Calorimetry Data Research Articles

Kinetic model of thermal decomposition of nitric acid solutions of hydrazine nitrate

The kinetic parameters of thermal decomposition of an aqueous solution containing 0.029 mass fractions of hydrazine nitrate and 0.44 mass fractions of nitric acid have been determined: onset temperature and specific thermal effect of exothermic reactions, activation energy, pre-exponential factor, reaction rate and order. Based on the data obtained, a mathematical model of thermal decomposition of nitric acid solutions of hydrazine nitrate has been proposed. It has been found that thermolysis of the solution has a multi-stage nature and can be described by a system of 5 equations of 1st and 2nd order. A comparison of two approaches to creating a mathematical model has been carried out: based on adiabatic calorimetry and differential scanning calorimetry data.

Chemical Reaction Neural Networks for fitting Accelerating Rate Calorimetry data

As the demand for lithium-ion batteries rapidly increases there is a need to design these cells in a safe manner to mitigate thermal runaway. Thermal runaway in batteries leads to an uncontrollable temperature rise and potentially battery fires, which is a major safety concern. Typically, when modeling the chemical kinetics of thermal runaway calorimetry data (e.g. Accelerating Rate Calorimetry (ARC)) is needed to determine the temperature-driven decomposition kinetics. Conventional methods of fitting Arrhenius Ordinary Differential Equation (ODE) thermal runaway models to ARC data make several assumptions that reduce the fidelity and generalizability of the obtained model. In this paper, Chemical Reaction Neural Networks (CRNNs) are trained to fit the kinetic parameters of N-equation Arrhenius ODEs to ARC data obtained from a Molicel 21700 P45B. The models are found to be better approximations of the experimental data. The flexibility of the method is demonstrated by experimenting with two-equation and four-equation models. Thermal runaway simulations are conducted in 3D using the obtained kinetic parameters, showing the applicability of the obtained thermal runaway models to large-scale simulations.

Chemiluminescence-based evaluation of styrene block copolymers’ recyclability

The study presents the chemiluminescence based (CL) evaluation of the recyclability of linear styrene block copolymers. This analysis can provide insight into the material’s degradation state and predict its suitability for further recycling cycles, helping to avoid unnecessary energy consumption during processing.The thermal stability of four similar copolymer structures − styrene-isoprene-styrene (SIS), styrene-butadiene-styrene (SBS) copolymers with different styrene/butadiene ratios, and styrene-ethylene-butadiene-styrene (SEBS) − was studied using isothermal and non-isothermal chemiluminescence (CL). The activation energies for oxidative degradation were calculated based on oxidation induction times indicated by the CL intensities evolution. The results, which highlight the influence of molecular structure on stability under aging conditions, as presented by the calculated for the activation energy (kJ mol−1), show the following sequence: SBS (styrene 30%) (117 kJ mol−1) ≈ SIS 120 (kJ mol−1) < SBS (styrene 40%) (176 kJ mol−1) < SEBS (180 kJ mol−1). The CL data were correlated with infrared (IR) spectroscopy and differential scanning calorimetry (DSC) data, providing a comprehensive understanding of the thermal stability and degradation mechanisms during recycling proces. The sequence of the composing units determines the degradation process, with weaker points predominantly attacked in the linear moieties of isoprene, butadiene, and vinyl segments. The experimental data indicate that SIS and SBS (30% styrene) copolymers degrade the fastest likely due to the rapid accumulation of hydroperoxide radicals. The SEBS copolymer also experiences significant degradation, but this occurs at higher temperatures (above 220 ⁰C) and progresses more gradually once it begins. In contrast, the SBS copolymer with 40% styrene content degrades more slowly and exhibits minimal mass loss, primarily due to the formation of less reactive keto degradation products.

Analysis of differential scanning calorimetry data for aged plutonium.

Differential scanning calorimetry data for samples of a 52 year old plutonium alloy with 3.3 at. % Ga that were heated beyond the melting point is analyzed using transition state theory to find activation energies for the δ to ɛ and ɛ to liquid phase transitions. A Bayesian statistical method involving a Gaussian process model is used to find mean values and confidence intervals for the activation energies. The activation energy for the δ to ɛ phase transition increases by 3.3 ± 3.8% per decade, relative to the case when all age related plutonium lattice point defects have been removed through annealing. The corresponding increase in activation energy for the ɛ to liquid transition is shown to be 7.1 ± 1.8% per decade. It is postulated that the change in activation energy with age for both phase transitions is caused, in part, by the accumulation of the same type of lattice point defects associated with the observed increase in elastic bulk modulus over time.

