Structure and Dynamics in Solid Electrolyte Composites of the Organic Ionic Plastic Crystal HMGFSI and Lithium Sulphonamide Functional Acrylate Polymer Nanoparticles.

Solid electrolyte composites between organic ionic plastic crystals (OIPCs) and polymers can potentially show enhanced mechanical properties and ion conduction. These properties can be determined by the formation of interfacial regions which affect the structure, thermal properties, and ion transport of the composite material. Here we studied the properties of composites between the OIPC hexamethylguanidinium bis(fluorosulfonyl)imide (HMGFSI) and acrylate polymer nanoparticles functionalised with lithium, using various techniques including solid-state NMR spectroscopy. An enhancement in ionic conductivity of three orders of magnitude as well as increased lithium and OIPC cation and anion dynamics were observed in the composite as prepared with 40 v% of polymer nanoparticles with respect to the pure OIPC at 50 °C. This was attributed to the increased overall structural disorder as a result of the formation of disordered interfacial regions, which were evidenced by solid-state NMR spectroscopy. In addition, the importance of the thermal history of these composites is highlighted, with differences in the conductivity and ion dynamics observed after melting and recrystallizing the OIPC component, leading to less disordered interfacial regions. This study enriches our fundamental understanding of the formation of interfacial regions in OIPC composites and their effect on the bulk properties of the electrolyte.

Water temperature at the time of the catch-and-release event is a better predictor of survival in Atlantic salmon (Salmo salar) than acute water temperature changes before and after.

Despite studies on the effect of catch-and-release on the survival of Atlantic salmon (Salmo salar) being widespread in the literature, studies to date have failed to evaluate the potential role of thermal history. Herein, we show that despite cooler conditions post-release, 4/18 (22%) salmon died when caught-and-released at water temperatures ≥20°C, whereas 1/13 (8%) salmon caught-and-released at water temperatures ≤20°C, but who encountered mean water temperatures ≥20°C post-release, died. We conclude water temperature at time of the catch-and-release event remains the most suitable predictor of post-release survival.

The effects of marine heatwaves on acute heat tolerance in corals.

Scleractinian coral populations are increasingly exposed to conditions above their upper thermal limits due to marine heatwaves, contributing to global declines of coral reef ecosystem health. However, historic mass bleaching events indicate there is considerable inter- and intra-specific variation in thermal tolerance whereby species, individual coral colonies and populations show differential susceptibility to exposure to elevated temperatures. Despite this, we lack a clear understanding of how heat tolerance varies across large contemporary and historical environmental gradients, or the selective pressures that underpin this variation. Here we conducted standardised acute heat stress experiments to identify variation in heat tolerance among species and isolated reefs spanning a large environmental gradient across the Coral Sea Marine Park. We quantified the photochemical yield (Fv /Fm ) of coral samples in three coral species, Acropora cf humilis, Pocillopora meandrina, and Pocillopora verrucosa, following exposure to four temperature treatments (local ambient temperatures, and + 3°C, +6°C and + 9°C above local maximum monthly mean). We quantified the temperature at which Fv /Fm decreased by 50% (termed ED50) and used derived values to directly compare acute heat tolerance across reefs and species. The ED50 for Acropora was 0.4-0.7°C lower than either Pocillopora species, with a 0.3°C difference between the two Pocillopora species. We also recorded 0.9°C to 1.9°C phenotypic variation in heat tolerance among reefs within species, indicating spatial heterogeneity in heat tolerance across broad environmental gradients. Acute heat tolerance had a strong positive relationship to mild heatwave exposure over the past 35 years (since 1986) but was negatively related to recent severe heatwaves (2016-2020). Phenotypic variation associated with mild thermal history in local environments provides supportive evidence that marine heatwaves are selecting for tolerant individuals and populations; however, this adaptive potential may be compromised by the exposure to recent severe heatwaves.

Warmer and more acidic conditions enhance performance of an endemic low-shore gastropod.

