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At least 955 records · Page 53
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Role of Bottlebrush Additives on the Structure of Block Copolymers in the Bulk and Thin Films

Blending block copolymers (BCP) with additives is a useful approach for controlling BCP morphology and properties. In athermal systems, blends of BCPs with polymer additives having very high molecular (M n ) mass generally result in macrophase separation. Bottlebrush polymers, which consist of a linear backbone and grafted side chains, present an interesting alternative where the overall M n of the system can be very large but the low M n side chains may drive miscibility with the BCP. Here, in this study, a bottlebrush with a polynorbornene backbone and polystyrene (PS) side chains is blended with PS-b-poly(methyl methacrylate) (PS-b-PMMA) of varying M n , and the resulting morphologies are examined in both the bulk and thin films. Two different M n of PS-b-PMMA were used in the bulk study, and the analysis of small-angle X-ray scattering data shows that the blends were miscible and lamellar at all concentrations. This deviates from reference series of both low and high M n linear polymer additives, which either showed morphological transitions from lamellae to cylinders (low M n ) or were immiscible at all mass fractions studied (high M n ). The relative molecular mass of the side chain (N SC ) and the corresponding component in the BCP (N A ) dictate the distribution of the bottlebrush throughout the BCP, analogous to BCP/linear blends or grafted nanoparticles in a homopolymer matrix. The studies on thin films show a thickness dependence for bottlebrush mass fractions at or above 0.17, a behavior which may be driven by conformational changes of the bottlebrush upon confinement.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Distinct Surface and Bulk Morphology Due to Solvent Additive Effects in PM6 Conjugated Polymer Films

Depth dependent molecular orientation and crystalline structure in conjugated polymer thin films is critical for organic electronic device performance and is affected by solvent additive choice during processing. Here, in this work, we focus on the electron donor polymer PM6 and uncover how the solvent additive 1-chloronaphthalene (CN) affects the molecular orientation and the crystalline structure with near edge X-ray absorption fine structure (NEXAFS) spectroscopy and grazing-incidence wide-angle X-ray scattering (GIWAXS), respectively. By quantitatively comparing molecular and crystallite orientations, we find that CN induces distinct surface and bulk morphologies. The polymer conjugated plane orientation at the surface is unaffected by CN, while this orientation is strongly affected in the bulk. Further, we find differences in surface vs bulk crystalline coherence lengths and relative degrees of crystallinity. These insights help provide links between solvent additive and device performance and demonstrate the strengths of a quantitative approach for characterizing organic thin film morphology.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Reversible 1,2-Addition of Water To Form a Nucleophilic Mn(I) Hydroxide Complex: A Thermodynamic and Reactivity Study

( iPr PN H P)Mn(CO) 2 (OH) (2; iPr PN H P = HN{CH 2 CH 2 (P i Pr 2 )} 2 ) was formed from the reversible 1,2-addition of water to ( iPr PNP)Mn(CO) 2 (1; iPr PNP = the deprotonated, amide form of the ligand, –N{CH 2 CH 2 (P i Pr 2 )} 2 ). This reversible reaction was probed via variable-temperature NMR experiments, and the energetics of the 1,2-addition/elimination was found to be slightly exothermic (-0.8 kcal/mol). The corresponding manganese hydroxide was found to react with aldehydes, yielding the corresponding manganese carboxylate complexes ( iPr PN H P)Mn(CO) 2 (CO 2 R), where R = H, methyl, phenyl. While no reaction between 1 and neat benzaldehyde was observed, in the presence of water, conversion to the corresponding manganese-bound benzoate with formation of H 2 was observed. The catalytic oxidation of benzaldehyde by water without additives was unsuccessful due to strong product inhibition, with the manganese benzoate formed under a variety of reaction conditions. Upon addition of base, a catalytic cycle for the conversion of aldehyde to carboxylate and hydrogen can be devised.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Enhanced Water Management of Polymer Electrolyte Fuel Cells with Additive-Containing Microporous Layers