Into the Groove: A Multitechnique Insight into the DNA–Vemurafenib Interaction

This study explores the interaction between Vemurafenib (VEM), a potent BRAF inhibitor, and calf thymus DNA (ctDNA) using a comprehensive array of biophysical and computational techniques. The primary objective is to understand the potential off-target effects of VEM on DNA, given its established role in melanoma therapy targeting the BRAF V600E mutation. The investigation employed methods such as ultraviolet–visible absorption spectroscopy, steady-state fluorescence, circular dichroism, isothermal titration calorimetry, and advanced molecular dynamics simulations. The results indicate that VEM interacts with DNA primarily through a minor groove-binding mechanism, causing minimal structural disruption to the DNA double helix. Viscosity measurements and melting temperature analyses further confirmed this non-intercalative mode of binding. Calorimetry data revealed an exothermic, thermodynamically favorable interaction between VEM and ctDNA, driven by both enthalpic and entropic factors. Finally, computer simulations identified the most probable binding site and mode of VEM within the minor groove of the nucleic acid, providing a molecular basis for the experimental findings.

Prediction Model for Coformer Screening of Energetic Eutectics Based on Flory‐Huggins Interaction Parameter

AbstractBased on intermolecular interactions, Flory‐Huggins interaction parameter χAB&gt;0 was presented as a prediction model to screen the coformer of energetic eutectics. To evaluate the predictive accuracy of this model, 80 energetic eutectics were collected from literatures. The molecular structures were optimized by computationally cheap molecular mechanics and high precision dispersion‐corrected density functional, respectively. Then the weighted Monte Carlo method was used to calculate the mixing energy ΔEmix of the binary system and thus derive the dimensionless χAB. The results show that the prediction accuracy is up to 85% based on M06‐2X‐D3/6‐311+G (d, p) optimization geometry and RESP charge, much greater than 45% of molecular mechanics method. Furthermore, size/shape mismatch between eutectic molecules was considered by shape index and molecular volume to enrich the prediction model. Based on this prediction model, a new energetic eutectic MTNP‐TNT was discovered, whose χAB value is 3.376 obtained by M06‐2X‐D3/6‐311+G (d, p) method. Experimentally, the classical “V” phase diagram drawn from the differential scanning calorimetry (DSC) data also suggests the MTNP‐TNT eutectic with eutectic temperature of 54.41°C at the molar ratio of 51.50: 48.50. Theoretical and experimental results successfully validate the χAB&gt;0 prediction model for screening the coformers of energetic eutectics. This work opens a way for the crystal engineering of energetic eutectic solid forms with attractive physicochemical properties using a computational approach.

Metabolic Profiles of Critically Ill COVID-19 Patients: A Comparative Analysis of Energy Expenditure.

Introduction and aims The COVID-19 pandemic has placed a significant burden on healthcare systems worldwide, especially in the management of critically ill patients. Accurate assessment of energy expenditure (EE) is crucial for providing optimal nutritional support and improving clinical outcomes in these patients. Indirect calorimetry (IC) is the preferred method for measuring EE, yet its use in critically ill COVID-19 patients has not been extensively documented. This study aims to evaluate EE in critically ill patients with and without COVID-19 to identify differences that may impact nutritional support strategies. Methods We conducted a retrospective observational study at a large tertiary university hospital, focusing on critically ill patients. The study compared calorimetry data between patients with and without COVID-19. Data collected included resting energy expenditure, energy expenditure per kilogram, and respiratory exchange rate quotient using IC. Statistical analysis was conducted using SPSS Version 28, with a significance level set at p < 0.05. Results The study included 95 critically ill patients, comprising 61 non-COVID-19 patients and 34 COVID-19 patients. It was found that COVID-19 patients had significantly lower Simplified Acute Physiology Score (SAPS) II compared to their non-COVID-19 counterparts. Although no significant differences in energy needs over time were detected between the two groups or within the COVID-19 group alone, there was a trend towards lower energy needs in COVID-19 patients. Significant differences were noted in respiratory quotient among COVID-19 patients, particularly between those with and without pulmonary thromboembolism, with the latter group exhibiting lower RQ values. Conclusion Our study suggests that while overall EE may not significantly differ between critically ill COVID-19 and non-COVID-19 patients, there are potential differences in substrate use that underline the necessity for individualized nutritional support. These findings highlight the importance of tailoring nutritional interventions to meet the specific needs of critically ill patients, particularly those with COVID-19.

