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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Influence of ontogenetic development, temperature, and pCO2 on otolith calcium carbonate polymorph composition in sturgeons

Changes to calcium carbonate (CaCO 3 ) biomineralization in aquatic organisms is among the many predicted effects of climate change. Because otolith (hearing/orientation structures in fish) CaCO 3 precipitation and polymorph composition are controlled by genetic and environmental factors, climate change may be predicted to affect the phenotypic plasticity of otoliths. We examined precipitation of otolith polymorphs (aragonite, vaterite, calcite) during early life history in two species of sturgeon, Lake Sturgeon, (Acipenser fulvescens) and White Sturgeon (A. transmontanus), using quantitative X-ray microdiffraction. Both species showed similar fluctuations in otolith polymorphs with a significant shift in the proportions of vaterite and aragonite in sagittal otoliths coinciding with the transition to fully exogenous feeding. We also examined the effect of the environment on otolith morphology and polymorph composition during early life history in Lake Sturgeon larvae reared in varying temperature (16/22 °C) and pCO 2 (1000/2500 µatm) environments for 5 months. Fish raised in elevated temperature had significantly increased otolith size and precipitation of large single calcite crystals. Interestingly, pCO 2 had no statistically significant effect on size or polymorph composition of otoliths despite blood pH exhibiting a mild alkalosis, which is contrary to what has been observed in several studies on marine fishes. These results suggest climate change may influence otolith polymorph composition during early life history in Lake Sturgeon.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Improvements in the utilization of calcium carbonate in promoting sustainability and environmental health

Calcium carbonate (CaCO 3 ) is an incredibly abundant mineral on Earth, with over 90% of it being found in the lithosphere. To address the CO 2 crisis and combat ocean acidification, it is essential to produce more CaCO 3 using various synthetic methods. Additionally, this approach can serve as a substitute for energy-intensive processes like cement production. By doing so, we have the potential to not only reverse the damage caused by climate change but also protect biological ecosystems and the overall environment. The key lies in maximizing the utilization of CaCO 3 in various human activities, paving the way for a more sustainable future for our planet.

Chemistry↗
NASA NTRS1991

Impregnating Coal With Calcium Carbonate

Relatively inexpensive process proposed for impregnating coal with calcium carbonate to increase rates of gasification and combustion of coal and to reduce emission of sulfur by trapping sulfur in calcium sulfide. Process involves aqueous-phase reactions between carbon dioxide (contained within pore network of coal) and calcium acetate. Coal impregnated with CO2 by exposing it to CO2 at high pressure.

Sharma, Pramod K.↗
DOE OSTI2025

Soft Nanoconfinement Nucleates and Stabilizes Ultrasmall Amorphous Calcium Carbonate from Aggregation

Organisms use soft confinement structures, such as vesicles and compartments, to direct the nucleation of calcium carbonate (CaCO 3 ) and its subsequent processes during biomineralization. Despite recent efforts elucidating confinement’s effects on CaCO 3 polymorph selection, we still poorly understand how the size and distribution of CaCO 3 are controlled within soft confinement. Here, using a size-controlled nanoemulsions system made from isooctane, Span 80, Tween 80, and aqueous solutions, we studied CaCO 3 formation in soft confinement. Small angle X-ray scattering (SAXS) confirmed that a 72 nm aqueous core in nanoemulsions served as the confined space for CaCO 3 formation. Unlike the ~ 50 nm CaCO 3 particles that formed in the unconfined solution, small angle neutron scattering (SANS) and transmission electron microscope (TEM) showed that ultrasmall and amorphous calcium carbonate precipitated within soft confinement and did not exhibit any aggregation/coalescence of nanoparticles even after 24 hrs of reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Differentiating the bonding states in calcium carbonate polymorphs by low-loss electron-energy-loss spectroscopy

