Search NASA⌕ Search

SEARCH · Search NASA

Results for “Calorimetry”

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

Application of Ibuprofen Sodium Dihydrate for Thermochemical Energy Storage

Thermochemical energy storage (TCES) offers a transformative approach to address grid instability by harnessing reversible chemical reactions for efficient heat storage and release. Here, we introduce pharmaceutical organic salt hydrates as a class of materials with exceptional performance for low-grade waste heat recovery. We demonstrate ibuprofen sodium dihydrate (ISD) as an example organic hydrate exhibiting a dehydration temperature range of 60-110 °C and a remarkable dehydration enthalpy of up to 59.5 kJ/mol of water, ideally suited for capturing industrial and residential waste heat. Using rigorous multimodal characterization, including thermogravimetric analysis, differential scanning calorimetry, in-situ FTIR, in-situ PXRD, and NMR, we demonstrate ISD's superior thermal, chemical, and structural stability over 150 hydration-dehydration cycles, achieving an unprecedented cycling efficiency of ~99.9%. Compared to conventional inorganic salt hydrates like strontium chloride hexahydrate and calcium oxalate monohydrate, ISD showcases enhanced durability without deliquescence or pulverization, even under high-humidity conditions. In-situ analyses confirm the transition from ISD to ibuprofen sodium anhydrous (ISA) proceeds with structural reorganization, thereby combining the dehydration mechanism with phase transitions, resulting in higher energy storage capacity. Microstructural analyses reveal that repeated water intercalation and structural transitions aid in creating significant porosity that enhances water transport kinetics, further improving the hydration/dehydration performance. By combining the phase change and chemical dehydration mechanisms, ISD paves the way for designing a new class of organic salt hydrates, offering tunable properties to meet diverse thermal energy storage demands and supporting sustainable grid resilience.

Thangaraj, Kavin C.↗

High–Nickel NMA: A Cobalt–Free Alternative to NMC and NCA Cathodes for Lithium–Ion Batteries

High-nickel LiNi 1–x–y Mn x Co y O 2 (NMC) and LiNi 1–x–y Co x Al y O 2 (NCA) are the cathode materials of choice for next-generation high-energy lithium-ion batteries. Both NMC and NCA contain cobalt, an expensive and scarce metal generally believed to be essential for their electrochemical performance. Herein, a high-Ni LiNi 1–x–y Mn x Al y O 2 (NMA) cathode of desirable electrochemical properties is demonstrated benchmarked against NMC, NCA, and Al–Mg-codoped NMC (NMCAM) of identical Ni content (89 mol%) synthesized in-house. Despite a slightly lower specific capacity, high-Ni NMA operates at a higher voltage by ≈40 mV and shows no compromise in rate capability relative to NMC and NCA. In pouch cells paired with graphite, high-Ni NMA outperforms both NMC and NCA and only slightly trails NMCAM and a commercial cathode after 1000 deep cycles. Further, the superior thermal stability of NMA to NMC, NCA, and NMCAM is shown using differential scanning calorimetry. Here, considering the flexibility in compositional tuning and immediate synthesis scalability of high-Ni NMA very similar to NCA and NMC, this study opens a new space for cathode material development for next-generation high-energy, cobalt-free Li-ion batteries.

25 ENERGY STORAGE↗

The Role of Demixing and Crystallization Kinetics on the Stability of Non‐Fullerene Organic Solar Cells

Abstract With power conversion efficiency now over 17%, a long operational lifetime is essential for the successful application of organic solar cells. However, most non‐fullerene acceptors can crystallize and destroy devices, yet the fundamental underlying thermodynamic and kinetic aspects of acceptor crystallization have received limited attention. Here, room‐temperature (RT) diffusion coefficients of 3.4 × 10 −23 and 2.0 × 10 −22 are measured for ITIC‐2Cl and ITIC‐2F, two state‐of‐the‐art non‐fullerene acceptors. The low coefficients are enough to provide for kinetic stabilization of the morphology against demixing at RT. Additionally profound differences in crystallization characteristics are discovered between ITIC‐2F and ITIC‐2Cl. The differences as observed by secondary‐ion mass spectrometry, differential scanning calorimetry (DSC), grazing‐incidence wide‐angle X‐ray scattering, and microscopy can be related directly to device degradation and are attributed to the significantly different nucleation and growth rates, with a difference in the growth rate of a factor of 12 at RT. ITIC‐4F and ITIC‐4Cl exhibit similar characteristics. The results reveal the importance of diffusion coefficients and melting enthalpies in controlling the growth rates, and that differences in halogenation can drastically change crystallization kinetics and device stability. It is furthermore delineated how low nucleation density and large growth rates can be inferred from DSC and microscopy experiments which could be used to guide molecular design for stability.

