Thermogravimetry Differential Scanning Calorimetry Research Articles

A drug–drug cocrystal strategy to regulate stability and solubility: A case study of temozolomide/caffeic acid

Temozolomide (TMZ) is a common clinical drug widely used to treat glioblastoma multiforme and gradual astrocytoma. Despite its widespread use in cancer treatment, issues remain with the solubility and stability of TMZ, which can be addressed by synthesizing novel pharmaceutical cocrystals. This study sought to enhance the physiochemical properties of TMZ. To this end, a pioneering pharmaceutical cocrystal of TMZ and caffeic acid (CAF), 2TMZ–CAF·0·5H2O (2:1:0.5) was synthesized and characterized using a solution method. The cocrystal structure was analyzed by molecular surface electrostatic potential (MESP), Hirshfeld surface analysis, and 2D fingerprinting. They were further characterized by single crystal X-ray diffraction, power X-ray diffraction, proton nuclear magnetic resonance, thermogravimetry-differential scanning calorimetry, dynamic vapor sorption, and Fourier transform infrared spectroscopy. Furthermore, the hygroscopicity, stability, and solubility of the TMZ–CAF cocrystal were investigated to evaluate their pharmaceutical applicability. In the asymmetric unit of the novel synthesized cocrystal, two complementary molecules of TMZ and CAF were found, forming planar hydrogen bonding pairs such as O–H···O, N–H···O, and O–H···N. Moreover, the cocrystals exhibited excellent stability compared to TMZ alone and regulated solubility during accelerated stabilization and dissolution processes. Hence, the cocrystals boast characteristics that can circumvent the rapid release of TMZ. In conclusion, the newly synthesized 2TMZ–CAF·0·5H2O cocrystals demonstrate enhanced physiochemical properties, including improved stability and solubility, compared to pure TMZ. This suggests potential utility in drug delivery systems. Additionally, the findings underscore the growing importance of pharmaceutical cocrystals in drug development, with implications for advancing cancer treatment and drug formulation strategies.

Thermal Stability and Non-Linear Optical and Dielectric Properties of Lead-Free K0.5Bi0.5TiO3 Ceramics.

Lead-free K0.5Bi0.5TiO3 (KBT) ceramics with high density (~5.36 g/cm3, 90% of X-ray density) and compositional purity (up to 90%) were synthesized using a solid-state reaction method. Strongly condensed KBT ceramics revealed homogenous local microstructures. TG/DSC (Thermogravimetry-differential scanning calorimetry) techniques characterized the thermal and structural stability of KBT. High mass stability (>0.4%) has proven no KBT thermal decomposition or other phase precipitation up to 1000 °C except for the co-existing K2Ti6O13 impurity. A strong influence of crystallites size and sintering conditions on improved dielectric and non-linear optical properties was reported. A significant increase (more than twice) in dielectric permittivity (εR), substantial for potential applications, was found in the KBT-24h specimen with extensive milling time. Moreover, it was observed that the second harmonic generation (λSHG = 532 nm) was activated at remarkably low fundamental beam intensity. Finally, spectroscopic experiments (Fourier transform Raman and far-infrared spectroscopy (FT-IR)) were supported by DFT (Density functional theory) calculations with a 2 × 2 × 2 supercell (P42mc symmetry and C4v point group). Moreover, the energy band gap was calculated (Eg = 2.46 eV), and a strong hybridization of the O-2p and Ti-3d orbitals at Eg explained the nature of band-gap transition (Γ → Γ).

Effects of pyrite, quartz and sodium sulfite on roasting of a refractory sulfide concentrate and gold, silver, copper leaching during cyanidation

The oxidation roasting pretreatment process, which is a mature and dominant industrial practice for treating complex polymetallic gold deposits, has a low recovery of associated silver and exhibits an unclear reaction sequence. This study takes a silver-containing gold ore as the research object and investigates the effect of (i) sodium sulfite as an additive, (ii) main gold-bearing mineral pyrite, and (iii) gangue mineral quartz, on silver during the roasting process in roasting and leaching tests. Characterization techniques included scanning electron microscopy–energy dispersive spectroscopy analysis, and thermogravimetry–differential scanning calorimetry analysis. The results based on thermodynamic calculations and characterization show that the main reason for the low extraction of silver is that the calcined product (i.e., iron silicate) formed by the reaction between pyrite and quartz during the roasting process is mutually absorbed and wrapped with silver oxide. In addition, silver minerals decompose some iron sulfides and iron oxides under high-temperature conditions, promoting the reaction of iron and quartz to form iron silicate while strengthening the secondary encapsulation of silver by products of roasting, thus deteriorating the extraction of silver. The addition of sodium sulfite reduces the formation of iron silicate and increases the extraction of silver by directly promoting the conversion of pyrite to iron oxide. This study provides a theoretical basis for further improving the roasting and leaching of silver.