The Effect of the Surrounding Matrix on Spin Transition Nanoparticles: How Shell Characteristics Alter Core Elastic Properties in Core‐Shell Particles

A surrounding matrix is known to alter nanoparticle spin transitions, the solid state structural phase changes associated with transitions between high spin (HS) and low spin(LS) states. To better quantify how the spin transition solid and surrounding matrix interact, several series of core‐shell particles were prepared based on RbxCo[Fe(CN)6]z∙nH2O, RbCoFe‐PBA, as spin transition core with isostructural shells of different compositions and thicknesses. Synchrotron PXRD through the thermal high HS to LS, the LS to photoexcited high spin (PXHS), and thermal PXHS to LS transitions, show the activation energy is lowered as shells become thicker and stiffer. Calorimetry data coupled with transition state theory analysis indicate the core stiffens in the core‐shell particles relative to the uncoated particles. The conclusion is supported by microstrain analysis that shows stiffer shells limit the extent to which the core distorts as individual sites transition, leading to the lower activation energy. Finally, differences in lattice mismatch with different shell materials are shown to alter the mechanism by which the transition progresses.

Predicting the heat release variability of Li-ion cells under thermal runaway with few or no calorimetry data

Accurate measurement of the variability of thermal runaway behavior of lithium-ion cells is critical for designing safe battery systems. However, experimentally determining such variability is challenging, expensive, and time-consuming. Here, we utilize a transfer learning approach to accurately estimate the variability of heat output during thermal runaway using only ejected mass measurements and cell metadata, leveraging 139 calorimetry measurements on commercial lithium-ion cells available from the open-access Battery Failure Databank. We show that the distribution of heat output, including outliers, can be predicted accurately and with high confidence for new cell types using just 0 to 5 calorimetry measurements by leveraging behaviors learned from the Battery Failure Databank. Fractional heat ejection from the positive vent, cell body, and negative vent are also accurately predicted. We demonstrate that by using low cost and fast measurements, we can predict the variability in thermal behaviors of cells, thus accelerating critical safety characterization efforts.

Synthesis and characterization of epoxy resin‐polydicyclopentadiene interpenetrating polymer networks by UV‐initiated simultaneously frontal polymerization

AbstractBy combination of UV curing and frontal polymerization, interpenetrating polymer networks (IPNs) based on diglycidyl ether of bisphenol‐A (DGEBA) epoxy resin and polydicyclopentadiene (PDCPD) were prepared by UV‐induced simultaneously frontal polymerization in this paper. Compared with the net DGEBA cured polymer, the tensile strength, elongation at break and impact strength of the IPNs were simultaneously improved. The maximum tensile strength and elongation at break of the IPNs reached 100 MPa and 4.64%, respectively, and the maximum impact strength reached 7.34KJ/m2 with an improvement of 115.2% over that of the net DGEBA cured polymer. Thermogravimetric analysis (TGA) results revealed that the IPNs could enhance the thermal stability. Data of the differential scanning calorimetry (DSC) and TGA testing shows that the IPN shows a single glass transition temperature (Tg) which is between the Tg of DGEBA and DCPD, indicating homogeneous phase and highly cross‐linked IPN formed. Morphologies and molecular structure of the IPNs polymer were observed by scanning electron microscope (SEM) and characterized by Fourier transform infrared spectroscopy (FTIR), respectively, whose results also proved the formation of ideal IPNs structures.

