Search Results (13)

The dissolution mechanism of YbOF in a fluoride-containing (LiF-CaF₂)_eut. molten salt is the basis for analyzing the structure of the resulting medium and optimizing the electrolytic preparation of rare-earth Yb alloys. In this study, isothermal saturation was used to analyze solubility changes of YbOF in the (LiF-CaF₂)_eut. system. Quantum chemical and molecular dynamics ab initio methods were used to study the basic properties of the components of the (LiF-CaF₂)_eut.-YbOF system and the microscopic structural changes during the dissolution process. In addition, structural changes in the YbOF-saturated (LiF-CaF₂)_eut. system were analyzed by combining cryogenic-temperature Raman spectroscopy with experimental methods. The results show the solubility of YbOF increased linearly in the temperature range of 1073–1323 K. As the melting temperature exceeded 1073 K, LiF and CaF₂ gradually dissociated into Li⁺, Ca²⁺, and F⁻. In the initial stages of YbOF dissolution (1073–1173 K), the Yb–F bond was less stable than the Yb–O bond; YbOF dissociated into YbO⁺ and F⁻ in this temperature range. When the temperature was increased above 1173 K, YbO⁺ further dissociated into Yb³⁺ and O²⁻. Overall, the dissolution of YbOF did not affect the main structure of the (LiF-CaF₂)_eut. system. Full article

Ferromanganese formations are widespread in the Earth’s aquatic environment. Of all the mechanisms of their formation, the biogenic one is the most debatable. Here, we studied the Fe-Mn crusts of hydrothermal fields near the underwater volcano Puy de Folles (rift valley of the Mid-Atlantic Ridge). The chemical and mineralogical composition (optical and electron microscopy with EDX, X-ray powder diffraction, X-ray fluorescence analysis, Raman and FTIR spectroscopy, gas chromatography—mass spectrometry (GC-MS)) and the magnetic properties (static and resonance methods, including at cryogenic temperatures) of the samples of Fe-Mn crusts were investigated. In the IR absorption spectra, based on hydrogen bond stretching vibrations, it was concluded that there were compounds with aliphatic (alkane) groups as well as compounds with double bonds (possibly with a benzene ring). The GC-MS analysis showed the presence of alkanes, alkenes, hopanes, and steranes. Magnetically, the material is highly coercive; the blocking temperatures are 3 and 13 K. The main carriers of magnetism are ultrafine particles and X-ray amorphous matter. The analysis of experimental data allows us to conclude that the studied ferromanganese crusts, namely in their ferruginous phase, were formed as a result of induced biomineralization with the participation of iron-oxidizing and iron-reducing bacteria. Full article

A simple and efficient method for the synthesis of biodegradable, highly branched polycaprolactone (PCL) is presented. The solvent-free (bulk) reaction was carried out via ring opening polymerization (ROP), catalyzed by tin octanoate Sn(Oct)₂, and it employed hyperbranched polyamide (HPPA) as a macro-initiator. The core–shell structure of the obtained products (PCL-HPPA), with the hyperbranched HPPA core and linear PCL chains as shell, was in the focus of the product characterization. ¹H nuclear magnetic resonance (¹H NMR) and elemental analysis confirmed the covalent incorporation of the HPPA in the products, as well as a high degree of grafting conversion of its amino functional groups. Confocal Raman Micro spectroscopy, and especially Time-of-Flight Secondary Ion Mass Spectrometry, further supported the existence of a core–shell structure in the products. Direct observation of macromolecules by means of cryogenic transmission electron microscopy, as well as gel permeation chromatography (GPC), suggested the existence of a minor ‘aggregated’ product fraction with multiple HPPA cores, which was attributed to transesterification reactions. Differential scanning calorimetry, as well as X-ray diffraction, demonstrated that the PCL-HPPA polymers displayed a similar degree of crystallinity to linear neat PCL, but that the branched products possessed smaller and less regular crystallites. Full article