Simultaneous Thermogravimetry-Differential Scanning Calorimetry (TG-DSC) in Nanoporous Materials: Examples of Data for Zeolites, Metal–Organic Frameworks (MOFs), Clay Based and Mesostructured Solids

AbstractThis article presents and discusses the results of a compilation of experimental results of thermogravimetry with simultaneous differential scanning calorimetry (TG-DSC), obtained in the same apparatus and under similar experimental conditions, for a selection of nanoporous materials with interesting properties as adsorbents and catalysts, namely clays and clay-based materials (such as pillared-clays and porous clays heterostructures), zeolites and related materials (such as titanosilicates), mesostructured silicas and MOFs. Materials functionalized with a relatively common silane, the (3-aminopropyl)triethoxysilane (APTES) were also analyzed and discussed.

Pore Structure Evolution and Failure Mechanism of Limestone in the Taiyuan Formation of the Ordos Basin under High Temperature.

The study on the destruction of the limestone microstructure after high-temperature treatment has a significant value in the airtightness and safety of underground high-temperature geotechnical engineering. In order to truly simulate the influence of the underground high-temperature environment on limestone, taking seven groups of limestones of the Taiyuan Formation in the Ordos Basin as examples, we carried out a high-temperature (25-1200 °C) heating experiment of limestone in an argon atmosphere. The pore structure of limestone after the high temperature is studied based on scanning electron microscopy (SEM), mercury intrusion porosimetry (MIP), porosity, and permeability, and the change in the fractal dimension of the limestone pore structure was discussed based on the thermodynamic fractal theory, combined with X-ray diffraction (XRD) and thermogravimetry differential scanning calorimetry (TG-DSC), the variation of mineral composition with temperature is characterized, and the evolution mechanism of the limestone microstructure under high temperature is discussed. The results show that the evaporation of pore water does not destroy the lattice structure of limestone minerals; however, with the increase of temperature, the complete decomposition of dolomite and calcite occurs, along with the tensile fracture of calcite crystals under the effect of swelling stress. Moreover, the new minerals generated by the decomposition products under the effect of temperature severely damage the crystal structure, leading to the rapid increase of porosity and permeability. The comprehensive results show that the decomposition, expansion, and recrystallization of calcite and dolomite minerals after 800 °C led to the development of limestone macropores and fissures, increased the pore throat radius, enhanced the pore connectivity, simplified the pore structure, and sharply increased the permeability; thus, 800 °C can be used as the critical temperature to change the limestone pores and fractures. The research results can provide data support for subsurface high-temperature geotechnical engineering.

Study on the mechanical properties, microstructure and hydration mechanism of phosphogypsum-based geopolymer cement with added micron-sized silica particles

Phosphogypsum (PG) is a solid waste product that is generated during the manufacture of phosphoric acid. In this study, beta-hemihydrate phosphogypsum (β-HPG), slag, sodium metasilicate (SM), citric acid (CA) and micron-sized silica particles (MSSP) were mixed to form a phosphogypsum-based geopolymer (PBG) cement. The results revealed that by adding 3 % MSSP, the 28-day unconfined compressive strength (UCS) reached its highest level of 59.2 MPa. Furthermore, adding 2 % MSSP resulted in the greatest water resistance, with a softening coefficient of 0.92. Additionally, X-ray diffractometry (XRD) Rietveld analysis, scanning electron microscopy-energy dispersive spectrometry (SEM-EDS) imaging, thermogravimetry-differential scanning calorimetry (TG-DSC) analysis, high-temperature XRD analysis, and mercury intrusion porosimetry (MIP) testing were employed to analyse the PBG cement. Results indicated that dihydrate gypsum (CaSO4·2H2O), ettringite (Ca6(Al(OH)6)2(SO4)3(H2O)26), and polymers (Nan{−(SiO2)zAlO2}n·ωH2O) were the principal hydration products in the PBG cement system. Also, the addition of MSSP led to reduced porosity, lower pore-specific surface area, and fewer cracks in the cement structure. After exceeding temperatures of 990.9 °C, these polymers gradually decomposed into Na6(AlSiO4)6, Al2O3, and SiO2. PBG cement is characterized by its easy processing, high strength, eco-friendly nature, and high PG incorporation. It shows promise as a potential substitute for traditional Portland cement in certain sectors, thereby facilitating the consumption of waste gypsum.

