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NASA NTRS2003

Nanolayered Features of Collagen-like Peptides

We have been investigating collagen-like model oligopeptides as molecular bases for complex ordered biomimetic materials. The collagen-like molecules incorporate aspects of native collagen sequence and secondary structure. Designed modifications to native primary and secondary structure have been incorporated to control the nanostructure and microstructure of the collagen-like materials produced. We find that the collagen-like molecules form a number of lyotropic rod liquid crystalline phases, which because of their strong temperature dependence in the liquid state can also be viewed as solvent intercalated thermotropic liquid crystals. The liquid crystalline phases formed by the molecules can be captured in the solid state by drying off solvent, resulting in solid nanopatterned (chemically and physically) thermally stable (to greater than 100 C) materials. Designed sequences which stabilize smectic phases have allowed a variety of nanoscale multilayered biopolymeric materials to be developed. Preliminary investigations suggest that chemical patterns running perpendicular to the smectic layer plane can be functionalized and used to localize a variety of organic, inorganic, and organometallic moieties in very simple multilayered nanocomposites. The phase behavior of collagen-like oligopeptide materials is described, emphasizing the correlation between mesophase, molecular orientation, and chemical patterning at the microscale and nanoscale. In many cases, the textures observed for smectic and hexatic phase collagens are remarkably similar to the complex (and not fully understood) helicoids observed in biological collagen-based tissues. Comparisons between biological morphologies and collagen model liquid crystalline (and solidified materials) textures may help us understand the molecular features which impart order and function to the extracellular matrix and to collagen-based mineralized tissues. Initial studies have utilized synthetic collagen-like peptides while future work will also focus on similar sequences generated via genetic engineering methods.

Valluzzi, Regina↗

NASA NTRS2016

Indigenous Carbonaceous Matter in the Nakhla Mars Meteorite

Detailed microanalysis of the Martian meteorite Nakhla has shown there are morphologically distinct carbonaceous features spatially associated with low-T aqueous alteration phases including salts and id-dingsite. A comprehensive suite of analytical instrumentation including optical microscopy, field emission scanning electron microscopy (FESEM), energy dispersive X-ray (EDX) spectroscopy, focused ion beam (FIB) microscopy, transmission electron microscopy (TEM), two-step laser mass spectrometry (mu-L(sup 2)MS), laser mu-Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), and nanoscale secondary ion mass spectrometry (NanoSIMS) are being used to characterize the carbonaceous matter and host mineralogy. The search for carbonaceous matter on Mars has proved challenging. Viking Landers failed to unambiguously detect simple organics at either of the two landing sites although the Martian surface is estimated to have acquired at least 10(exp15) kg of C as a consequence of meteoritic accretion over the last several Ga. The dearth of organics at the Martian surface has been attributed to various oxidative processes including UV photolysis and peroxide activity. Consequently, investigations of Martian organics need to be focused on the sub-surface regolith where such surface processes are either severely attenuated or absent. Fortuitously since Martian meteorites are derived from buried regolith materials they provide a unique opportunity to study Martian organic geochemistry.

Clemett, S. J.↗

NASA NTRS2013

Nanoscale Mineralogy and Composition of Experimental Regolith Agglutinates Produced under Asteroidal Impact Conditions

On the Moon, the energetics of smaller impactors and the physical/chemical characteristics of the granular regolith target combine to form a key product of lunar space weathering: chemically reduced shock melts containing optically-active nanophase Fe metal grains (npFe0) [1]. In addition to forming the optically dark glassy matrix phase in lunar agglutinitic soil particles [1], these shock melts are becoming increasingly recognized for their contribution to optically active patina coatings on a wide range of exposed rock and grain surfaces in the lunar regolith [2]. In applying the lessons of lunar space weathering to asteroids, the potential similarities and differences in regolith-hosted shock melts on the Moon compared to those on asteroids has become a topic of increasing interest [3,4]. In a series of impact experiments performed at velocities applicable to the asteroid belt [5], Horz et al. [6] and See and Horz [7] have previously shown that repeated impacts into a gabbroic regolith analog target can produce melt-welded grain aggregates morphologically very similar to lunar agglutinates [6,7]. Although these agglutinate-like particles were extensively analyzed by electron microprobe and scanning electron microscopy (SEM) as part of the original study [7], a microstructural and compositional comparison of these aggregates to lunar soil agglutinates at sub-micron scales has yet to be made. To close this gap, we characterized a representative set of these aggregates using a JEOL 7600 field-emission scanning electron microscope (FE-SEM), and JEOL 2500SE field-emission scanning transmission electron microscope (FE-STEM) both optimized for energy dispersive X-ray spectroscopy (EDX) compositional spectrum imaging at respective analytical spatial resolutions of 0.5 to 1 micron, and 2 to 4 nm.