Effect of glass content on the phase assemblage and processing requirements of zirconolite glass-ceramics for actinide immobilisation

Zirconolite is a candidate wasteform for actinides (U/Pu/Th), and glass incorporation to form glass-ceramics provides flexibility to accommodate heterogeneous wastes while simplifying processing requirements; however, the glass content required to optimise these benefits remains unestablished. This systematic study investigated the effect of glass content on zirconolite crystallisation, phase assemblage, phase composition, cerium valence states and partitioning. Cerium-bearing zirconolite glass-ceramics were fabricated by targeting zirconolite (Ca0.8Ce0.2ZrTi1.6Al0.4O7; Ce as actinide surrogate) with varying amounts (0–100 vol%) of glass addition (NaAl1.5B0.5Ca0.7Ti0.2Si2O8.6). Differential scanning calorimetry data revealed that glass addition lowered the zirconolite crystallisation temperature (1283°C to 1200°C). X-ray diffraction, scanning electron microscopy, and energy dispersive X-ray spectroscopy analyses showed that glass addition lowered the temperature (1320°C to 1270°C) required to fabricate phase-pure zirconolite glass-ceramics and minimise CeO2/ZrO2 phases, with > 90 % of cerium preferentially partitioned into zirconolite. X-ray absorption near edge spectroscopy data showed predominantly Ce4+ within zirconolite as targeted.

Solid–Liquid Phase Equilibrium of the n-Nonane + n-Undecane System for Low-Temperature Thermal Energy Storage

The current article presents an exploration of the solid–liquid phase diagram for a binary system comprising n-alkanes with an odd number of carbon atoms, specifically n-nonane (n-C9) and n-undecane (n-C11). This binary system exhibits promising characteristics for application as a phase change material (PCM) in low-temperature thermal energy storage (TES), due to the fusion temperatures of the individual components, thereby motivating an in-depth investigation of the solid–liquid phase diagram of their mixtures. The n-nonane (n-C9) + n-undecane (n-C11) solid–liquid phase equilibrium study herein reported includes the construction of the phase diagram using Differential Scanning Calorimetry (DSC) data, complemented with Hot–Stage Microscopy (HSM) and low-temperature Raman Spectroscopy results. From the DSC analysis, both the temperature and the enthalpy of solid–solid and solid–liquid transitions were obtained. The binary system n-C9 + n-C11 has evidenced a congruent melting solid solution at low temperatures. In particular, the blend with a molar composition xundecane = 0.10 shows to be a congruent melting solid solution with a melting point at 215.84 K and an enthalpy of fusion of 13.6 kJ·mol–1. For this reason, this system has confirmed the initial signs to be a candidate with good potential to be applied as a PCM in low-temperature TES applications. This work aims not only to contribute to gather information on the solid–liquid phase equilibrium on the system n-C9 + n-C11, which presently are not available in the literature, but especially to obtain essential and practical information on the possibility to use this system as PCM at low temperatures. The solid–liquid phase diagram of the system n-C9 + n-C11 is being published for the first time, as far as the authors are aware.

Effect of Temperature and Frequency on the Viscoelastic Behavior of Commercial 6082 (Al–Mg–Si) Alloy

&lt;div&gt;The viscoelastic response of pure Al and commercial 6082 and 6082-T6 (Al–Mg–Si) alloys is measured with dynamic–mechanical analyzer as a function of temperature (ranging from 35 to 425°C) and loading frequency (ranging from 0.01 to 100 Hz). The measured data (the storage modulus, loss modulus, and mechanical damping) are compared to available transmission electron microscopy and differential scanning calorimetry data, to ascertain whether unexplained variations of the viscoelastic behavior of the alloys can be correlated to phase transformations. The results suggest that some of these variations may be controlled by the formation and dissolution of metastable phases, such as Guinier–Preston (GP) zones and phases β″, β′, and B′. Indeed, GP zones and phase β″ have been reported to control other mechanical properties. However, due to the high complexity of the aging path of Al–Mg–Si alloys, with formation and dissolution reactions of many precipitate types overlapping along wide temperature intervals, further research is necessary to establish unequivocally the contribution of each individual phase transformation to the overall viscoelastic behavior. Finally, an internal friction peak related to grain boundary sliding is significantly smaller in the alloys compared to pure Al, probably because the precipitates pin the grain boundaries.&lt;/div&gt;

An Algorithm for Modeling Thermoplastic Spherulite Growth Using Crystallization Kinetics.

