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At least 199 records · Page 11

Reversible two-way tuning of thermal conductivity in an end-linked star-shaped thermoset

Polymeric thermal switches that can reversibly tune and significantly enhance their thermal conductivities are desirable for diverse applications in electronics, aerospace, automotives, and medicine; however, they are rarely achieved. Here, we report a polymer-based thermal switch consisting of an end-linked star-shaped thermoset with two independent thermal conductivity tuning mechanisms—strain and temperature modulation—that rapidly, reversibly, and cyclically modulate thermal conductivity. The end-linked star-shaped thermoset exhibits a strain-modulated thermal conductivity enhancement up to 11.5 at a fixed temperature of 60 °C (increasing from 0.15 to 2.1 W m –1 K –1 ). Additionally, it demonstrates a temperature-modulated thermal conductivity tuning ratio up to 2.3 at a fixed stretch of 2.5 (increasing from 0.17 to 0.39 W m –1 K –1 ). When combined, these two effects collectively enable the end-linked star-shaped thermoset to achieve a thermal conductivity tuning ratio up to 14.2. Moreover, the end-linked star-shaped thermoset demonstrates reversible tuning for over 1000 cycles. The reversible two-way tuning of thermal conductivity is attributed to the synergy of aligned amorphous chains, oriented crystalline domains, and increased crystallinity by elastically deforming the end-linked star-shaped thermoset.

42 ENGINEERING↗

Controlled n –Doping of Naphthalene Diimide–Based Two–Dimensional Polymers

Two-dimensional polymers (2DPs) are promising as structurally well-defined, permanently porous, organic semiconductors. However, 2DPs are nearly always isolated as closed shell organic species with limited charge carriers, which leads to low bulk conductivities. Here, we enhance the bulk conductivity of two naphthalene diimide (NDI)-containing 2DP semiconductors by controllably n-doping the NDI units using cobaltocene (CoCp 2 ). Optical and transient microwave spectroscopy reveals that both as-prepared NDI-containing 2DPs are semiconducting with sub-2 eV optical bandgaps and photoexcited charge-carrier lifetimes of tens of nanoseconds. Following reduction with CoCp 2 , both 2DPs largely retain their periodic structures and exhibit optical and electron-spin resonance spectroscopic features consistent with the presence of NDI-radical anions. Here, while the native NDI-based 2DPs are electronically insulating, maximum bulk conductivities of >10 –4 S cm –1 are achieved by substoichiometric levels of n-doping. Density functional theory calculations show that the strongest electronic couplings in these 2DPs exist in the out-of-plane (π-stacking) crystallographic directions, which indicates that cross-plane electronic transport through NDI stacks is primarily responsible for the observed electronic conductivity. Taken together, this study underlines that controlled molecular doping is a useful approach to access structurally well-defined, paramagnetic, 2DP n-type semiconductors with measurable bulk electronic conductivities of interest for electronic or spintronic devices.

2D polymers↗

Search for a Grotthuss mechanism through the observation of proton transfer

The transport of protons is critical in a variety of bio- and electro-chemical processes and technologies. The Grotthuss mechanism is considered to be the most efficient proton transport mechanism, generally implying a transfer of protons between ‘chains’ of host molecules via elementary reactions within the hydrogen bonds. Although Grotthuss proposed this concept more than 200 years ago, only indirect experimental evidence of the mechanism has been observed. Here we report the first experimental observation of proton transfer between the molecules in pure and 85% aqueous phosphoric acid. Employing dielectric spectroscopy, quasielastic neutron, and light scattering, and ab initio molecular dynamic simulations we determined that protons move by surprisingly short jumps of only ~0.5–0.7 Å, much smaller than the typical ion jump length in ionic liquids. Our analysis confirms the existence of correlations in these proton jumps. However, these correlations actually reduce the conductivity, in contrast to a desirable enhancement, as is usually assumed by a Grotthuss mechanism. Furthermore, our analysis suggests that the expected Grotthuss-like enhancement of conductivity cannot be realized in bulk liquids where ionic correlations always decrease conductivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Iso-cost-performance of thermal energy storage

