Search Results (162)

Classical thermodynamics omits rigidity, which property distinguishes solids from gases and liquids. By accounting for rigidity (i.e., Young’s elastic modulus, ϒ), we recently amended historical formulae and moreover linked heat capacity, thermal expansivity, and ϒ. Further exploration is motivation by the importance of classical thermodynamics to various applied sciences. Based on heat performing work, we show here, theoretically, that density times sublimation enthalpy divided by the molar mass (ρΔH_sub/M, energy per volume), depends linearly on ϒ (1 GPa = 10⁹ J m⁻³). Data on diverse metals, non-metallic elements, chalcogenides, simple oxides, alkali halides, and fluorides with cubic structures validate this relationship at ambient conditions. Furthermore, data on hcp metals and molecular solids show that ρΔH_sub/M is proportional to ϒ for anisotropic materials. Proportionality constants vary only from 0.1 to 0.7 among these different material types (>100 substances), which shows that the elastic energy reservoir of solids is large. Proportionality constants depend on whether molecules or atoms are sublimated and are somewhat affected by structure. We show that ductility of refractory, high-ϒ metals affect high-temperature determinations of their ΔH_sub. Our results provide information on sublimation processes and subsequent gas phase reactions, while showing that elasticity of solids is the key parameter needed to assessing their energetics. Implications are highlighted. Full article

This study describes both experimental and numerical investigations into the heat and mass transfer processes governing the vacuum freeze drying of camel milk, with a specific focus on improving the energy efficiency. A three-dimensional model was developed and solved using the finite element method to simulate temperature evolution and sublimation interface progression during drying. The numerical model was validated against experimental data, achieving strong agreement, with an $R^2$ value of 0.94. A detailed parametric analysis examined the effects of the shelf temperature, sample thickness, and chamber pressure on the drying kinetics and energy input. The results indicate that optimising these parameters can significantly reduce the energy consumption and processing time while maintaining product quality. Notably, reducing the sample thickness to 4 mm shortened the drying time by up to 40% and reduced the specific energy consumption (SEC) from 358 to 149 kWh/kg. These findings offer valuable insights for the design of more energy-efficient freeze drying systems, with implications for sustainable milk powder production and industrial-scale process optimisation. Full article

The new mineral achyrophanite (K,Na)₃(Fe³⁺,Ti,Al,Mg)₅O₂(AsO₄)₅ was found in high-temperature sublimates of the Arsenatnaya fumarole at the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. It is associated with aphthitalite-group sulfates, hematite, alluaudite-group arsenates (badalovite, calciojohillerite, johillerite, nickenichite, hatertite, and khrenovite), ozerovaite, pansnerite, arsenatrotitanite, yurmarinite, svabite, tilasite, katiarsite, yurgensonite, As-bearing sanidine, anhydrite, rutile, cassiterite, and pseudobrookite. Achyrophanite occurs as long-prismatic to acicular or, rarer, tabular crystals up to 0.02 × 0.2 × 1.5 mm, which form parallel, radiating, bush-like, or chaotic aggregates up to 3 mm across. It is transparent, straw-yellow to golden yellow, with strong vitreous luster. The mineral is brittle, with (001) perfect cleavage. D_calc is 3.814 g cm^–3. Achyrophanite is optically biaxial (+), α = 1.823(7), β = 1.840(7), γ = 1.895(7) (589 nm), 2V (meas.) = 60(10)°. Chemical composition (wt.%, electron microprobe) is: Na₂O 3.68, K₂O 9.32, CaO 0.38, MgO 1.37, MnO 0.08, CuO 0.82, ZnO 0.48, Al₂O₃ 2.09, Fe₂O₃ 20.42, SiO₂ 0.12, TiO₂ 7.35, P₂O₅ 0.14, V₂O₅ 0.33, As₂O₅ 51.88, SO₃ 1.04, and total 99.40. The empirical formula calculated based on 22 O apfu is Na_1.29K_2.15Ca_0.07Mg_0.34Mn_0.01Cu_0.11Zn_0.06Al_0.44Fe³⁺_2.77Ti_1.00Si_0.02P_0.02S_0.14V_0.04As_4.90O₂₂. Achyrophanite is orthorhombic, space group P222₁, a = 6.5824(2), b = 13.2488(4), c = 10.7613(3) Å, V = 938.48(5) ų and Z = 2. The strongest reflections of the PXRD pattern [d,Å(I)(hkl)] are 5.615(59)(101), 4.174(42)(022), 3.669(31)(130), 3.148(33)(103), 2.852(43)(141), 2.814(100)(042, 202), 2.689(29)(004), and 2.237(28)(152). The crystal structure of achyrophanite (solved from single-crystal XRD data, R = 4.47%) is unique. It is based on the octahedral-tetrahedral M-T-O pseudo-framework (M = Fe³⁺ with admixed Ti, Al, Mg, Na; T = As⁵⁺). Large-cation A sites (A = K, Na) are located in the channels of the pseudo-framework. The achyrophanite structure can be described as stuffed, with the defect heteropolyhedral pseudo-framework derivative of the orthorhombic Fe³⁺AsO₄ archetype. The mineral is named from the Greek άχυρον, straw, and φαίνομαι, to appear, in allusion to its typical straw-yellow color and long prismatic habit of crystals. Full article

