Thermal Calorimetry Research Articles

Thermal analysis and calorimetry in Europe

Thermal analysis and calorimetry in Europe

Synthesis and Thermal Energy Storage Analysis of Copper Oxide Nano fluid for Heat Transfer Applications

In this paper we have discussed about the synthesis and thermal analysis of nanofluid as phase change material (PCM). Enhancement of thermal conductivity rate serves as a greatest challenge in the present scenario and to overcome this hindrance, nanofluid synthesis was made. Copper oxide nanoparticle was synthesised by double precipitation method and the nanofluid was prepared by two step method. Paraffin was selected as a base material in which the CuO-nanoparticle was dispersed. To check the thermal storage enhancement Differential scanning calorimetry (DSC) test was carried out. With the melting and solidification curve analysis we were able to infer that the latent thermal storage enhancement was increased drastically with the nanoparticle dispersed sample, than with the ordinary base material. The above nanofluid was subjected to laser flash analysis (LFA) to obtain the thermal conductivity enhancement rate. Thus, we can come up with a suggestion of using CuO nanofluid as an effective phase change material (PCM) for heating applications..

Potential application of fish scales as feedstock in thermochemical processes for the clean energy generation

The replacement of fossil fuels by renewable sources has been discussed globally, because fossil fuels account for a large portion of the pollutant emissions into the atmosphere. Several cities along the Brazilian coast produce a variety of fish types, generating a large amount of waste, including viscera and fish scales, which are already used in several industrial processes. However, these cities still face a large environmental problem, i.e., residue disposal from commercial establishments, e.g., fishmongers, which are often discarded in a disordered and/or unplanned manner in inappropriate places. Within this scenario, the energy utilization of an animal biomass supplied by a fishery in the city of São Luís was investigated, submitting samples to combustion (synthetic air) and pyrolysis (100% N2) processes for the bioenergy generation. Physicochemical properties from fish scales were evaluated by proximate and ultimate analyzes, scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), X-Ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and inductively coupled plasma - optical emission spectroscopy (ICP-OES). The thermal behavior of samples was evaluated by thermogravimetry/derivative thermogravimetry (TG/DTG), differential thermal analysis (DTA) and calorimetry (HHV/LHV). It was verified that the fish scales have carbon and oxygen the major elements, and insignificant amounts of sulfur and heavy metals (lead, copper, chromium, lithium, zinc). This material also presented a large amorphous region (89%), in addition to the presence of collagen fibers and hydroxyapatite crystals. The thermal and physicochemical characteristics of this material were evaluated and compare it to other biomasses already in use, predicting its use for the bioenergy generation.

Characterisation of pyrolysis and combustion parameters of charring materials most frequently found in buildings

Correction to this article published: Correction to: Characterisation of pyrolysis and combustion parameters of charring materials most frequently found in buildings (Journal of Thermal Analysis and Calorimetry, (2020), 139, 5, (2985-2999), 10.1007/s10973-019-08688-6)

Nickel selenate: a deep and efficient characterization

This work aims to determine the nickel selenate hexahydrate thermal behavior by simultaneous thermogravimetry–differential thermal analysis and differential scanning calorimetry and characterize its thermal intermediates decomposition. Moreover, at 25 °C, this material is a green-colored compound; however, with the temperature increase (until 420 °C), a color change from yellowish green to yellowish orange and finally to yellow was observed. This characteristic is due to the water molecules release, changing the ultraviolet–visible/near-infrared spectroscopy analysis absorption spectra and consequently modifying the crystal structure, as confirmed by X-ray powder diffraction, and resulting in visual changes in photo-DSC. The new data are essential to determine the better conditions to use this material as a precursor in synthesis and also to use it in future applications.