Study on the mechanical properties and strength formation mechanism of high-volume graphite tailings concrete

Graphite tailings and coal gangue (CG) are solid wastes produced by mines. The large accumulation of surface materials poses great harm globally, and resource utilization is an urgent problem to be solved. In this paper, steel slag (SS), granulated blast furnace slag (GGBS), and fly ash (FA) are used as binder materials. Graphite tailings sand (GTS) is used as a fine aggregate. Using coal gangue and natural gravel as coarse aggregates, high-volume tailings aggregate concrete was prepared by the alkali excitation method. The strength formation mechanism of concrete was analyzed by combining scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and thermogravimetry-differential scanning calorimetry (TG-DSC). The results showed that with increasing tailings replacement rate, the strength of concrete containing natural gravel and coal gangue as coarse aggregates gradually decreased. The strength of coal gangue aggregate concrete is 10-15 MPa lower than that of natural gravel aggregate concrete. The uniaxial compressive failure of GTS concrete is divided into three stages: quasielasticity, stable expansion, and critical stress. A small amount of steel scoria (less than 30 %) can provide a good calcium ion (Ca2+) environment for the hydration reaction. The concrete hydration products are mainly calcium silicate hydrate (C-S-H) gel, sodium aluminosilicate hydrate (N-(A)-S-H) gel, ettringite (AFt), etc., and the formation of calcium silicate hydrate C-S-H gel and N-(A)-S-H gel can inhibit the cracks that proceed by shrinkage deformation and improve the durability of concrete. GTS concrete can reduce carbon emissions and solidify some of the harmful substances of raw materials.

Preparation of alkali-activated nickel slag-based cemented tailings backfill: Workability, strength characteristics, localized deformation and hydration mechanism

To solve the problems of high magnesium nickel slag (HMNS) and tailing stacks with large storage and environmental pollution, alkali-activated HMNS-based cementitious materials were prepared by using NaOH, phosphogypsum (PG), HMNS and ground granulated blast furnace slag (GGBFS), and cemented tailings backfill (CTB) was prepared using tailings as aggregates. The workability, strength characteristics, localized deformation and hydration mechanism of CTB were studied. Based on the digital speckle correlation method (DSCM), the localized deformation of CTB was analyzed. The hydration mechanism of CTB was analyzed by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), thermogravimetry-differential scanning calorimetry (TGDSC), mercury intrusion porosimetry (MIP) and scanning electron microscopy and energy dispersive spectroscopy (SEMEDS). The results showed that the optimal mix proportions for the cementitious material were 8%, 30%, 6%, and 0.38 for PG content, GGBFS content, alkali dosage, and water/binder ratio, respectively. The best performance of CTB was achieved when the bone glue ratio (BGR) and mass concentration (MC) were 5:1 and 79%, respectively; the slump, slump flow, and consistency of CTB decreased continuously with increasing BGR and MC; the layering degree, bleeding rate, and linear shrinkage of CTB continuously increased with increasing BGR, and decreased with increasing MC; the unconfined compressive strength of CTB increased with increasing maintenance age and MC and decreased with increasing BGR; when the BGR was small (3:1), CTB exhibited shear failure, and when the BGR was large (6:1), CTB exhibited tensile failure. The main hydration products of CTB were C-S-H gel, M-S-H gel, ettringite (AFt), Ca(OH)2 and CaCO3. In the early stage of curing, CTB has more pores, fewer hydration products and a relatively loose internal structure, flocculation, sheet, network and needle rod hydration products coated tailing particles, porosity decreased, and CTB became dense.