This work describes the performance improvement of a polymer electrolyte fuel cell with a novel class of microporous layers (MPLs) that incorporates hydrophilic additives: one with 30 μm aluminosilicate fibers and another with multiwalled carbon nanotubes with a domain size of 5 μm. Higher current densities at low potentials were observed for cells with the additive-containing MPLs compared to a baseline cell with a conventional MPL, which correlate with improvements in water management. This is also observed for helium and oxygen experiments and by the lower amount of liquid water in the cell, as determined by neutron radiography. Furthermore, carbon-nanotube-containing MPLs demonstrates improved durability compared to the baseline MPL. Microstructural analyses including nanotomography demonstrate that the filler material in both the additive-containing MPLs provide preferential transport pathways for liquid water, which correlate with ex situ measurements. In conclusion, the main advantage provided by these MPLs is improved liquid-water removal from the cathode catalyst layer, resulting in enhanced oxygen delivery to the electrocatalyst sites.

25 ENERGY STORAGE↗
DOE OSTI2021

Additive Lithography–Organic Monolayer Patterning Coupled with an Area-Selective Deposition

The combination of area-selective deposition (ASD) with a patternable organic monolayer provides a versatile additive lithography platform, enabling the generation of a variety of nanoscale feature geometries. Stearate hydroxamic acid self-assembled monolayers (SAMs) were patterned with extreme ultraviolet (λ = 13.5 nm) or electron beam irradiation and developed with ASD to achieve line space patterns as small as 50 nm. Density functional theory was employed to aid in the synthesis of hydroxamic acid derivatives with optimized packing density to enhance the imaging contrast and improve dose sensitivity. Near-edge X-ray absorption fine structure spectroscopy and infrared spectroscopy reveal that the imaging mechanism is based on improved deposition inhibition provided by the cross-linking of the SAM to produce a more effective barrier during a subsequent deposition step. With patterned substrates composed of coplanar copper lines and silicon spacers, hydroxamic acids selectively formed monolayers on the metal portions and could undergo a pattern-wise exposure followed by ASD in the first combination of a patternable monolayer with ASD. This material system presents an additional capability compared to traditional ASD approaches that generally reflect a starting patterned surface. Finally, this bottoms-up additive approach to lithography may be a viable alternative to subtractive nanoscale feature generation.

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

Mechanistic Study of Controlled Zinc Electrodeposition Behaviors Facilitated by Nanoscale Electrolyte Additives at the Electrode Interface

Nanoparticle organic hybrid materials (NOHMs) are liquid-like materials composed of an inorganic core to which a polymeric canopy is ionically tethered. NOHMs have unique properties including negligible vapor pressure, high oxidative thermal stability, and the ability to bind to reactive species of interest due to the tunability of their polymeric canopy. This makes them promising multifunctional materials for a wide range of energy and environmental technologies, including electrolyte additives for electrochemical energy storage (e.g., flow batteries) and the electrochemical conversion of CO 2 to chemicals and fuels. Due to their unique transport behaviors in fluid systems, an understanding of the near-electrode surface behavior of NOHMs in electrolyte solutions and their effect on electrochemical reactions is still lacking. In this work, the complexation of zinc (Zn) by NOHMs with an ionically tethered polyetheramine canopy (HPE) (NOHM-I-HPE) was studied using attenuated total reflectance Fourier transform infrared and Carbon-13 nuclear magnetic resonance spectroscopy. Additionally, various electrochemical techniques were employed to discern the role of NOHM-I-HPE during zinc electrodeposition, and the results were compared to those of the electrochemical system containing untethered HPE polymers. Our findings confirmed that NOHM-I-HPE and HPE reversibly complex zinc in the aqueous electrolyte. NOHM-I-HPE and HPE were found to block some of the electrode active sites, reducing the overall current density during electrodeposition, while facilitating the formation of smooth zinc deposits, as revealed by surface imaging and diffraction techniques. Observed variations in the current density responses and the degree of passivation created by the NOHM-I-HPE and HPE adsorbed on the electrode surface revealed that their different packing behaviors at the electrode–electrolyte interface influence the zinc deposition mechanism. The presence of the nanoparticle and ordering offered by the NOHMs as well as the structured conformation of the polymeric canopy allowed the formation of void spaces and free volumes for enhanced transport behaviors. Furthermore, these findings provided insights into how structured electrolyte additives such as NOHMs can allow for advancements in electrolyte design for controlled deposition of metal species from energy-dense electrolytes or for other electrochemical reactions.