In this work, detailed information on the phase-transition thermodynamics of the analgesic and antipyretic drug phenazone, also known as antipyrine, is reported. It was found that the compound forms two polymorphs. Fusion thermodynamics of both forms was studied between 298.15 K and T_m using the combination of differential scanning calorimetry and solution calorimetry. The vapor pressures above crystalline and liquid phenazone were measured for the first time using thermogravimetry—fast scanning calorimetry technique. These studies were complemented by computation of the ideal gas entropy and heat capacity and by measurements of the condensed phase heat capacities. On the basis of experiments performed, we derived sublimation and vaporization enthalpies and vapor pressure above liquid and both crystalline modifications of phenazone in a wide range of temperatures. Full article

In this work, the influences of the Ar flow-rate and sublimation temperature on the phase composition and morphological structure of the sublimation products of analytical reagent MoO₃ are investigated. The results show that the sublimation products are always composed of thermodynamically stable orthorhombic molybdenum trioxide (α-MoO₃) and metastable monoclinic molybdenum trioxide (β-MoO₃) under different reaction conditions, among which the proportion of β-MoO₃ gradually increases with the increase in Ar flow-rate and the decrease in sublimation temperature. The formation temperature of α-MoO₃ is mainly between 780 K and 847 K, with the particles exhibiting an obvious sheet-like morphology. This work also finds that β-MoO₃ is mainly generated below 500 K; however, due to the co-actions of the deposition of gaseous MoO₃ molecules, the adsorption of Ar molecules, and the collision effect between the different particles, the newly formed β-MoO₃ is more inclined to take a spherical-shaped morphology in order to maintain its lowest energy state. Full article

Niobium, with its unique properties, plays a key role in high-tech industries, but its recovery from secondary sources remains poorly studied. The kinetics of niobium leaching from niobium-containing middlings obtained via the water treatment of dust chamber sublimations of titanium chlorinators is considered in this study. The leaching process was conducted using a fluoride–sulphuric acid solution. The experiments were performed at 25–90 °C in agitation mode. Kinetic data were analysed using compression-core and mixed-control models, which made it possible to establish the limiting stages of the process. A mixed mechanism, including a chemical reaction on the surface and diffusion through a layer of products with an activation energy of 30.05 kJ/mol, was established. The niobium recovery degree increased from 35.25 to 93.5% as the temperature increased, highlighting its effect on the process. The insoluble residue, rich in titanium, and the liquid phase with niobium and zirconium have the potential for further processing. The results provide the basis to optimise technologies intended to recover niobium from man-made raw materials, contributing to an increase in resource efficiency. Full article

Knowledge of the solubility of metal precursors in supercritical (sc) CO₂ is a key factor for determining the best operation conditions for the synthesis of supported metallic nanoparticles. In this paper, new experimental solubility data of Cu(acac)₂, Pd(acac)₂, and Pt(acac)₂ in scCO₂ for temperatures from 313 to 353 K and pressures from 10 to 40 MPa are presented and compared with the literature data and correlated with semi-empirical density-based models (Chrastil, extended Kumar and Johnston, extended Bartle, and the original and modified Méndez–Santiago–Teja). In addition, literature data for the solubility of Cu(tmhd)₂, Pd(tmhd)₂, and Pt(cod)me₂ in scCO₂ were also correlated with the above-mentioned models. The best result, i.e., the best agreement between the experimental and calculated solubility datasets, was observed for the Chrastil model. Applying the Chrastil and extended Bartle models, the dissolution, sublimation, and solvation enthalpies were estimated. Furthermore, these correlation results were compared with the results from Ushiki et al., who correlated the solubilities of metal acetylacetonates in scCO₂ from the literature using the PC-SAFT equation of state. This comparison showed that the original Méndez–Santiago–Teja model enabled a better description of the experimental data by a factor of three. Full article