Calcium carbonate is one of the important building components in organisms, especially the two most common polymorphs, calcite and aragonite. Here, to understand the difference in bonding state, the two polymorphs are characterized by valence (low-loss) electron energy loss spectroscopy. It is found that the difference in Ca M 23 edge originating from 3p to 3d states is consistent with the change of Ca-O bonds in the two studied polymorphs. Surprisingly, the measured Ca M 23 edge is in qualitative agreement with the calculated partial density of states (PDOS) of Ca-d states in contrast to their L edges (from 2p to 3d states) which are strongly influenced by atomic multiplet effect (spin-orbit coupling). This is because the atomic multiplet effect is much reduced for the Ca 3p orbital, which permits the corresponding Ca M 23 edge to be compared with the PDOS results. Our findings show insights that PDOS can potentially be used to interpret the M 23 edge of lighter 3d transition metals such as scandium, titanium, vanadium and chromium when such interpretation may not be achieved for their L edges.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Electrochemical Production of Calcium Hydroxide from Calcium Carbonate [Poster]

Cement production involves the decomposition of limestone (calcium carbonate) at high temperatures (~900°C) to produce CaO, a major constituent in Portland cement (60-70%). Our unique approach will eliminate the high temperature process and introduce a low-temperature electrochemical process to produce Ca(OH) 2 which can be converted into CaO through dehydration process. This program will allow SRNL to become a leading organization in an open and unexplored field that addresses many of the technical challenges.

36 MATERIALS SCIENCE↗
DOE OSTI2022

The nano- and meso-scale structure of amorphous calcium carbonate

Abstract Understanding the underlying processes of biomineralization is crucial to a range of disciplines allowing us to quantify the effects of climate change on marine organisms, decipher the details of paleoclimate records and advance the development of biomimetic materials. Many biological minerals form via intermediate amorphous phases, which are hard to characterize due to their transient nature and a lack of long-range order. Here, using Monte Carlo simulations constrained by X-ray and neutron scattering data together with model building, we demonstrate a method for determining the structure of these intermediates with a study of amorphous calcium carbonate (ACC) which is a precursor in the bio-formation of crystalline calcium carbonates. We find that ACC consists of highly ordered anhydrous nano-domains of approx. 2 nm that can be described as nanocrystalline. These nano-domains are held together by an interstitial net-like matrix of water molecules which generate, on the mesoscale, a heterogeneous and gel-like structure of ACC. We probed the structural stability and dynamics of our model on the nanosecond timescale by molecular dynamics simulations. These simulations revealed a gel-like and glassy nature of ACC due to the water molecules and carbonate ions in the interstitial matrix featuring pronounced orientational and translational flexibility. This allows for viscous mobility with diffusion constants four to five orders of magnitude lower than those observed in solutions. Small and ultra-small angle neutron scattering indicates a hierarchically-ordered organization of ACC across length scales that allow us, based on our nano-domain model, to build a comprehensive picture of ACC formation by cluster assembly from solution. This contribution provides a new atomic-scale understanding of ACC and provides a framework for the general exploration of biomineralization and biomimetic processes.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2026

Direct Ink Write and Processing of Complex 3D Marine Compatible Structures with Calcium Carbonate Slurries

Ocean acidification heavily impacts marine ecosystems by reducing calcification. Many coral-algae symbiotic relationships are in jeopardy due to the destruction of coral reefs. Here, a ceramic ink compatible with the direct ink write additive manufacturing technique was formulated and used to print marine compatible structures that could grow algae and restore that relationship. A diacrylate polymer was mixed with calcium carbonate, a material that comprises a coral skeleton, to create a slurry with shear thinning properties. Rheology studies were conducted to confirm printing properties and characterize the slurry. Printed parts demonstrated strong control over print features, including size and infill design. Various infill patterns and percentages were attempted to optimize printability and potential algae growth. Thermogravimetric analysis helped determine a logical burnout and sintering procedure to avoid large cracking. This project developed a printable and sinter-able calcium carbonate ceramic slurry for complex marine-compatible structures and algae growth. This research was conducted in the support of the Eco Reef project.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Thermodynamic modeling of calcium carbonate scale precipitation: aqueous Na + -Ca 2+ -Cl – -HCO 3 – -CO 3 2– -CO 2 system