Hu, Huawei↗

Giant and Reversible Barocaloric Effect in Trinuclear Spin–Crossover Complex Fe 3 (bntrz) 6 (tcnset) 6

A giant barocaloric effect (BCE) in a molecular material Fe 3 (bntrz) 6 (tcnset) 6 (FBT) is reported, where bntrz = 4-(benzyl)-1,2,4-triazole and tcnset = 1,1,3,3-tetracyano-2-thioethylepropenide. The crystal structure of FBT contains a trinuclear transition metal complex that undergoes an abrupt spin-state switching between the state in which all three FeII centers are in the high-spin (S = 2) electronic configuration and the state in which all of them are in the low-spin (S = 0) configuration. Despite the strongly cooperative nature of the spin transition, it proceeds with a negligible hysteresis and a large volumetric change, suggesting that FBT should be a good candidate for producing a large BCE. Powder X-ray diffraction and calorimetry reveal that the material is highly susceptible to applied pressure, as the transition temperature spans the range from 318 at ambient pressure to 383 K at 2.6 kbar. Despite the large shift in the spin-transition temperature, its nonhysteretic character is maintained under applied pressure. Such behavior leads to a remarkably large and reversible BCE, characterized by an isothermal entropy change of 120 J kg –1 K –1 and an adiabatic temperature change of 35 K, which are among the highest reversible values reported for any caloric material thus far.

36 MATERIALS SCIENCE↗

Simultaneously Blocking Chemical Crosstalk and Internal Short Circuit via Gel-Stretching Derived Nanoporous Non-Shrinkage Separator for Safe Lithium-Ion Batteries

The separator, an ionic permeable and electronic insulating membrane between cathode and anode, plays a crucial role in the electrochemical and safety performance of batteries. However, the commercial polyolefin separators not only suffer from inevitable thermal shrinkage at elevated temperature, but also fail to inhibit the hidden chemical crosstalk of reactive gases such as O 2 , leading to often reported thermal runaway (TR) and hence preventing large-scale implementation of high-energy-density lithium-ion batteries. Herein, a nanoporous non-shrinkage separator (GS-PI) was fabricated via a novel gel-stretching orientation approach to eliminate TR. In situ synchrotron small angle X-ray scattering during heating clearly showed that the as-prepared thin GS-PI separator exhibits superior mechanical tolerance at high temperature, thus effectively preventing internal short circuit. Meanwhile, the unique nanoporous structure design further blocks chemical crosstalk and the associated exothermic reactions. Accelerating Rate Calorimetry test revealed that the practical 1 Ah LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM622)/graphite pouch cell using GS-PI nanoporous separator show a maximum temperature rise (dT/dt max ) of only 3.7 °C s -1 compared to 131.6 °C s -1 in the case of Al 2 O 3 @PE macroporous separator. Furthermore, despite the reduced pore size, the GS-PI separator demonstrates better cycling stability than conventional Al 2 O 3 @PE separator at high temperature without sacrificing specific capacity and rate capability.

