alloying the core/shell structure can become metastable, or even unstable, if the shell is too thick. This can cause result in an irregular shell or even island growth. But if the shell is too thin thermallyactivated transport of the hole to surface traps can occur. In our LDRD we have developed a fundamental atomistic modeling capability, based on Stillinger-Weber and Bond-Order potentials we developed for the entire II-VI class. These pseudo-potentials have enabled us to conduct large-scale atomistic simulations that have led to the computation of phase diagrams of II-VI QDs. These phase diagrams demonstrate that at elevated temperatures the zinc blende phase of CdTe with CdSe grown on it epitaxially becomes thermodynamically unstable due to alloying. This is accompanied by a loss of hole confinement and a severe drop in the QY and emission lifetime, which is confirmed experimentally for the zinc blende core/shell QDs prepared at low temperatures. These QDs have QYs as high as 95%, which makes them very attractive for lighting. Finally, to address strain relaxation in these materials we developed a model for misfit dislocation formation that we have validated through atomistic simulations.
Methods of inducing vigorous noncontact fluid flow are important to technologies involving heat and mass transfer and fluid mixing, since they eliminate the need for moving parts, pipes and seals, all of which compromise system reliability. Unfortunately, traditional noncontact flow methods are few, and have limitations of their own. We have discovered two classes of fields that can induce fluid vorticity without requiring either gravity or a thermal gradient. The first class we call Symmetry-Breaking Rational Fields. These are triaxial fields comprised of three orthogonal components, two ac and one dc. The second class is Rational Triad Fields, which differ in that all three components are alternating. In this report we quantify the induced vorticity for a wide variety of fields and consider symmetry transitions between these field types. These transitions give rise to orbiting vorticity vectors, a technology for non-contact, non-stationary fluid mixing.
We recently reported two methods of inducing vigorous fluid vorticity in magnetic particle suspensions. The first method employs symmetry-breaking rational fields. These fields are comprised of two orthogonal ac components whose frequencies form a rational number and an orthogonal dc field that breaks the symmetry of the biaxial ac field to create the parity required to induce deterministic vorticity. The second method is based on rational triads, which are fields comprised of three orthogonal ac components whose frequency ratios are rational (e.g., 1 : 2 : 3). For each method a symmetry theory has been developed that enables the prediction of the direction and sign of vorticity as functions of the field frequencies and phases. However, this theory has its limitations. It only applies to those particular phase angles that give rise to fields whose Lissajous plots, or principal 2-d projections thereof, have a high degree of symmetry. Nor can symmetry theory provide a measure of the magnitude of the torque density induced by the field. In this paper a functional of the multiaxial magnetic field is proposed that not only is consistent with all of the predictions of the symmetry theories, but also quantifies the torque density. This functional can be applied to fields whose Lissajous plots lack symmetry and can thus be used to predict a variety of effects and trends that cannot be predicted from the symmetry theories. These trends include the dependence of the magnitude of the torque density on the various frequency ratios, the unexpected reversal of flow with increasing dc field amplitude for certain symmetry-breaking fields, and the existence of off-axis vorticity for rational triads, such as 1 : 3 : 5, that do not have the symmetry required to analyze by symmetry theory. Experimental data are given that show the degree to which this functional is successful in predicting observed trends.
In this paper, we show that multiaxial fields can induce time-averaged, noncentrosymmetric interactions between particles having polarization anisotropy, yet the multiaxial field itself does not exert either a force or a torque on an isolated particle. These induced interactions lead to particle assemblies whose energy is strongly dependent on both the translational and orientational degrees of freedom of the system. The situation is similar to a collection of permanent dipoles, but the symmetry of the time-averaged interaction is quite distinct, and the scale of the system energy can be dynamically controlled by the magnitude of the applied multiaxial field. In this paper, the case of polarizable rods is considered in detail, and it is suggested that collections of rods embedded in spheres can be used to create a material with a dynamically tunable magnetic permeability or dielectric permittivity. We report on Monte Carlo simulations performed to investigate the behavior of assemblies of both multiaxial-field induced dipoles and permanent dipoles arranged onto two-dimensional lattices. The ground state of the induced dipoles is an orientational soft mode of aligned dipoles, whereas that of the permanent dipoles is a vortex state.