To allow for accurate calculations of calcium carbonate scaling in highly saline produced waters, we present a comprehensive thermodynamic model based on the electrolyte nonrandom two-liquid (eNRTL) activity coefficient equation for the aqueous Na ⁺ -Ca ²⁺ -Cl – -HCO 3 – -CO 3 ²– -CO 2 system. The eNRTL binary interaction parameters for the H 2 O:(Na ⁺ -CO 3 2– ) pair, the H 2 O:(Na ⁺ -HCO 3 – ) pair, the (Na⁺-Cl–):(Na ⁺ -CO 3 2– ) pair, and the (Na ⁺ -Cl – ):(Na ⁺ -HCO 3 – ) pair are identified in this work via the regression of thermodynamic, calorimetric, and phase equilibria experimental data. The binary interaction parameters associated with the H 2 O:(Na ⁺ -Cl – ) pair, the CO 2 :(Na ⁺ -Cl – ) pair, the H 2 O:(Ca ²⁺ -Cl – ) pair, and the (Na ⁺ -Cl – ):(Ca ²⁺ -Cl – ) pair are retrieved from the literature. The remaining binary interaction parameters are retrieved from Aspen Plus or set to zero. In addition, the solubility product constants are identified for Na 2 CO 3 ·10H 2 O (s) , Na 2 CO 3 · 7H 2 O (s) , Na 2 CO 3 ·H 2 O (s) , Na 2 CO 3 ·NaHCO 3 2H 2 O (s) , Na 2 CO 3 ·3NaHCO 3 (s) , and CaCO 3(s) via regression of solubility data. Here, the model is capable of accurately calculating all phase equilibria and calorimetric properties at temperatures up to 473.15 K and salt concentrations up to saturation.

42 ENGINEERING↗
NASA NTRS1996

Were kinetics of Archean calcium carbonate precipitation related to oxygen concentration?

Archean carbonates commonly contain decimetre- to metre-thick beds consisting entirely of fibrous calcite and neomorphosed fibrous aragonite that precipitated in situ on the sea floor. The fact that such thick accumulations of precipitated carbonate are rare in younger marine carbonates suggests an important change in the modes of calcium carbonate precipitation through time. Kinetics of carbonate precipitation depend on the concentration of inhibitors to precipitation that reduce crystallization rates and crystal nuclei formation, leading to kinetic maintenance of supersaturated solutions. Inhibitors also affect carbonate textures by limiting micrite precipitation and promoting growth of older carbonate crystals on the sea floor. Fe2+, a strong calcite-precipitation inhibitor, is thought to have been present at relatively high concentrations in Archean seawater because oxygen concentrations were low. The rise in oxygen concentration at 2.2-1.9 Ga led to the removal of Fe2+ from seawater and resulted in a shift from Archean facies, which commonly include precipitated beds, to Proterozoic facies, which contain more micritic sediment and only rare precipitated beds.

Non-NASA Center↗
DOE OSTI2026

Alginate–Amorphous Calcium Carbonate Hydrogels for Controlled Therapeutic Release

Alginate hydrogels are widely explored as biocompatible matrices for transdermal delivery of therapeutic compounds but burst release and mechanical stability remain persistent challenges in drug delivery systems. This experimental study investigated alginate–amorphous calcium carbonate (ACC) hydrogel composites designed to regulate release of model anti-inflammatory compound, ibuprofen. Hydrogels containing 1.6–2.0 wt% sodium alginate were crosslinked with CaCl₂ and combined with ACC through two incorporation pathways: (i) separate addition of ACC and ibuprofen or (ii) co-precipitation of ACC onto ibuprofen prior to hydrogel incorporation. Hydrogels without ACC served as Control. Biocomposite structure and properties were characterized and release profiles quantified using Korsmeyer–Peppas (KP) model.Burst release was curbed as crosslinking time increased, highlighting importance of network density in diffusion control. Co-precipitating ACC with ibuprofen prior to incorporating into the hydrogel suppressed burst release and sustained release for > ~72 h. Rheological measurements indicate ACC reinforces hydrogel network, increasing storage modulus while maintaining hydration and flexibility. KP model indicates release is diffusion-controlled, with deviations reflecting contributions from diffusion barriers and morphologic/structural changes near the ACC coated ibuprofen. ACC within alginate hydrogels provides a strategy for tuning drug release while preserving mechanical properties relevant to transdermal applications.