Halogenated benzaldehydes possess unique chemical properties that render them valuable in pharmaceutical synthesis, pesticide formulation, and dye production. However, thorough thermodynamic data for these compounds remain scarce. This study aims to fill this knowledge gap by investigating key physical properties of several halogenated benzaldehydes, namely 4-chlorobenzaldehyde, 4-bromobenzaldehyde, 2,3-dichlorobenzaldehyde, 2,4-dichlorobenzaldehyde, and 2,6-dichlorobenzaldehyde. The physical properties determined in this study include volatility, phase transitions, and water solubility, all of which are crucial for predicting the environmental fate of these compounds. The vapor pressures of both crystalline and liquid phases were measured using a reliable static method, allowing for the determination of standard molar enthalpies, entropies, and Gibbs energies of sublimation and vaporization, as well as their triple points. The melting temperature and molar enthalpy, along with the isobaric molar heat capacity of the crystalline phase, were assessed using differential scanning calorimetry. Water solubility was evaluated at 25 °C through the saturation shake-flask method, complemented by ultra-violet visible spectroscopy. By combining sublimation and solubility data, additional properties such as Gibbs energies of hydration and Henry’s law constants were derived. The experimental results were integrated into existing databases, enhancing the predictive models for properties including melting temperature, vapor pressure, solubility, Gibbs energy of hydration, and Henry’s constant. These findings significantly improve the environmental modeling capabilities, providing valuable insights into the mobility and fate of halogenated benzaldehydes in various environmental contexts. Full article

The aim of this study was to determine the optimal conditions for copigmentation and encapsulation of anthocyanins extracted from blue and pink cornflower (Centaurea cyanus L.) flowers and to produce encapsulates resistant to environmental factors. Extracts rich in anthocyanins were encapsulated using spray-drying and sublimation techniques. Baicalin and chlorogenic acid were successfully used as copigmentation agents for blue and pink cornflower anthocyanins. The extracts and encapsulates obtained were subjected to stability tests to assess the stability of color and changes in total anthocyanins content, total phenolic compounds content, and antioxidant activity under exposure to high temperature and UV radiation. The developed encapsulation method effectively protects anthocyanins from adverse environmental conditions. The obtained preparations were characterized by a high content of anthocyanins and phenolic compounds as well as a strong antioxidant potential. The highest stability was demonstrated by anthocyanin encapsulates isolated from the pink flowers of the cornflower, obtained by spray-drying with the addition of a copigment (chlorogenic acid or baicalin) and with a weight ratio of anthocyanin extract to carrier of 1:10. The results of this study suggest that anthocyanin preparations from cornflower, after encapsulation and copigmentation with baicalin or chlorogenic acid, can be used as stable colorants in the food industry as well as functional ingredients providing high levels of antioxidant activity. Full article

This paper investigates a novel combined laser and plasma heating test technique. Integrating the 1.5 kW Raycus RFL-C1500 laser source into the VGU-4 Inductively Coupled Plasma Facility (IPMech RAS) allowed the study of fine-grain MPG-7 graphite ablation in the high-temperature range from 2920 to 3865 K under exposure to subsonic nitrogen plasma flow and combined exposure to nitrogen plasma flow and laser irradiation. Graphite nitridation and sublimation were observed. The subsonic nitrogen plasma flow was characterized by numerical modeling, probes, and spectral measurements. The proposed experimental approach is promising for simulating the entry conditions of planetary mission vehicles into different atmospheres. Full article

This study presents a combined numerical and experimental analysis of heat and mass transfer in mare’s milk during vacuum sublimation drying, which is a process essential for producing high-quality powdered products. The numerical model was developed using two-dimensional simulations and validated against experimental data obtained for varying sample thicknesses (3 mm, 5 mm, and 7 mm). Results demonstrated a strong agreement between the model and experimental temperature data, with a coefficient of determination ($R^2$) of 95% during the sublimation process. The findings revealed that thinner samples (3 mm) exhibited a 20% faster drying rate than thicker samples (7 mm), highlighting the critical role of sample thickness in sublimation dynamics. Additionally, the effects of heat flux distribution and mass loss due to sublimation were analyzed to understand the drying dynamics. This study highlights the importance of optimizing process parameters such as chamber pressure, shelf temperature, and sample thickness to enhance drying efficiency and reduce processing time. The findings provide valuable insights for scaling vacuum sublimation drying of mare’s milk for industrial applications. Full article

