Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “surface area”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 235 records · Page 13

A combined experimental and modelling study of granite hydrothermal alteration

Geochemical reactions can induce significant changes of rock reservoir porosity and permeability via mineral dissolution and precipitation processes, affecting the long-term fluid behaviour within various geological systems. Here, the understanding and quantification of these reactions rely on field and experimental studies and on the predictions of reactive transport models. The present study was aimed at assessing the extent to which current geochemical models integrating available mineral dissolution/precipitation rate equations can reproduce the experimental data obtained from 4 to 17-day long hydrothermal alteration experiments of a muscovite-biotite granite and, thus, help provide an accurate description of the evolution of geothermal systems within granitic reservoirs. The experiments were conducted at a constant temperature of 180 °C and over an aqueous fluid pH range of 2 to 8.5, using both mixed-flow and static batch reactors. Modelled major element (K, Al, Si, Ca, and Mg) concentrations were generally in satisfactory agreement with the corresponding measured elemental fluxes – the differences between modelled and experimental values were generally within a factor of 5 – and the predicted identity and mass of formed secondary phases were consistent with the microscopic observations of the reacted solids. However, larger differences between measured and modelled element concentrations were observed when significant amounts of secondary phases formed, notably at pH 2 to 3, and for longer-term batch experiments. Much of this concentration difference stems from the underestimation of the amounts of Al-phases formed at acid to near-neutral pH. Although an idealized rock composition was considered, the observed mismatch between model calculations and experimental data can be attributed to inadequate mineral precipitation reaction rates and a poor description of reactive surface areas in existing geochemical modelling codes. More accurate quantification of precipitation kinetics, including nucleation and growth, and improved descriptions of the temporal change of mineral surface area would enhance the predictive capabilities of reactive transport models and benefit, particularly, the efforts aimed at increasing the sustainability of EGS reservoirs.

58 GEOSCIENCES↗

Strategies for Post-Synthetic Functionalization of Mesoporous Carbon Nanomaterial Surfaces

Most widely used carbon-based materials feature a bulk framework tolerant of extreme pH and temperature conditions while maintaining physical robustness, electrical conductivity, and biological relevance due to its inherent nontoxicity. At the nanoscale, the study of porous carbons has been of interest because of the enhanced accessible surface area relative to nonporous analogues. The evolution of synthetic techniques has developed structural allotropes with tunable internal pore diameter averages spanning from sub-nanometer to micron-plus sizes. Within the mesopore range, surface chemical phenomena abide by a kinetic-limited ruleset (ignoring the effects of bulk diffusion, as they do not pertain to this size regime). Further, mesopores provide sufficient volume and surface area for hosting guest species, including metal nanoparticles (MNP), polymers, small organics, and enzymes. These two unique features of mesoporous carbon (MC) drive interest in surface modifications to create new physicochemical functionality to these systems and their hosted species. As a result, the evolution of surface modification techniques has been scattered to disparate niches across the literature. This review compiles the array of elegant methods by which these carbon systems are topically engineered.

functionalization↗

Effects of graphene surface functionalities towards controlled reinforcement of a lignin based renewable thermoplastic rubber

In this report, we describe methods to enhance mechanical properties of a renewable thermoplastic rubber by incorporating functional graphene platelets into an equal-mass mixture of lignin, a feedstock from plant biomass, and a nitrile-butadiene rubber having 41 mol % acrylonitrile content (NBR41) that form a nanocomposite. Not all lignins yield mechanically strong material when they are combined with NBR41, and thus, limit its use for such rubbery products. Here, we evaluate different graphene oxides (GO) and reduced graphene oxides (rGO) dry-powders with different surface areas, functionality, and wettability in the synthesis of performance-enhanced nanocomposites of soft lignin/NBR41 matrix via a solvent-free, high shear reactive process. High surface area GO (HSGO) platelets with strong hydrophilicity exhibit good dispersion in the multiphase lignin/NBR41 composites with lignin dispersion varying from 200 to 2000 nm, resulting in superior reinforcement over other graphene derivatives. The addition of 1–4 wt % HSGO increased the tensile stress of the lignin/NBR41 thermoplastic rubber matrix by 60–160% (15–24 MPa) and the modulus by 200–700% (60–140 MPa). Scanning electron microscopy and small angle X-ray scattering results show that the well-dispersed HSGO platelets effectively disrupt the lignin-rich aggregates in NBR41 matrix, resulting in both strength and stiffness enhancements in the formed nanocomposites. This report on performance enhancement of lignin-based renewable polymers via the production of nanocomposite would increase potential for ‘finding the value of lignin’—a grand challenge associated with modern biorefineries.