Changing ocean temperatures are predicted to challenge marine organisms, especially when combined with other factors, such as ocean acidification. Acclimation, as a form of phenotypic plasticity, can moderate the consequences of changing environments for biota. Our understanding of how altered temperature and acidification together influence species' acclimation responses is, however, limited compared with that of responses to single stressors. This study investigated how temperature and acidification affect the thermal tolerance and righting speed of the girdled dogwhelk, Trochia cingulata. Whelks were acclimated for 2 weeks to combinations of three temperatures (11°C: cold, 13°C: moderate and 15°C: warm) and two pH regimes (8.0: moderate and 7.5: acidic). We measured the temperature sensitivity of the righting response by generating thermal performance curves from individual data collected at seven test temperatures and determined critical thermal minima (CTmin) and maxima (CTmax). We found that T. cingulata has a broad basal thermal tolerance range (∼38°C) and after acclimation to the warm temperature regime, both the optimal temperature for maximum righting speed and CTmax increased. Contrary to predictions, acidification did not narrow this population's thermal tolerance but increased CTmax. These plastic responses are likely driven by the predictable exposure to temperature extremes measured in the field which originate from the local tidal cycle and the periodic acidification associated with ocean upwelling in the region. This acclimation ability suggests that T. cingulata has at least some capacity to buffer the thermal changes and increased acidification predicted to occur with climate change.

Unravelling thermal history during additive manufacturing of martensitic stainless steel.

In-situ thermal cycling neutron diffraction experiments were employed to unravel the effect of thermal history on the evolution of phase stability and internal stresses during the additive manufacturing (AM) process. While the fully-reversible martensite-austenite phase transformation was observed in the earlier thermal cycles where heating temperatures were higher than Af, the subsequent damped thermal cycles exhibited irreversible phase transformation forming reverted austenite. With increasing number of thermal cycles, the thermal stability of the retained austenite increased, which decreased the coefficient of thermal expansion. However, martensite revealed higher compressive residual stresses and lower dislocation density, indicating inhomogeneous distributions of the residual stresses and microstructures on the inside and on the surface of the AM component. The compressive residual stresses that acted on the martensite resulted preferentially from transformation strain and additionally from thermal misfit strain, and the decrease in the dislocation density might have been due to the strong recovery effect near the Ac1 temperature.

Temperature affects susceptibility of intertidal limpets to bird predation.

High temperatures resulting in physiological stress and the reduced ability to resist predation can have life-or-death consequences for an organism. We investigated the effects of temperature on the susceptibility to predation for an ectothermic intertidal mollusc (the owl limpet, Lottia gigantea) and its predator (the black oystercatcher, Haematopus bachmani). The ability of L. gigantea to resist bird predation during low tide is determined by the tenacity of attachment to the rock. We developed a transducer to measure the force of predatory attacks on limpets by a captive black oystercatcher, and tested the hypothesis that exposure to warm temperatures during low tide emersion would affect the limpet's ability to resist dislodgement in trials with a morphometrically accurate beak mimic and a live bird. In beak mimic trials, four times as many limpets exposed to warm low tides were removed, as compared with limpets exposed to cool low tides or in 'no low tide' submerged conditions. Minimum time before limpet removal in captive bird trials was more than six times longer for limpets in cool low tide or no low tide treatments compared with limpets in the warm low tide treatment. We measured shear forces up to 36.63 N during predatory strikes. These direct measurements of the forces exerted by a living oystercatcher provide context for interactions with multiple prey species. Our data suggest that naturally occurring variation in body temperatures among individual prey items in the field could be an important driver of predator-prey interactions and subsequently community patterns.

Tunable Supramolecular Gel Properties by Varying Thermal History.

The possibility of using differential pre-heating prior to supramolecular gelation to control the balance between hydrogen-bonding and aromatic stacking interactions in supramolecular gels and obtain consequent systematic regulation of structure and properties is demonstrated. Using a model aromatic peptide amphiphile, Fmoc-tyrosyl-leucine (Fmoc-YL) and a combination of fluorescence, infrared, circular dichroism and NMR spectroscopy, it is shown that the balance of these interactions can be adjusted by temporary exposure to elevated temperatures in the range 313-365 K, followed by supramolecular locking in the gel state by cooling to room temperature. Distinct regimes can be identified regarding the balance between H-bonding and aromatic stacking interactions, with a transition point at 333 K. Consequently, gels can be obtained with customizable properties, including supramolecular chirality and gel stiffness. The differential supramolecular structures also result in changes in proteolytic stability, highlighting the possibility of obtaining a range of supramolecular architectures from a single molecular structure by simply controlling the pre-assembly temperature.