As thermal energy storage (TES) systems gain increasing recognition as next-generation energy storage solutions, evaluating their techno-economic performance is crucial. This perspective analyzes the cost-performance of latent heat-based TES systems and introduces the concept of iso-cost-performance—maintaining a constant cost per unit energy ($\$$/kWh) despite material degradation. Using an empirical degradation model, we show that after 1200 thermal cycles, the thermal conductivity and volumetric energy density of a paraffin-based phase change material (PCM) decreased by 36.0% and 26.1%, respectively, resulting in a 31.2% reduction in the figure of merit (FOM) and, consequently, the system cost-performance. However, by introducing thermally conductive additives to enhance effective thermal conductivity, the TES system can recover its initial FOM, achieving iso-cost-performance operation. This framework quantitatively demonstrates how degradation-mitigation strategies—such as improving thermal conductivity—can offset material degradations and maintain long-term cost-effectiveness. Beyond PCM-based TES, the proposed FOM-based approach provides a generalized pathway for cost-performance optimization across various TES technologies.

25 ENERGY STORAGE↗

Single-beam ion source enhanced growth of transparent conductive thin films

A single-beam ion source was developed and used in combination with magnetron sputtering to modulate the film microstructure. The ion source emits a single beam of ions that interact with the deposited film and simultaneously enhances the magnetron discharge. The magnetron voltage can be adjusted over a wide range, from approximately 240 to 130 V, as the voltage of the ion source varies from 0 to 150 V, while the magnetron current increases accordingly. The low-voltage high-current magnetron discharge enables a 'soft sputtering mode', which is beneficial for thin-film growth. Indium tin oxide (ITO) thin films were deposited at room temperature using a combined single-beam ion source and magnetron sputtering. Furthermore, the ion beam resulted in the formation of polycrystalline ITO thin films with significantly reduced resistivity and surface roughness. Single-beam ion-source-enhanced magnetron sputtering has many potential applications in which low-temperature growth of thin films is required, such as coatings for organic solar cells.

36 MATERIALS SCIENCE↗

Enhanced flexibility and thermal conductivity of HfC decorated carbon nanofiber mats

Future-generation spacecraft components allude discovery of novel materials that can withstand extreme environments (>2000 °C). The combined effect of ultra-high temperature ceramics (UHTCs) and carbon fibers (C f ) can satisfy the demanding requirements of aerospace applications. A novel, hybrid, and flexible hafnium carbide (HfC)-decorated carbon nanofiber (C nf ) mat was fabricated via electrospinning. Enhanced thermal stability of the flexible HfC decorated C nf over C nf can be elucidated from the 20-fold increment in thermal conductivity and the onset of degradation at higher temperatures (840 °C). Successful integration of multi-layered sandwich lattice using in-housed fabricated HfC decorated C nf showed retention of the fibrous structure even after extreme spark plasma sintering (SPS) process at 1850 °C. Fabricating a similar multi-layered structure using procured C f was unsuccessful due to bundled agglomeration and micron-sized fibers. High-load indentation suggests that HfC decorated C nf interlayer is stronger (~2.3 times) than the parent UHTC with no cracking at the interface. Compared with the HfC matrix, the indentation-damaged area at the interface reduced up to ~56% due to toughening mechanisms such as C nf , fiber pull-out and bridging. The synthesized HfC decorated Cnf mat is proposed as an ultra-thin filler material for joining similar or dissimilar UHTCs while maintaining similar chemistry and better mechanical integrity at the interface. Furthermore, the findings insinuate a new paradigm in designing hybrid and flexible ceramic-containing materials for thermal protection systems (TPS) of future-generation spacecraft components that can mitigate failure in extreme environments (>2000 °C).