Effect of Experimental Conditions and Methods for Processing DTA and DSC Results on Reliability of Kinetic Calculations of Parameters of Curing Thermoset Prepregs

The methods of differential thermal analysis (DTA) and differential scanning calorimetry (DSC) have been used to study the kinetics of curing a thermoset epoxy binder, complicated by intensive self-heating, in an adhesive prepreg based on aramid Ruslan fiber. The most adequate reaction scheme has been chosen and the kinetic parameters of the curing reaction have been determined for each elementary stage. A generalized kinetic model of the reaction has been constructed based on experimental data obtained by DTA and DSC. The selected model has been tested by solving an opposite problem—namely, constructing a series of calculated DTA and DSC curves and evaluating their compliance with the experimental data.

Comments on: Generalization of thermodynamics in of fractional-order derivatives and calculation of heat-transfer properties of noble gases, Journal of Thermal Analysis and Calorimetry (2018) 133:1189–1194

It is shown that the equations for pressure, entropy and the isochoric heat capacity obtained by using generalization of the equilibrium thermodynamics in fractional derivatives in the paper mentioned above are approximate, the comparison of the equations with the experimental (tabulated) data for Neon and Argon made in the paper is incorrect, and the conclusions of the paper made on the basis of the comparison could be incorrect. The conditions for validity of the equations are established. It is also established that the question about a physical sense of the exponent of the derivative of a fractional order is still open.

Анализ фазовых равновесий в тройной системе Ge–P–Sn

На основании анализа характера фазовых равновесий в двойных системах, ограняющих диаграмму состояний тройной системы Ge – P – Sn, предложены теоретически возможные схемы ее фазового субсолидусного разграничения. Исследование методом рентгенофазового анализа образцов, принадлежащих политермическим сечениям Sn4P3-Ge, Sn4P3-GeP, показало, что разделение трехкомпонентной диаграммы состояния ниже солидуса осуществляется с помощью сечений Sn4P3-Ge, Sn4P3 -GeP и SnP3-GeP. Построенная по данным дифференциального термического анализа фазовая диаграмма сечения Sn4P3-Ge представляет диаграмму эвтектического типа с координатами эвтектической точки 800 К, 15 mol % Ge.
 
 
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Toughening Poly(lactic acid) with Thermoplastic Elastomers Modified by Thiol–ene Click Chemistry

Due primarily to the inherent brittleness of poly(lactic acid) (PLA), numerous studies have sought to improve the mechanical properties (e.g., fracture toughness) of PLA for a wide range of contemporary applications. In this study, we report a facile method by which to prepare esterified poly[styrene-b-(ethylene-alt-propylene)-b-styrene] (eSEPS) as a toughening agent for PLA through the use of thiol–ene click chemistry. The effects of adding 1 to 30 wt % eSEPS on the thermomechanical properties and morphological characteristics of PLA/eSEPS blends have been systematically investigated. Since eSEPS copolymers are more thermodynamically compatible with PLA than their parent partially hydrogenated SIS copolymer, we find a measurable reduction in the thermal properties of PLA from thermal calorimetry and enhanced dispersion of eSEPS within the PLA matrix according to electron microscopy. Considerable boosts in mechanical properties such as toughness (∼60 MJ/m3) and elongation at break (∼470%) are about 16× an...

Impact of water saturation on the tensile and thermal properties of heat-treated mangrove/high-density polyethylene composites

The main barrier in the use of natural fiber (NF) as a reinforcing material in thermoplastic composites meant for outdoor applications is NF’s hydrophilicity. Thus, heat treatment of vacuum-dried mangrove was conducted at 120°C in order to reduce the hydrophilic nature of mangrove. The untreated and heat-treated mangrove particles were compounded with high-density polyethylene (HDPE) at 10, 20, and 30 wt% in a twin-screw extruder and injection molded into dog-bone-shaped test pieces for tensile tests and thermal analysis (thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC)). Test pieces were immersed in distilled water for 1440 h at ambient temperature (approximately 27°C) and a relative humidity of 60–65%. The results revealed that the earliest and latest water saturation were observed at 480 and 792 h for 10 wt% treated and 30 wt% untreated composites, respectively. The dry composites maintained higher tensile strength and modulus but lower tensile strain than the water-saturated composites irrespective of treatment. Scanning electron microscopy of tensile fractured surfaces confirmed an improved mangrove-HDPE interfacial interaction of treated composites in both dry and water-saturated conditions. The TGA and DSC data showed that the maximum degradation temperature of dry composites is higher than the wet composites. Overall, the treated composites at dry and water-saturated conditions indicated better tensile and thermal stability than the untreated mangrove-filled HDPE composites; these are possible indications of better performance during outdoor applications.