Primordial black holes and the origin of the matter-antimatter asymmetry.

We review here a new scenario of hot spot electroweak baryogenesis where the local energy released in the gravitational collapse to form primordial black holes (PBHs) at the quark-hadron (QCD) epoch drives over-the-barrier sphaleron transitions in a far from equilibrium environment with just the standard model CP violation. Baryons are efficiently produced in relativistic collisions around the black holes and soon redistribute to the rest of the universe, generating the observed matter-antimatter asymmetry well before primordial nucleosynthesis. Therefore, in this scenario there is a common origin of both the dark matter to baryon ratio and the photon to baryon ratio. Moreover, the sudden drop in radiation pressure of relativistic matter at H0/W±/Z0 decoupling, the QCD transition and e+e- annihilation enhances the probability of PBH formation, inducing a multi-modal broad mass distribution with characteristic peaks at 10-6, 1, 30 and 106 M⊙, rapidly falling at smaller and larger masses, which may explain the LIGO-Virgo black hole mergers as well as the OGLE-GAIA microlensing events, while constituting all of the cold dark matter today. We predict the future detection of binary black hole (BBH) mergers in LIGO with masses between 1 and 5 M⊙, as well as above 80 M⊙, with very large mass ratios. Next generation gravitational wave and microlensing experiments will be able to test this scenario thoroughly. This article is part of a discussion meeting issue 'Topological avatars of new physics'.

Elucidation of the variability in consistency of pharmacopoeia quality petrolatum.

The Pharmacopeia monograph for petrolatum poorly defines the material's physical properties. Indeed, differences between petrolatum grades can be substantial; yield stress varies between 65 and 280 Pa which can be compared with the consistency of respectively thin cream or thick ointment. This variation is not only due to differences in composition or refining process but also as a result of different processing; for example, thermal history influences petrolatum structure considerably. Slow cooling of petrolatum resulted in a yield stress of 26 Pa and fast cooling in 79 Pa. X-ray showed that crystallinity was 0.7% for the first cooling case and 1.5% for the second one. Crystallite size was estimated to be 20-50 nm. To investigate if this relatively small difference in crystallinity may induce the difference in consistency, 15 nm SiO2 particles were added to petrolatum. Indeed, a small increase in SiO2 concentration led to a major increase in yield stress. This was argued to be due to the small size of the particles, resulting in a large increase in absolute number of particles. The Pharmacopeia does not unambiguously define the pharmaceutical excipient petrolatum. As a consequence, the formulator has to take care of selecting the appropriate grade as well as to carefully control the processing of the material in order to achieve a consistent pharmaceutical product.

Thermal comfort of people in the hot and humid area of China-impacts of season, climate, and thermal history.

We conducted a climate chamber study on the thermal comfort of people in the hot and humid area of China. Sixty subjects from naturally ventilated buildings and buildings with split air conditioners participated in the study, and identical experiments were conducted in a climate chamber in both summer and winter. Psychological and physiological responses were observed over a wide range of conditions, and the impacts of season, climate, and thermal history on human thermal comfort were analyzed. Seasonal and climatic heat acclimatization was confirmed, but they were found to have no significant impacts on human thermal sensation and comfort. The outdoor thermal history was much less important than the indoor thermal history in regard to human thermal sensation, and the indoor thermal history in all seasons of a year played a key role in shaping the subjects' sensations in a wide range of thermal conditions. A warmer indoor thermal history in warm seasons produced a higher neutral temperature, a lower thermal sensitivity, and lower thermal sensations in warm conditions. The comfort and acceptable conditions were identified for people in the hot and humid area of China.

Cracking the Si Shell Growth in Hexagonal GaP-Si Core-Shell Nanowires.