36 MATERIALS SCIENCE↗

Understanding Platinum Ionomer Interface Properties of Polymer Electrolyte Fuel Cells

A well-designed cathode catalyst layer with optimal ionomer distribution is critical to minimizing amount of Platinum (Pt) content in polymer electrolyte fuel cells (PEFCs). The impact of Pt loading, ionomer content and carbon support types on the catalyst/ionomer interface were also investigated at dry and wet conditions. Higher Pt loadings resulted in higher double layer capacity (C dl ) and similar electrochemical surface area (ECSA) due to well dispersed ionic phase material. Higher ionomer content resulted in higher ionic conductivity but also showed similar SO 3 − group coverage. High surface area (HSA) carbon support had larger ECSA and C dl at both dry and wet conditions, as less agglomerated Pt was well dispersed in the meso-pores of the support. Lower SO 3 − group coverages were observed for HSA carbon than for Vulcan carbon due to Pt particles being buried within the porous HSA carbon support. The effect of cell conditioning and voltage recovery on the PEFC cathode catalyst layer was shown to have minimal impact on SO 3 − group coverage despite a decrease in C dl and ECSA due to the size increase of Pt particles. At dry condition, a significant increases in SO 3 − group coverage were observed for all MEAs due to higher adsorptivity of ionomer in dry conditions.

25 ENERGY STORAGE↗

Silicate coprecipitation reduces green rust crystal size and limits dissolution-precipitation during air oxidation

Green rusts (GR) are mixed-valence iron (Fe) hydroxides which form in reducing redox environments like riparian and wetland soils and shallow groundwater. In these environments, silicon (Si) can influence Fe oxides’ chemical and physical properties but its role in GR formation and subsequent oxidative transformation have not been studied starting at initial nucleation. Green rust sulfate [GR(SO 4 )] and green rust carbonate [GR(CO 3 )] were both coprecipitated from salts by base titration in increasing % mol Si (0, 1, 10, and 50). The minerals were characterized before and after rapid (24 h) aqueous air-oxidation by x-ray diffraction (XRD), scanning electron microscopy (SEM), Fe extended x-ray absorption fine structure spectroscopy (EXAFS), and N 2 -BET surface area. Results showed that only GR(SO4) or GR(CO3) was formed at every tested Si concentration. Increasing % mol Si caused decreased plate size and increased surface area in GR(CO3) but not GR(SO4). GR plate basal thickness was not changed at any condition indicating a lack of Si interlayering. Air oxidation of GR(SO4) at all % mol Si contents transformed by dissolution and reprecipitation into lepidocrocite and goethite, favoring ferrihydrite with higher % Si content. Air oxidation of GR(CO3) transformed into magnetite and goethite but increasing Si caused GR to oxidize while retaining its hexagonal plate structure via solid-state oxidation. Our results indicate that Si has the potential to cause GR to form in smaller particles and upon air oxidation, Si can either stabilize the plate structure or alter transformation to ferrihydrite.

36 MATERIALS SCIENCE↗

Formulation of Conductive Inks for DIW Printed Battery Electrodes

Ink formulations for DIW printing of Li ion battery electrodes were optimized for high conductivity, surface area and printability. Our focus is particularly on optimizing Li-ion battery electrodes for low temperature applications by 3-D printing the cathodes into high surface area shapes. The sluggish kinetics of ion transport at the solid-electrolyte phase boundary can be a major problem in batteries at low temperatures, so optimizing for ion transport can help combat these issues. Two families of DIW ink were investigated; aqueous conductive polymer suspension with graphene nano platelets (GNP) ink, and “oil in water” graphene oxide (GO) micro emulsion ink which carbonizes to an open cell graphene aerogel. By iterative formulation changes, the conductivity of PEDOT:PSS based ink was increased over tenfold, and stiffness of GO emulsion ink was increased to provide better printability without sacrificing porosity.