We report on the strain behavior of compound mixtures of model group II-VI semiconductors. We use the Stillinger-Weber Hamiltonian that we recently introduced, specifically developed to model binary mixtures of group II- VI compounds such as CdTe and CdSe. We employ molecular dynamics simulations to examine the behavior of thin sheets of material, bilayers of CdTe and CdSe. The lattice mismatch between the two compounds leads to a strong bending of the entire sheet, with about a 0.5 to 1° deflection between neighboring planes. To analyze bilayer bending, we introduce a simple onedimensional model and use energy minimization to find the angle of deflection. The analysis is equivalent to a least-squares straight line fit. We consider the effects of bilayers which are asymmetric with respect to the thickness of the CdTe and CdSe parts. From this we learn that the bending can be subdivided into four kinds depending on the compressive/tensile nature of each outer plane of the sheet. We use this approach to directly compare our findings with experimental results on the bending of CdTe/CdSe rods. To reduce the effects of the lattice mismatch we explore diffuse interfaces, where we mix (i.e. alloy) Te and Se, and estimate the strain response.
Noncontact methods of generating strong fluid vorticity are important to problems involving heat and mass transfer, fluid mixing, active wetting, and droplet transport. Furthermore, because zero or even negative shear viscosities can be induced, vorticity can greatly extend the control range of the smart fluids used in magnetorheological devices. In recent work we have shown that a particular class of ac/ac/dc triaxial fields (symmetry-breaking rational fields) can create strong vorticity in magnetic particle suspensions and have presented a theory of the vorticity that is based on the symmetry of the 2-d Lissajous trajectories of the field and its converse. In this paper we demonstrate that there are three countably infinite sets of fully alternating ac/ac/ac triaxial fields whose frequencies form rational triads that have the symmetry required to drive fluid vorticity. The symmetry of the 3-d Lissajous trajectories of the field and its converse can be derived and from this the direction of the vorticity axis can be predicted, as can the dependence of the sign of the vorticity on the phase relations between the three field components. Experimental results are presented that validate the symmetry theory. These discoveries significantly broaden the class of triaxial fields that can be exploited to produce strong noncontact flow.
Recent synthetic advances have made available very monodisperse zincblende CdSe/CdS quantum dots having near-unity photoluminescence quantum yields. Because of the absence of nonradiative decay pathways, accurate values of the radiative lifetimes can be obtained from time-resolved PL measurements. Radiative lifetimes can also be obtained from the Einstein relations, using the static absorption spectra and the relative thermal populations in the angular momentum sublevels. One of the inputs into these calculations is the shell thickness, and it is useful to be able to determine shell thickness from spectroscopic measurements. We use an empirically corrected effective mass model to produce a "map" of exciton wavelength as a function of core size and shell thickness. These calculations use an elastic continuum model and the known lattice and elastic constants to include the e ffect of lattice strain on the band gap energy. The map is in agreement with the known CdSe sizing curve and with the shell thicknesses of zincblende core/shell particles obtained from TEM images. If selenium-sulfur diffusion is included and lattice strain is omitted from the calculation then the resulting map is appropriate for wurtzite CdSe/CdS quantum dots synthesized at high temperatures, and this map is very similar to one previously reported (J. Am. Chem. Soc. 2009, 131, 14299). Radiative lifetimes determined from time-resolved measurements are compared to values obtained from the Einstein relations, and found to be in excellent agreement. For a specific core size (2.64 nm diameter, in the present case), radiative lifetimes are found to decrease with increasing shell thickness. This is similar to the size dependence of one-component CdSe quantum dots and in contrast to the size dependence in type-II quantum dots. (Graph Presented).
