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"Electrostructural Phase Changes" In Charged Particulate Clouds: Planetary and Astrophysical Implications

There is empirical evidence that freely-suspended triboelectrostatically charged particulate clouds of dielectric materials undergo rapid conversion from (nominally) monodispersed "aerosols" to a system of well-defined grain aggregates after grain motion or fluid turbulence ceases within the cloud. In United States Microgravity Laboratory Space Shuttle experiments USML-1 and USML-2, it was found that ballistically-energized grain dispersions would rapidly convert into populations of filamentary aggregates after natural fluid (air) damping of grain motion. Unless continuously disrupted mechanically, it was impossible to maintain a non-aggregated state for the grain clouds of sand-size materials. Similarly, ground- based experiments with very fine dust-size material produced the same results: rapid, impulsive "collapse" of the dispersed grains into well-defined filamentary structures. In both ground-based and microgravity experiments, the chains or filaments were created by long-range dipole electrostatic forces and dipole-induced dielectric interactions, not by monopole interactions. Maintenance of the structures was assisted by short-range static boundary adhesion forces and van der Waals interactions. When the aggregate containers in the USML experiments were disturbed after aggregate formation, the quiescently disposed filaments would rearrange themselves into fractal bundles and tighter clusters as a result of enforced encounters with one another. The long-range dipole interactions that bring the grains together into aggregates are a product of randomly-distributed monopole charges on the grain surfaces. In computer simulations, it has been shown that when the force vectors of all the random charges (of both sign) on a grain are resolved mathematically by assuming Coulombic interaction between them, the net result is a dipole moment on individual grains, even though the grains are electrically neutral insofar as there is no predominance, on their surface, of one charge sign over another. The random charges of both sign derive from natural grain-to-grain interactions that produce triboelectrification via charge exchange every time grain surfaces make contact with one another. The conversion from a random distribution of grains (upon which there are randomly distributed charges) into an organization of electrostatically-ordered aggregates, can be regarded (within the framework of granular-material science) as an "electrical or Coulombic phase change" of the particulate cloud. It is not totally dissimilar from the more normal phase-change concept in which, for example, a gas with long free-path-molecules suddenly becomes a solid as a result of structural ordering of the molecules (notably, also the result of electronic forces, albeit at a different scale). In both the gas-to-solid case, and the aerosol-to-aggregate case, the same materials and charges are present before and after the phase change, but their arrangement now has a higher degree of order and a lower-energy configuration. An input of energy into the system is required to reverse the situation. The aggregates in the USML experiments were observed to undergo at least two phase changes as noted above. The point about phase changes, and by implication, the "electrostructural" reorganizations in particulate clouds, is the following: (a) they can occur very rapidly, almost spontaneously, above a critical cloud density, (b) in going from a higher energy state to a lower energy state, they convert to a denser system, (c) energy must be required to reverse the situation, implying that energy is released during the high-to-low energy phase change. In applying this information to natural particulate clouds, some inferences can be made (it is stressed that reference is still to dielectric materials attracted by dipole forces). There are several natural settings to which the USML observations apply, and to which the phase-change implications likewise apply. Dense clouds of triboelectrically-charged, kinetically-energized grains are to be found in volcanic eruptions (particularly on earth), aeolian dust storms (particularly on Mars), meteorite impact ejecta curtains (on all planets), in "immature" debris rings around planets (e.g., that from which our own Moon may have condensed), and in gravitationally collapsing protoplanetary dust/planetesimal debris disks where dielectric granules are being increasingly brought into collisional relationships with one another (increasing both charge exchange and physical proximity). It is noted that in many of these cases, the degree of electrical charging on the grains is likely to be much higher than that in the USML experiments where charging was not enhanced above the "normal", naturally encountered level for the particular materials (quartz, glass, and various silicate minerals). Application of the phase-change concept suggests that volcanic, aeolian, and impact debris clouds may, under certain circumstances, undergo rapid, impulsive, or even catastrophic collapse into a denser state that will lead to rapid precipitation or fall-out of suspended particulates. Although this idea has been suggested previously by the author , the phase change concept possibly permits some new insights into cloud-system behavior. For example, in a protoplanetary debris disk, the work of gravity may suddenly be enhanced by electrostatically driven collapse of the system when materials reach a critical intergranular spacing or grain number density. This might reduce the rate of planet formation by orders of magnitude (considering the ratio of g-forces to electrostatic ones for very small grains in close proximity), and indeed, it might drive the collapse into a system configuration that would perhaps not be created by gravity alone. Additional information is contained in the original.

Marshall, J. R.↗

Gelation in Aerosols; Non-Mean-Field Aggregation and Kinetics

Nature has many examples of systems of particles suspended in a fluid phase; colloids when in a liquid, aerosols when in a gas. These systems are inherently unstable since if the particles can come together, van der Waals forces will keep them together. In this work we studied the aggregation kinetics of particulate systems, most often aerosols. The emphasis of our work was to study dense systems and systems that gel since previous work had not considered these. Our work obtained a number of significant discoveries and results which are reported here.