36 MATERIALS SCIENCE↗

Construction of Fluorine- and Piperazine-Engineered Covalent Triazine Frameworks Towards Enhanced Dual-Ion Positive Electrode Performance

Organic positive electrodes featuring lightweight, and tunable energy storage modes by molecular structure engineering have promising application prospects in dual-ion batteries. Herein, a series of highly porous covalent triazine frameworks (CTFs) were synthesized under ionothermal conditions using fluorinated aromatic nitrile monomers containing a piperazine ring. Fluorinated monomers can result in more defects in CTFs, leading to a higher surface area up to 2515 m 2 /g and a higher N content of 11.34 wt% compared to the products from the non-fluorinated monomer. The high surface area and abundant redox sites of these CTFs afforded high specific capacities (up to 279 mAh/g at 0.1 A/g), excellent rate performance (89 mAh/g at 5 A/g), and durable cycling performance (92.3% retention rate after 500 cycles at 2.0 A g -1 ) as dual-ion positive electrodes

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of chemical composition and physicochemical properties of poplar biomass on the performance of 3D printed poplar-reinforced PLA materials

Lignocellulosic biomass has been well-acknowledged as a filler for making 3D printed composites. The technical performances of composites were influenced by the characteristics of the components. The correlations between poplar biomass properties and the mechanical and thermal performances of the 3D printed poplar-plastic composites were investigated. The characteristics of poplar were modified by different pretreatment methods, including using hot water, dilute acid, and organic solvent (organosolv), and each treated poplar biomass was applied as a filler in a polylactic acid (PLA) polymer matrix to produce eco-friendly materials. These solvent pretreatments increased the hydrophobicity and surface area of poplar. Organosolv treated poplar showed the highest cellulose content and significantly increased Young's modulus of its biocomposites. Principal component analysis revealed that the specific surface area and water contact angle of biomass contributed to the thermal stability of biocomposites. Additionally, the degree of polymerization of cellulose and xylan content within the biomass correlated with the biocomposites' break stress. Notably, the crystallinity of biocomposites impacted the modulus of these materials. The reported relationships between biomass characteristics and 3D printed composite behaviors provide guidance for optimizing biomass processing in biocomposite applications.

Ji, Anqi [State Univ. of New York (SUNY), Syracuse↗

Cellulose regulated lignin/cellulose-based carbon materials with hierarchical porous structure for energy storage

Lignin has gained extensive attention as an ideal carbon precursor due to its abundance and high carbon content. However, the agglomeration of lignin and additional corrosive and unrecyclable reagents in direct pyrolysis still limit the development of lignin-based porous carbons. Herein, a facile and eco-friendly strategy was proposed to fabricate hierarchical porous lignin/cellulose-based carbon materials (LCs). In the process, cellulose nanofibrils acted as the skeleton of the bio-aerogels, which supported lignin and benefit the preparation of the LCs. Moreover, the specific surface area and the graphitization degree of LCs can be regulated by varying the cellulose content. Without activation, the bio-based carbon material (LC30) had a high specific surface area of 1770 m 2 g –1 , which displayed high specific capacitance of 216.2 F g –1 at the current density of 0.5 A g –1 . The supercapacitor based on LC30 also showed outstanding energy density of 12.3 Wh kg –1 at the power density of 50 W kg –1 . The sustainable raw material, simple and harmless preparation process, and remarkable electrochemical performance enable LC30, a promising supercapacitor electrode for energy storage.

25 ENERGY STORAGE↗

The Role of Lignin Molecular Weight on Activated Carbon Pore Structure

Over the past decade, the production of biofuels from lignocellulosic biomass has steadily increased to offset the use of fuels from petroleum. To make biofuels cost-competitive, however, it is necessary to add value to the “ligno-” components (up to 30% by mass) of the biomass. The properties of lignin, in terms of molecular weight (MW), chemical functionality, and mineral impurities often vary from biomass source and biorefinery process, resulting in a challenging precursor for product development. Activated carbon (AC) is a feasible target for the lignin-rich byproduct streams because it can be made from nearly any biomass, and it has a market capacity large enough to use much of the lignin generated from the biorefineries. However, it is not known how the variability in the lignin affects the key properties of AC, because, until now, they could not be well controlled. In this work, various fractions of ultraclean (<0.6% ash) lignin are created with refined MW distributions using Aqueous Lignin Purification using Hot Agents (ALPHA) and used as precursors for AC. AC is synthesized via zinc chloride activation and characterized for pore structure and adsorption capacity. We show that AC surface area and the adsorption capacity increase when using lignin with increasing MW, and, furthermore, that reducing the mineral content of lignin can significantly enhance the AC properties. The surface area of the AC from the highest MW lignin can reach ~1830 m2/g (absorption capacity). Furthermore, single step activation carbonization using zinc chloride allows for minimal carbon burn off (<30%), capturing most of the lignin carbon compared to traditional burn off methods in biorefineries for heat generation.