Photodetectors that can operate over a wide range of temperatures, from cryogenic to elevated temperatures, are crucial for a variety of modern scientific fields, including aerospace, high-energy science, and astro-particle science. In this study, we investigate the temperature-dependent photodetection properties of titanium trisulfide (TiS₃)- in order to develop high-performance photodetectors that can operate across a wide range of temperatures (77 K–543 K). We fabricate a solid-state photodetector using the dielectrophoresis technique, which demonstrates a quick response (response/recovery time ~0.093 s) and high performance over a wide range of temperatures. Specifically, the photodetector exhibits a very high photocurrent (6.95 × 10⁻⁵ A), photoresponsivity (1.624 × 10⁸ A/W), quantum efficiency (3.3 × 10⁸ A/W·nm), and detectivity (4.328 × 10¹⁵ Jones) for a 617 nm wavelength of light with a very weak intensity (~1.0 × 10⁻⁵ W/cm²). The developed photodetector also shows a very high device ON/OFF ratio (~32). Prior to fabrication, the TiS₃ nanoribbons were synthesized using the chemical vapor technique and characterized according to their morphology, structure, stability, and electronic and optoelectronic properties; this was performed using scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, X-ray diffraction (XRD), thermogravimetric analysis (TGA), and a UV–Visible–NIR spectrophotometer. We anticipate that this novel solid-state photodetector will have broad applications in modern optoelectronic devices. Full article

In this study, ZnTe crystal was applied to provide precise thermal sensing for cryogenic temperatures. Multiple techniques, namely Raman and photoluminescence spectroscopies, were used to broaden the operating temperature range and improve the reliability of the proposed thermometers. Raman-based temperature sensing could be applied in the range of 20–100 K, while luminescence-based thermometry could be utilized in a narrower range of 20–70 K. However, the latter strategy provides better relative thermal sensitivity and temperature resolution. The best thermal performances based on a single temperature-dependent parameter attain S_r = 3.82% K⁻¹ and ΔT = 0.12 K at T = 50 K. The synergy between multiple linear regression and multiparametric thermal sensing demonstrated for Raman-based thermometry results in a ten-fold improvement of _Sr and a two-fold enhancement of ΔT. All studies performed testify that the ZnTe crystal is a promising multimode contactless optical sensor for cryogenic thermometry. Full article

In this work, we have, for the first time, experimentally verified the hypothesis of reducing the agglomeration rate of aerosol nanoparticles produced by spark discharge upon decreasing the carrier gas temperature in the range of 24 °C to –183 °C. The synthesis of nanoparticles was implemented as a result of spark ablation of electrodes manufactured from Au with a purity of 99.998% installed in a specially designed gas chamber dipped into liquid nitrogen (−196 °C) to cool down the carrier gas supplied through one of hollow electrodes. It follows from the analysis of transmission electron microscopy images that both the average size of primary nanoparticles and the degree of their sintering become lower if the gas is cooled. For example, in the case of using nitrogen as a carrier gas, the average size of primary nanoparticles decreases from 9.4 nm to 6.6 nm as the gas temperature decreases from 24 °C to –183 °C. This also causes the aggregates to become more branched, manifested by the reduction in their solidity from 92% to 76%. The agglomeration model of Feng based on Smoluchowski theory was employed to calculate particle size distributions that were found to be consistent with the experimental data. The gold nanoparticles synthesized at room and cryogenic temperatures of the carrier gas (N₂, Ar + H₂, He) were used to pattern plasmonic nanostructures on ceramic alumina substrates by using aerosol jet printing technology for the purpose of demonstrating the possibility of their application in surface-enhanced Raman spectroscopy (SERS). The SERS enhancement factor was estimated at 2 × 10⁶ from the analysis of SERS and normal Raman spectra of 1,2-bis(4-pyridyl)ethylene used as an analyte. Full article