Semiconductor nanowires have increased the palette of possible heterostructures thanks to their more effective strain relaxation. Among these, core-shell heterostructures are much more sensitive to strain than axial ones. It is now accepted that the formation of misfit dislocations depends both on the lattice mismatch and relative dimensions of the core and the shell. Here, we show for the first time the existence of a new kind of defect in core-shell nanowires: cracks. These defects do not originate from a lattice mismatch (we demonstrate their appearance in an essentially zero-mismatch system) but from the thermal history during the growth of the nanowires. Crack defects lead to the development of secondary defects, such as type-I1 stacking faults and Frank-type dislocations. These results provide crucial information with important implications for the optimized synthesis of nanowire-based core-shell heterostructures.

How triacylglycerol thermal history impacts film removal by surfactant solution.

HYPOTHESIS: The physical and mechanical properties of triacylglycerols (TAGs), or 'fats', depend on their composition and thermal history which, in turn, impact crystal structure and morphology. We examine whether thermal history can be mechanistically related to film removal by a surfactant solution. EXPERIMENTS: Model TAG mixtures, comprising triolein:tripalmitin:tristearin 0.5:0.3:0.2, were subjected to a range of cooling profiles from the melt (0.5-80°C/min, Newtonian and annealed), and the resulting solid films characterised by microscopy, X-ray diffraction, infrared spectroscopy, and contact angle measurements. Film removal from a model glass substrate by an aqueous surfactant solution of sodium dodecylsulphate and dodecyldimethylamine oxide at room temperature fixed at 25°C was examined under quiescent flow conditions. FINDINGS: Quantitative relations are established between TAG cooling profile, crystal structure and morphology, surface energy γSFE, and removal (or 'cleaning'). In general, films cooled slowly from the melt yield heterogeneous morphologies with predominantly ß1' phase, higher polar γSFE, and faster removal timescales. By contrast, rapid cooling results in homogeneous films, rich in ß2' phase, low polar γSFE, and long removal times. Our results elucidate the non-trivial impact of TAG thermal history, connecting the multiscale semi-crystalline structure to surface energy, and eventually to film delamination by micellar solutions.

Efficient dissolution of cellulose in slow-cooling alkaline systems and interacting modes between alkali and urea at the molecular level.

The dissolution of microcrystalline cellulose (MCC) in a urea-NaOH system is beneficial for its mechanical processing. The apparent MCC solubility was greatly improved to 14 wt% under a slow-cooling condition with a cooling rate of -0.3 °C/min. The cooling curve or thermal history played a crucial role in the dissolution process. An exotherm (-54.7 ± 3 J/g MCC) was detected by DSC only under the slow-cooling condition, and the cryogenic dissolution of MCC was attributed to the exothermic interaction between MCC and solvent. More importantly, the low cooling rate promoted the dissolution of MCC by providing enough time for the diffusion of OH- and urea into MCC granules at higher temperatures. The Raman spectral data showed that the intramolecularly and intermolecularly hydrogen bonds in cellulose were cleaved by NaOH and urea, respectively. XPS and solid-state 13C NMR results showed that hydrogen bonds were generated after dissolution, and a dual-hydrogen-bond binding mode between urea and cellulose was confirmed by DFT calculations. Both the decrease of enthalpy and increase of entropy dominated the spontaneity of MCC dissolution, and that is the reason for the indispensability of cryogenic environment. The high apparent solubility of MCC in the slow-cooling process and the dissolution mechanism are beneficial for the studies on cellulose modification and mechanical processing.

Determining critical periods for thermal acclimatisation using a distributed lag non-linear modelling approach.

Rapid changes in thermal environments are threatening many species worldwide. Thermal acclimatisation may partially buffer species from the impacts of these changes, but currently, the knowledge about the temporal dynamics of acclimatisation remains limited. Moreover, acclimatisation phenotypes are typically determined in laboratory conditions that lack the variability and stochasticity that characterise the natural environment. Through a distributed lag non-linear model (DLNM), we use field data to assess how the timing and magnitude of past thermal exposures influence thermal tolerance. We apply the model to two Scottish freshwater Ephemeroptera species living in natural thermal conditions. Model results provide evidence that rapid heat hardening effects are dramatic and reflect high rates of change in temperatures experienced over recent hours to days. In contrast, temperature change magnitude impacted acclimatisation over the course of weeks but had no impact on short-term responses. Our results also indicate that individuals may de-acclimatise their heat tolerance in response to cooler environments. Based on the novel insights provided by this powerful modelling approach, we recommend its wider uptake among thermal physiologists to facilitate more nuanced insights in natural contexts, with the additional benefit of providing evidence needed to improve the design of laboratory experiments.