25 ENERGY STORAGE↗

Additive Manufacturing of Poly(phenylene Sulfide) Aerogels via Simultaneous Material Extrusion and Thermally Induced Phase Separation

Abstract Additive manufacturing (AM) of aerogels increases the achievable geometric complexity, and affords fabrication of hierarchically porous structures. In this work, a custom heated material extrusion (MEX) device prints aerogels of poly(phenylene sulfide) (PPS), an engineering thermoplastic, via in situ thermally induced phase separation (TIPS). First, pre‐prepared solid gel inks are dissolved at high temperatures in the heated extruder barrel to form a homogeneous polymer solution. Solutions are then extruded onto a room‐temperature substrate, where printed roads maintain their bead shape and rapidly solidify via TIPS, thus enabling layer‐wise MEX AM. Printed gels are converted to aerogels via postprocessing solvent exchange and freeze‐drying. This work explores the effect of ink composition on printed aerogel morphology and thermomechanical properties. Scanning electron microscopy micrographs reveal complex hierarchical microstructures that are compositionally dependent. Printed aerogels demonstrate tailorable porosities (50.0–74.8%) and densities (0.345–0.684 g cm −3 ), which align well with cast aerogel analogs. Differential scanning calorimetry thermograms indicate printed aerogels are highly crystalline (≈43%), suggesting that printing does not inhibit the solidification process occurring during TIPS (polymer crystallization). Uniaxial compression testing reveals that compositionally dependent microstructure governs aerogel mechanical behavior, with compressive moduli ranging from 33.0 to 106.5 MPa.

Chemistry↗

MXene Reinforced Thermosetting Composite for Lightning Strike Protection of Carbon Fiber Reinforced Polymer

Ti 3 C 2 – a member of the MXenes (2D transition metal carbides and nitrides) family, is investigated as an effective filler to improve the electrical, mechanical, and thermal properties of divinylbenzene (DVB) thermosetting resin. Consequently, its performance as a lightning strike protection (LSP) coating for carbon fiber reinforced polymer (CFRP) is evaluated. Polyaniline (PANI) – dodecylbenzene sulfonic acid (DBSA) complex is used to cure the DVB resin. The synergic effect of MXenes (with surface that is negatively charged) with polyaniline (positive charge) shows electrostatic bonding and improved electrical conductivity in the composite. We also find that the addition of MXenes at 2 wt% into the PANI-DVB composite shows ≈139%, 10%, and 9% improvement in electrical conductivity, flexural strength, and flexural modulus, respectively, compared to the neat PANI-DVB composite. The composites are investigated using various material characterization techniques including Fourier transforms infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry, and scanning electron microscopy. Furthermore, MXenes-DVB is utilized to create a conductive thermosetting coating on top of a CFRP substrate and tested against a lightning strike of 100 kA. CFRP with MXenes-DVB coating reduced the surface damage from 40.61 cm 2 (reference CFRP panel) to 13.29 cm 2 (CFRP coated with MXenes-DVB).

36 MATERIALS SCIENCE↗

Understanding the Role of Hydroxyl Functionalization in Linear Poly(Ethylenimine) for Oxidation‐Resistant Direct Air Capture of CO 2

Aminopolymer-based adsorbents are a prominent class of materials being used for direct air capture of CO 2 at the industrial scale. However, improving their working lifetime, specifically by increasing their resilience to oxidative degradation, remains an ongoing challenge. Toward this end, functionalization of aminopolymers with non-amine functionalities such as hydroxyls has emerged in recent years as a promising strategy toward improving adsorbent lifetime. Although there is a growing body of work demonstrating the effectiveness of this approach and investigating the origin of this improved stability, studies to date have primarily focused on branched aminopolymer systems such as branched poly(ethylenimine). In this work, hydroxyl-functionalized linear poly(ethylenimine) is used to continue to probe the underlying protective mechanism of this strategy. A combination of thermogravimetric analysis, NMR relaxometry, differential scanning calorimetry, and computational simulations is used to better understand the relationship between the extent of chemical functionalization, physical properties, and adsorbent performance.

amine-based adsorbent↗

Guiding Principles for the Rational Design of Hybrid Materials: Use of DFT Methodology for Evaluating Non‐Covalent Interactions in a Uranyl Tetrahalide Model System