Reduction of agglomeration effect by aluminum trihydride in solid propellant combustion

AbstractAluminum trihydride (AlH3) has gained considerable attention as a substitute fuel for aluminum in solid propellants. In this study, we conducted a systematic investigation to evaluate the effects of AlH3 content, ranging from 0 % to 18 %, on propellant ignition, combustion, and agglomeration. Experimental methods such as thermogravimetry−differential scanning calorimetry (TG‐DSC), laser ignition, high‐speed photography, and collecting condensed combustion products (CCPs) were employed. The results indicate that AlH3 significantly promotes the high‐temperature decomposition of ammonium perchlorate (AP). Meanwhile, the addition of cyclotetramethylene tetranitramine (HMX) in propellant does not affect the hydrogen release reaction of AlH3. As the AlH3 content increases from 0 % to 18 %, the spectral emission intensity of the propellants decreases, and the ignition delay time initially increases from 253 ms to 321 ms, and then decreases to 258 ms. Furthermore, the burning rate increases with increasing the AlH3 content, while the pressure exponent is reduced from 0.551 to 0.460. The inclusion of AlH3 in propellants significantly inhibits aluminum agglomeration near the burning surface. Additionally, as the AlH3 content increases, the mean particle size D43 of the CCPs decreases from 50.95 μm to 8.28 μm at 1 MPa. The agglomeration degree of aluminum is very weak at 7 MPa, especially when the AlH3 content exceeds 9 %. The conclusions drawn from this study can serve as valuable guidance for optimizing propellant formulations.

Study on reaction mechanism for the synthesis of vanadium nitride by carbothermic reduction nitridation method

Vanadium nitride (VN), as a typical transition metal nitride, has widespread applications in various fields due to its high melting point, high hardness, and excellent thermal and chemical stability. In this study, VN was synthesized through the carbon thermal reduction nitridation method using V2O3 as the main material, and the reaction mechanism was thoroughly examined. Thermodynamic analysis, coupled with thermogravimetry-differential scanning calorimetry (TG-DSC), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD), revealed that the reaction mechanism was not simply a direct nitridation process nor a two-step coupling of reduction and carburization. Instead, it was the result of multiple reaction mechanisms working in conjunction. Direct nitridation of V2O3 occurred throughout the entire reaction process, while indirect nitridation of VO and VC also occurred with the variation of temperature. A kinetic model was constructed based on the material thermal weight loss curve and revealed that in the carbothermal reduction nitridation system of V2O3, the solid phase reaction followed a three-dimensional diffusion model, with an activation energy of 160.244 kJ/mol, while the gas phase reaction with the solid phase followed a one-dimensional interface model, with an activation energy of 169.015 kJ/mol.

Thermal behavior of minerals in shale and its influence on evolution of gas-flow channels under thermal shock

Thermal shock-induced damage can significantly enhance the connectivity of the rock's fracture network. Thermal Enhanced Recovery (TER) technology holds promising potential for application in shale gas production. Nevertheless, there is still a lack of direct experimental studies focusing on the evolution of shale's gas-flow channels and the mechanism of thermal fracturing in shale under the influence of thermal shock. In this study, we initially investigated the impact of thermal shock on various minerals in shale through X-ray diffraction (XRD) analysis and scanning electron microscope (SEM) imaging, and examined the mass and heat variation with temperature using Thermogravimetry-Differential Scanning Calorimetry (TG-DSC) testing. Subsequently, we assessed the alterations in shale's internal structure due to thermal shock through low-temperature gas (N2) adsorption (LTGA) analysis, and observed the distribution and expansion patterns of shale fractures under thermal shock using computed tomography (CT). Finally, we evaluated the changes in shale permeability before and after thermal shock. The findings indicate that quartz, feldspar, and clay exhibit relatively stable behavior in shale under thermal shock, whereas carbonate and pyrite are prone to crack. Under the combined influence of mineral cracking and thermal stress, the internal pore structure of shale tends to enlarge in size while reducing in surface area. The substantial decrease in pore specific surface area highlights the considerable reduction in gas adsorption capacity. Furthermore, fractures expand along the bedding planes as surface fractures. The expansion of pores and fractures promotes the formation of primary gas-flow channels. In addition, the aforementioned test results demonstrate a high level of consistency, specifically highlighting a distinct threshold temperature (500 °C) for the alteration of various physical parameters of shale during thermal shock. This study is anticipated to offer insights into the implementation of TER technology in the oil and gas industry.