Crystallization kinetics were used to develop a spherulite growth model, which can determine local crystalline distributions through an optimization algorithm. Kinetics were used to simulate spherulite homogeneous nucleation, growth, and heterogeneous nucleation in a domain discretized into voxels. From this, an overall crystallinity was found, and an algorithm was used to find crystallinities of individual spherulites based on volume. Then, local crystallinities within the spherulites were found based on distance relative to the nucleus. Results show validation of this model to differential scanning calorimetry data for polyether ether ketone at different cooldown rates, and to experimental microscopic images of spherulite morphologies. Application of this model to various cooldown rates and the effect on crystalline distributions are also shown. This model serves as a tool for predicting the resulting semi-crystalline microstructures of polymers for different manufacturing methods. These can then be directly converted into a multiscale thermomechanical model.

Properties of La2F4Se, B–LaFSe phases. Phase diagram of the LaF3–La2Se3 system

Lanthanum selenidofluorides belong to wide-gap semiconductors and are promising for optoelectronics. La2F4Se, B–LaFSe compounds were obtained by the ampoule method from binary compounds. Crystals La2F4Se, R-3m, a = 4.18245(11) Å, c = 23.2939(6) Å, Z = 3, B–LaFSe P63/mmc, a = 4.21989(5) Å, c = 8.19140(10) Å, Z = 2 have a layered grain structure, their microhardnesses are 340 and 450 HV, which allows samples processing. The optical bandgap of La2F4Se is 4.5 eV. The optical bandgaps of La2F4Se and B–LaFSe were analyzed by comparing the calculated absorption spectra and the experimental Kubelka-Munk Functions. It was shown that this approach is attractive in explaining optical properties in the vicinity of fundamental absorption onset and in neighboring regions. In LaF3–La2Se3 system, temperatures and enthalpies of five phase transformations were determined, and their balance equations were obtained. It was shown that La2F4Se, B–LaFSe compounds melt incongruently and that an eutectic is formed between the phases. A phase diagram of LaF3–La2Se3 system was constructed. The liquidus calculated by Redlich-Kister polynomial agrees with the data of differential scanning calorimetry.

Effect of carnitine supplementation on energy utilization in patients with type 2 diabetes and long-term tube feeding: A CARE-compliant case report

Introduction: Carnitine is essential for the energy utilization of long-chain fatty acids. However, the effects of carnitine supplementation on patients undergoing tube feeding remain unclear, and some enteral formula products do not contain carnitine. In order to gain insights into the role of carnitine supplementation on energy utilization in patients with long-term tube feeding, we observed the changes in respiratory quotient (RQ) of patients before and after the addition of carnitine due to the renewal of an enteral formula product. Case presentation: We observed 6 patients who continued tube feeding with the same enteral formula product scheduled for renewal. All 6 participants had diabetes, and indirect calorimetry data were available for 4 patients. Participants were observed for 3 months after switching to the new formulation. After the switching, a carnitine supplementation of 120 to 180 mg/day was provided, depending on the intake amount. One month after switching, blood free carnitine and total carnitine levels in all 6 patients increased from below the lower limit to within the range of the Japanese reference standard. In 3 of the 4 patients for whom indirect calorimetry was possible, the fasting RQ at baseline was &gt;0.90, suggesting impaired lipid utilization. The mean fasting RQ significantly decreased 2 months after the switch. The 1- and 2-hour postprandial RQ also showed a significant decrease after switching. Conclusion: Carnitine supplementation of enteral formulas may be important for normal energy utilization of lipids in patients receiving long-term tube feeding. An evaluation using randomized controlled trials with a larger number of patients is required.

Bimetallic Ba(II)-Cr(III) and trimetallic Ba(II)-Ln(III)-Cr(III) (Ln(III) = Gd, Tb, Dy, Ho, Er, Yb, Y) coordination polymers formed by Cr(III)-containing building blocks with cyclopropane-1,1-dicarboxylate anions