Diamond-like carbon (DLC) coatings deposited onto high-speed-steel surfaces were subjected to deep cryogenic treatment (DCT) at temperatures of −120 to −196 °C to investigate the evolution of microstructure, bonding structure, and mechanical properties. The surface morphology and the bonding structure of the DLC coatings were studied using scanning electron microscopy, transmission electron microscopy, micro-Raman spectroscopy, and X-ray photoelectron spectroscopy. It is found that DCT affects the surface morphology, especially the size and the height of the aggregates. For those DLCs with more than 50% sp³ C fraction, the sp² C → sp³ C transformation occurred in coatings treated at a temperature of −120 to −160 °C; and the maximum fraction of sp³ C was obtained after treatment at −140 °C. Almost keeping the wear resistance of DLCs, DCT can improve the adhesion strength, and surface hardness. The findings of this study indicate that DCT will be a potential post-treatment method to tune the microstructure and mechanical performance of DLC coatings. Full article

The polymorphism of molecular crystals is a well-known phenomenon, resulting in modifications of physicochemical properties of solid phases. Low temperatures and high pressures are widely used to find phase transitions and quench new solid forms. In this study, L-Leucinium hydrogen maleate (LLHM), the first molecular crystal that preserves its anomalous plasticity at cryogenic temperatures, is studied at extreme conditions using Raman spectroscopy and optical microscopy. LLHM was cooled down to 11 K without any phase transition, while high pressure impact leads to perceptible changes in crystal structure in the interval of 0.0–1.35 GPa using pentane-isopentane media. Surprisingly, pressure transmitting media (PTM) play a significant role in the behavior of the LLHM system at extreme conditions—we did not find any phase change up to 3.05 GPa using paraffin as PTM. A phase transition of LLHM to amorphous form or solid–solid phase transition(s) that results in crystal fracture is reported at high pressures. LLHM stability at low temperatures suggests an alluring idea to prove LLHM preserves plasticity below 77 K. Full article

Silk, as a protein fiber characterized by high biocompatibility, biodegradability, and low toxicity, is mainly used as textile structures for various purposes, including for biological applications. The key issue for unlimited silk applicability as a modifier is to prepare its relevant form to cover or introduce to other materials. This study presents silk powder fabrication from Bombyx mori cocoons and non-dyed silk woven fabric through cryogenic milling. The cocoons were milled before and after the degumming process to obtain powders from raw structures and pure fibroin. The powder morphology and composition were analyzed using scanning electron microscopy and energy dispersive spectroscopy. The influence of the milling on the silk structure was studied using infrared and Raman spectroscopies, indicating that silk powders retained dominant β-sheet structure. The powders were also analyzed by differential scanning calorimetry and thermogravimetric techniques. The thermal endothermic peak and onset temperature characteristic for silk decomposition shifted to the lower values for all powders, indicating less thermal stability. However, the process was found to be an efficient way to obtain silk powders. The new milled form of silk can allow its introduction into different matrices or form coatings without using any harsh solvents, enriching them with new features and make more biologically friendly. Full article

Gold nanoparticles have the potential to be used in biomedical applications from diagnostics to drug delivery. However, interactions of gold nanoparticles with different biomolecules in the cellular environment result in the formation of a “protein corona”—a layer of protein formed around a nanoparticle, which induces changes in the properties of nanoparticles. In this work we developed methods to reproducibly synthesize spheroidal and star-shaped gold nanoparticles, and carried out a physico-chemical characterization of synthesized anionic gold nanospheroids and gold nanostars through transmission electron microscopy (TEM), dynamic light scattering (DLS), zeta potential (ZP), nanoparticles tracking analysis (NTA), ultraviolet-visible (UV–Vis) spectroscopy and estimates of surface-enhanced Raman spectroscopy (SERS) signal enhancement ability. We analyzed how they interact with proteins after pre-incubation with bovine serum albumin (BSA) via UV–Vis, DLS, ZP, NTA, SERS, cryogenic TEM (cryo-TEM) and circular dichroism (CD) spectroscopy. The tests demonstrated that the protein adsorption on the particles’ surfaces was different for spheroidal and star shaped particles. In our experiments, star shaped particles limited the protein corona formation at SERS “hot spots”. This benefits the small-molecule sensing of nanostars in biological media. This work adds more understanding about protein corona formation on gold nanoparticles of different shapes in biological media, and therefore guides design of particles for studies in vitro and in vivo. Full article