In this review we discuss recent research on driving self assembly of magnetic particle suspensions subjected to alternating magnetic fields. The variety of structures and effects that can be induced in such systems is remarkably broad due to the large number of variables involved. The alternating field can be uniaxial, biaxial or triaxial, the particles can be spherical or anisometric, and the suspension can be dispersed throughout a volume or confined to a soft interface. In the simplest case the field drives the static or quasi-static assembly of unusual particle structures, such as sheets, networks and open-cell foams. More complex, emergent collective behaviors evolve in systems that can follow the time-dependent field vector. In these cases energy is continuously injected into the system and striking °ow patterns and structures can arise. In fluid volumes these include the formation of advection and vortex lattices. At air-liquid and liquid-liquid interfaces striking dynamic particle assemblies emerge due to the particle-mediated coupling of the applied field to surface excitations. These out-of-equilibrium interface assemblies exhibit a number of remarkable phenomena, including self-propulsion and surface mixing. In addition to discussing various methods of driven self assembly in magnetic suspensions, some of the remarkable properties of these novel materials are described.
This late-start LDRD explores chemical strategies that will enable sub-micron alignment accuracy of dies and wafers by exploiting the interfacial energies of chemical ligands. We have micropatterned commensurate features, such as 2-d arrays of micron-sized gold lines on the die to be bonded. Each gold line is functionalized with alkanethiol ligands before the die are brought into contact. The ligand interfacial energy is minimized when the lines on the die are brought into registration, due to favorable interactions between the complementary ligand tails. After registration is achieved, standard bonding techniques are used to create precision permanent bonds. We have computed the alignment forces and torque between two surfaces patterned with arrays of lines or square pads to illustrate how best to maximize the tendency to align. We also discuss complex, aperiodic patterns such as rectilinear pad assemblies, concentric circles, and spirals that point the way towards extremely precise alignment.
Field-structured magnetic particle composites are an important new class of materials that have great potential as both sensors and actuators. These materials are synthesized by suspending magnetic particles in a polymeric resin and subjecting these to magnetic fields while the resin polymerizes. If a simple uniaxial magnetic field is used, the particles will form chains, yielding composites whose magnetic susceptibility is enhanced along a single direction. A biaxial magnetic field, comprised of two orthogonal ac fields, forms particle sheets, yielding composites whose magnetic susceptibility is enhanced along two principal directions. A balanced triaxial magnetic field can be used to enhance the susceptibility in all directions, and biased heterodyned triaxial magnetic fields are especially effective for producing composites with a greatly enhanced susceptibility along a single axis. Magnetostriction is quadratic in the susceptibility, so increasing the composite susceptibility is important to developing actuators that function well at modest fields. To investigate magnetostriction in these field-structured composites we have constructed a sensitive, constant-stress apparatus capable of 1 ppm strain resolution. The sample geometry is designed to minimize demagnetizing field effects. With this apparatus we have demonstrated field-structured composites with nearly 10,000 ppm strain.
Field-structured composites (FSCs) were produced by hosting micron-sized gold-coated nickel particles in a pre-polymer and allowing the mixture to cure in a magnetic field environment. The feasibility of controlling a composite's electrical conductivity using feedback control applied to the field coils was investigated. It was discovered that conductivity in FSCs is primarily determined by stresses in the polymer host matrix due to cure shrinkage. Thus, in cases where the structuring field was uniform and unidirectional so as to produce chainlike structures in the composite, no electrical conductivity was measured until well after the structuring field was turned off at the gel point. In situations where complex, rotating fields were used to generate complex, three-dimensional structures in a composite, very small, but measurable, conductivity was observed prior to the gel point. Responsive, sensitive prototype chemical sensors were developed based on this technology with initial tests showing very promising results.