36 MATERIALS SCIENCE↗

Experimental and numerical investigation of fracture conductivity between non-smooth rock surfaces with and without proppant

The enhancement of fracture conductivity is vital for the efficient recovery of subsurface resources, such as geothermal energy and petroleum hydrocarbons. Proppants, granular materials injected into hydraulic fractures to maintain their conductivity, have been studied primarily in the context of smooth fractures (i.e., fractures between smooth rock surfaces). However, non-smooth fractures (i.e., fractures between rough rock surfaces) are common in geoenergy reservoirs and thus require further investigations. In this study, we conducted laboratory measurements of fracture conductivity on shale slabs with non-smooth surfaces and carried out numerical simulation using the lattice Boltzmann (LB) method, which aimed to investigate the conductivity of non-smooth fractures with and without proppants placement. When ceramic proppant with an areal concentration of 2 lb/ft 2 was placed in the fracture, the conductivity was enhanced by roughly 3-8 times compared to fractures without proppant. In fractures with proppant, gas-measured conductivity was higher than that measured with water due to proppant embedment caused by water. The experiments demonstrate the advantages of using proppant in fractures, even if the rock surface roughness can provide certain fracture conductivity via the self-propping mechanism. For fractures without proppants, high rock surface roughness is not necessarily favorable for enhancing fracture conductivity because the self-propping mechanism requires shear slip along the fracture surface. If there is no shear slip, high rock surface roughness can cause a detrimental effect on the fracture conductivity due to the interlocking effect. Utilizing advanced experimental equipment and LB modeling, this research explores the interplays between proppant placement, fracture geometry, and stress conditions to develop a comprehensive understanding of the productivity in non-smooth fractures. Further, the outcomes of this investigation indicate the importance of creating fractures with surface roughness during hydraulic fracturing and will contribute to the development of more efficient stimulation techniques for subsurface energy extraction.

15 GEOTHERMAL ENERGY↗

Mechanisms of proton transport in aqueous acid solutions

The fundamental understanding of proton transport, specifically the Grotthuss-like mechanism, is critical for many technological applications. The present study presents a comprehensive analysis of proton transport in aqueous solutions of sulfuric and phosphoric acids using quasielastic neutron and light scattering, broadband dielectric spectroscopy, rheology, pulsed-field gradient-NMR measurements, and ab initio molecular dynamic simulations. Results show that in all systems, proton transport occurs through short “jumps” of ~0.5 Å that are faster than structural relaxation. However, proton hopping appears to be coupled to structural relaxation in aqueous solutions of sulfuric acid, while these processes are decoupled in phosphoric acid. Neutron scattering indicates that all protons have the same fast mobility in phosphoric acid systems, while at least one proton per sulfuric molecule remains slower than other protons. Analysis reveals correlated proton jumps, but these correlations suppress conductivity, suggesting that expected Grotthuss-like enhancement of conductivity is unlikely in bulk liquids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development of Design Standards and Guidelines for Electromagnetic Compatibility and Lightning Protection for Spacecraft Utilizing Composite Materials

This final report presents information concerning technical accomplishments by Tec-Masters, Inc. (TMI) for this contract effort. This effort included the accomplishment and/or submission by TMI of the following items: (1) Literature Survey Report, Electrical Properties of Non-Metallic Composites by Mr. Hugh W. Denny; (2) Interim Report, Composite Materials - Conductivity, Shielding Effectiveness, and Current Carrying Capability by Mr. Ross W. Evans; (3) Fault Current Test Plan by Mr. Ross W. Evans (4) Fault Current Test Procedure by Mr. Ross W. Evans (5) Test Report, Fault Current Through Graphite Filament Reinforced Plastic, NASA CR-4774, Marshall Space Flight Center, Alabama, September 1996, by Mr. Ross W. Evans; (6) Test Plan, Lightning Effects on Composite Materials by Mr. Ross W. Evans; (7) Test Report, Lightning Effects on Composite Materials, NASA CR-4783, Marshall Space Flight Center, Alabama, February 1997, by Mr. Ross W. Evans; (8) Design Guidelines for Shielding Effectiveness, Current Carrying Capability, and the Enhancement of Conductivity of Composite Materials, NASA CR-4784, Marshall Space Flight Center, Alabama, September 1996, by Mr. Ross W. Evans. These items are not attached but are considered to be a part of this final report. Efforts on two additional items were accomplished at no increase in cost to NASA/MSFC. These items consisted of updating the 'MSFC EMC Design and Interference Control Handbook,' and revising the 'Design Guidelines for Shielding Effectiveness, Current Carrying Capability, and the Enhancement of Conductivity of Composite Materials.'

