Differential Scanning Calorimetry Measurements Research Articles

Ferroelectric and antiferroelectric chiral multilactate liquid crystalline materials with negative dielectric anisotropy

In this work, the mesomorphic, electro-optic and dielectric properties have been discussed in the light of molecular structure-property correlations of two chiral multilactate liquid crystalline materials possessing the orthogonal paraelectric Smectic A* phase, tilted ferroelectric Smectic C* phase and the tilted antiferroelectric Smectic CA* phase, over a substantially broad temperature range. Interestingly, a reasonably rare re-entrant Smectic C* phase (SmCre*) has also been identified in one of the investigated materials. These materials differ in their linkage groups (keto or ether) and an additional chiral unit in the terminal chain. The phase transition temperatures and transition enthalpies were determined from Polarizing Optical Microscopy and Differential Scanning Calorimetry (DSC) measurements. The compounds exhibit negative dielectric anisotropy (Δε) throughout the mesomorphic range (maximum −18 and −4 in SmA* for both the compounds) and moderately high values of spontaneous polarization (∼153 nC/cm2 in SmCre* phase). The temperature dependence of the response time (τ), bulk viscosity (η) and the activation energies (Ea) throughout the mesomorphic phase have been determined from the spontaneous polarization measurements. To emphasize the structure-property correlations in more detail, dielectric spectroscopy measurement has also been performed to measure the dielectric strength, dielectric loss, frequency dependent permittivities, relaxation time and relaxation frequencies. The clear evidence of the relatively rare SmCre* phase has also been confirmed from the temperature and frequency dependence of the dielectric permittivity. These results shed important light on the emergence of these materials as a smart alternative for their application in multicomponent mixtures targeted for advanced electro-optic and photonic devices.

Thermodynamic modeling of CsF with LiF-NaF-KF for molten fluoride-fueled reactors

Gibbs energy models were developed to describe the thermochemical behavior of CsF in molten FLiNaK (46.5LiF-11.5NaF-42KF mol%), a proposed molten salt reactor (MSR) fuel solvent and coolant, as cesium is of concern due to its high radiotoxicity and volatility. Initially, it was necessary to obtain a more accurate Gibbs energy function for CsF which required fitting parameters to reported vapor pressures over condensed phase CsF. The pseudo-binary systems CsF-LiF, CsF-NaF and CsF-KF were then evaluated utilizing phase equilibria and enthalpy of mixing (ΔmixH) values, together with original differential scanning calorimetry (DSC) measurements performed for the CsF-LiF and CsF-KF systems. The CsF-LiF-NaF, CsF-LiF-KF and CsF-NaF-KF pseudo-ternary system representations were obtained by interpolation of the constituent pseudo-binary systems, with DSC measurements performed for the CsF-LiF-NaF system to corroborate the calculated liquidus temperature. Ultimately, the pseudo-ternary systems were interpolated to obtain Gibbs energy models for the pseudo-quaternary CsF-LiF-NaF-KF system, supported by DSC measurements at low CsF compositions (1–10 mol%), yielding computed equilibria and cesium-containing vapor pressures that compare favorably with reported values. The Molten Salt Thermal Properties Database – Thermochemical (MSTDB-TC) was subsequently expanded to include these Gibbs energy models allowing description of the thermochemical behavior of the CsF-LiF-NaF-KF system.

Thermal stability of organic Phase Change Materials (PCMs) by accelerated thermal cycling technique

Phase change materials (PCMs) can improve thermal comfort of occupants acting as thermal energy storage systems. During their service life, PCMs undergo many phase change transitions. However, there is a lack of feasible and cost-effective techniques to evaluate the effect of thermal cycling on the long-term stability and performance of PCMs, which can influence their selection and restrict a broader acceptance of these materials by the construction sector. This study developed a novel accelerated thermal cycling multi-technique to assess the stability and reliability of PCMs under dynamic thermal conditions. All investigated PCMs showed remarkable stability in terms of phase change temperature and latent heat energy even after undergoing 10,000 thermal cycles. The Thermogravimetric Analysis (TGA) results underscore the suitability of these PCMs for built environments, with minimal mass loss at lower temperatures (below 150 °C). The Fourier Transform Infrared spectroscopy (FT-IR) and 1H Nuclear Magnetic Resonance (NMR) results revelled no molecular changes induced by thermal cycling. The novel accelerated thermal cycling technique provides more accurate results than thermal cycling using Differential Scanning Calorimetry (DSC) only, overcoming the issues of contamination and subcooling of smaller samples in DSC measurements.