Various analytical techniques have been developed to determine the solution composition of fluid inclusions, including destructive, non-destructive, single-inclusion, and bulk-inclusion methods. Cryogenic Raman spectroscopy, as a non-destructive and single-inclusion method, has emerged as a potentially powerful tool of quantitative analysis of fluid inclusion composition. A method of point analysis using cryogenic Raman spectroscopy has been previously proposed to quantitatively estimate the solute composition of H₂O-NaCl-CaCl₂ solutions, but there are uncertainties related to heterogeneity of frozen fluid inclusions and potential bias in the processing of Raman spectra. A new method of quantitative analysis of solute composition of H₂O-NaCl-CaCl₂ solutions using Raman mapping technology is proposed in this study, which can overcome the problems encountered in the point analysis. It is shown that the NaCl/(NaCl + CaCl₂) molar ratio of the solution, X(_{NaCl, m}), can be related to the area fraction of hydrohalite over hydrohalite plus antarcticite, F_hydrohalite, by the equation X(_{NaCl, m}) = 1.1435 F_hydrohalite − 0.0884, where F_hydrohalite = hydrohalite area/(hydrohalite area + antarcticite area). This equation suggests that the molar fraction of a salt component may be estimated from the fraction of the Raman peak area of the relevant hydrate. This study has established a new way of estimating solute composition of fluid inclusions using cryogenic Raman mapping technique, which may be extended to other solutions. Full article

The composition and properties of ore-forming fluids are key to understanding the mechanisms of mineralization in ore deposits. These characteristics can be understood by studying fluid inclusions. Hydrates in fluid inclusions containing NaCl–H₂O and MgCl₂–H₂O were studied using cryogenic Raman spectroscopy. The intensity ratio of peaks at 3401, 3464, 3514, and 3090 cm⁻¹ shows a positive correlation with the concentration of hydrates in the inclusions, as does the ratio of the total integrated area of the MgCl₂ hydrate peak (3514 cm⁻¹) to the 3090 cm⁻¹ peak with the concentration of MgCl₂ (correlation coefficient >0.90). These correlations are important in the quantitative analysis of MgCl₂ in synthetic and natural NaCl–MgCl₂–CaCl₂–H₂O-bearing fluid inclusions. Semi-quantitative analysis of NaCl–MgCl₂–H₂O solutions indicates that peaks at 3437 and 3537 cm⁻¹ reflect the presence of NaCl in the solution. Further, a peak at 3514 cm⁻¹ is indicative of the presence of MgCl₂. The relative intensities of these peaks may be related to the relative abundances of NaCl and MgCl₂. A quantitative attempt was made on NaCl–MgCl₂–CaCl₂–H₂O system, but it was found that quantifying NaCl, MgCl₂ and CaCl₂ separately in NaCl–MgCl₂–CaCl₂–H₂O system by the secondary freezing method is difficult. Full article

Low-temperature electronics operating in below zero temperatures or even below the lower limit of the common −65 to 125 °C temperature range are essential in medical diagnostics, in space exploration and aviation, in processing and storage of food and mainly in scientific research, like superconducting materials engineering and their applications—superconducting magnets, superconducting energy storage, and magnetic levitation systems. Such electronic devices demand special approach to the materials used in passive elements and sensors. The main goal of this work was the implementation of a fully transparent, flexible cryogenic temperature sensor with graphene structures as sensing element. Electrodes were made of transparent ITO (Indium Tin Oxide) or ITO/Ag/ITO conductive layers by laser ablation and finally encapsulated in a polymer coating. A helium closed-cycle cryostat has been used in measurements of the electrical properties of these graphene-based temperature sensors under cryogenic conditions. The sensors were repeatedly cooled from room temperature to cryogenic temperature. Graphene structures were characterized using Raman spectroscopy. The observation of the resistance changes as a function of temperature indicates the potential use of graphene layers in the construction of temperature sensors. The temperature characteristics of the analyzed graphene sensors exhibit no clear anomalies or strong non-linearity in the entire studied temperature range (as compared to the typical carbon sensor). Full article