Thermal Response and Degressive Reaction Study of Oxo-Biodegradable Plastic Products Exposed to Various Degradation Media

In this work, three plastic film products commonly used as commodity thermoplastic articles were analysed with the aim of characterizing their thermal behaviour and stability. The test specimens were subjected to a series of analytical tests to confirm their biodegradable nature. The specimens ranged between 30 and 70 μm in thickness and showed high concentrations of regulated metals, namely, lead (Pb), postchemical analysis which can lead to its migration to natural sinks. The specimens were also exposed to degressive media, namely, accelerated (UV induced) weathering and soil burial field testing. The weight loss measured exceeded 58% after soil burial indicating deterioration under natural environmental stressors. In addition, the thermal characterization campaign executed with the aim of determining the product’s thermal response followed internationally recognised experimental protocols for the determination of thermal stability. The methodology used followed the International Confederation for Thermal Analysis and Calorimetry (ICTAC) recommendation for thermal stability and the computation of kinetic parameters. The degradation reaction kinetics were also determined postexposure to degressive media. Thermogravimetric analysis coupled with differential scanning calorimetry heat flow analysis and Fourier infrared spectroscopy results was also used in studying the degradation behaviour of the specimens. Analytical kinetic estimation methods relying on model free solutions enabled the determination of the apparent activation energy (Ea) of the specimens postexposure to degradation media. A shift in the degradation mechanism was also detected after studying the kinetic parameters which showed a range of Ea between 86.64 and 226.90 kJ mol-1 depending on the type of specimens and exposure media. It can be concluded that the oxo-biodegradable films are well suited for thermal treatment in the future as discarded plastic solid waste (PSW) articles. This work also paves the way for developing national standards and future plans for societies burdened with PSW accumulation.

Thermal conductivity of high density polyethylene: Cold plasma modified graphite composites

AbstractNatural graphite particles (NG) were surface modified via ethylene plasma treatment and characterized by infrared and Raman spectroscopy, thermo‐gravimetric analysis, scanning electron microscopy, X‐ray diffraction, and X‐ray photoelectron spectroscopy. Ethylene polymerized during plasma treatment forming both a thin layer on the graphite particles surface and polyethylene particles that penetrate into the graphite layers, favoring its delamination or exfoliation. This beneficial effect finally impacts in the thermal properties of the composites: in fact, thermal conductivity (k) determined via modulated differential thermal calorimetry is, in general, larger than that of the pure polyethylene because of the graphite contribution and, with a major increase for graphite composites obtained with the treated than untreated NG because of the better dispersion.

Tailoring cream by modifying the composition of the fat and interfacial proteins to modulate stirred milk gel texture

The formulation-structure-texture relationship in stirred emulsion-filled food gels has rarely been analysed, let alone in realistic conditions. By studying thermal (calorimetry), structural (laser diffraction, confocal microscopy and mathematical morphology analysis) and textural (rheology and tribology) properties, this work advanced the understanding of this relationship in stirred gels made entirely from milk ingredients. Indeed, tailoring the fat composition (AMF, olein or stearin fractions) and interfacial proteins (native or heat-aggregated WPI) in cream resulted in different properties. Crystallisation of the fat droplets and probably their interactions (aggregation or partial coalescence), pore size, microgel size and the coarseness of the protein network in stirred milk gels were all modified by the cream formulation. The changes in properties led to different textures and lubrication behaviours of the stirred milk gels. The highlighted relationships between formulation, structure and texture are recapitulated in a concluding diagram.