Biochemistry & Molecular Biology↗

Zinc-iodine secondary energy storage methods, devices, and electrolytes

Disclosed are cathodes having electron-conductive high-surface-area materials, aqueous non-halide-containing electrolytes, secondary zinc-iodine energy storage devices using the same, and methods for assembling the same. The disclosed high-surface-area materials and the aqueous non-halide-containing electrolyte solutions can contribute together to the confinement of the active iodine species in the cathode and to the minimization of shuttle effects and self-discharging. The non-halide-containing electrolyte salts can facilitate preferential adsorption of the iodine species to the cathode material rather than dissolution in the aqueous electrolyte solution, thereby contributing to the confinement of the active iodine species.

25 ENERGY STORAGE↗

Rigid Supramolecular Aramid Nanotubes as Catalyst Supports

Solution‐phase heterogeneous catalysts benefit from nanoscale dimensions, which maximize specific surface area and enhance catalytic activity. However, the ease of recovering such nanocatalysts depends on the design of the support materials, which are often particle‐like. Rigid 1D nanomaterials are proposed as supports that can enhance separability while offering high volumetric specific surface area for greater catalyst loading and activity. Here, aramid amphiphiles (AAs) are designed to spontaneously self‐assemble in water into high‐aspect‐ratio supramolecular nanotubes with tunable surface chemistry. These AA nanotubes exhibit high persistence lengths (P = 750 ± 340 µm) and mechanical stiffnesses (3 N/m). Incorporating surface thiol groups enables immobilization of catalytic gold nanoparticles. The resulting AA nanotube‐gold nanoparticle complexes exhibit high catalytic activity, efficient recoverability via simple microfiltration, and sustained reusability over ten reaction cycles. This study demonstrates the utility of molecular self‐assembled 1D nanomaterials as versatile scaffolds for the reuse and recovery of nanoscale catalysts.

1D nanomaterials↗

Toward Optimizing Electrospun Nanofiber Fuel Cell Catalyst Layers: Polymer–Particle Interactions and Spinnability

We investigate the effect of the poly(acrylic acid) (PAA) carrier polymer concentration on the microstructure and rheological properties of catalyst inks for electrospun polymer–electrolyte membrane fuel-cell catalyst layers. Characterization of an ink microstructure using oscillatory shear rheology showed that the catalyst particles (platinum on carbon) are significantly agglomerated in the absence of PAA or an ionomer. Both the ionomer and PAA promoted the stability of the particles against agglomeration via electrosteric stabilization by adsorbing onto the particle surface. Increasing the PAA concentration increased the stability of the particles (or reduced the agglomerated structure) due to increasing PAA coverage onto the free surface area of the particles. However, beyond a certain increase in concentration, PAA was found to predominantly remain as an excess free polymer in the ink due to an insufficient free/available surface area on the particles for further PAA coverage. Extensional rheology measurements demonstrated that PAA enhances the extensional viscosities of the inks. Consequently, increasing the PAA concentration in the ink promoted the evolution of uniform nanofibers. However, beyond a certain concentration, a significant increase in the shear viscosities of the inks led to defective fiber morphologies because of the onset of flow instabilities. Electrochemical performance comparisons between catalyst layers with different PAA concentrations showed maximum performance at the PAA concentration that led to the least agglomerated structure of the catalyst, most uniform fiber morphologies, and low concentrations of free (non-adsorbing) PAA in the electrode. These results provide a rationale for optimization of electrospun catalyst nanofibers for both spinnability and electrochemical performance.