Porous nanosheets of TKX-50 by ice-templating strategy with excellent thermal decomposition and combustion properties

ABSTRACT Nanostructured energetic materials have attracted considerable research interests during the past decades because of their improved performances in thermal decomposition and combustion. In this work, a porous nanosheet structure of dihydroxylammonium 5, 5′-bistetrazole-1, 1′-diolate (TKX-50) has been fabricated by a facile ice templating strategy, which is based on the self-assembly of TKX-50 during rapid recrystallization. Thermal decomposition properties were determined by differential scanning calorimetry/thermogravimetry (DSC/TG) and TG-FTIR analyses. The laser-ignited and constant-volume combustions and mechanical sensitivity were conducted. As-prepared TKX-50 mainly presents porous nanosheets (NS-TKX-50) assembled by the secondary nanoparticles. NS-TKX-50 is typical of mesoporous materials with high specific surface area and pore volume. Compared with raw material, NS-TKX-50 exhibits lower thermal decomposition peak temperature and higher active energy. In thermal decomposition process, a great deal of gaseous products have been generated in a very narrow temperature range. These thermal decomposition features suggest a quick energy-release rate and high energy output. Contrary to incomplete combustion of raw material, NS-TKX-50 shows high-efficiency and self-sustaining laser-ignited combustion feature with a drastically decreased ignition threshold. And its pressurization rate and peak pressure are remarkably increased. Sensitivity results confirmed the visibly reduced impact and friction sensitivity of NS-TKX-50.

Developing amino acid-citric acid-based deep eutectic solvent for food applications: Preparation, characterization, antibacterial activity, biosafety, and formation mechanism exploration

The deep eutectic solvent (DES) is a novel environmentally-friendly solvent that shows promising potential for applications in the field of functional food. However, the current development of choline-based DESs faces limitations due to their toxicity levels, which restrict their application in the food industry. Therefore, in this study, amino acid (AA)-citric acid (CA) DESs suitable for functional food applications were developed using natural food additives as raw materials. The purity and thermodynamic properties of the AA-CA DESs were characterized by simultaneous thermogravimetry/differential scanning calorimetry (TG-DSC) and DSC analysis. The molecular interactions within the AA-CA DESs were investigated using FT-IR, NMR, and molecular dynamics (MD) simulations. The rheometer was used to study the viscosity of AA-CA DESs. The density of the AA-CA DESs was tested using a pycnometer and mutually verified with MD simulations. The antibacterial activity and biological safety of DESs were investigated by bacteriostatic and cell experiments. FT-IR, NMR, and MD simulations studies indicated that AA-CA DESs primarily form through hydrogen bonding interactions. Antibacterial experiments demonstrated that AA-CA DESs exhibited significantly enhanced antibacterial activity against P. aeruginosa and E. coli compared to pure substrates Gly, Ala, and Arg, respectively, indicating improved antibacterial properties. The cell experiments showed that AA-CA DESs possess good biological safety. In conclusion, this study successfully developed a class of AA-CA DESs and found that AA-CA DESs have good antibacterial activity and biosafety. This finding provides theoretical guidance for the sustainable development and application of DESs in the field of functional foods.

Investigation on the microstructures, mechanical properties and impact initiation characteristics of Al/PTFE reactive materials reinforced by TiH2 particles

Aluminum/Polytetrafluoroethylene (Al/PTFE) is a representative energetic material, which can be used in many fields including defense weapon fragments, insensitive penetrator or oil-well perforation. However, the insufficient mechanical strength of traditional ingredient has seriously restricted its penetration ability, and traditional additives improve its compressive strength at the expense of reactivity. Hence, innovative component design and advanced manufacturing technology should be applied to Al/PTFE composite. In this investigation, TiH2 as a new reinforcement is introduced into Al/PTFE to improve both strength and reactivity. Quasi-static and dynamic compressive tests were conducted, and the impact reaction process was recorded by high-speed camera. The results shown Al/PTFE/TiH2 composites are all elasto-plastic materials, significant strain hardening and strain rate hardening phenomenon were observed. The compressive strength increased first and then decreased with increase in TiH2 content, reached the maximum of 185.1 MPa at the strain rate of 5000 s−1 when TiH2 content was 30 %, which increased by 30.4 % compared to traditional Al/PTFE. A newly-developed drop-weight device was used to quantitatively characterize reactivity, and the reaction efficiency reached 8.2 % when TiH2 content was 30 %, increased by 43.2 % compared to Al/PTFE. The formation of oriented PTFE nano-fibers was considered the important strengthening mechanism. The established Johnson–Cook model was agreed well with experimental results. Combining the results of thermogravimetry-differential scanning calorimetry (TG-DSC) tests with X-ray diffraction (XRD) analysis of reaction residues, the reaction mechanism was clarified. The impact initiation reaction was in a mechano-chemical manner and the reactivity was speculated to be the results of multiple actions between Al/PTFE and TiH2.