Abstract Together with the synthesis and experimental characterization of 14 hybrid materials containing [UO 2 X 4 ] 2− (X=Cl − and Br − ) and organic cations, we report on novel methods for determining correlation trends in their formation enthalpy (ΔH f ) and observed vibrational signatures. Δ H f values were analyzed through isothermal acid calorimetry and a Density Functional Theory+Thermodynamics (DFT+T) approach with results showing good agreement between theory and experiment. Three factors (packing efficiency, cation protonation enthalpy, and hydrogen bonding energy [ ]) were assessed as descriptors for trends in Δ H f . Results demonstrated a strong correlation between and Δ H f , highlighting the importance of hydrogen bonding networks in determining the relative stability of solid‐state hybrid materials. Lastly, we investigate how hydrogen bonding networks affect the vibrational characteristics of uranyl solid‐state materials using experimental Raman and IR spectroscopy and theoretical bond orders and find that hydrogen bonding can red‐shift U≡O stretching modes. Overall, the tightly integrated experimental and theoretical studies presented here bridge the trends in macroscopic thermodynamic energies and spectroscopic features with molecular‐level details of the geometry and electronic structure. This modeling framework forms a basis for exploring 3D hydrogen bonding as a tunable design feature in the pursuit of supramolecular materials by rational design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fine grinding of thermoplastics by high speed friction grinding assisted by guar gum

High speed friction grinding has been used to grind plant and food substances in water but never been explored for grinding of thermoplastics like polylactic acid (PLA), low and high density polyethylene and polypropylene. Such grinding was investigated in this work and was made possible by using 0.5% guar gum solution instead of just water because increasing the viscosity of water reduced their settling and the speed of passing through the grinder. Additionally, tensile, flexural, and impact strengths of the plastics were studied and higher grinding efficiency of PLA could be explained by its low elongation-at-break compared to low density polyethylene, high density polyethylene, and polypropylene. The microplastics (2000–45 μm) were studied for mass and particle size distributions and by scanning electron microscopy, 13 C CP/MAS NMR, Fourier transform infrared spectroscopy, differential scanning calorimetry, and thermogravimetric analysis. In addition, viscosity of guar gum and contact angles was measured. This new technology can produce finely ground microplastics (710–45 μm) for a variety of applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Polymer grafted aramid nanofiber reinforces immiscible waste polypropylene/poly(ethylene terephthalate)

Polypropylene (PP) and poly(ethylene terephthalate) (PET) are plastics commonly used for packaging because of their excellent barrier and mechanical properties. The properties of these plastics are often diminished after mechanical recycling, inevitably causing down-cycling. Furthermore, this problem is exacerbated when different kinds of polymers mix. Aramid nanofibers have the potential to improve the mechanical properties of polymers due to their excellent mechanical properties but their poor dispersion in polymers is a challenge. Grafting polymers onto nanofibers can help address this challenge. In this work, different loading levels (1%, 2%, and 5%) of polymer grafted aramid nanofibers (ANFs) are blended with waste PP/PET (90/10), simulating a PP waste stream containing traces of PET contaminants. Scanning electronic microscopy, rheology, and differential scanning calorimetry results show the affinity of PP functionalized aramid nanofibers (PP_ANF) towards the PP matrix. At 1 wt% of the nanofiber, the size of the PET droplets in the PP matrix of the PP_ANF blend range from 0.2 to 2.0 μm while that of unmodified ANF and PET_ANF blends are in the range of 0.1–6.2 and 0.5–7.4 μm, respectively. In summary, polymer grafted ANFs have the tendency of improving properties of its like polymers due to similarity in the grafting polymer and the polymer matrix.

36 MATERIALS SCIENCE↗

Self‐Assembly Methods Induce Different Individual‐Polymer‐Block Solvation Responses

An understanding of block-specific responses to stimuli in self-assembled copolymers is essential for the effective design of responsive materials. Here, materials formed from different post-reaction processing methods of the same ROMP block copolymer exhibit different block-specific solvent responses, as characterized in situ by fluorescence lifetime imaging microscopy (FLIM). FLIM data were acquired by tagging the polar or nonpolar block separately with a covalently incorporated viscosity-sensitive fluorescent molecular rotor to measure the changing tightness or looseness of assembly upon changes in solvent composition. Rapid precipitation from an insoluble solvent to form a film results in tighter assembly and less difference in tightness/looseness between the two blocks. Further, it interrupts individual block-solvent response behavior. Both results indicate an apparent disruption of the core–shell assembly. This model from FLIM is further supported by differential scanning calorimetry (DSC) and small-angle X-ray scattering (SAXS) data from isolated solids, which show tighter long-range interactions and more long-range order in these kinetically trapped states. Here, the experiments develop FLIM as a method for pinpointing stimuli-responsive behaviors from different processing methods to individual blocks. Together these outcomes provide a future handle for tailoring solvent-triggered assembly/disassembly behavior.