Sorensen, C. M.↗

Restructuring of Dust Aggregates in the Solar Nebula

We discuss the results of a recent effort to analyze the mechanical stability of dust aggregates with a detailed model of the physical properties of a contact between grains. This model contains both elastic repulsion forces and attractive van der Waals/dipole/metallic forces along with a description of the energy dissipation due to rolling, sliding, and breaking of contacts. We find that (1) aggregates formed from single sized grains via Particle-Cluster-Aggregation remain fluffy, (2) collisions with other aggregates and with large grains may lead to compaction (3) the velocities of small grains and aggregates in the early solar nebula are too small to produce marked compaction as long as the aggregates are small, and (4) internal restructuring of aggregates is a potentially large sink of energy which could enable the sticking of large bodies even at collision velocities of the order of several hundred cm/s.

Dominik, C.↗

Electrostatic Enhancement of Coagulation in Protoplanetary Nebulae

Microgravity experiments suggest that electrostatic forces (overwhelmed by normal Earth gravity) could greatly enhance cohesive strength of preplanetary aggregates. Cohesive forces may be 103 times larger than those for van der Waals adhesion. Additional information is contained in the original extended abstract.

Marshall, J.↗

Computer Modeling of Electrostatic Aggregation of Granular Materials in Planetary and Astrophysical Settings

Electrostatic forces strongly influence the behavior of granular materials in both dispersed (cloud) systems and semi-packed systems. These forces can cause aggregation or dispersion of particles and are important in a variety of astrophysical and planetary settings. There are also many industrial and commercial settings where granular matter and electrostatics become partners for both good and bad. This partnership is important for human exploration on Mars where dust adheres to suits, machines, and habitats. Long-range Coulombic (electrostatic) forces, as opposed to contact-induced dipoles and van der Waals attractions, are generally regarded as resulting from net charge. We have proposed that in addition to net charge interactions, randomly distributed charge carriers on grains will result in a dipole moment regardless of any net charge. If grains are unconfined, or fluidized, they will rotate so that the dipole always induces attraction between grains. Aggregates are readily formed, and Coulombic polarity resulting from the dipole produces end-to-end stacking of grains to form filamentary aggregates. This has been demonstrated in USML experiments on Space Shuttle where microgravity facilitated the unmasking of static forces. It has also been demonstrated in a computer model using grains with charge carriers of both sign. Model results very closely resembled micro-g results with actual sand grains. Further computer modeling of the aggregation process has been conducted to improve our understanding of the aggregation process, and to provide a predictive tool for microgravity experiments slated for Space Station. These experiments will attempt to prove the dipole concept as outlined above. We have considerably enhanced the original computer model: refinements to the algorithm have improved the fidelity of grain behavior during grain contact, special attention has been paid to simulation time steps to enable establishment of a meaningful, quantitative time axis, and calibration of rounding accuracies have been conducted to test cumulative numerical influences in the model. The model has been run for larger grain populations, variable initial cloud densities, and we have introduced random net charging to individual grains, as well as a net charge to the cloud as a whole. The model uses 3 positive and 3 negative charges randomly distributed on each grain, with up to 160 grains contained within various size "boxes" that define the initial number densities in the clouds. Each charge represents localized charged region on a grain, but does not necessarily imply single quantized charge carriers. The Coulomb equations are then allowed to interact for each monopole: dipoles and any higher order charge coupling is a natural product of these "free" interactions over which the modeler exerts no influence. The charges are placed on surfaces of grains at random locations. A series of runs was conducted for neutral grains that had a perfect balance of negative and positive char carriers. Runs were also conducted with grains having additional fractional charges ranging between 0 and 1. By adding fractional charges of one sign, the model created grain populations in which all grains had excess charges the same sign, giving the cloud an overall net charge. This simulates clouds subjected to ionizing radiation (e. protoplanetary debris disk around a protosun), or any other process of charge biasing in a grain population (e.g., volcanic plumes). In another run series, random fractional charges of either sign were added to the grains so th some grains had a slight net positive charge while others had a slight net negative charge. This simulates triboelectrically-charged grain populations in which acquisition of an electron by one surface is at the expense creating a hole elsewhere. This dual sign charging was applied in two ways: in one case the cloud remained neutral by ensuring that all grain excess charges added to zero; in the other case, the cloud was permitted slight net char by not imposing a charge-balance condition. Additional information is contained in the original.

Marshall, J.↗

Statistical crystallography of surface micelle spacing

The aggregation of the recently reported surface micelles of block polyelectrolytes is analyzed using techniques of statistical crystallography. A polygonal lattice (Voronoi mosaic) connects center-to-center points, yielding statistical agreement with crystallographic predictions; Aboav-Weaire's law and Lewis's law are verified. This protocol supplements the standard analysis of surface micelles leading to aggregation number determination and, when compared to numerical simulations, allows further insight into the random partitioning of surface films. In particular, agreement with Lewis's law has been linked to the geometric packing requirements of filling two-dimensional space which compete with (or balance) physical forces such as interfacial tension, electrostatic repulsion, and van der Waals attraction.