Calorimetry and thermal analysis in food science

Food science is a domain of life science. Applications of thermal analysis and calorimetry (TAC) to food products deal with many investigation targets spanning from the characterization of the systems at molecular and supramolecular level to the description of the microbial metabolism. Food products are multi-phase and multi-component metastable systems where several processes can occur simultaneously during the preparation process and the shelf life. One therefore has to disentangle various contributions to the overall instrumental outputs, using appropriate data treatments and kinetic models, and/or results from other experimental approaches. The paper reports an updated survey of TAC applications to food products through specific examples of data treatments.

Morphological Evolution of Mg-Al-La-Ca Alloy Induced by a Mechanical Stirring Process

This paper aims to evaluate the morphological evolution of a magnesium-aluminum alloy (Mg-6Al-3La-1Ca) processed by a mechanical stirring process (MSP) with different stirring times. An apparatus for semisolid metal alloy processing was used to melt and obtain rheocast material. Transformation temperatures were determined at a slow cooling rate using computer-aided cooling curve thermal analysis (CA-CCTA) and differential scanning calorimetry (DSC). Isothermal mechanical stirring (605 °C), at 950 rpm, was carried out with a solid fraction of 0.29 and stirring times of 0, 1, 2, 4, 8 and 10 min, followed by fast cooling in water. The results showed that the microstructure after conventional casting (0 min—no stirring) is composed of an α-Mg dendritic matrix, Al11La3, (Al,Mg)2Ca and Mg2Ca compounds. With the 1-min stirring time, it was not possible to obtain globular structures. For stirring times longer than 2 min, a primary α-Mg globular morphology was obtained. Microstructures with 2 min of stirring time showed better globularization than those obtained under the other conditions. Morphological changes were observed for Al11La3 and (Al,Mg)2Ca after the MSP followed by fast cooling.

Biopolymer-Grafted, Magnetically Tuned Halloysite Nanotubes as Efficient and Recyclable Spongelike Adsorbents for Anionic Azo Dye Removal.

The quest for sustainable development and green chemistry had led to the design and synthesis of advanced adsorbent materials for efficient removal of pollutants in industrial effluents. Magnetic halloysite nanotubes with chitosan nanocomposite sponges were prepared by combining solution-mixing and freeze-drying. Magnetic@chitosan/halloysite (Fe3O4–HNT/CS) and spongelike chitosan/halloysite (HNT/CS) were used as adsorbents for the removal of Congo red dye in aqueous solution in a batch process. The as-prepared composites were characterized using scanning electron microscopy, energy-dispersive X-ray analysis, X-ray diffraction, vibrating-sample magnetometry, thermal gravimetry–differential scanning calorimetry, and Fourier transform infrared spectroscopy. Data from kinetic study were analyzed with pseudo-first-order and pseudo-second-order models, whereas the mechanism was analyzed using Bangham’s, Elovich’s, intraparticle, and double-exponential diffusion models. The equilibrium data were evaluated using Langmuir, Freundlich, Temkin, and Dubinin–Radushkevich isotherm models. The adsorption kinetics of dye removal followed the pseudo-first-order model with average rate constants of 0.260 and 0.196 min–1 for Fe3O4–HNT/CS and HNT/CS, respectively. The Langmuir adsorption isotherm best fitted the equilibrium data with R2 > 0.9 with maximum adsorption capacities of 41.54 and 54.49 mg g–1 obtained for HNT/CS and Fe3O4–HNT/CS, respectively. Negative values of ΔG° obtained from thermodynamic studies revealed that the adsorption process was spontaneous. The values of ΔH° and ΔS° obtained for Congo red dye removal were 69.46 and 39.54 kJ mol–1 and 240.5 and 145.1 J mol–1 K–1 for HNT/CS and Fe3O4–HNT/CS, respectively. The results indicated that CS–HNT is an excellent adsorbent; however, its magnetic modification further improved its recyclability and enhanced the performance for the removal of Congo red dye from aqueous solution.