We demonstrate through experiment and simulation that when mono-domain Fe nanoparticles are formed into chains by the application of a magnetic field, the susceptibility of the resulting structure is greatly enhanced (11.4-fold) parallel to the particle chains and is much larger than transverse to the chains. Simulations show that this significant enhancement is expected when the susceptibility of the individual particles approaches 5 in MKS units, and is due to the spontaneous magnetization of individual particle chains, which occurs because of the strong dipolar interactions. This large enhancement is only possible with nanoparticles, because demagnetization fields limit the susceptibility of a spherical multi-domain particle to 3 (MKS). Experimental confirmation of the large susceptibility enhancement is presented, and both the enhancement and the susceptibility anisotropy are found to agree with simulation. The specific susceptibility of the nanocomposite is 54 (MKS), which exceeds the highest value we have obtained for field-structured composites of multi-domain particles by a factor of four.
We describe the synthesis of highly magnetic iron nanoparticles using a novel surfactant, a {beta}-diketone. We have produced 6 nm iron nanoparticles with an unusually high saturation magnetization of more than 80% the value of bulk iron. Additionally, we measured a particle susceptibility of 14 (MKS units), which is far above the value possible for micron-scale spherical particles. These properties will allow for formation of composites that can be highly structured by magnetic fields.
We report on the use of triaxial magnetic fields to create a variety of isotropic and anisotropic magnetic particle/polymer composites with significantly enhanced magnetic susceptibilities. A triaxial field is a superposition of three orthogonal ac magnetic fields, each generated by a Helmholtz coil in series resonance with a tunable capacitor bank. Field frequencies are in the range of 150-400 Hz. Because both the field amplitudes and frequencies can be varied, a rich variety of structures can be created. Perhaps the most unusual effects occur when either two or three of the field components are heterodyned to give beat frequencies on the order of 1 Hz. This leads to a striking particle dynamics that evolves into surprising structures during resin gelation. These structures are found to have perhaps the highest susceptibility that a particle composite can have. The susceptibility anisotropy of these composites can be controlled over a wide range by judicious adjustment of the relative field amplitudes. These experimental data are supported by large-scale Brownian dynamics simulations of the complex many-body interactions that occur in triaxial magnetic fields. These simulations show that athermal three-dimensional field heterodyning leads to structures with a susceptibility that is as high as that achieved with thermal annealing. Thus with coherent particle motions we can achieve magnetostatic energies that are quite close to the ground state.
We have used a nonionic inverse micelle synthesis technique to form nanoclusters of platinum and palladium. These nanoclusters can be rendered hydrophobic or hydrophilic by the appropriate choice of capping ligand. Unlike Au nanoclusters, Pt nanoclusters show great stability with thiol ligands in aqueous media. Alkane thiols, with alkane chains ranging from C6 to C18, were used as hydrophobic ligands, and with some of these we were able to form two-dimensional and/or three-dimensional superlattices of Pt nanoclusters as small as 2.7 nm in diameter. Image processing techniques were developed to reliably extract from transmission electron micrographs (TEMs) the particle size distribution, and information about the superlattice domains and their boundaries. The latter permits us to compute the intradomain vector pair correlation function of the particle centers, from which we can accurately determine the lattice spacing and the coherent domain size. From these data the gap between the particles in the coherent domains can be determined as a function of the thiol chain length. It is found that as the thiol chain length increases, the interparticle gaps increase more slowly than the measured hydrodynamic radius of the functionalized nanoclusters in solution, possibly indicating thiol chain interdigitation in the superlattices.