Camp, Dennis W.↗

Evidence for a Solid-Electrolyte Inductive Effect in the Superionic Conductor Li 10 Ge 1– x Sn x P 2 S 12

Strategies to enhance ionic conductivities in solid electrolytes typically focus on the effects of modifying their crystal structures or of tuning mobile-ion stoichiometries. A less-explored approach is to modulate the chemical bonding interactions within a material to promote fast lithium-ion diffusion. Recently, the idea of a solid-electrolyte inductive effect has been proposed, whereby changes in bonding within the solid-electrolyte host framework modify the potential energy landscape for the mobile ions, resulting in an enhanced ionic conductivity. Direct evidence for a solid-electrolyte inductive effect, however, is lacking—in part because of the challenge of quantifying changes in local bonding interactions within a solid-electrolyte host framework. Here, we consider the evidence for a solid-electrolyte inductive effect in the archetypal superionic lithium-ion conductor Li 10 Ge 1–x Sn x P 2 S 12 . Substituting Ge for Sn weakens the {Ge,Sn}–S bonding interactions and increases the charge density associated with the S 2– ions. This charge redistribution modifies the Li + substructure causing Li + ions to bind more strongly to the host framework S 2– anions, which in turn modulates the Li + ion potential energy surface, increasing local barriers for Li + ion diffusion. Each of these effects is consistent with the predictions of the solid-electrolyte inductive effect model. Density functional theory calculations predict that this inductive effect occurs even in the absence of changes to the host framework geometry due to Ge → Sn substitution. These results provide direct evidence in support of a measurable solid–electrolyte inductive effect and demonstrate its application as a practical strategy for tuning ionic conductivities in superionic lithium-ion conductors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrically conductive anodized aluminum coatings

A process for producing anodized aluminum with enhanced electrical conductivity, comprising anodic oxidation of aluminum alloy substrate, electrolytic deposition of a small amount of metal into the pores of the anodized aluminum, and electrolytic anodic deposition of an electrically conductive oxide, including manganese dioxide, into the pores containing the metal deposit; and the product produced by the process.

Alwitt, Robert S.↗

Enhancement of effective thermal conductivity of rGO/Mg nanocomposite packed beds

Engineering thermophysical properties of metal hydrides nanocomposites is crucial for effective thermal management during hydrogen storage reactions; however, the effect of microstructure on thermal transport mechanisms is still unclear. Here, we employed an integrated experiment-modeling approach to investigate microstructural factors that determine the effective thermal conductivity of individual reduced graphene oxide-magnesium (rGO/Mg) nanocomposites and their packed bed. Here the effective thermal conductivity of the rGO/Mg nanocomposite packed bed was measured by using guarded hot-plate method under various atmospheric conditions (i.e., vacuum, Ar and He). A microstructure-aware mesoscopic modeling revealed that anisotropy of the effective thermal conductivity of individual rGO/Mg nanocomposites plays an important role in determining the effective thermal conductivity of their packed bed. The validated mesoscopic model also disclosed a nontrivial interplay between the intrinsic rGO properties and the extrinsic composite structural features. Finally, quantitative sensitivity analysis based on the modeling framework is used to provide practical engineering guidance for controlling the thermal transport within nanocomposite packed beds.

36 MATERIALS SCIENCE↗

VISTA Enhancer browser: an updated database of tissue-specific developmental enhancers

Regulatory elements (enhancers) are major drivers of gene expression in mammals and harbor many genetic variants associated with human diseases. Here, we present an updated VISTA Enhancer Browser (https://enhancer.lbl.gov), a database of transgenic enhancer assays conducted in developing mouse embryos in vivo. Since the original publication in 2007, the database grew nearly 20-fold from 250 to over 4500 experiments and currently harbors over 23 500 images. The updated database provides structured information on experiments conducted at different stages of embryonic development, including enhancer activities of human pathogenic and synthetic variants and sequences derived from a variety of species. In addition to manually curated results of thousands of individual experiments, the new database also features hundreds of manually curated comparisons between alleles. The VISTA Enhancer Browser provides a crucial resource for study of human genetic variation, gene regulation and developmental biology.