We report the synthesis and characterization of new, user-friendly gold(I) [Au₄(μ-(NH)₂CC₂F₅)₄]_n coordination polymer and [Au₂Cl₂(NH₂(NH=)CC₂F₅)₂]_n complex. These compounds were investigated for potential application as precursors in chemical vapor deposition (CVD) and focused electron/ion beam-induced deposition (FEBID/FIBID), which are additive methods to produce nanomaterials. Single-crystal X-ray diffraction, elemental analysis, and infrared spectroscopy were used to determine the complexes’ composition and structure. We studied their thermal stability and volatility using thermal analysis and variable-temperature infrared spectroscopy (VT IR) and by conducting sublimation experiments. The gold(I) amidinate [Au₂(μ-(NH)₂CC₂F₅)₂]_n sublimates at 413 K under 10⁻² mbar pressure. The electron-induced decomposition of the complexes’ molecules in the gas phase and of their thin layers on silicon substrates was analyzed using electron impact mass spectrometry (EI MS) and microscopy studies (SEM/EDX), respectively, to provide insights for FEBID and FIBID precursor design. The [Au₂Cl₂(NH₂(NH=)CC₂F₅)₂]_n hydrogen chloride molecules evolved during heating, with the formation of gold(I) amidinate. The obtained results revealed that the new gold(I) amidinate may be a promising source of metal for nanomaterial fabrication by gas-assisted methods. Full article

It is necessary to overcome the relatively low conductivity of ionic liquids (ILs) caused by steric hindrance effects to improve their ability to passivate defects and inhibit ion migration to boost the photovoltaic performance of perovskite solar cells (PSCs). Herein, we designed and prepared a kind of low-concentration 1-butyl-3-methylimidazolium tetrafluoroborate (BMIMBF₄) diluted with propylene carbonate (PC) via an ultrasonic technique (PC/IL). The decrease in the decomposition temperature related to the IL part and the increase in the sublimation temperature related to the PC part facilitated the use of PC/IL to effectively delay the crystallization process and passivate the defects in multiple ways to obtain high-quality perovskite films. Moreover, the increased conductivity of PC/IL and the more matched band alignment accelerated electron transport and collection. Finally, the MAPbI₃- and CsMAFA-based PSCs achieved PCE values of 20.87% and 23.29%, respectively, and their stabilities were greatly improved. This work provides a promising approach to optimizing ILs to achieve multiple functions and boost the performance of PSCs. Full article

Background: Proteins are commonly used in the healthcare industry to treat various health conditions, and most proteins are sensitive to physical and chemical changes. Lyophilization, also known as freeze-drying, involves sublimating water in the form of ice from a substance at low pressure, forming a freeze-dried powder that increases its shelf life. Extreme pressure and varying temperatures in the freeze-drying process may damage the protein’s structural integrity. Lyoprotectants are commonly used to protect protein conformations. It is important to choose a suitable lyoprotectant to ensure optimal effectiveness. Method: Twenty articles screened from Scopus, Web of Science, and PubMed were included in this review that discussed potential lyoprotectants and their effectiveness with different protein models. Results: Lyoprotectants were categorized into sugars, polyols, surfactants, and amino acids. Lyoprotectants can exhibit significant protective effects towards proteins, either singularly or in combination with another lyoprotectant. They exert various interactions with the protein to stabilize it, such as hydrogen bonding, hydrophobic interactions, electrostatic interactions, and osmoprotection. Conclusions: This review concludes that disaccharides are the most effective lyoprotectants, while other groups of lyoprotectants are best used in combination with other lyoprotectants. Full article

The synthesis and characterisation (UV-Vis, IR, HRESI-MS, ¹H and ¹³C NMR spectroscopies, electrochemistry) is reported of the novel title material (1: alternatively named rac-1-(2′-benzothiazolyl)-2-ferrocenyl-2-propanol): a rare example of a ferrocenyl-benzothiazole hybrid species. Compound 1 is produced by the low temperature reaction of acetylferrocene (3) with a solution of the methyl anion derived via the deprotonation of 2-methyl-1,3-benzothiazole. The yield of 1 is moderate (34%) after purification and is an air and thermally stable solid under ambient conditions. Attempts to sublime 1, however, result in decomposition with one of the products being identified (NMR) as 3. The spectroscopic features of 1 are presented. Attempts to obtain suitable crystalline material of 1 for a single crystal X-ray diffraction study were unfortunately unsuccessful. Compound 1 also does not form stable coordination complexes with various metal salts (e.g., Ni[2+], Co[2+], etc.) under the conditions tested. Full article