Effects of Coloration of Spinel CoAl2O4 Cobalt Blue Pigments: Composition, Structure, and Cation Distribution

Cobalt blue ceramic pigments mainly consisting of CoAl2O4 are subject to the difficulty of color control. Here, a perspective is reported regarding research on the reasons for color change based on the control of the heat treatment and ratio of components. Macroscopically, the composition of pigment powders determines the color. Microscopically, the crystallite characters including size, cation distribution, and structure have an important effect on the color. The ingredient, structural, and color properties of the pigment powders are analyzed using thermo gravimetry–differential scanning calorimetry (TG–DSC), X-ray diffraction (XRD) measurement, Rietveld refinement, energy dispersive spectrometer (EDS), and colorimetry analysis. The color is proven to be associated with cation distribution, such as that of Co2+ and Co3+. It is indicated that high heating temperature, long heating time, and a large proportion of Al3+ can, respectively, induce the Co2+ and Al3+ in tetrahedral and octahedral sites.

Bi-salts composites to enhance the hydration kinetics and heat storage capacity

In this study, salt hydrates were deposited on a porous carbon (PC) support to address the challenges associated with maintaining heat capacity and slow hydration kinetics in thermochemical heat storage (THS) systems. Mono-salt (MgSO4) or binary salt (MgSO4-MgCl2) composites on the PC were analyzed by thermogravimetry/differential scanning calorimetry (TG/DSC). The results show that binary salt composites exhibit faster hydration kinetics and higher water adsorption capacity than monosalt composites. The addition of MgCl2 overcomes the kinetic drawbacks caused by the hydrophobic nature of the support and the presence of salt aggregates. The PC_60binary composite achieves a water uptake of 0.75 g/g, exceeding the water uptake of PC_60MgSO4 (0.48 g/g). Furthermore, the heat released by the composites follows a similar trend to water sorption. PC_60MgSO4 produces 52 % (1356 J/g) of the heat released by pure MgSO4, while PC_60binary achieves 70 % (1840 J/g) of the heat released by pure mixed salts. These results suggest that the newly developed binary salt composites are promising for long-term heat storage applications. These experimental results highlight the improved performance of binary salt composites in terms of hydration kinetics, water adsorption and heat release. This study provides valuable pointers for the development of more efficient THS systems.

L and S band microwave absorption properties of Z-type hexaferrite Ba3Co2Fe24O41 synthesized at low temperature

The L-band and S-band electromagnetic waves are widely utilized in radar and satellite communications. This paper reports the successful synthesis of 85.8% content Ba3Co2Fe24O41 (Co2Z) at a relatively low temperature of 1150 °C using the solid-phase method with BaFe12O19 (BaM) and Ba2Co2Fe12O22 (Co2Y) as precursors. The Co2Z samples were confirmed to have been successfully synthesized using X-ray diffraction (XRD) and thermogravimetry/differential scanning calorimetry (TG-DSC) spectra. Scanning electron microscopy (SEM) images revealed that the sintered samples exhibited large grains (>10 µm). Vibrating-sample magnetometry (VSM) data indicated that the synthesized Co2Z samples possessed distinct soft magnetic properties. X-ray photoelectron spectroscopy (XPS) results showed that the Fe3+ content decreased with the increase in synthesis temperature. The samples synthesized at 1110 °C − 1280 °C had a permeability of 10–20, a cut-off frequency of approximately 1 GHz, and a dielectric constant of 10–30. When the thickness of the sample synthesized at 1150 °C was 3.9 mm, the frequency range of the reflection loss (RL)< −10 dB was 2.55 GHz (0.98–3.53 GHz), with 1.77 GHz as the center frequency, and RLmin was − 57.8 dB. This observation indicates that the effective absorption bandwidth of the samples covers the entire L and S bands, which significantly satisfies practical applications within the military and civilian sectors.

