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Assembly of Colloidal Materials Using Bioadhesive Interactions

We have pursued the use of biological crosslinking molecules of several types to make colloidal materials at relatively low volume fraction of colloidal particles. The objective is to make binary alloys of colloidal particles, made of two different colloidal particles coated with complementary biological lock-and-key binding molecules, which assemble due to the biological specificity. The long-term goal is to use low affinity lock-and-key biological interactions, so that the can anneal to form crystalline states. We have used a variety of different surface chemistries in order to make colloidal materials. Our first system involved using selectin-carbohydrate (sialyl-Lewis) interactions; this chemistry is derived from immune system. This chemical interaction is of relatively low affinity, with timescales for dissociation of several seconds. Furthermore, the adhesion mediated by these molecules can be reversed by the chelation of calcium atoms; thus assembled structures can be disassembled reversibly. Our second system employed avidin-biotin chemistry. This well-studied system is of high affinity, and is generally irreversible on a laboratory time-scale. Thus, we would expect selectin-carbohydrate interactions at high molecular density and avidin-biotin interactions to give kinetically-trapped structures; however, at low densities, we would expect significant differences in the structure and dynamics of the two materials, owing to their very different release rates. We have also begun to use a third chemistry - DNA hybridization. By attaching single stranded DNA oligonucleotide chains to beads, we can drive the assembly of colloidal materials by hybridization of complementary DNA chains. It is well known that DNA adenosine-thymine (A-T) and guanine-cytosine (G-C) bases hybridize pairwise with a Gibbs free energy change of 1.7 kcal/mol per base; thus, the energy of the assembly can be modulated by altering the number of complementary bases in the DNA chains. Using these different crosslinking molecules, we have assembled colloidal materials from different-sized colloidal particles, A and B. In the first sets of experiment, we used high densities of adhesion molecules, and 0.96 micron (A) and 5.5 micron (B) diameter particles. The high density of adhesion molecules means that the structures are kinetically trapped in nonequilibrium configurations. The structure of the suspension can be varied by changing the number ratio of the two types of colloidal particles, NA and NB, where A is the smaller particle. With carbohydrate-selectin or avidin-biotin interactions, large NA/NB leads to the formation of colloidal micelles, with the large center B particle surrounded by many smaller A particles. As the ratio NA/NB decreases, the structures become more extended, approaching the formation of macro-Rouse polymers - extended linear chains where A beads are connected with intervening small B linkers.

Hammer, Daniel A.↗

Modeling of Ultrasonically Generated Liquid-Liquid Dispersions During Controlled Directional Solidification

There are innumerable two-component systems in which two very different liquid phases co-exist in equilibrium over a range of temperature and composition, e.g., oil and water, salt fluxes and solders, aluminum and lead. Often it is of practical concern to fabricate a solid component consisting of a uniform dispersion of one phase in the other. Unfortunately, uniform microstructural development during solidification of two immiscible liquids is hampered by inherent, often large, density differences between the phases that lead to severe segregation. Uniformity is also compromised by preferential wetting and coalescence phenomena. It is, however, well known that ultrasonic energy can initiate and maintain a fine liquid-liquid dispersion. The work presented here extends that observation by application of ultrasonic energy to promote uniform phase incorporation during controlled directional solidification. To this end experiments with the transparent organic, immiscible, succinonitrile-glycerol system were conducted and the numerous processing parameters associated with this technique were evaluated in view of optimizing dispersion uniformity. In view of the initial experimental results a model that predicts the dispersed liquid droplet size as a function of material properties, sample geometry, and applied energy has been developed. In the mathematical model we consider the ultrasonic field in an experimental ampoule of length L and diameter D induced by a probe having a vibration frequency of f=2OKhz (circular frequency omega = 2 pi f). The amplitude is adjustable from A=65 to 13Omicrons. The probe tip diameter is d, the liquid has a density of p, in which the speed of sound and surface tension are, respectively, c and sigma. The mathematical model and numerical investigation for the experiments [1] is done using the following assumptions: (i) The droplet size is small in comparison to the sound wave length; (ii) The forces between droplets are neglected (relative concentration is small); (iii) The droplet is stable if the kinetic energy, E(sub K), of the liquid motion due to ultrasonic field influence is less then the binding energy, E(sub S), due to the surface tension (it is easy to show that the surface energy of two droplets resulting from one is larger by about a factor of two.); (iv) The stability limit is characterized by E(sub S) to approx. E(sub K).