Christoffersen, Roy↗

NASA NTRS2020

An Evolutionary System of Mineralogy. Part I: Stellar Mineralogy (>13 to 4.6 Ga)

Minerals preserve records of the physical, chemical, and biological histories of their origins and subsequent alteration, and thus provide a vivid narrative of the evolution of Earth and other worlds through billions of years of cosmic history. Mineral properties, including trace and minor elements, ratios of isotopes, solid and fluid inclusions, external morphologies, and other idiosyncratic attributes, represent information that points to specific modes of formation and subsequent environmental histories—information essential to understanding the co-evolving geosphere and biosphere. This perspective suggests an opportunity to amplify the existing system of mineral classification, by which minerals are defined solely on idealized end-member chemical compositions and crystal structures. Here we present the first in a series of contributions to explore a complementary evolutionary system of mineralogy—a classification scheme that links mineral species to their paragenetic modes. The earliest stage of mineral evolution commenced with the appearance of the first crystals in the universe at >13 Ga and continues today in the expanding, cooling atmospheres of countless evolved stars, which host the high-temperature (T > 1000 K), low-pressure (P < 10-2 atm) condensation of refractory minerals and amorphous phases. Most stardust is thought to originate in three distinct processes in carbon- and/or oxygen-rich mineral-forming stars: (1) condensation in the cooling, expanding atmospheres of asymptotic giant branch stars; (2) during the catastrophic explosions of supernovae, most commonly core collapse (Type II) supernovae; and (3) classical novae explosions, the consequence of runaway fusion reactions at the surface of a binary white dwarf star. Each stellar environment imparts distinctive isotopic and trace element signatures to the micro- and nanoscale stardust grains that are recovered from meteorites and micrometeorites collected on Earth’s surface, by atmospheric sampling, and from asteroids and comets. Although our understanding of the diverse mineral-forming environments of stars is as yet incomplete, we present a preliminary catalog of 41 distinct natural kinds of stellar minerals, representing 22 official International Mineralogical Association (IMA) mineral species, as well as 2 as yet unapproved crystalline phases and 3 kinds of non-crystalline condensed phases not codified by the IMA.

Robert M. Hazen↗

NASA NTRS2004

Numerical Simulation of Nanostructure Growth

Nanoscale structures, such as nanowires and carbon nanotubes (CNTs), are often grown in gaseous or plasma environments. Successful growth of these structures is defined by achieving a specified crystallinity or chirality, size or diameter, alignment, etc., which in turn depend on gas mixture ratios. pressure, flow rate, substrate temperature, and other operating conditions. To date, there has not been a rigorous growth model that addresses the specific concerns of crystalline nanowire growth, while demonstrating the correct trends of the processing conditions on growth rates. Most crystal growth models are based on the Burton, Cabrera, and Frank (BCF) method, where adatoms are incorporated into a growing crystal at surface steps or spirals. When the supersaturation of the vapor is high, islands nucleate to form steps, and these steps subsequently spread (grow). The overall bulk growth rate is determined by solving for the evolving motion of the steps. Our approach is to use a phase field model to simulate the growth of finite sized nanowire crystals, linking the free energy equation with the diffusion equation of the adatoms. The phase field method solves for an order parameter that defines the evolving steps in a concentration field. This eliminates the need for explicit front tracking/location, or complicated shadowing routines, both of which can be computationally expensive, particularly in higher dimensions. We will present results demonstrating the effect of process conditions, such as substrate temperature, vapor supersaturation, etc. on the evolving morphologies and overall growth rates of the nanostructures.

Hwang, Helen H.↗