Noever, David A.↗

Lack of Evidence for Prenucleation Aggregate Formation in Lysozyme Crystal Growth Solutions

There have been numerous claims of large concentrations of prenucleation aggregates in supersaturated as well as undersaturated lysozyme solutions at high salt concentrations. The presence of these aggregates was derived from measurements of the light or neutron scattering intensity, ultracentrifugation and dialysis behavior, as well as over-simplified crystal growth kinetics considerations. In all these interpretations it has been assumed that lysozyme solutions are either ideal or that protein interactions are independent of salt concentration. Contrary to these presumptions, our static and dynamic light scattering experiments provide evidence that lysozyme forms highly non-ideal, strongly interacting solutions. At low salt concentrations, the scattering intensities fall well below the values expected for an ideal, monomeric solution at the same protein concentration, while diffusivities increase with increasing protein concentration. Upon increase in salt concentration, these trends are eventually reversed. This enhancement in scattering intensity and decrease in diffusivity was widely interpreted as sign of aggregate formation. Yet, a quantitative interpretation of the scattering behavior over the whole salt concentration range can only be given in terms of a transition from net repulsion to net attraction between lysozyme monomers. Increased salt screening of the electrostatic repulsion among the protein macro-ions, together with attractive protein interactions, such as van der Waals, hydrophobic and hydration forces, provide an unambiguous mechanism for the observed transition and a more physical interpretation of the various observations.

Muschol, Martin↗

Semi-Annual Report: October 15, 1961

Investigations are proposed involving an experimental and theoretical program designed to investigate various properties of the structure of helium both in its atomic form and in the aggregates of the liquid and solid states. The key to the possibilities of performing the experiments lies in the relatively weak electric fields existing in liquid and solid helium and the possibility of producing external fields almost comparable with the internal fields. It is proposed to examine a) the melting pressure curve for helium as a function of electric field b) the dielectric constant of helium as a function of pressure and electric field c) in future, the effect of electric fields on the lambda transition. From the results of these experiments one would expect to be able to gather at least corroborative evidence on a) the crystal structure of solid helium on b) the effect of the Van der Waal interaction of the electric polarizability of helium, c) the possibility of producing helium molecules d) the effective volume available to helium atoms in the liquid and possibly e) the effect of particle interactions on the Bose-Einstein condensation.

HELIUM↗

Formation of Ordered Arrays of Proteins on Surfaces

Van der Waals (dispersion) forces contribute to interactions of proteins with other molecules or with surfaces, but because of the structural complexity of protein molecules, the magnitude of these effects is usually estimated based on idealized models of the molecular geometry, e.g., spheres or spheroids. The calculations reported here seek to account for both the geometric irregularity of protein molecules and the material properties of the interacting media. While the latter are found to fall in the generally accepted range, the molecular shape is shown to cause the magnitudes of the interactions to differ significantly from those calculated using idealized models, with important consequences. First, the roughness of the molecular surface leads to much lower average interaction energies for both protein-protein and protein-surface cases relative to calculations in which the protein molecule is approximated as a sphere. These results indicate that a form of steric stabilization may be an important effect in protein solutions. Underlying this behavior is appreciable orientational dependence, one reflection of which is that molecules of complementary shape are found to exhibit very strong attractive dispersion interactions. Although this has been widely discussed previously in the context of molecular recognition processes, the broader implications of these phenomena may also be important at larger molecular separations, e.g., in the dynamics of aggregation, precipitation and crystal growth.

Lenhoff, A. M.↗

Van der Waals Interactions Involving Proteins

Van der Waals (dispersion) forces contribute to interactions of proteins with other molecules or with surfaces, but because of the structural complexity of protein molecules, the magnitude of these effects is usually estimated based on idealized models of the molecular geometry, e.g., spheres or spheroids. The calculations reported here seek to account for both the geometric irregularity of protein molecules and the material properties of the interacting media. Whereas the latter are found to fall in the generally accepted range, the molecular shape is shown to cause the magnitudes of the interactions to differ significantly from those calculated using idealized models. with important consequences. First, the roughness of the molecular surface leads to much lower average interaction energies for both protein-protein and protein-surface cases relative to calculations in which the protein molecule is approximated as a sphere. These results indicate that a form of steric stabilization may be an important effect in protein solutions. Underlying this behavior is appreciable orientational dependence, one reflection of which is that molecules of complementary shape are found to exhibit very strong attractive dispersion interactions. Although this has been widely discussed previously in the context of molecular recognition processes, the broader implications of these phenomena may also be important at larger molecular separations, e.g., in the dynamics of aggregation, precipitation, and crystal growth.

Roth, Charles M.↗