Nature of Thermal Hysteresis of Thermoelectric Properties in Ag2TexS1-x Compounds.

Ag2TexS1-x usually undergo various phase structures upon heating or cooling processes; however, the correlation between the heat treatment, the phase structure, and the physical properties is still a controversy. Herein, three different phases are realized for Ag2TexS1-x (0.35 ≤ x ≤ 0.65) samples during the heat treatment, including the low-temperature crystalline phase, amorphous phase, and high-temperature cubic phase. The metastable amorphous phase is an intermediate phase formed during transition from the high-temperature cubic phase to the low-temperature crystalline phase upon cooling via a solid-state conversion rather than the conventional liquid quenching process. The relative content of these three phases is highly sensitive to the heat treatment process. This as-formed low-temperature crystalline phase, amorphous phase, and high-temperature cubic phase convert into the low-temperature crystalline phase and high-temperature cubic phase through long-time dwelling at the temperature below or above the transition temperature around 567 K, respectively. The status of the low-temperature crystalline phase, amorphous phase, and high-temperature cubic phase significantly affects the thermoelectric properties, resulting in the thermal hysteresis of thermoelectric properties. Below the phase transition temperature (TM), the electrical conductivity of the amorphous phase surpasses that of the low-temperature crystalline phase, which shows a growth of 112% for the Ag2Te0.60S0.40 sample annealed at 823 K in comparison with that of the sample annealed at 473 K. For Ag2Te0.50S0.50 samples annealed at 473 K, the maximum ZT value reaches 1.02 at 623 K during the initial test, while the maximum ZT value is improved to 1.34 at 523 K in the second-round test.

Solid-Emission-Tunable Squaraine with Thermal-Promoted Aggregate-State Transitions for Fast Thermal History Sensing.

Determining thermal history is crucial in many industrial processes, but reliable and sensitive organic thermal history indicators are currently absent. Herein, we report on the development of a squaraine-based fluorescent molecule, DPEA-SQ, for the detection of thermal exposure histories up to 436 K. DPEA-SQ forms multiple single crystals (DPEA-SQ-I, DPEA-SQ-II, and DPEA-SQ-III) with different conformations and aggregate-state packing modes, contributing to their different fluorescence wavelengths, lifetimes, and efficiencies. Interestingly, DPEA-SQ-I and DPEA-SQ-III undergo aggregate-state structural transitions to form the thermodynamically more stable DPEA-SQ-II, which are accompanied by changes in their fluorescence. By taking advantage of similar aggregate-state structural transformations during heating, a high-temperature thermal exposure history of up to 436 K is recorded and reflected by their fluorescence. To demonstrate the potential practical applications of DPEA-SQ, a DPEA-SQ-Powder/PDMS film is prepared and coated on an electric circuit board, which enables real-time monitoring of localized overheating by the naked eye. Additionally, the fluorescence peaks of DPEA-SQ-Powder and DPEA-SQ-Powder/PDMS films remain unchanged after storage at 373 K for 52 days, demonstrating high aggregate-state stability. The fast and reliable responses of this system make it an excellent candidate for the detection of overtemperature traces in electronic components and circuit diagnosis.

A Robust Recurrent Neural Networks-Based Surrogate Model for Thermal History and Melt Pool Characteristics in Directed Energy Deposition.

In directed energy deposition (DED), accurately controlling and predicting melt pool characteristics is essential for ensuring desired material qualities and geometric accuracies. This paper introduces a robust surrogate model based on recurrent neural network (RNN) architectures-Long Short-Term Memory (LSTM), Bidirectional LSTM (Bi-LSTM), and Gated Recurrent Unit (GRU). Leveraging a time series dataset from multi-physics simulations and a three-factor, three-level experimental design, the model accurately predicts melt pool peak temperatures, lengths, widths, and depths under varying conditions. RNN algorithms, particularly Bi-LSTM, demonstrate high predictive accuracy, with an R-square of 0.983 for melt pool peak temperatures. For melt pool geometry, the GRU-based model excels, achieving R-square values above 0.88 and reducing computation time by at least 29%, showcasing its accuracy and efficiency. The RNN-based surrogate model built in this research enhances understanding of melt pool dynamics and supports precise DED system setups.