Amantadine interactions with phase separated lipid membranes

Amantadine, a small amphilphic organic compound that consists of an adamantane backbone and an amino group, was first recognized as an antiviral in 1963 and received approval for prophylaxis against the type A influenza virus in 1976. Since then, it has also been used to treat Parkinson’s disease-related dyskinesia and is being considered as a treatment for corona viruses. Since amantadine usually targets membrane-bound proteins, its interactions with the membrane are also thought to be important. Biological membranes are now widely understood to be laterally heterogeneous and certain proteins are known to preferentially co-localize within specific lipid domains. Does amantadine, therefore, preferentially localize in certain lipid composition domains? To address this question, we studied amantadine’s interactions with phase separating membranes composed of cholesterol, DSPC (1,2-distearoyl-sn-glycero-3-phosphocholine), POPC (1-palmitoyl-2-oleoyl-glycero-3-phosphocholine), and DOPC (1,2-dioleoyl-sn-glycero-3-phosphocholine), as well as single-phase DPhPC (1,2-diphytanoyl-sn-glycero-3-phos-phocholine) membranes. From Langmuir trough and differential scanning calorimetry (DSC) measurements, we determined, respectively, that amantadine preferentially binds to disordered lipids, such as POPC, and lowers the phase transition temperature of POPC/DSPC/cholesterol mixtures, implying that amantadine increases membrane disorder. Further, using droplet interface bilayers (DIBs), we observed that amantadine disrupts DPhPC membranes, consistent with its disordering properties. Finally, we carried out molecular dynamics (MD) simulations on POPC/DSPC/cholesterol membranes with varying amounts of amantadine. Consistent with experiment, MD simulations showed that amantadine prefers to associate with disordered POPC-rich domains, domain boundaries, and lipid glycerol backbones. Since different proteins co-localize with different lipid domains, our results have possible implications as to which classes of proteins may be better targets for amantadine.

Synthesis and molecular dynamics simulation of biobased “bottle-brush” polyfarnesene via aqueous radical polymerization

The farnesene monomer, obtained through bio-fermentation, offers a unique long side chain structure that serves as an excellent platform for the synthesis of bottle-brush polymers with exceptional thermal properties. Such polymers have immense potential in the production of polyurethane elastomers and adhesives. Molecular dynamics simulations of polyfarnesene were performed using Materials Studio to calculate pivotal mechanical parameters like glass transition temperature (Tg), cohesive energy density (CED), and free volume. The Tg was verified by comparing the results from the simulations with measured values obtained through experimental tests. Additionally, hydroxyl-terminated polyfarnesene was cured with a variety of isocyanate cross-linking agents, using a cross-linking script, to evaluate its mechanical and energetic characteristics. The results from the simulation of trans-1,4-polyfarnesene exhibited a Tg of 202 K, which was in close agreement with the Tg (197 K) obtained from differential scanning calorimetry (DSC) measurements. Moreover, the mechanical properties of hydroxyl-terminated polyfarnesene were significantly enhanced through cross-linking, with the multi-isocyanate (N100) curing system demonstrating the highest efficacy. These findings demonstrate the usefulness of molecular dynamics (MD) simulations in providing a thorough qualitative and quantitative understanding of the intricate connection between the properties and structure of polymers.

Effect of core–sheath bi‐polymeric scaffolds fabricated from acid‐soluble collagen and poly(lactic acid) derivatives on wound healing