25 ENERGY STORAGE↗
DOE OSTI2018

Improved Lubricating Performance by Combining Oil-Soluble Hairy Silica Nanoparticles and an Ionic Liquid as an Additive for a Synthetic Base Oil

This article reports on improved lubricating performance by combining oil-soluble poly(lauryl methacrylate) brush-grafted silica nanoparticles (hairy NPs or HNP) and an oil-miscible phosphonium-phosphate ionic liquid (IL) as a friction-reducing additive for a polyalphaolefin (PAO) oil. The HNP was synthesized by surface-initiated reversible addition–fragmentation chain transfer polymerization. At a total concentration of 2% and sufficiently high individual concentrations for HNP and IL in PAO, high-contact stress, ball-on-flat reciprocating tribological tests showed that the friction decreased by up to 23% compared with 2% HNP alone in PAO and by up to 35% compared to the PAO mixed with 2% IL. Scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy (XPS) analysis revealed that the tribofilm formed from the PAO containing 1% HNP + 1% IL was enriched with both Si and P, indicating that both hairy NPs and IL were involved in the tribochemical reactions. In addition, the O 1s and Si 2p peaks in the core-level XPS spectra exhibited significant shifts for the mixture of 1% HNP + 1% IL compared to those for 2% HNP, suggesting the possible formation of new covalent bonds. These results indicated that HNP and IL reacted with each other and also with the metal substrate during the rubbing process, which likely strengthened the tribofilm and its bonding with the substrate and thus further improved the lubrication.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Amorphous TiCu-Based Additives for Improving Hydrogen Storage Properties of Magnesium Hydride

Magnesium hydride has long been regarded as a promising candidate material for hydrogen and heat storage due to its high hydrogen capacity, reversibility, and low cost. Catalytic doping has been demonstrated as one of the most effective methods to improve hydrogen storage properties of MgH 2 . In this study, amorphous Ti 45 Cu 41 Ni 9 Zr 5 and Ti 40 Cu 47 Zr 10 Sn 3 alloys are used as additives for MgH 2 . Nanostructured MgH 2 doped with amorphous or crystalline TiCu-based alloys are prepared by using a high-energy mechanochemical synthesis method. Results show that the amorphous TiCu additives provide enhanced catalytic effects compared to crystalline alloys of the same composition. Doping MgH 2 using an amorphous Ti 45 Cu 41 Ni 9 Zr 5 alloy yielded improved dehydrogenation kinetics compared to using crystalline Ti 40 Cu 47 Zr 10 Sn 3 alloy. The analysis using transmission electron microscopy reveals that there are nanostructured catalytic particles uniformly distributed in the amorphous TiCu-catalyzed MgH 2 . The MgH 2 system catalyzed by amorphous TiCu-based alloy shows little degradation during hydrogenation and dehydrogenation cycling at 300 °C. The amorphous TiCu-based catalysts are thermally stable at temperatures up to 360 °C. Heating the amorphous Ti 45 Cu 41 Ni 9 Zr 5 -catalyzed MgH 2 to temperatures above 360 °C led to disproportionation of the catalyst alloy and the formation of MgCu 2 and Ti 2 Cu. In addition, PCI analysis of the amorphous Ti 45 Cu 41 Ni 9 Zr 5 -catalyzed MgH 2 shows a slight increase in hydrogen equilibrium pressure, resulting in a reaction enthalpy of -78.7 kJ/mol • H 2 and an entropy of 145.0 J/K•mol•H 2 . As a result, the entropy calculated from this study is approximately 10 J/K•mol•H 2 higher than values previously reported for undoped and catalyzed Mg-H systems.