Grugel, R. N.↗

X-Ray Photoelectron Spectroscopy

The interaction of photon and the electron goes back to the early part of 19th century emanating from the photo-electric effect depicted by none other than Albert Einstein (Ref 1) described in 1905, and the redistribution of kinetic energy resulting from the interaction of x-ray and solids reported during early part of the century (Ref.2). The spectrum resolutions obtained at that time was not sufficient to observe distinct peaks in spectra for materials. Thus, these phenomena hardly attracted any attention for many years following these discoveries. The modern X-ray Photoelectron Spectroscopy (XPS) has been possible by the extensive and significant contribution from Kai Siegbahn and others (Ref.3, 4) of Uppsala University. Siegbahn developed and employed a high-resolution electron spectrometer that revealed electron peaks in a spectrum emerging from the interaction of x-rays and solids. Eventually, Kai Siegbahn received Nobel Prize in 1981 for his contributions to XPS. Around 1958, shifts in elemental peaks were realized in compounds when the same elements are bound to other but different elements. This discovery resulted in the chemical state identification in various chemicals as well as the oxidation states of atoms in compounds. Because of these useful physical effects, the Uppsala group named XPS with a synonymous name of ESCA (Electron Spectroscopy for Chemical Analysis) used widely today and will be used here alternatively. Therefore, XPS or ESCA not only identifies the element, but also the compound these elements form, from their chemical shifts. Compared to other micro-analytical techniques such as Energy Dispersive (EDS) or Wavelength Dispersive (WDS) techniques, XPS analyzes only few atomic layers present on the surface. This was discovered early in 1966 (Ref. 5). While this has awarded a merit to the analytical technique to analyze very thin layers such as films and coatings, it often analyzes the adsorbed superficial gases and contaminations on a sample introduced to its analytical chamber. This necessitates the surface is cleaned and the underlying material, material of interest, is exposed in a clean environment such that the material of interest is analyzed. The cleaning is accomplished by a scanning ion gun within the analytical chamber of the instrument. Ion gun uses an argon gas and is commonly attached in most modern machines. Reliable and efficient vacuum systems employed in modern machines does not allow adsorbed layers to rebuild after the surface is cleaned. Development of efficient and reliable vacuum pumps over these developmental years is yet another important step in the commercialization of XPS machines. Vacuum levels of better than 10-7 torr are essential to increase the mean free path of electrons released from the sample surface. Thus, modern machines are equipped with high capacity ion, turbo or cryogenic pumps in their analytical chambers. Today, XPS has advanced from an applied physics laboratory to industry for use in quality control as well as analysis of contaminants and has taken a dominant role in microanalysis. Its uniqueness arises from the fact that it is considered non-destructive compared to other common micro-analytical techniques using the electron and ion excitation sources. Polymers and plastics could be analyzed since the binding energies of saturated and unsaturated bonds in atoms could be separated. Extremely thin layers could be analyzed including materials with layered structures. The technique, though did not advance for many years, has now opened a new window for research as well as applications in industry due to its ability to separate and measure the chemical shifts in bound elements. Principles

Panda, Binayak↗

Tetragonal Lysozyme Nucleation and Crystal Growth: The Role of the Solution Phase