AbstractThe core–sheath bi‐polymeric scaffold has been proven as an encouraging material based on the requirement of scaffolds. This study aims to prepare electrospun core–sheath scaffolds by using acid‐soluble collagen (ASC) as core material and poly(lactic acid) (PLA) or PLA‐g‐VAc as sheath material to get the most in combination from a hydrophilic and a hydrophobic polymer. ASC is extracted from waste Tilapia fish skin conserving the triple helix structure of the α1 (130 kDa) chain, and a α2 (120 kDa) chain cross‐linked with the β (280 kDa) chain confirmed by amino acid profile, sodium dodecyl sulphate‐polyacrylamide gel electrophoresis. PLA‐g‐VAc is prepared by grafting vinyl acetate (VAc) onto the PLA chain using benzoyl peroxide as the initiator. FT‐IR, 1H NMR, and 13C NMR of PLA‐g‐VAc reveal that grafting occurs between the double bond of VAc and the methine group of PLA. The morphology of the scaffolds is determined by the field emission scanning electron microscope. FT‐IR, thermogravimetric analysis, differential scanning calorimetry, XRD, and water contact angle measurements are used for further characterization of scaffolds. In vivo, cytotoxicity analysis on the Vero cell line exposes that scaffolds are biocompatible. Application of scaffolds to the surgically produced wounding of skin in a rat model followed by histological assay indicates the enhanced properties of core–sheath scaffolds rather than the single polymeric scaffolds.

Agricultural by-product filled poly(lactic acid) biocomposites with enhanced biodegradability: The effect of flax seed meal and rapeseed straw

The purpose of this research was to develop “green” materials by combining poly(lactic acid) (PLA) with two agricultural by-products, namely flax seed meal (FSM) and rapeseed straw (RSS). The natural fillers (0–20 wt.%) were mixed with PLA through extrusion and then injection molded into specimens. The samples were analyzed for their thermal, morphological, mechanical, and physical features and biodegradability. Thermal properties and crystallinity were analyzed using Differential Scanning Calorimetry (DSC), while the morphology was investigated by Scanning Electron Microscopy (SEM). Mechanical properties were characterized through tensile, flexural, and impact measurements, while surface hardness was evaluated by Shore D tests. Water absorption and biodegradability of the samples were also examined. DSC measurements revealed a nucleating effect of both bio-fillers. Based on the tensile tests, major improvement in stiffness was found with the biocomposites having up to ∼16 % higher Young's modulus than neat PLA (2.5 GPa). It came, however, at the cost of tensile strength, which decreased from 56 to 51 MPa even in the presence of the lowest amount (2.5 wt.%) of FSM. Loss in strength was due to the limited adhesion between the components, as also supported by SEM images. The hardness slightly (1–2 %) improved in the presence of even 2.5 wt.% bio-filler and it remained at that level at higher filler loading as well. Laboratory-scale composting revealed that both fillers facilitated biodegradation with FSM being superior. In the presence of 10–20 wt.% FSM, the rate of decomposition was found to be twice as fast compared to neat PLA.

Effect of functional fillers in solvent‐free polyurethane adhesives: Processing and characterization

AbstractThe present work is focused on the study of polyurethane adhesives in the presence of functional fillers (encapsulated enzymes) intended to make them degradable. This is part of a general strategy aiming to recycle multilayer films for packaging, at their end of life, by means of separating the constituent layers as a result of adhesives degradation. Primarily, it was found that the presence of small quantities of functional filler greatly affects both, the quality of the coating process and the kinetics of the adhesive curing. The former, because of the dependency on particle size distribution, leads to high variations in thickness and mechanical properties of multilayers and, the latter, because of a significant catalytic effect (higher curing rates). Indeed, an assessment of the adhesives' kinetics by rheology showed that the pot‐life and the cross‐over point (G′ = G″) for the enzyme‐containing system were obtained three times faster in comparison to the control formulation. These findings were also confirmed by differential scanning calorimetry measurements. On the other hand, by reducing and homogenizing the filler's particle size using separated sieved material (≤50 μm), improvements in coating control as well as in the quality and final properties of the multilayers were evidenced.Highlights Recycling multilayer plastic films for flexible packaging. Encapsulated enzymes to degrade the polyurethane adhesive in specific conditions. The presence of functional fillers affects the coating process. Process optimization to ensure the coating quality control.