Subtle variation in lattice parameter and thermal expansion due to heating and cooling of a high-entropy fluorite oxide (Zr0.2Ce0.2Hf0.2Y0.2Al0.2)O2-δ between 1200 and 1500 °C in air

High-entropy fluorite oxides (HEFOs) must be evaluated under various test conditions to be used as advanced thermal barrier coating (TBC) materials. This study investigated the chemical valence, lattice parameters, and thermal expansion coefficient (TEC) of an HEFO (Zr0.2Ce0.2Hf0.2Y0.2Al0.2)O2-δ heated and cooled between 1200 °C and 1500 °C in air. Thermogravimetry-differential scanning calorimetry (TG-DSC) was used to probe the temperature ranges of the reduction and oxidation reactions, and X-ray photoelectron spectroscopy was used to determine the valence states of the chemical elements. In-situ high-temperature X-ray diffraction was used for examining the crystal phase and calculating the TECs. The results show that chemical valences related to Zr, Hf, Y, and Al oxidation states were maintained during the entire thermal cycle, whereas these for Ce underwent partial valence transitions. In other words, Ce4+ was partially reduced to Ce3+ when heated from (1200–1300) °C, and Ce3+ was partially re-oxidized to Ce4+ as the temperature increased from 1400 °C to 1500 °C. Such chemical reactions correlate well with the TG-DSC results. The TEC values ranged from (9.58–9.28) × 10−6 K−1 and exhibited a weak, nonlinear dependency on temperature, decreasing with an increase in temperature, except when heated from 1200 °C to 1240 °C. The reduction and oxidation reactions had a minor effect on the TEC and the differences due to heating and cooling were appreciable yet subtle when compared to that at the same temperature, with the maximum difference being less than 0.2 × 10−6 K−1.

Physical properties of zircon‐filled poly(methyl methacrylate) composites following heating around its glass transition temperature

AbstractZircon‐filled poly(methyl methacrylate) (PMMA) composites were synthesized, and their physical properties after ambient heat treatments were investigated. The sub‐micron zircon filler was obtained by purifying local zircon sand. The heat treatments were at 25°C (untreated), 55°C, and 70°C, around the glass transition temperature of PMMA. The crystal and molecular structures of the samples were investigated using X‐ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy. The thermomechanical, optical, and thermal (between RT and 550°C) properties of all composites were examined using dynamic mechanical analysis (DMA), UV–Vis spectroscopy, and differential thermal/thermogravimetric analysis (DT/TGA) instruments. XRD patterns showed that there were no crystal structure changes. FTIR peaks were reduced due to the heat treatment indicating the presence of PMMA molecular degradation in the heat‐treated samples. Meanwhile, DMA data showed that the heat‐treated samples exhibit a much lower room temperature storage modulus, that is, up to half as compared to the untreated ones. Furthermore, the heat treatment also affects the optical properties, including a slight drop of transmittance in UV‐A and visible regions but a slight increase of transmittance in UV‐B and UV‐C regions. Finally, the differential scanning calorimetry/thermogravimetry (DSC/TG) data show that the heat‐treated pure PMMAs become more challenging to undergo thermal degradation (i.e., mass drop).

Reactivity Enhancement of Lignin Extracted from Preconditioning Refiner Chemical-Recycle Bleached Mechanized Pulp (PRC-RBMP) Black Liquor by Phenolation

Despite black liquor’s (BL) renown as a difficult-to-manage contaminant in the pulp and paper industry, BL has been found as a viable alternative material for adhesive formulation due to its high lignin content. Nevertheless, modification is required to enhance lignin’s reactivity, and there is currently a lack of study focusing on this aspect for BL-lignin. This study aims to increase the phenolic hydroxyl content of BL-lignin by phenolation. After being phenolated at lignin to phenol ratio of 1:1, at a temperature of 100°C for 110 minutes, and with the addition of 8% sulfuric acid (H2SO4) as a catalyst, the phenolic hydroxyl content improved by 51.5%. The results of Fourier transform infrared spectroscopy (FTIR), UV/Vis spectrophotometry, proton nuclear magnetic resonance (1H-NMR), thermogravimetry-differential scanning calorimetry (TG-DSC), and its differential curve showed that the structural change in phenolated lignin opened up more active sites, implying that this lignin could be a good substitute for phenol in phenol-formaldehyde resin manufacturing.