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.
The use of triaxial magnetic fields to create a variety of isotropic and anisotropic magnetic particle/polymer composites with significantly enhanced magnetic susceptibilities was analyzed. It was shown that a rich variety of structures can be created because both the field amplitudes and frequencies can be varied. It was found that the susceptibility anisotropy of these composites can be controlled over a wide range by judicious adjustment of the relative field amplitudes. The results show that with coherent particle motions, magnetostatic energies that are quite close to the ground state can be achieved.
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 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.
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.