Directed energy deposition of 18NiM300 steel: effect of process and post processing conditions on microstructure and properties

ABSTRACT This current study investigates the effect of Direct Energy Deposition (DED) process conditions on the properties and microstructure of M300 maraging steel samples. The investigation centers on two key factors: laser power and deposition environment. The microstructure of this tool steel is analyzed by computing the Primary Cellular Arm Spacing. The findings revealed a significant influence of both inert atmosphere and laser power on cooling conditions. These different cooling rates influence the phase content as demonstrated by X-Ray Diffraction and Electron Backscatter Diffraction measurements. It was demonstrated the presence of different content of residual austenite at cell boundaries. These distinct microstructural features caused variations in the hardness values of the printed samples. Furthermore, a direct aging heat treatment was implemented, that was chosen from Differential Scanning Calorimetry measurements results. This heat treatment proves effective in achieving consistent hardness increases and eliminated the differences among samples built in different process conditions. This outcome suggests the possibility of selecting the most economically viable DED parameters for optimal results.

Chemistry Informed Machine Learning-Based Heat Capacity Prediction of Solid Mixed Oxides.

Knowing heat capacity is crucial for modeling temperature changes with the absorption and release of heat and for calculating the thermal energy storage capacity of oxide mixtures with energy applications. The current prediction methods (ab initio simulations, computational thermodynamics, and the Neumann-Kopp rule) are computationally expensive, not fully generalizable, or inaccurate. Machine learning has the potential of being fast, accurate, and generalizable, but it has been scarcely used to predict mixture properties, particularly for mixed oxides. Here, we demonstrate a method for the generalizable prediction of heat capacity of solid oxide pseudobinary mixtures using heat capacity data obtained from computational thermodynamics and descriptors from ab initio databases. Models trained through this workflow achieved an error (mean absolute error of 0.43 J mol-1 K-1) lower than the uncertainty in differential scanning calorimetry measurements, and the workflow can be extended to predict other properties derived from the Gibbs free energy and for higher-order oxide mixtures.

Influence of Increasing Density of Microstructures on the Self‐Propagating Reaction of Al/Ni Reactive Nanoscale Multilayers

Surface structuring methods are crucial in semiconductor manufacturing, as they enable the creation of intricate structures on the semiconductor surface, influencing the material's electrical, mechanical, and chemical properties. Herein, one such structuring method known as reactive ion etching to create black Si structures on silicon substrates is employed. After thermal oxidation, their influence on the reaction of Al/Ni nanoscale multilayers is studied. It reveals distinct reactive behaviors without corresponding differences in energy release during differential scanning calorimetry measurements. Higher oxidized black Si structure densities result in elevated temperatures and faster reaction propagation, showing fewer defects and reduced layer connections in cross‐sectional analyses. The properties of the reactive multilayers (RML) on high structure density show the same performance as a reaction on flat thermal SiO2, causing delamination when exceeding 23 structures per μm2. Conversely, lower structure density ensures attachment of RML to the substrate due to an increased number of defects, acting as predetermined breaking points for the AlNi alloy. By establishing the adhesion between the reacted multilayer and the substrate, surface structuring could lead to a potential increase in bond strength when using RML for bonding.

Significant improvement of adsorption thermal energy storage of zeolite by simple cation exchange, inducing strong polarization of water

A series of zeolite 13X with various cations was tested as a candidate for water-adsorption-based thermal storage. In the case of pristine commercial zeolite 13X pellet, >99.9 % of cation in the zeolite is confirmed to be Na+. Via conventional cation-exchange method, the Na+ could be almost completely exchanged to Li+, K+, Cs+, Mg2+, Ca2+, and Ba2+ to the thermodynamical levels. The improvement of adsorption thermal storage requires both the increases of water adsorption capacity and heat of desorption. Thermogravimetric analysis (TGA) and Differential Scanning Calorimetry (DSC) measurements were performed for the zeolites, showing that Li+-, and Mg2+-ion form zeolite samples exhibited 26 % and 29 % higher water adsorption capacities at room temperature under fully saturation condition than pristine sample, respectively, and that especially Mg2+-ion form shows 18 % higher heat of desorption than pristine Na+-form. Although Li+-ion form shows notably high water adsorption capacity, its desorption occurs mostly at low temperature (<388 K). The increase of thermal storage as exchanging the cation to Mg2+ and Li+ was fundamentally explained by density functional theory calculation. The cations induce the strong polarization of the adsorbed water molecules, which leads to strong interactions between water molecules and an increase in the amount of water stored.