Steady and oscillatory shear 3-D simulations of electro- and magnetorheology in uniaxial and biaxial fields are presented, and compared to the predictions of the chain model. These large scale simulations are three dimensional, and include the effect of Brownian motion. In the absence of thermal fluctuations, the expected shear thinning viscosity is observed in steady shear, and a striped phase is seen to rapidly form in a uniaxial field, with a shear slip zone in each sheet. However, as the influence of Brownian motion increases, the fluid stress decreases, especially at lower Mason numbers, and the striped phase eventually disappears, even when the fluid stress is still high. In a biaxial field, an opposite trend is seen, where Brownian motion decreases the stress most significantly at higher Mason numbers. To account for the uniaxial steady shear data we propose a microscopic chain model of the role played by thermal fluctuations on the rheology of ER and MR fluids that delineates the regimes where an applied field can impact the fluid viscosity, and gives an analytical prediction for the thermal effect. In oscillatory shear, a striped phase again appears in a uniaxial field, at strain amplitudes greater than ∼0.15, and the presence of a shear slip zone creates strong stress nonlinearities at low strain amplitudes. In a biaxial field, a shear slip zone is not created, and so the stress nonlinearities develop only at expected strain amplitudes. The nonlinear dynamics of these systems is shown to be in good agreement with the Kinetic Chain Model.
Three dimensional steady shear simulations of electrorheology (ER) and magnetorheology (MR) in a uniaxial field are presented and included the effects of Brownian motion. The shear thinning viscosity was observed in the absence of thermal fluctuations. The fluid stress decreased, especially at low Mason numbers, as the influence of Brownian motion increased. A microscopic chain model of the role played by thermal fluctuations on the rheology of ER and MR fluids was proposed.
The authors report high pressure liquid chromatography, (HPLC), and transmission electron microscopy, (TEM), studies of the size distributions of nanosize gold clusters dispersed in organic solvents. These metal clusters are synthesized in inverse micelles at room temperature and those investigated range in diameter from 1--10 nm. HPLC is sensitive enough to discern changes in hydrodynamic volume corresponding to only 2 carbon atoms of the passivating agent or metal core size changes of less than 4 {angstrom}. The authors have determined for the first time how the total cluster volume (metal core + passivating organic shell) changes with the size of the passivating agent.
The authors have investigated the formation of 2-D and 3-D superlattices of Au nanoclusters synthesized in nonionic inverse micelles, and capped with alkyl thiol ligands, with alkane chains ranging from C{sub 6} to C1{sub 18}. The thiols are found to play a significant role in the ripening of these nanoclusters, and in the formation of superlattices. Image processing techniques were developed to reliably extract from transmission electron micrographs (TEMs) the particle size distribution, and information about the superlattice domains and their boundaries. The latter permits one to compute the intradomain vector pair correlation function, from which one can accurately determine the lattice spacing and the coherent domain size. From these data the gap between the particles in the coherent domains can be determined as a function of the thiol chain length. It is found that as the thiol chain length increases, the nanoclusters become more polydisperse and larger, and the gaps between particles within superlattice domains increases. Annealing studies at elevated temperatures confirm nanocluster ripening. Finally, the effect of the particle gaps on physical properties is illustrated by computing the effective dielectric constant, and it is shown that the gap size now accessible in superlattices is rather large for dielectric applications.
We have discovered that small polyols are reasonably effective at stabilizing colloidal silica against aggregation, even under the conditions of high pH and salt concentration. Both quasielastic and elastic light scattering were used to show that these polyols dramatically decrease the aggregation rate of the suspension, changing the growth kinetics from diffusion-limited cluster-cluster aggregation to reaction-limited cluster-cluster aggregation. These polyols maybe useful in the treatment of tank wastes at the Hanford site.
Composites of carbon black particles in polyethylene are known to exhibit an unusually rapid increase in resistivity as the applied field is increased, making this material useful in automatically resettable fuses. In this application the composite is in series with the circuit it is protecting: at low applied voltages this circuit is the load, but at high applied voltages the composite becomes the load, limiting the current to the circuit. We present a simple model of this behavior in terms of a network of nonlinear conductors. Each conductor has a conductance that depends on its instantaneous Joule heating. It is shown that in the fusing regime, where the current through the composite decreases with increasing voltage, an plate-like dissipation instability develops normal to the applied field. Experimental evidence of this phenomena is described.