08 HYDROGEN↗
DOE OSTI2021

Controlling the Aspect Ratios of Au Nanocrystals with Ag+ Addition Time in Seed-Mediated Synthesis: Implications for Surface-Enhanced Raman Scattering

Among various factors playing pivotal roles in the typical seed-mediated growth of Au nanocrystals (NCs), the role of Ag (AgNO3) has remained debatable over time and seminal research efforts have helped us in reaching a consensus, albeit from the standpoint of [Ag+] concentration. This study aims to provide an understanding of the role of Ag+ from the perspective of time. Here, we show that different Au NCs with tunable aspect ratios (ARs) can be generated in one system in high yield simply by varying the time of addition of Ag+ in the growth solution. The generality of the method has been demonstrated in tuning the ARs of anisotropic Au NCs like concave cuboid (CCB, AR = 2) and elongated tetrahexahedra (AR = 2.5), where the delayed addition of Ag+ leads to the formation of their isotropic counterpart concave cube (CC, AR = 1) and tetrahexahedra (AR = 1), respectively. This work, apart from establishing timed addition of Ag+ as a crucial parameter in controlling the AR, may also help in the realization of a universal growth mechanism of Au NCs. The Au NCs with varying ARs (CCB, AR = 2 and CC, AR = 1) have been further explored as potential substrates for surface-enhanced Raman scattering (SERS) due to the presence of their high-index facets and sharp tips.

KEYWORDS:Au nanoparticles seed-mediated growth hig↗
DOE OSTI2025

Alkane Dehydrogenation and H/D Exchange by a Cationic Pincer-Ir(III) Hydride: Cooperative C–H Addition and β -H Elimination Modes Induce Anomalous Selectivity

We report that the cationic iridium complex ( iPr PCP)IrH + catalyzes the transfer-dehydrogenation of alkanes to give alkenes and hydrogen isotope exchange (HIE) of alkanes and arenes. Contrary to established selectivity trends found for C–H activation by transition metal complexes, strained cycloalkanes, including cyclopentane, cycloheptane, and cyclooctane, undergo C–H addition much more readily than n-alkanes, which in turn are much more reactive than cyclohexane. Aromatic C–H bonds also undergo H/D exchange much less rapidly than those of the strained cycloalkanes, but much more favorably than cyclohexane. The order of reactivity toward dehydrogenation correlates qualitatively with the reaction thermodynamics, but the magnitude is much greater than can be explained by thermodynamics. Accordingly, the cycloalkenes corresponding to the strained cycloalkanes undergo hydrogenation much more readily than cyclohexene, despite the less favorable thermodynamics of such hydrogenations. Here, computational (DFT) studies allow rationalization of the origin of reactivity and the unusual selectivity. Specifically, the initial C–H addition is strongly assisted by β-agostic interactions, which are particularly favorable for the strained cycloalkanes. Subsequent to α-C–H addition, the H atom of the β-agostic C–H bond is transferred directly to the hydride ligand of ( iPr PCP)IrH + to give a dihydrogen ligand.

02 PETROLEUM↗
DOE OSTI2014

Ionic liquids composed of phosphonium cations and organophosphate, carboxylate, and sulfonate as lubricant antiwear additives

Oil-soluble phosphonium-based ionic liquids (ILs) have recently been reported as potential ashless lubricant additives. This study is to expand the IL chemistry envelope and to achieve fundamental correlations between the ion structures and ILs’ physiochemical and tribological properties. Here we present eight ILs containing two different phosphonium cations and seven different anions from three groups: organophosphate, carboxylate, and sulfonate. The oil solubility of ILs seems largely governed by the IL molecule size and structure complexity. When used as oil additives, the ranking of effectiveness in wear protection for the anions are: organophosphate > carboxylate > sulfonate. All selected ILs outperformed a commercial ashless anti-wear additive. Surface characterization from the top and the cross-section revealed the nanostructures and compositions of the tribo-films formed by the ILs. Some fundamental insights were achieved: branched and long alkyls improve the IL’s oil solubility, anions of a phosphonium-phosphate IL contribute most phosphorus in the tribofilm, and carboxylate anions, though free of P, S, N, or halogen, can promote the formation of an anti-wear tribofilm.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Additively manufacturable micro-mechanical logic gates