High entropy alloys (FeCoNi)0.75Cr0.25-xCux – thermal stability and physical properties

The paper reports on the phase stability of the (FeCoNi)0.75Cr0.25-xCux HEA system with equimolar ratio of Fe, Co and Ni by differential scanning calorimetry (DSC) and measurements of physicochemical properties: density, electrical resistivity, Seebeck coefficient, thermal conductivity, and magnetic behaviour in a broad temperature region as well as hardness and elastic modulus at room temperature as a function of the gradual substitution of chromium by copper in a series of (FeCoNi)0.75Cr0.25-xCux alloys with different mole fraction of Cu (x = 0, 0.05, 0.1, 0.15 and 0.2). DSC measurements showed that all alloys are thermally stable. Increasing content of Cu was found (i) to increase the formation of a fcc Cu-rich phase, (ii) to strengthen ferromagnetic interactions, resulting in rising ordered magnetic moments, as well as in growing ferromagnetic transition temperatures, and (iii) to distinctly change physical properties like electrical resistivity, thermal expansion, and mechanical properties. Experimental data regarding the phase stability are supported by CALPHAD calculations.

Microplastic analysis in sediments of the Elbe River by electrostatic separation and differential scanning calorimetry

This study presents the most extensive investigation of microplastic (MP) contents in sediment from the Elbe River. We employed electrostatic separation (ES) and differential scanning calorimetry (DSC) to overcome limitations of sample throughput and time-consuming analysis. In total 43 sediment samples were collected using a Van-Veen grab. Subsequently, coarse materials (d10 > 100 μm) and fine materials (d10 ≤ 100 μm) were enriched using ES and density separation. DSC was utilized for MP identification and quantification, based on the phase-transition signals of eight different polymers. MP presence was detected in 25 samples, with successful quantification in 12 samples. The MP content in coarse material samples from shoreline areas ranged from 0.52 to 1.30 mg/kg, while in fine material samples from harbor basins, it ranged from 5.0 to 44.6 mg/kg. The most prevalent polymers identified were LD-PE, HD-PE, PP, and PCL. These findings confirmed the suitability of DSC for analyzing MP in complex environmental samples. MP hotspots were identified in harbor basins, where natural sedimentation processes and increased anthropogenic activities contribute to MP accumulation. Additionally, industrial sewage potentially contributed to MP content in sediment samples. The highest pollution levels were observed in the middle Elbe, between the confluences of Mulde and Havel. Lowest MP contents were found in the lower Elbe, potentially influenced by tides. Future studies should focus on holistic investigations of selected river sections, encompassing sediment, water, and biota samples, rather than the entire catchment area. This approach would facilitate the generation of spatiotemporal data on MP distribution in freshwater streams. In addition, more research is needed to explore potential interactions between different MP and sediment types during DSC measurements.

Synthesis, crystal structure and properties of the trigonal-bipyramidal complex tris-(2-methyl-pyridine N-oxide-κO)bis-(thio-cyanato-κN)cobalt(II).

Reaction of Co(NCS)2 with 2-methyl-pyridine N-oxide in a 1:3 ratio in n-butanol leads to the formation of crystals of tris-(2-methyl-pyridine N-oxide-κO)bis-(thio-cyanato-κN)cobalt(II), [Co(NCS)2(C6H7NO)3]. The asymmetric unit of the title compound consists of one CoII cation two thio-cyanate anions and three crystallographically independent 2-methyl-pyridine N-oxide coligands in general positions. The CoII cations are trigonal-bipyramidally coordinated by two terminal N-bonding thio-cyanate anions in the trans-positions and three 2-methyl-pyridine N-oxide coligands into discrete complexes. These complexes are linked by inter-molecular C-H⋯S inter-actions into double chains that elongate in the c-axis direction. Powder X-ray diffraction (PXRD) measurements prove that all batches are always contaminated with an additional and unknown crystalline phase. Thermogravimetry and differential analysis of crystals selected by hand reveal that the title compound decomposes at about 229°C in an exothermic reaction. At about 113°C a small endothermic signal is observed that, according to differential scanning calorimetry (DSC) measurements, is irreversible. PXRD measurements of the residue prove that a poorly crystalline and unknown phase has formed and thermomicroscopy indicates that some phase transition occurs that is accompanied with a color change of the title compound.