59 BASIC BIOLOGICAL SCIENCES↗

Enhanced Thermal Stability of Conductive Mercury Telluride Colloidal Quantum Dot Thin Films Using Atomic Layer Deposition

Colloidal quantum dots (CQDs) are valuable for their potential applications in optoelectronic devices. However, they are susceptible to thermal degradation during processing and while in use. Mitigating thermally induced sintering, which leads to absorption spectrum broadening and undesirable changes to thin film electrical properties, is necessary for the reliable design and manufacture of CQD-based optoelectronics. Here, low-temperature metal–oxide atomic layer deposition (ALD) was investigated as a method for mitigating sintering while preserving the optoelectronic properties of mercury telluride (HgTe) CQD films. ALD-coated films are subjected to temperatures up to 160 °C for up to 5 h and alumina (Al 2 O 3 ) is found to be most effective at preserving the optical properties, demonstrating the feasibility of metal–oxide in-filling to protect against sintering. HgTe CQD film electrical properties were investigated before and after alumina ALD in-filling, which was found to increase the p-type doping and hole mobility of the films. The magnitude of these effects depended on the conditions used to prepare the HgTe CQDs. With further investigation into the interaction effects of CQD and ALD process factors, these results may be used to guide the design of CQD–ALD materials for their practical integration into useful optoelectronic devices.

36 MATERIALS SCIENCE↗

High-Temperature Adhesives for Thermally Stable Aero-Assist Technologies

Aero-assist technologies are used to control the velocity of exploration vehicles (EVs) when entering Earth or other planetary atmospheres. Since entry of EVs in planetary atmospheres results in significant heating, thermally stable aero-assist technologies are required to avoid the high heating rates while maintaining low mass. Polymer adhesives are used in aero-assist structures because of the need for high flexibility and good bonding between layers of polymer films or fabrics. However, current polymer adhesives cannot withstand temperatures above 400 C. This innovation utilizes nanotechnology capabilities to address this need, leading to the development of high-temperature adhesives that exhibit high thermal conductivity in addition to increased thermal decomposition temperature. Enhanced thermal conductivity will help to dissipate heat quickly and effectively to avoid temperature rising to harmful levels. This, together with increased thermal decomposition temperature, will enable the adhesives to sustain transient high-temperature conditions.

Eberts, Kenneth↗

Elucidating the effect of preheating temperature on melt pool morphology variation in Inconel 718 laser powder bed fusion via simulation and experiment

In laser powder bed fusion (L-PBF) additive manufacturing, the mechanical performance, microstructure and defects of fabricated parts are closely associated with the melt pool morphology, e.g., its dimension and shape through the building process. Past studies have largely focused on how the process parameters such as laser power and scan speed affect melt pool characteristics. In this study, the melt pool morphology variation as a function of preheating temperature in the conduction, transition, and keyhole regimes and the underlying mechanisms in each regime are investigated through ex-situ sample characterization and computation thermal fluid dynamics (CtFD) simulation. Single tracks with different combinations of laser power and scan speed are deposited on an Inconel 718 bare plate preheated to a temperature range of 100–500 °C in the experiment. Significant changes are observed in melt pool morphology as a function of preheating temperature from optical measurements of melt track cross sections. The depth of melt pool in the three regimes increases monotonically with preheating temperature, e.g., at 500 °C, the experimental melt pool depth is increased by 49% in conduction regime, 34% in transition regime and 33% in keyhole regime, respectively, while the variation of melt pool width in each regime does not all follow an increasing trend but depends on the melt pool regimes. Melt pool width variation in the conduction and transition regimes is found to depend on the enhanced heat conduction directly related to temperature dependent thermal properties. Through validated CtFD simulations, it is found that in the keyhole regime the evaporation mass, recoil pressure, and laser drilling effect is enhanced with higher preheating temperature, which gives rise to a deeper melt pool. The simulations also reveal that preheating temperature significantly elongates the melt track length due to the increased flow rate and strong recoil pressure that accelerates the backward flow.

36 MATERIALS SCIENCE↗