Early examples of computers were almost exclusively based on mechanical devices. Although electronic computers became dominant in the past 60 years, recent advancements in three-dimensional micro-additive manufacturing technology provide new fabrication techniques for complex microstructures which have rekindled research interest in mechanical computations. Here we propose a new digital mechanical computation approach based on additively-manufacturable micro-mechanical logic gates. The proposed mechanical logic gates (i.e., NOT, AND, OR, NAND, and NOR gates) utilize multi-stable micro-flexures that buckle to perform Boolean computations based purely on mechanical forces and displacements with no electronic components. A key benefit of the proposed approach is that such systems can be additively fabricated as embedded parts of microarchitected metamaterials that are capable of interacting mechanically with their surrounding environment while processing and storing digital data internally without requiring electric power.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Tailoring thermal insulation architectures from additive manufacturing

Abstract Tailoring thermal transport by structural parameters could result in mechanically fragile and brittle networks. An indispensable goal is to design hierarchical architecture materials that combine thermal and mechanical properties in a continuous and cohesive network. A promising strategy to create such a hierarchical network targets additive manufacturing of hybrid porous voxels at nanoscale. Here we describe the convergence of agile additive manufacturing of porous hybrid voxels to tailor hierarchically and mechanically tunable objects. In one strategy, the uniformly distributed porous silica voxels, which form the basis for the control of thermal transport, are non-covalently interfaced with polymeric networks, yielding hierarchic super-elastic architectures with thermal insulation properties. Another additive strategy for achieving mechanical strength involves the versatile orthogonal surface hybridization of porous silica voxels retains its low thermal conductivity of 19.1 mW m −1 K −1 , flexible compressive recovery strain (85%), and tailored mechanical strength from 71.6 kPa to 1.5 MPa. The printed lightweight high-fidelity objects promise thermal aging mitigation for lithium-ion batteries, providing a thermal management pathway using 3D printed silica objects.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Additive manufacturing of an ultrastrong, deformable Al alloy with nanoscale intermetallics

Abstract Light-weight, high-strength, aluminum (Al) alloys have widespread industrial applications. However, most commercially available high-strength Al alloys, like AA 7075, are not suitable for additive manufacturing due to their high susceptibility to solidification cracking. In this work, a custom Al alloy Al 92 Ti 2 Fe 2 Co 2 Ni 2 is fabricated by selective laser melting. Heterogeneous nanoscale medium-entropy intermetallic lamella form in the as-printed Al alloy. Macroscale compression tests reveal a combination of high strength, over 700 MPa, and prominent plastic deformability. Micropillar compression tests display significant back stress in all regions, and certain regions have flow stresses exceeding 900 MPa. Post-deformation analyses reveal that, in addition to abundant dislocation activities in Al matrix, complex dislocation structures and stacking faults form in monoclinic Al 9 Co 2 type brittle intermetallics. This study shows that proper introduction of heterogeneous microstructures and nanoscale medium entropy intermetallics offer an alternative solution to the design of ultrastrong, deformable Al alloys via additive manufacturing.

Science & Technology - Other Topics↗
DOE OSTI2024

Electricity use in big area additive manufacturing of fiber-reinforced polymer composites

In recent years, additive manufacturing (AM), especially large-format additive manufacturing (LFAM), has gained momentum in the manufacturing industry. While LFAM offers benefits over conventional manufacturing processes, such as minimizing material waste and providing vast geometric freedom, assessing its sustainability remains challenging due to limited data, particularly on energy consumption. Most existing data pertain to small-scale or desktop AM and are not directly applicable to LFAM. In this study, we conducted real-time measurements of electricity usage for a type of LFAM known as big area additive manufacturing (BAAM), which typically uses fiber-reinforced polymer pellets as feedstock. We collected electricity usage data from fifteen printing jobs over two months in an industrial production setting. These data fill the existing gap and can be reused to enhance the community’s understanding of LFAM electricity usage, support further research, and promote sustainable development in advanced manufacturing technologies.