The reaction of chromium(III) nitrate with Ba(cpdc) (H2cpdc = cyclopropane-1,1-dicarboxylic acid) in a ratio of 1:3 yielded a 1D coordination polymer {[Ba2Cr2(OH)2(cpdc)4(H2O)8]·5H2O}n (1) formed by binuclear units [Cr2(OH)2(cpdc)4]4− and a 3D polymer [Ba2Cr(cpdc)3(NO3)(H2O)6]n (2) constructed from tris-chelate blocks [Cr(cpdc)3]3−. The addition of rare-earth metal nitrates (Cr:Ln = 1:2) in this reaction led to the formation of a series of trimetallic 3D coordination polymers {[Ba3Ln2Cr4(cpdc)12(H2O)24]·8H2O}n (3Ln, Ln = Gd, Tb, Dy, Ho, Er, Yb, Y), in whose structures tris-chelate fragments [Cr(cpdc)3]3− are bound in layers by Ln3+ ions and, further, in a framework due to the coordination of Ba2+ ions. The crystal structures of 1, 2, and 3Gd were determined by single-crystal X-ray diffraction (XRD), and isostructurality of all the compounds in the series 3Ln was proved by powder X-ray diffraction (PXRD). DC-magnetic susceptibility measurements revealed weak ferromagnetic exchange interactions between Cr3+ ions in compound 1 (J = +0.74 cm−1). According to ac-magnetic susceptibility measurements, complexes 3Er and 3Y exhibit field-induced slow relaxation of magnetization. According to the data of simultaneous thermal analysis (STA) and differential scanning calorimetry (DSC) performed under Ar atmosphere, dehydration of the compounds obtained takes place in one (for 1 and 3Gd) or three stages (for 2). The initial temperature of the organic part degradation process decreases when moving from compound 1 containing dimerized bis-chelate fragments [Cr2(OH)2(cpdc)4]4− (330 °C) to compounds 2 (276 °C) and 3Gd (261 °C) based on tris-chelate units [Cr(cpdc)3]3−.

Kinetics of Martensite/Austenite Decomposition during Tempering of Ultrafine Nano-Bainitic Steels.

In this study, the decomposition of a martensite/austenite (M/A) microconstituent in bainitic steels was analyzed using differential scanning calorimetry (DSC) data in conjunction with Kissinger's and Johnson-Mehl-Avrami-Kolmogorov (JMAK)'s formulas. In bainitic steel subjected to austempering heat treatment, the presence of an M/A microstructure adversely affects the mechanical properties. According to the kinetic equations derived, it is observed that after tempering the sample at 600 °C for 4000 s, the generation of each phase reaches its maximum. The SEM images taken before and after tempering reveal extensive decomposition of the M/A constituent in the microstructure. The proportion of the M/A microstructure decreased significantly from about 10% before tempering to less than 1% after. Additionally, the content of residual austenite also reduced nearly to zero. These observations are consistent with the predictions of the kinetic equations.

Protecting Lyophilized Escherichia coli Adenylate Kinase.

Drying protein-based drugs, usually via lyophilization, can facilitate storage at ambient temperature and improve accessibility but many proteins cannot withstand drying and must be formulated with protective additives called excipients. However, mechanisms of protection are poorly understood, precluding rational formulation design. To better understand dry proteins and their protection, we examine Escherichia coli adenylate kinase (AdK) lyophilized alone and with the additives trehalose, maltose, bovine serum albumin, cytosolic abundant heat soluble protein D, histidine, and arginine. We apply liquid-observed vapor exchange NMR to interrogate the residue-level structure in the presence and absence of additives. We pair these observations with differential scanning calorimetry data of lyophilized samples and AdK activity assays with and without heating. We show that the amino acids do not preserve the native structure as well as sugars or proteins and that after heating the most stable additives protect activity best.

Effect of phosphorus-doping on ternesite: Structure, thermal stability and hydration

The successful synthesis of the solid solution Ca5(Si1-x/2O4)2S1-x/2PxO4 (C5S2S̅Px, x = 0.05, 0.10, 0.15, 0.20) was confirmed through analysis of X-ray diffraction and energy dispersive spectrometer data. Rietveld refinement revealed that the purity of ternesite can reach up to 99.42 % at a doping concentration of 5 %. Furthermore, changes in X-ray diffraction peaks and morphology suggest a shift in the preferred growth direction of crystallites as a result of the introduction of impurity element. The incorporation of P elements in C5S2S̅Px not only effectively reduces weight loss under high-temperature conditions but also elevates the temperature at which decomposition occurs. Isothermal calorimetry data indicates that C5S2S̅Px-CSA samples display higher cumulative heat release compared to C5S2S̅–CSA. Furthermore, the presence of C5S2S̅P0.20 accelerates the hydration kinetics of CSA cement by hindering ettringite formation. Moreover, varying levels of phosphorus doping in C5S2S̅Px have resulted in enhanced compressive strength at various ages of CSA cement maturation.