Tethered-flight performance of thermally-acclimated pest fruit flies (Diptera: Tephritidae) suggests that heat waves may promote the spread of Bactrocera species.

BACKGROUND: Thermal history may induce phenotypic plasticity in traits that affect performance and fitness. One type of plastic response triggered by thermal history is acclimation. Because flight is linked to movement in the landscape, trapping and detection rates, and underpins the success of pest management tactics, it is particularly important to understand how thermal history may affect pest insect flight performance. We investigated the tethered-flight performance of Ceratitis capitata, Bactrocera dorsalis and Bactrocera zonata (Diptera: Tephritidae), acclimated for 48 h at 20, 25 or 30 °C and tested at 25 °C. We recorded the total distance, average speed, number of flight events and time spent flying during 2-h tests. We also characterized morphometric traits (body mass, wing shape and wing loading) that can affect flight performance. RESULTS: The main factor affecting most flight traits was body mass. The heaviest species, B. dorsalis, flew further, was faster and stopped less often in comparison with the two other species. Bactrocera species exhibited faster and longer flight when compared with C. capitata, which may be associated with the shape of their wings. Moreover, thermal acclimation had sex- and species-specific effects on flight performance. Flies acclimated at 20 °C stopped more often, spent less time flying and, ultimately, covered shorter distances. CONCLUSION: Flight performance of B. dorsalis is greater than that of B. zonata and C. capitata. The effects of thermal acclimation are species-specific. Warmer acclimation temperatures may allow pest fruit flies to disperse further and faster. © 2023 The Authors. Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Effect of Post-Printing Cooling Conditions on the Properties of ULTEM Printed Parts.

This paper aimed to estimate the effect of post-printing cooling conditions on the tensile and thermophysical properties of ULTEM® 9085 printed parts processed by fused deposition modeling (FDM). Three different cooling conditions were applied after printing Ultem samples: from 180 °C to room temperature (RT) for 4 h in the printer (P), rapid removal from the printer and cooling from 200 °C to RT for 4 h in the oven (O), and cooling at RT (R). Tensile tests and dynamic mechanical thermal analysis (DMTA) were carried out on samples printed in three orthogonal planes to investigate the effect of the post-printing cooling conditions on their mechanical and thermophysical properties. Optical microscopy was employed to relate the corresponding macrostructure to the mechanical performance of the material. The results obtained showed almost no difference between samples cooled either in the printer or oven and a notable difference for samples cooled at room temperature. Moreover, the lowest mechanical performance and sensitivity to the thermal cooling conditions were defined for the Z printing direction due to anisotropic nature of FDM and debonding among layers.

The difference in thermal comfort between southern and northern Chinese living in the Xi'an cold climate region.

A year-long longitudinal survey regarding perceptions of outdoor thermal conditions and thermal comfort was conducted in Xi'an, a City in a Chinese cold region. The survey included micrometeorological measurements and a longitudinal questionnaire. The thermal comfort and adaptability of southern Chinese (people from Changsha and Guangzhou) and northern Chinese (people from Xi'an) in Xi'an were studied from the three aspects of psychological, physiological, and behavioral differences. The results of similar studies in other regions were compared with those of this study. Regarding psychological differences, northerners were more adapted to Xi'an's climate than southerners, with an expected temperatures of 20.7℃ and 24.1℃ for northerners and for southerners, respectively. Regarding physiological differences, the neutral temperature of the northern population was 22.12℃, while that of the southern population was 21.12℃. The neutral temperature for the southern population in Xi'an is similar to that of northern people living in Xi'an. Regarding behavioral differences, northerners were more likely than southerners to maintain their thermal comfort by adjusting their clothing when they experienced a change in the outdoor environment. This study not only indicates that there were differences regarding the thermal comfort of people originating different regions but also provided support for fully explaining the mechanism of climate adaptation of human thermal comfort. In addition, this work provides basic data regarding formulating outdoor thermal comfort standards and provided data support for personalized thermal comfort.