López, Pía A. [University of California, Irvine, C↗

An International Laboratory Comparison Study on Approximating the Enthalpy of Adsorption via the Clausius‐Clapeyron Approach

Materials-based gas capture and storage is an increasingly important area of research. Robust and accurate determination of material properties is required for judicial selection of materials for specific applications and for engineering materials–based systems at scale. One key property is the strength of the adsorbate–adsorbent interaction often quantified via the isosteric enthalpy of adsorption. The heat of adsorption can be measured directly through calorimetry; however, a more widely used approach is to apply the Clausius-Clapeyron (CC) equation to adsorption isotherms collected at different temperatures. While this approach appears to be straightforward, there exist multiple variants in the application of the methodologies employed. This raises the question on how these variations may or may not affect the determined results. Presented here is a discussion of the most common methodologies and a comparison of indirect determinations (via CC) of the isosteric enthalpy of adsorption by different laboratories on identical material. Included in that comparison are discussions on the measurement and analysis reproducibility. Importantly, details of the methodologies are shown to be critical when comparing enthalpies among laboratories, and different methodologies contribute to significant discrepancies and artifacts in the results. Recommendations are provided to promote robust determination and the reporting thereof.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Woven Supramolecular Metal‐Organic Framework Comprising a Ruthenium Bis(terpyridine) Complex and Cucurbit[8]uril: Enhanced Catalytic Activity toward Alcohol Oxidation

Abstract The self‐assembly of a diamondoid woven supramolecular metal–organic framework wSMOF‐1 has been achieved from intertwined [Ru(tpy) 2 ] 2+ (tpy=2,2′,6′,2′′‐terpyridine) complex M1 and cucurbit[8]uril (CB[8]) in water, where the intermolecular dimers formed by the appended aromatic arms of M1 are encapsulated in CB[8]. wSMOF‐1 exhibits ordered pore periodicity in both water and the solid state, as confirmed by a combination of 1 H NMR spectroscopy, UV‐vis absorption, isothermal titration calorimetry, dynamic light scattering, small angle X‐ray scattering and selected area electron diffraction experiments. The woven framework has a pore aperture of 2.1 nm, which allows for the free access of both secondary and primary alcohols and tert ‐butyl hydroperoxide (TBHP). Compared with the control molecule [Ru(tpy) 2 ]Cl 2 , the [Ru(tpy) 2 ] 2+ unit of wSMOF‐1 exhibits a remarkably higher heterogeneous catalysis activity for the oxidation of alcohols by TBHP in n ‐hexane. For the oxidation of 1‐phenylethan‐1‐ol, the yield of acetophenone was increased from 10 % to 95 %.

Zhang, Yun‐Chang↗

In Operando Calorimetric Measurements for Activated Carbon Electrodes in Ionic Liquid Electrolytes under Large Potential Windows