ecology↗
DOE OSTI2024

High-performance cementitious composites containing nanostructured carbon additives made from charred coal fines

Carbon-based nanomaterials, such as carbon nanoplatelets, graphene oxide, and carbon quantum dots, have many possible end-use applications due to their ability to impart unique mechanical, electrical, thermal, and optical properties to cement composites. Despite this potential, these materials are rarely used in the construction industry due to high material costs and limited data on performance and durability. In this study, domestic coal is used to fabricate low-cost carbon nanomaterials that can be used economically in cement formulations. A range of chemical and physical processing approaches are employed to control the size, morphology, and chemical functionalization of the carbon nanomaterial, which improves its miscibility with cement formulations and its impact on mechanical properties and durability. At loadings of 0.01 to 0.07 wt.% of coal-derived carbon nanomaterial, the compressive and flexural strength of cement samples are enhanced by 24% and 23%, respectively, in comparison to neat cement. At loadings of 0.02 to 0.06 wt.%, the compressive and flexural strength of concrete composites increases by 28% and 21%, respectively, in comparison to neat samples. Additionally, the carbon nanomaterial additives studied in this work reduce cement porosity by 36%, permeability by 86%, and chloride penetration depth by 60%. These results illustrate that low-loadings of coal-derived carbon nanomaterial additives can improve the mechanical properties, durability, and corrosion resistance of cement composites.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Crack mitigation in additively manufactured AlCrFe 2 Ni 2 high-entropy alloys through engineering phase transformation pathway

The far-from-equilibrium solidification during additive manufacturing often creates large residual stresses that induce solid-state cracking. Here we present a strategy to suppress solid-state cracking in an additively manufactured AlCrFe 2 Ni 2 high-entropy alloy via engineering phase transformation pathway. We investigate the solidification microstructures formed during laser powder-bed fusion and directed energy deposition, encompassing a broad range of cooling rates. At high cooling rates (10 4 –10 6 K/s), we observe a single-phase BCC/B2 microstructure that is susceptible to solid-state cracking. At low cooling rates (10 2 –10 4 K/s), FCC phase precipitates out from the BCC/B2 matrix, resulting in enhanced ductility (~10 %) and resistance to solid-state cracking. Site-specific residual stress/strain analysis reveals that the ductile FCC phase can largely accommodate residual stresses, a feature which helps relieve residual strains within the BCC/B2 phase to prevent cracking. Our work underscores the value of exploiting the toolbox of phase transformation pathway engineering for material design during additive manufacturing.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Dual-precipitates enhance fatigue resistance in an additively manufactured high-entropy alloy

To accomplish the intense desire of high-strength materials for enhanced energy-efficiency, recent research applies a combined strategy of additive-manufacturing and precipitation-strengthening in high entropy alloys. In a context, Al 0.2 Co 1.5 CrFeNi 1.5 Ti 0.3 nanoprecipitation-strengthened system was developed, demonstrating very convincing strength and toughness. Moreover, additive-manufacturing facilitated additional strength by well-decorated cell-boundaries with blocky L2 1 precipitates and homogeneously distributed L1 2 precipitates. However, fatigue research of this alloy remained unexplored despite being the main precursor for structural applications. In this study low-cycle fatigue behavior of this alloy in both as-built and precipitation-strengthened (aged) conditions has been explored, combined with in-situ neutron diffraction investigation. Findings revealed a substantial cyclic-stress profile and a notable fatigue-life below ±0.50% strain-amplitude, exceeding 10 5 cycles at ±0.30% strain-amplitude. These demonstrate the potential to carry higher payloads with marked engineering-reliability. Residual-stress estimation revealed strain-compatibility between the matrix and L1 2 precipitate, indicating a crack-initiation immune interface. A comparative examination of dislocation character revealed shifting towards pure edge-character in aged alloy indicates precipitates promoted planar-slip during deformation.

36 MATERIALS SCIENCE↗