Lysozyme, and most particularly the tetragonal form of the protein, has become the default standard protein for use in macromolecule crystal nucleation and growth studies. There is a substantial body of experimental evidence, from this and other laboratories, that strongly suggests this proteins crystal nucleation and growth is by addition of associated species that are preformed by standard reversible concentration-driven self association processes in the bulk solution. The evidence includes high resolution AFM studies of the surface packing and of growth unit size at incorporation, fluorescence resonance energy transfer measurements of intermolecular distances in dilute solution, dialysis kinetics, and modeling of the growth rate data. We have developed a selfassociation model for the proteins crystal nucleation and growth. The model accounts for the obtained crystal symmetry, explains the observed surface structures, and shows the importance of the symmetry obtained by self-association in solution to the process as a whole. Further, it indicates that nucleation and crystal growth are not distinct mechanistically, but identical, with the primary difference being the probability that the particle will continue to grow or dissolve. This model also offers a possible mechanism for fluid flow effects on the growth process and how microgravity may affect it. While a single lysozyme molecule is relatively small (M.W. = 14,400), a structured octamer in the 4(sub 3) helix configuration (the proposed average sized growth unit) would have a M.W. = 115,000 and dimensions of 5.6 x 5.6 x 7.6 nm. Direct AFM measurements of growth unit incorporation indicate that units as wide as 11.2 nm and as long as 11.4 nm commonly attach to the crystal. These measurements were made at approximately saturation conditions, and they reflect the sizes of species that both added or desorbed from the crystal surface. The larger and less isotropic the associated species the more likely that it will be oriented to some degree in a flowing boundary layer, even at the low flow velocities measured about macromolecule crystals. Flow-driven effects resulting in misorientation upon addition to and incorporation into the crystal need only be a small fraction of a percentage to significantly affect the resulting crystal. One Earth, concentration gradient driven flow will maintain a high interfacial concentration, i.e., a high level (essentially that of the bulk solution) of solute association at the interface and higher growth rate. Higher growth rates mean an increased probability that misaligned growth units are trapped by subsequent growth layers before they can be desorbed and try again, or that the desorbing species will be smaller than the adsorbing species. In microgravity the extended diffusive boundary layer will lower the interfacial concentration. This results in a net dissociation of aggregated species that diffuse in from the bulk solution, i.e., smaller associated species, which are more likely able to make multiple attempts to correctly bind, yielding higher quality crystals.