25 ENERGY STORAGE↗

Metallurgical Analysis of the High Flux Isotope Reactor (HFIR) Carrier Lifting Bails (Rev.1)

The dissolution rates of the aluminum alloys in the High Flux Isotope Reactor (HFIR) element carriers and the Material Test Reactor (MTR) L-bundles in the H-Canyon facility have been identified as the possible cause of extended dissolutions that result in significant time and financial expenditures. A study, carried out by Savannah River National Laboratory (SRNL) to determine relationships between the dissolution rates and the metallurgical properties of the aluminum alloy materials of construction of the HFIR carriers and the L-bundles, considered the dissolution rates of aluminum alloy (AA) series 1100, 6061, and 6063. The study determined that the aluminum alloy compositions played a principal role in the dissolution rate of the carrier/bundle components. Higher dissolution rates were correlated with lower concentrations of the minor element additions in the alloys and with specific element concentrations. Aluminum alloys 1100 and 6063 were found to have similar dissolution rates that were approximately two orders of magnitude (100X) greater than those of AA6061. Based on the results of the dissolution behavior study, a Technical Assistance Request (TAR) was first issued to determine if the replacement of AA6061-T6 with AA6063-T6 is feasible for the HFIR carrier lifting bails. A Technical Task Request was then issued to consider AA6063-T5 as well as other alloys to improve possible supply chain issues. The metallurgical properties of the L-bundle (specifically the end caps) were not evaluated in this report because L-Bundle drawings already allow for the use of AA6063-T6 in all structural components. The HFIR carriers are composed of thin-walled components with significant surface areas that allow for relatively quick overall dissolution times. Conversely, the carrier lifting bails and the supporting constituents are composed of solid bars and thick plate regions with relatively small surface areas that experience longer overall dissolution times. While the MTR L-bundle design includes allowances for the materials of construction to be either AA6061-T6 or AA6063-T6, the HFIR carriers are specified to be constructed fully with AA6061-T6 alloy. This report analyzes the recommendations of the dissolution behavior study to replace the materials of construction of the HFIR carrier lifting bails. The analysis considers the operational requirements of the lifting bail and its supporting structures. To decrease dissolution times, the analysis considers direct replacement of the material as well as reductions in the thicknesses of the components to decrease the mass of the elements. Material reductions are considered on options for using either AA6061 and/or AA6063. The calculations are based on specifications from the American Society of Mechanical Engineer (ASME) and The Aluminum Association, Inc. design codes. The analysis finds that direct replacement of the lifting bail material of construction with AA6063-T6, and AA6063-T5 as well as reductions in the dimensions of the lifting bail components are acceptable. Note that this study considers the structural suitability of the alloys. It does not consider their dissolution rates in the dissolvers.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Solvent-Treated Zirconium-Based Nanoporous UiO-66 Metal–Organic Frameworks for Enhanced CO 2 Capture

Metal–organic framework (MOF)-derived nanoscale porous materials are widely deployed in carbon capture, but the CO 2 capacity is varied by different post-treatments, and its mechanism is still unclear. In this work, we prepared UiO-66 and treated it with methanol solvent and thermal activation approaches, which showed ~3 times enhanced CO 2 capacities from 15.1 to 45.0 mg/g and excellent recyclability of 10 cycles. The methanol treatment efficiently removes the residual guest molecules, including N,N-dimethylformamide, dangling organic linkers, and their derivatives, in the micropores (~0.8 nm) of UiO-66 and improves the surface area, pore volume, and void fraction to enhance the CO 2 capacity close to the ideal UiO-66 materials. The molecular dynamics simulation also proved a good linear relationship between the surface areas, void fraction, and CO 2 capacity. This work provides a deep understanding of the MOF’s activation mechanism and its applications in CO 2 capture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Engineering catalytical electrodes for applications in energy areas

An ink formulation and electrode that enhances hydrogen production, oxygen production, carbon dioxide reduction and other electrocatalytic reactions. Embodiments include an ink formulation with polymer binders having different catalytical precursors and a 3D electrode produced by additive manufacturing from the inventor's ink formulation. Various embodiments of the inventor's apparatus, systems, and methods provide inks that that are 3D-printed into patterns that optimize surface area and flow. The catalytic materials are imbedded into the ink matrix which is then printed into a 3D structure that has architecture that optimizes surface area and flow properties.

Liang, Siwei↗