Pressure-freezing of dodecane: exploring the crystal structures, formation kinetics and phase diagrams for colossal barocaloric effects in <i>n</i>-alkanes

Poręba, Tomasz; Kicior, Inga

doi:10.1039/d3ra06957e

Cited by 4 publications

(5 citation statements)

References 121 publications

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“…Owing to their large Δ V tr , the phase transitions for all three dialkylammonium halide compounds studied here are predicted to exhibit high sensitivity to pressure, with calculated barocaloric coefficients of 33, 30, and 30 K kbar –1 for Cl, Br, and I analogues, respectively (Figure c). These values are comparable to some of the highest coefficients reported for barocaloric materials of any type (Table S10 and Figure S52) and are larger than those associated with melting transitions in n -alkanes (20 K kbar –1 ). , We note that the higher pressure sensitivity compared to n -alkanes results from the lower relative Δ S tr of dialkylammonium halides rather than a difference in Δ V tr .…”

Section: Results and Discussionmentioning

confidence: 99%

“…The foregoing results establish dialkylammonium halide salts as a new class of highly tunable barocaloric materials with excellent energy density, reversibility, processability, and stability. Through a systematic investigation of barocaloric effects in these organic materials, this work contributes to the rapidly growing knowledge base around pressure-induced phase transitions in organic salts, ,, long-chain hydrocarbons, ,− and plastic crystals. − Efforts to further investigate thermal conductivity, dynamics of disordered phases, and barocaloric effects across a wider range of soft materials are currently underway in our laboratory.…”

Section: Discussionmentioning

confidence: 98%

“…These values are comparable to some of the highest coefficients reported for barocaloric materials of any type (Table S10 and Figure S52) and are larger than those associated with melting transitions in n-alkanes (20 K kbar −1 ). 44,45 We note that the higher pressure sensitivity compared to n-alkanes results from the lower relative ΔS tr of dialkylammonium halides rather than a difference in ΔV tr .…”

Section: Solid-state Phase Transitions At Ambient Pressurementioning

confidence: 92%

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Barocaloric Effects in Dialkylammonium Halide Salts

Seo,

Ukani,

Zheng

et al. 2024

J. Am. Chem. Soc.

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Barocaloric effects�solid-state thermal changes induced by the application and removal of hydrostatic pressure�offer the potential for energy-efficient heating and cooling without relying on volatile refrigerants. Here, we report that dialkylammonium halides� organic salts featuring bilayers of alkyl chains templated through hydrogen bonds to halide anions�display large, reversible, and tunable barocaloric effects near ambient temperature. The conformational flexibility and soft nature of the weakly confined hydrocarbons give rise to order−disorder phase transitions in the solid state that are associated with substantial entropy changes (>200 J kg −1 K −1 ) and high sensitivity to pressure (>24 K kbar −1 ), the combination of which drives strong barocaloric effects at relatively low pressures. Through high-pressure calorimetry, X-ray diffraction, and Raman spectroscopy, we investigate the structural factors that influence pressure-induced phase transitions of select dialkylammonium halides and evaluate the magnitude and reversibility of their barocaloric effects. Furthermore, we characterize the cyclability of thin-film samples under aggressive conditions (heating rate of 3500 K s −1 and over 11,000 cycles) using nanocalorimetry. Taken together, these results establish dialkylammonium halides as a promising class of pressure-responsive thermal materials.

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Section: Results and Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 98%

Section: Solid-state Phase Transitions At Ambient Pressurementioning

confidence: 92%

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Barocaloric Effects in Dialkylammonium Halide Salts

Seo,

Ukani,

Zheng

et al. 2024

J. Am. Chem. Soc.

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“…In recent years, the colossal BCE of the S−L transition has garnered increased attention. 12,13,23 To date, high operating pressures induced barocaloric effects based on solid−liquid phase transitions poses challenges for achieving refrigeration at low pressures in practical applications. 2,24 Therefore, the focus of research remains on finding new materials capable of exhibiting a BCE at lower pressures, and the selection criteria for barocaloric effect materials are proposed as follows.…”

mentioning

confidence: 99%

“…The barocaloric effect of the S–L transition is generally much higher than that of the structural transition in the solid state because of its larger structural difference between the solid and liquid states than that of the structure transition within the solid state. In recent years, the colossal BCE of the S–L transition has garnered increased attention. ,, To date, high operating pressures induced barocaloric effects based on solid–liquid phase transitions poses challenges for achieving refrigeration at low pressures in practical applications. , Therefore, the focus of research remains on finding new materials capable of exhibiting a BCE at lower pressures, and the selection criteria for barocaloric effect materials are proposed as follows. (1) The phase transition temperature should be as close to room temperature as possible.…”

mentioning

confidence: 99%

Colossal Barocaloric Effect near Ambient Temperature in 1-Dodecanol under a Low Pressure

Zhang,

Xiong,

Zhang

et al. 2024

J. Phys. Chem. Lett.

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Solid-state refrigeration based on the barocaloric effect is an effective alternative to traditional vapor compression refrigeration. Here 1dodecanol has been studied due to its large latent heat at a solid−liquid phase transition point around room temperature. The transition temperature will vary with the applied hydrostatic pressure, exhibiting with a sensitivity of 0.14 K MPa −1 , which indicates its potential for refrigeration. A pressure of 40 MPa can result in a large isothermal entropy change of 520 J kg −1 K −1 (equivalent to that obtained in vapor compression refrigeration) at 297 K. A large adiabatic temperature change of >20 K in 1-dodecanol was acquired by direct measurement. A wide temperature window of ∼50 K (288−337 K) can be obtained in 1-dodecanol, which demonstrates broad application prospects. These discoveries offer promising prospects for barocaloric cooling and high-efficiency refrigeration technologies relying on solid−liquid phase transitions.

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Endo- and exothermal mechanocaloric response in rubbers

Matsuo,

Takajo

2024

J Therm Anal Calorim

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We investigated mechanocaloric properties of two silicone rubbers using an in-house made apparatus. Tension $$f$$ f and temperature change $$\Delta T$$ Δ T of the rubber samples in the form of tapes were measured as they were extended up to a normalized length $$\lambda \approx 2$$ λ ≈ 2 at a constant rate. Endothermal and exothermal components of the thermal response were observed and separated. The engineering stress and (decrease of) the entropy density derived from the data were analyzed. The number densities of the partial chains and the coefficients of the positive (endothermal) entropy contribution were determined as material constants of the rubbers. Non-idealities were revealed by the large difference between the work done on the rubber for the extension and the heat that evolved in the process. It decreased to a considerable extent when the heat was corrected for the endothermal effect arising from the above-mentioned endothermal entropy contribution. This may be understood as an indication of hidden near-ideality of silicone rubbers. Dissipation of the work into heat is quantified using the difference between the temperature changes on extension and contraction.

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Pressure-freezing of dodecane: exploring the crystal structures, formation kinetics and phase diagrams for colossal barocaloric effects in n-alkanes

Abstract: Soft BC materials, such as n-dodecane, provide cheaper and more energy efficient alternatives to traditional refrigerants.

Cited by 4 publications

References 121 publications

Barocaloric Effects in Dialkylammonium Halide Salts

Barocaloric Effects in Dialkylammonium Halide Salts

Colossal Barocaloric Effect near Ambient Temperature in 1-Dodecanol under a Low Pressure

Endo- and exothermal mechanocaloric response in rubbers

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