Pusey, Marc L.↗

TRIDENT Drill Validation at Mars and Lunar Analog Field Sites

Drilling on Earth is typically a human-intensive activity. Drilling on other planets is further complicated by the lack of prior local field surveys of their target area, hence blindly drilling into uncertain target rocks. Field conditions on the Moon or Mars are also different than for shallow drilling on Earth: lower temperatures and pressures, less power available, low masses (hence less weight-on-bit). Given the cost of transport from Earth, no drilling muds or working fluids are likely to be available to carry away cuttings. And impact-gardened regolith and dust vary mechanically and texturally from most terrestrial soils. The Regolith and Ice Drill for Exploration of New Terrains (TRIDENT) is a rotary-percussive 1m-class drill from Honeybee Robotics. It is low-power (rotary and percussive actuators are 200 W each) and lightweight (<20 kg) with the maximum weight on bit limited to 200 N. TRIDENT has been manifested for the Volatiles Investigating Polar Exploration Rover (VIPER) and PRIME-1 lunar south pole missions in 2024, has previously been field tested at a hot, dry analog site in the Atacama Desert, and in lunar conditions in thermal vacuum chamber tests. TRIDENT was also part of the 2019 Icebreaker Mars Discovery proposal, as well as in the Mars Life Explorer concept. During ARADS tests, drill control and fault recovery automation software enabled hands-off operations of a rover-mounted TRIDENT drill. TRIDENT Drill Analog Site Validation: Past TRIDENT tests in thermal vacuum (TVAC) chambers targeted containers of manufactured lunar simulants with added volatiles. 2022 TRIDENT ambient testing at NASA Ames drilled into cemented lunar simulant materials. Low cuttings-permeability led to cuttings buildup, and drill choking and binding was observed. The Atacama analog site in ARADS had desiccated unconsolidated sediments that did not challenge the TRIDENT design. However, lunar polar regolith is expected to be diverse and heterogeneous with varying clast sizes, with abundant impactites and perhaps subsurface ice deposits. Neither the simulants nor Atacama testing had completely covered the TRIDENT-targeted field characteristics, motivating further analog tests prior to the planned lunar missions. To gain more insight into the behavior of the TRIDENT hardware in diverse impactites and subsurface ice, and to verify the software automation in that environment, in August 2023 TRIDENT was brought to Haughton Crater, a field analog site in the Canadian Arctic. In September 2023 the same drill was brought to the Bishop Tuff in southern California to verify whether drilling binding behaviors previously seen in lunar simulant testing would be observed in naturally occurring fine-grained massive layers. The ~22 Ma Haughton Crater impact structure is located at 75 ̊22’ N, 89 ̊41’ W, on northwestern Devon Island, Nunavut, Canada. Numerous deposits of pale-grey crater-fill polymictic impact-melt breccia are found within the crater with a typical thickness reaching ~125 m or greater and covering ~60 km -2 . An approximately 600m-thick permafrost layer is also present with ice typically found within 0.5-0.6m of the surface. The volcanic tableland north of Bishop, CA exposes densely welded tuff laid down during the eruption that created the Long Valley Caldera at approximately 0.76 Ma. Extensional faults and the Owens River gorge expose cross-sections across the plateau. The area is viewed as an analog site for Mars features believed to be of pyroclastic origin. Results: Haughton Crater.Drilling tests were conducted 8-13 August 2023 at a previously undisturbed area separated 5-10 m from past years’ Drill Hill test sites (75.4208, -089.7613). In six days, TRIDENT drilled 8 holes to nearly 1 m depth each, totaling 7.80 m. The active layer/ice boundary was at ~67 cm depth, with a total of approximately 2.4 m drilled into ice or ice-cemented impact breccia. During drilling, five drill fault states were observed and successfully recovered. Holes 23-1, 4 and 7 were drilled under manual control, using Honeybee’s Thorax user interface. Holes 23-5, 6, and 8 were drilled with the Ames IBexec automated drilling control software. TRIDENT was observed to have little difficulty in the thawed uncemented impact breccia above the active layer boundary, but required percussion to make slower headway in the ice-cemented breccia. In Hole 23-7 (Fig.1), drilling slowed down in a massive unit just above the active-layer boundary (perhaps a large rock extending into the ice-cementation?), with only 7cm progress made in 27 minutes of high auger torque and constant percussion, leading to a choking fault and then a binding fault. A similar pattern had been observed in TRIDENT Rio Tinto test data from 2017 [6] as well as in the 2022laboratory tests.Bishop Tuff.A team from NASA Ames and the US Geological Survey deployed the same TRIDENT drill to Bishop Sites 1B and 1C (37.4203, -118.4289; 37.4265, -118.4215) on 13-16 September 2023, on the Bishop Tuff plateau. A third drill site was used 17-18 September 2023(37.4598, -118.3667) in an abandoned pumice mine. Four holes (totaling 2.5m depth) were drilled into the fine-grained, meters-thick tuff units at Sites 1B and 1C, and a further two boreholes (totaling 1.98m depth) were made at the pumice site. Drill behavior in the tuff below 10 cm depth was similar to that seen at 65-74 cm depth in Haughton Hole 23-7 (Fig. 1) and that seen in the 2022 lab simulant drilling. Drill safety torque limits were exceeded multiple times resulting in drill stops downhole. These freezes then required external added torques (with a pipe wrench) to resume rotation, to unstick the drill for withdrawal. To prevent this choking and binding behavior we found that more-frequent cuttings removal was necessary, e.g., reducing the “drill bite” size from the nominal 10 cm to 2 cm per bite --bringing the auger up to the surface more frequently, as seen in Bishop Site 1C Hole 2 (Fig.2). This permitted slow progress without drill binding and without external interventions. Conversely, TRIDENT drilling in the more porous pumice target material showed no cuttings buildup issue, and single bites as large as 40 cm were demonstrated. Discussion: We observed that TRIDENT easily penetrated unconsolidated heterogeneous soils (both above the active layer boundary at Haughton and previously in the Atacama). Cemented or consolidated targets that were cuttings-permeable (icy impact breccia, pumice) required more energy applied and percussion. However, in non-cuttings-permeable targets (welded microporous tuff, cemented simulants, boulder) TRIDENT was observed to be prone to excessive cuttings accumulation leading to choking/binding faults and stalling. The wedge cutting bit, used by TRIDENT in field tests and in its flight versions, pulverizes the target rock and creates fine cuttings that ideally are transported up the auger spirals for removal. In porous, fractured or vesicular target materials (such as at the Bishop pumice site) a significant portion of the cuttings are pushed aside, but for non-fractured, microporous targets the cuttings remain in the borehole and accumulate. Rock powder is relatively incompressible as a working fluid at only 100-200N downward force (TRIDENT limits) and hence eventual drilling progress slows or stops. Our recommended strategy for improving TRIDENT cuttings removal in massive target units with low cuttings-permeability is to reduce TRIDENT bite sizes when encountering these units, from 10cm to as little as 1-2cm, to effectively bail the accumulating cuttings. This approach was demonstrated to reduce choking and allowed slow progress to continue in cuttings-impermeable microporous target units (viz. the Bishop tuff in our September 2023 tests or cemented simulants in 2022 ambient tests).

robotic drilling↗