Modulated Differential Scanning Calorimetry Measurements of 14 High-Purity Industrially Significant Compounds

Modulated Differential Scanning Calorimetry Measurements of 14 High-Purity Industrially Significant Compounds

Curing of epoxy adhesives between thin metal foils by means of inductive heating

Metal foils are being widely used, from the chemical or electronics sector to household appliances. The joining of these foils by adhesive bonding is often the preferred method due to discolouring and warping under the thermal stresses of other joining methods, such as welding. However, long curing times are a disadvantage of adhesive bonding compared to welding. The use of electromagnetic induction is a promising solution for accelerated curing. This work investigates induction heating for accelerated curing of 1-C epoxy adhesives for bonding of thin nickel foils. Process parameters for rapid curing of the adhesives were determined based on reaction kinetics using differential scanning calorimetry measurements. According to those results peel test specimens were fabricated, and the peel resistance was evaluated using a 90° peel load.

A high-throughput differential scanning fluorimetry method for rapid detection of thermal stability and iron saturation in lactoferrin

Thermal stability and iron saturation of lactoferrin (LF) are of great significance not only for the evaluation of the biological activities of LF but also for the optimization of the isolation and drying process parameters. Differential scanning calorimetry (DSC) is a well-established and efficient method for thermal stability and iron saturation detection in LF. However, multiple DSC measurements are typically performed sequentially, thus time-consuming and low throughput. Herein, we introduced the differential scanning fluorimetry (DSF) approach to overcome such limitations. The DSF can monitor LF thermal unfolding with a commonly available real-time PCR instrument and a fluorescent dye (SYPRO orange or Glomelt), and the measured melting temperature of LF is consistent with that determined by DSC. On the basis of that, a new quantification method was established for determination of iron saturation levels using the linear correlation of the degree of ion saturation of LF with DSF measurements. Such DSF method is simple, inexpensive, rapid (<15 min), and high throughput (>96 samples per experiment), and provides a valuable alternative tool for thermal stability detection of LF and other whey proteins.

Design and Characterization of a Novel NiAl–(Cr,Mo) Eutectic Alloy

To enhance the mechanical properties of NiAl–(Cr,Mo) in situ composites for high‐temperature structural use, achieving a regular eutectic microstructure is crucial. A novel alloy with a composition of Ni30.6Al36Cr31.4Mo2 is developed that exhibits a significantly reduced solidification interval compared to well‐studied alloys such as Ni33Al33Cr28Mo6. This advancement results from using the in‐house developed alloy design tool PyMultOpt and Calculation of Phase Diagrams analysis to minimize the solidification interval. The refined alloy demonstrates a theoretical solidification interval of 0 K. These results are verified with differential scanning calorimetry measurements at different heating rates for the new alloy and compared with the established alloy Ni33Al33Cr28Mo6. The small solidification interval leads to a uniform eutectic microstructure consisting of a (Cr,Mo) phase embedded in the NiAl matrix without primary NiAl dendrites present. This indicates that deviating from the stoichiometric NiAl composition results in a significantly lower solidification interval and thus in an actual eutectic composition of the NiAl–(Cr,Mo) system.

Solvent selective gelation of cetyltrimethylammonium bromide: structure, phase evolution and thermal characteristics.

We report herein the gelation behaviour of cetyltrimethylammonium bromide (CTAB), a cationic surfactant, in a variety of solvent compositions. A turbid gel of CTAB in a binary solvent mixture at a critical composition was observed to be 1 : 3 v/v toluene : water. The molecular structure of the as-formed gel was investigated by X-ray diffraction and microscopic techniques, namely, optical and polarizing microscopy, scanning electron microscopy and small-angle X-ray scattering (SAXS). The phase evolution has been studied using UV-visible transmittance measurements and the thermal characteristics of the gel by differential scanning calorimetry measurements. SAXS studies, in conjunction with molecular modelling, revealed the gel to assemble as lamellae with high interdigitation of bilayer assembly of CTAB molecules with predominant non-covalent interactions, where the gel lamellae were inferred from the interplanar spacings. Rheological studies revealed the viscoelastic nature of the CTAB gels. The ability to form a gel has been evaluated in several polar solvents, such as methanol and chloroform, and non-polar solvents, such as toluene and carbon tetrachloride.