36 MATERIALS SCIENCE↗
DOE OSTI2026

A mild calcium carbonate treatment improves moisture resistance and mechanical/interfacial properties of jute and hemp fibers

Natural fibers are attractive, sustainable reinforcements, but often exhibit high moisture uptake and weak bonding with polymer matrices. In this study, jute and hemp were treated by immersion in aqueous calcium carbonate (CaCO3) suspensions (10–40?wt.%, 1.5?h, room temperature) and were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), moisture sorption testing, single-fiber tensile testing, and bundle pull-out testing. SEM showed granular CaCO3 deposition on fiber surfaces, with particulates bridging surface voids and microcracks. At 40 wt.% CaCO3, equilibrium moisture uptake decreased to ~5% (hemp) and ~3% (jute), while tensile strength increased to ~904 MPa (hemp) and ~960 MPa (jute). Apparent interfacial shear strength from pull-out testing increased up to ~1.35 MPa (hemp) and ~0.56 MPa (jute). These results indicate that CaCO3 deposition is a mild, scalable surface treatment that improves moisture resistance, fiber tensile strength, and interfacial load transfer relevant to semi-structural composite applications, including interior and secondary automotive components.

Calcium carbonate treatment↗
DOE OSTI2021

Patterns of Element Incorporation in Calcium Carbonate Biominerals Recapitulate Phylogeny for a Diverse Range of Marine Calcifiers

Elemental ratios in biogenic marine calcium carbonates are widely used in geobiology, environmental science, and paleoenvironmental reconstructions. It is generally accepted that the elemental abundance of biogenic marine carbonates reflects a combination of the abundance of that ion in seawater, the physical properties of seawater, the mineralogy of the biomineral, and the pathways and mechanisms of biomineralization. Here we report measurements of a suite of nine elemental ratios (Li/Ca, B/Ca, Na/Ca, Mg/Ca, Zn/Ca, Sr/Ca, Cd/Ca, Ba/Ca, and U/Ca) in 18 species of benthic marine invertebrates spanning a range of biogenic carbonate polymorph mineralogies (low-Mg calcite, high-Mg calcite, aragonite, mixed mineralogy) and of phyla (including Mollusca, Echinodermata, Arthropoda, Annelida, Cnidaria, Chlorophyta, and Rhodophyta) cultured at a single temperature (25°C) and a range of p CO 2 treatments (ca. 409, 606, 903, and 2856 ppm). This dataset was used to explore various controls over elemental partitioning in biogenic marine carbonates, including species-level and biomineralization-pathway-level controls, the influence of internal pH regulation compared to external pH changes, and biocalcification responses to changes in seawater carbonate chemistry. The dataset also enables exploration of broad scale phylogenetic patterns of elemental partitioning across calcifying species, exhibiting high phylogenetic signals estimated from both uni- and multivariate analyses of the elemental ratio data (univariate: λ = 0–0.889; multivariate: λ = 0.895–0.99). Comparing partial R 2 values returned from non-phylogenetic and phylogenetic regression analyses echo the importance of and show that phylogeny explains the elemental ratio data 1.4–59 times better than mineralogy in five out of nine of the elements analyzed. Therefore, the strong associations between biomineral elemental chemistry and species relatedness suggests mechanistic controls over element incorporation rooted in the evolution of biomineralization mechanisms.