On the Kinetics of Degradation Reaction Determined Post Accelerated Weathering of Polyolefin Plastic Waste Blends.

Polyolefin (PO) polymers constitute the majority of consumer plastic commodities. The reliance on such materials make it near imposable to avoid touching one in any given day. Therefore, the accumulation of plastic solid waste (PSW) in developed and developing societies alike requires immediate attention to manage and valorize this type of waste. In this work, PSW originating from real life sources and virgin linear low-density polyethylene (LLDPE) films were compounded in a mechanical recycling effort. The recycled blends constituted up to 100% (by weight) of the waste material. Accelerated weathering (aging) was conducted on the blends, reaching threshold limit of exposure to study the major changes occurring on the recycled blends. Thermogravimetry and differential scanning calorimetry (DSC) were used to determine their characteristics and applicability for future recycling using thermo-chemical treatment (TCT) methods. Analytical solution methods following the international committee of thermal analysis and calorimetry (ICTAC) were followed in conducting the measurements and kinetic calculations alike. A novel analytical mathematical solution model is also introduced to determine both the pre-exponential factor (Ao) and apparent activation energy (Ea) of the degradation reaction. The model proved to be a more accurate analysis tool, and the work in whole enabled the determination of future plans for using such waste components as a feedstock to thermal units.

Annealing-assisted high-pressure torsion in Zr55Cu30Al10Ni5 metallic glass

For bulk metallic glasses (BMGs) structural anisotropy has been studied for many years, but usually for small creep strains, rather than for large strains associated with the viscoplastic flow. In this study, the structural modifications in the short-to-medium range order of Zr55Cu30Al10Ni5 BMG is deliberated for the first time upon simultaneous high-pressure torsion (HPT) and in-situ annealing around the glass transition temperature (Tg). The changes are evaluated in terms of hardness by microindentation, thermal properties by differential thermal calorimetry, chemistry by energy dispersive X-ray, and structural properties by synchrotron X-ray diffraction and transmission electron microscopy. A remarkable increase of the glass transition temperature and the absence of the shoulder of the crystallization peak along with remarkable softening and shear thinning reveals that even at Tg the material gains flow characteristics because of the extreme pressure applied. A clear shift towards smaller wave vector Q in the peak positions of the partial distribution function G(r), and reconfiguration of the bonding between Zr−Zr and Zr−Cu atomic pairs extracted from the deconvolution of the radial distribution function RDF(r) are observed with changing the processing temperature. The findings give insight into the atomic and nano-scale modifications in BMGs due to high-pressure torsion at different temperatures which would be essential to tune the intrinsic properties of BMGs to attain the desirable hardness and thermal stability for a specific application.

Editorial for the Topical Issue “Thermal analysis and calorimetry techniques applied to the characterization of materials and fluids for energy”

Editorial for the Topical Issue “Thermal analysis and calorimetry techniques applied to the characterization of materials and fluids for energy”

Preparation and application of temperature-sensitive affinity chromatographic materials for enrichment of phosphoric acid compounds

Based on the surface initiated-reversible addition fragmentation chain transfer (SI-RAFT) method, an immobilized metal ion affinity chromatographic material, silica@ploy(N-isopropylacrylamide-co-(aminomethyl)phosphonic acid)-titanium(Ⅳ) (silica@p(NIPAAm-co-AMPA)-Ti4+), was synthesized by the method of rapid introduction of functional groups. The synthesis of the material was confirmed by FT-IR and X-ray photoelectron spectroscopy. The grafting ratio and lower critical solution temperature (LCST) of the material were measured by thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC). The results showed that the material had excellent temperature-sensitive properties and could successfully capture and release adenosine triphosphate successfully. The service life of the material could be extended by online supplementation of Ti4+.