This study aims to investigate the effect of the potential window on heat generation in carbon-based electrical double layer capacitors (EDLCs) with ionic-liquid (IL)-based electrolytes using in operando calorimetry. The EDLCs consisted of two identical activated-carbon electrodes with either neat 1-butyl-1-methylpyrrolidinium bis(trifluoromethane-sulfonyl)imide ([Pyr 14 ][TFSI]) electrolyte or 1.0 m [Pyr 14 ][TFSI] in propylene carbonate (PC) as electrolyte. The instantaneous heat generation rate at each electrode was measured under galvanostatic cycling for different potential windows ranging from 1 to 4 V. First, the heat generation rates at the positive and negative electrodes differed significantly in neat IL owing to the differences in the ion sizes and diffusion coefficients. However, these differences were minimized when the IL was diluted in PC. Second, for EDLC in neat [Pyr 14 ][TFSI] at high potential window (4 V), a pronounced endothermic peak was observed at the beginning of the charging step at the positive electrode owing to TFSI - intercalation in the activated carbon. On the other hand, for EDLC in 1.0 m [Pyr 14 ][TFSI] in PC at potential window above 3 V, an endothermic peak was observed only at the negative electrode owing to the decomposition of PC. Third, for both neat and diluted [Pyr 14 ][TFSI] electrolytes, the irreversible heat generation rate increased with increasing potential window and exceeded Joule heating. This was attributed to the effect of potential-dependent charge redistribution resistance. Additionally, a further increase in the irreversible heat generation rate was observed for the largest potential windows owing to the degradation of the PC solvent. Finally, for both types of electrolyte, the reversible heat generation rate increased with increasing potential window because of the increase in the amount of ion adsorbed/desorbed at the electrode/electrolyte interface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Unveiling real‐time crystallization with nucleators and thickeners for zinc nitrate hexahydrate as a phase change material

Abstract The primary challenge of salt hydrates as phase change materials (PCMs) is their high degree of supercooling (∆ T Sup ). Past studies have attempted to alleviate ∆ T Sup by incorporating nucleators possessing similar lattice structure, without a thorough analysis of the nucleator/PCM interactions. This work presents a novel in‐operando study to visually observe the crystallization process of zinc nitrate hexahydrate (ZNH) in real‐time using suitable nucleators and a thickener. We have introduced a new dataset where zinc acetate dihydrate (ZnAc.2H) has been employed as an additive to ZNH for thermal energy storage (TES). According to our in‐operando study, ZnAc.2H underwent hydrolysis in molten ZNH to precipitate needle‐like ZnO particles, which acted as nucleators for the PCM. In the absence of a thickener, the crystal propagation of ZNH exhibited a preferential directional tendency, whereas incorporation of thickener made the phase change process uniform along all directions. Self‐hydrolysis of ZnAc.2H generated excess water which caused the undesirable effect of broadening the endothermic peak. The addition of carboxymethyl cellulose (CMC) thickener could restrict the activity of excess water and reduce the broadening of the endothermic peak. Differential scanning calorimetry (DSC) revealed that 5 wt% ZnAc.2H additive and 2 wt% CMC thickener added to ZNH can considerably improve the TES properties of ZNH PCM (∆ H Fusion 125.9 J·g −1 , ∆ T Sup 3.0°C, melting point [M.P.] 29.0°C). Our in‐operando studies can unveil real‐time phase change behaviors to better design PCM systems with desired characteristics.

Chakraborty, Anirban↗

Hygrothermal aging and recycling effects on mechanical and thermal properties of recyclable thermoplastic glass fiber composites

Abstract Glass fiber‐reinforced polymer composites are widely used in marine applications, including renewable energy devices and submarines, due to their strength‐to‐weight ratios and corrosion resistance. As sustainability becomes more important, recyclable thermoplastic composites are gaining attention in marine energy applications. These materials face harsh conditions such as high chloride water, UV radiation, pressurization, and thermal cycling, which can affect their durability and recyclability. This study examines the impact of hygrothermal aging on the recyclability of an Elium glass fiber (GF) composite. Samples were mechanically ground for recycling, and mechanical and thermal properties were compared between aged and unaged samples. After seawater aging, the tensile strength and modulus of the unaged composite dropped by 25% and 13% respectively, due to water ingress along the fiber‐matrix interface. The recycled composite showed reduced flexural strength as the long fiber composite was converted into short fibers during the process. Differential scanning calorimetry (DSC) revealed no change in glass transition temperature after aging. Weight loss (25%) was attributed to the thermal stability of the glass fibers. Dynamic mechanical analysis (DMA) showed that the storage modulus increased with aging, and fracture analysis confirmed a mixed mode of failure for aged composites. Highlights Hygrothermal aging lowers mechanical performance of Elium® GF composites. Failure mechanism tends to be matrix cracking and interface bonding. Glass transition temperature is not reduced by hygrothermal aging. Fractured composite was successfully recycled via thermoforming. Flexural strength of the recycled composite is lower.

17 WIND ENERGY↗