58 GEOSCIENCES↗
DOE OSTI2025

Affinity for OH – Produces Four-Coordinated Zn 2+ Impurities in Hydrated Amorphous Calcium Carbonate

Using ab initio based molecular dynamics and electronic structure calculations, we show that Zn impurities in hydrated amorphous calcium carbonate (ACC) have a much lower coordination number than other divalent impurities due to covalent interactions between the 3d Zn shell and the oxygen atoms of the carbonate and water groups. Further, the local structure around Zn in ACC, including the predicted low coordination number, is confirmed by X-ray absorption spectroscopy of synthetic Zn-bearing ACC. The strong Zn–O chemical interaction leads to substantial water dissociation and slightly disrupts the hydrogen bonding network. Implications of Zn 2+ incorporation for ACC stability are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Calcium Sulfate and Calcium Carbonate Scaling of Thin-Film Composite Polyamide Reverse Osmosis Membranes with Surface-Tethered Polyacrylic Acid Chains

The gypsum and calcite scaling propensities of the thin-film composite polyamide (PA-TFC) reverse osmosis (RO) membrane, modified with a tethered surface layer of polyacrylic acid (PAA) chains, was evaluated and compared to the scaling of selected commercial RO membranes. The tethered PAA layer was synthesized onto a commercial polyamide membrane (i.e., base-PA) via atmospheric pressure plasma-induced graft polymerization (APPIGP). The PAA nano-structured (SNS) base-PA membrane (SNS-PAA-PA) was scaled to a lesser degree, as quantified by a lower permeate flux decline and surface imaging, relative to the tested commercial membranes (Dow SW30, Toray SWRO, and BWRO). The cleaning of gypsum-scaled membranes with D.I. water flushing achieved 100% water permeability recovery for both the SNS-PAA-PA and Dow SW30 membranes, relative to 92–98% permeability restoration for the Toray membranes. The calcium carbonate scaling of SNS-PAA-PA membranes was also lower relative to the commercial membranes, but permeability recovery after D.I. water cleaning was somewhat lower (94%) but consistent with the level of surface scale coverage. In contrast, the calcite and gypsum-scaled membrane areas of the commercial membranes post-cleaning were significantly higher than for the SNS-PAA-PA membrane but with 100% permeability recovery, suggesting the potential for membrane damage when mineral scaling is severe.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Directing polymorph specific calcium carbonate formation with de novo protein templates

Biomolecules modulate inorganic crystallization to generate hierarchically structured biominerals, but the atomic structure of the organic-inorganic interfaces that regulate mineralization remain largely unknown. We hypothesized that heterogeneous nucleation of calcium carbonate could be achieved by a structured flat molecular template that pre-organizes calcium ions on its surface. To test this hypothesis, we design helical repeat proteins (DHRs) displaying regularly spaced carboxylate arrays on their surfaces and find that both protein monomers and protein-C a2+ supramolecular assemblies directly nucleate nano-calcite with non-natural {110} or {202} faces while vaterite, which forms first in the absence of the proteins, is bypassed. These protein-stabilized nanocrystals then assemble by oriented attachment into calcite mesocrystals. We find further that nanocrystal size and polymorph can be tuned by varying the length and surface chemistry of the designed protein templates. Thus, bio-mineralization can be programmed using de novo protein design, providing a route to next-generation hybrid materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2004

Sulfur Cycling Mediates Calcium Carbonate Geochemistry in Modern Marine Stromatolites