Magnetic field-structured-composites (FSCs) are made by structuring magnetic particle suspensions in uniaxial or biaxial (e.g. rotating) magnetic fields, while polymerizing the suspending resin. A uniaxial field produces chain-like particle structures, and a biaxial field produces sheet-like particle structures. In either case, these anisotropic structures affect the measured magnetic hysteresis loops, with the magnetic remanence and susceptibility increased significantly along the axis of the structuring field, and decreased slightly orthogonal to the structuring field, relative to the unstructured particle composite. The coercivity is essentially unaffected by structuring. We present data for FSCs of magnetically soft particles, and demonstrate that the altered magnetism can be accounted for by considering the large local fields that occur in FSCs. FSCS of magnetically hard particles show unexpectedly large anisotropies in the remanence, and this is due to the local field effects in combination with the large crystalline anisotropy of this material.
The electrostriction of composites consisting of dielectric particles embedded in a gel or elastomer is discussed. It is shown that when these particles are organized by a uniaxial field before gelation, the resulting field-structured composites are expected to exhibit enhanced electrostriction in a uniform field applied along the same axis as the structuring field. The associated stresses might be large enough to form the basis of a polymer-based fast artificial muscle.
In this report the authors describe the methods they have developed for producing stable periodic mesoporous silica gels, thin films of mesoporous silica for sensor applications, a route to nonaqueous synthesis, and the use of various additives in controlling the pore size and structure of these materials. Mesoporous silica is formed by templating silica precursors around micelles of cationic quaternary ammonium surfactants. During the synthesis these micelles undergo a phase transition to a hexagonal, lamellar or cubic liquid crystalline state, thus imposing periodic order on the amorphous silica which occupies the interface of the hydrophilic cationic headgroups of the surfactants. The product of the bulk wet synthesis is a gel composed of micron size silica/surfactant particles, each of which consists of one or more crystalline domains of silica condensed around the surfactant template. The wet gel can then be washed and pyrolyzed to remove the surfactant template, yielding the periodic mesoporous silica product.
Nanostructured materials can be synthesized by utilizing the domain growth that accompanies first-order phase separation. Structural control can be achieved by appropriately selecting the quench depth and the quench time, but in order to do this in a mindful fashion one must understand the kinetics of domain growth. The authors have completed detailed light scattering studies of the evolution of structure in both temperature- and field-quenched phase transitions in two and three dimensional systems. They have studied these systems in the quiescent state and in shear and have developed theoretical models that account for the experimental results.
We have conducted a real time, two-dimensional light scattering study of the nonlinear dynamics of field-induced structures in an electrorheological fluid subjected to oscillatory shear. We have developed a kinetic chain model of the observed dynamics by considering the response of a fragmenting/aggregating particle chain to the prevailing hydrodynamic and electrostatic forces. This structural theory is then used to describe the nonlinear rheology of ER fluids.
The viscous response of electrorheological fluids is usually manipulated through the use of DC or uniaxial AC electric fields. The result is that fibrillated structures parallel to the field form in a quiescent fluid; the distortion of such structures in a flow determines the enhanced viscous response, at least at low and moderate flow rates. We have conducted preliminary studies of electrorheological response in a different field configurations rotating electric field. With respect to the uniaxial AC case. there are two new developments in this type of field. The structures formed are disk-like, in the plane of the rotating field. Furthermore, the structures rotate either with or against the field, depending on the dielectric or conductivity contrast with the surrounding fluid.
Electroheological suspensions typically contain particles of approximately one {mu}m in diameter. Thus light-scattering offers a natural method of probing the microstructure of these suspensions. We report the development of an index matched single-scattering fluid, as well a slight-scattering studies of this fluid in both a quiescent and sheared regime. In the first case, the results are in agreement with a phenomenological theory of coarsening based on thermal fluctuations. In the second case, they agree with an ``independent droplet`` model of the suspensions structure under shear.