Modem marine stromatolites forming in Highborne Cay, Exumas (Bahamas), contain microbial mats dominated by Schizothrix. Although saturating concentrations of Ca2+ and CO32- exist, microbes mediate CaCO3 precipitation. Cyanobacterial photosynthesis in these stromatolites aids calcium carbonate precipitation by removal of HS+ through CO2 use. Photorespiration and exopolymer production predominantly by oxygenic phototrophs fuel heterotrophic activity: aerobic respiration (approximately 60 umol/sq cm.h) and sulfate reduction (SR; 1.2 umol SO42-/sq cm.h) are the dominant C- consuming processes. Aerobic microbial respiration and the combination of SR and H2S oxidation both facilitate CaCO3 dissolution through H+ production. Aerobic respiration consumes much more C on an hourly basis, but duel fluctuating O2 and H2 depth profiles indicate that overall, SR consumes only slightly less (0.2-0.5) of the primary production. Moreover, due to low O2 concentrations when SR rates are peaking, reoxidation of the H2S formed is incomplete: both thiosulfate and polythionates are formed. The process of complete H2S oxidation yields H+. However, due to a low O2 concentration late in the day and relatively high O2 concentrations early in the following morning, a two-stage oxidation takes place: first, polythionates are formed from H2S, creating alkalinity which coincides with CaCO3 precipitation; secondly, oxidation of polythionates to sulfate yields acidity, resulting in dissolution, etc. Vertical profiles confirmed that the pH peaked late in the afternoon (greater than 8.8) and had the lowest values (less than 7.4) early in the morning. Thus, the effect of this S-cycling through alkalinity production, followed by acidification during H2S oxidation, results in a six times stronger fluctuation in acidity than photosynthesis plus aerobic respiration accomplish. This implies that anaerobic processes play a pivotal role in stromatolite formation.

Visscher, P. T.↗
NASA NTRS2006

Lab-Scale Study of the Calcium Carbonate Dissolution and Deposition by Marine Cyanobacterium Phormidium subcapitatum

Suggestions that calcification in marine organisms changes in response to global variations in seawater chemistry continue to be advanced (Wilkinson, 1979; Degens et al. 1985; Kazmierczak et al. 1986; R. Riding 1992). However, the effect of [Na+] on calcification in marine cyanobacteria has not been discussed in detail although [Na+] fluctuations reflect both temperature and sea-level fluctuations. The goal of these lab-scale studies therefore was to study the effect of environmental pH and [Na+] on CaCO3 deposition and dissolution by marine cyanobacterium Phormidium subcapitatum. Marine cyanobacterium P. subcapitatum has been cultivated in ASN-III medium. [Ca2+] fluctuations were monitored with Ca(2+) probe. Na(+) concentrations were determined by the initial solution chemistry. It was found that the balance between CaCO3 dissolution and precipitation induced by P. subcapitatum grown in neutral ASN III medium is very close to zero. No CaCO3 precipitation induced by cyanobacterial growth occurred. Growth of P. subcapitatum in alkaline ASN III medium, however, was accompanied by significant oscillations in free Ca(2+) concentration within a Na(+) concentration range of 50-400 mM. Calcium carbonate precipitation occurred during the log phase of P. subcapitatum growth while carbonate dissolution was typical for the stationary phase of P. subcapitatum growth. The highest CaCO3 deposition was observed in the range of Na(+) concentrations between 200-400 mM. Alkaline pH also induced the clamping of P. subcapitatum filaments, which appeared to have a strong affinity to envelop particles of chemically deposited CaCO3 followed by enlargement of those particles size. EDS analysis revealed the presence of Mg-rich carbonate (or magnesium calcite) in the solution containing 10-100 mM Na(+); calcite in the solution containing 200 mM Na(+); and aragonite in the solution containing with 400 mM Na(+). Typical present-day seawater contains xxmM Na(+). Early (Archean) seawater was likely less saline. The division of marine cyanobacterium P. subcapitatum is associated with periodic deposition and dissolution of CaCO3, the rhythms and intensity of which are dependent on concentrations of both OH(-) and Na(+). Thus, the role of present-day marine cyanobacteria in the global carbonate cycle might be reduced to aggregation and recrystallization of available CaCO3 particles in marine water rather than long-term precipitation and accumulation of CaCO3 deposits. For lower Na(+) concentrations, precipitation of carbonates by cyanobacteria would be even less significant. These results suggest that the lack of calcified cyanobacteria in stromatalite-bearing Precambrian sequences can be explained not only by high dissolved inorganic carbon concentrations but also by lower salinity, as well as possible lower pH compared to present-day oceans.

Karakis, S. G.↗