Thermal and electrical properties of Ca5Mg4−xZnx(VO4)6 (0 ≤ x ≤ 4)

Calcium vanadates Ca₅Mg_4−xZn_x(VO₄)₆ (0 ≤ x ≤ 4) have been studied for the first time using a set of high-temperature methods of analysis. The onset of melting process determined from differential scanning calorimetry decreases from 1158 to 881 °C (± 1.5 °C) with increasing of x (dopant’s content). CTE temperature dependence is found to show a hysteresis. Electrical transport properties measured by impedance spectroscopy in air of different humidity are also discussed. The value of electrical conductivity does not depend on air humidity. It is found to equal to 1.5 × 10⁻⁶ S cm⁻¹ at 720 °C for Ca₅Mg₄(VO₄)₆ which is specific for garnet-related crystals.

     

Investigation of isothermal and dynamic cure kinetics of epoxy resin/nadic methyl anhydride/dicyandiamide by differential scanning calorimetry (DSC)

Isothermal and dynamic differential scanning calorimetry (DSC) was exploited to study the curing behavior of diglycidyl ether bisphenol-A epoxy resin with various combining ratios of dicyandiamide (DICY) and nadic methyl anhydride (NMA). Curves of prepared samples indicated that the enthalpy of the reaction decreased with increasing the molar ratios (NMA/DICY) up to 40% after which an exothermic peak peculiar to the effect of anhydride appeared at a higher temperature. The curing behavior examination of the samples containing the aforementioned molar ratio of NMA/DICY (= 40%) was carried out using isothermal condition at different temperatures (130–145 °C) and dynamic condition DSC at various heating rates (2.5–20 °C min⁻¹). Under the isothermal condition, by constructing a master curve, the values of activation energy (E_a) and pre-exponential factor (A) were calculated 89.3 kJ mol⁻¹ and 1.2 × 10⁺⁹ s⁻¹, respectively. The activation energy of the curing reactions in a dynamic mode was obtained 85.32 kJ mol⁻¹ and 88.02 kJ mol⁻¹ using Kissinger and Ozawa methods, respectively. Likewise, pre-exponential factors were also calculated 3.35 × 10⁺⁸ and 7.4 × 10 ⁺⁸ s⁻¹, respectively. The overall order of reaction for both conditions was found to be a value around 3.

     

Qualitative and quantitative analysis of arctiin and arctigenin in Arctium tomentosum Mill. by high-performance thin-layer chromatography

A sensitive, reliable and rapid high-performance thin-layer chromatography (HPTLC) method for the determination of arctiin and arctigenin in Arctium tomentosum Mill. was established. A. tomentosum Mill. extract was used for chromatographic analysis. The ratio of chloroform and methanol was 48:5 as mobile phase. Temperature is 20–23 °C and humidity is less than 30%. The scanning wavelength is 280 nm. The results showed that arctiin had a good linear relationship in the range of 0.5315–5.8465 μg, r = 0.9982; arctigenin had a good linear relationship in the range of 0.5654–6.2194 μg, r = 0.9951. Precision analysis showed that the RSD < 3.0%. The stability study showed that the sample was stable within 24 h at room temperature, RSD < 2.0%. The average recoveries were 103.07 ± 1.57% and 98.55 ± 2.71%, respectively. The antioxidant activity of Arctium tomentosum Mill. was also identified. The results showed that the antioxidant component identified by thin-layer chromatography–1, 1-diphenyl-2-trinitrophenylhydrazine (TLC-DPPH) was arctigenin not arctiin. The proposed HPTLC is a simple and accurate method for the qualitative and quantitative analysis of arctiin and arctigenin in Arctium tomentosum Mill. from different areas.

     

Preparation of TiO<Subscript>2</Subscript> nanoparticles by sonochemical method,isotherm, thermodynamic and kinetic studies on the sorption of strontium

The objective of this study is to evaluate the use of titanium dioxide nanoparticles which were prepared by novel sonochemical method as an ion exchange material for the removal of Sr from aqueous solution. The pH effect on the Sr²⁺ sorption was investigated. The data obtained have been correlated with Freundlich, Temkin and Dubinin–Radushkevich (D–R) isotherm models. Thermodynamic parameters fort he sorption system have been determined at four temperatures. Simple kinetic models have been applied to the rate and isotherm sorption data and the relevant kinetic parameters were determined from the graphical presentation of these models at 298°K. Results explained that the pseudo second-order sorption mechanism is predominant and the overall rate constant of sorption process appears to be controlled by chemical sorption process. The value of sorption energy E = 13 kJ/mol at 298°K and the value of Gibbs free energy ∆G° = 3,222 kJ/mol at 298°K prove that the sorption of strontium on titanium dioxide nanoparticles is an endothermic and non-spontaneous process.     

Thermal and oxidative stability assessment of synergistic blends of sunflower and sesame oils tailored for nutritionally stable composition of omega fatty acids

The thermal stability of ω-6 fatty acid-rich oils is a bewildering problem. The synergistic blends of sunflower (SO) (50–80%) and sesame oil (SEO) (20–50%) were optimized for improved thermal stability, better retention of antioxidants, and balanced ratio of ω-fatty acids (ω-6 and 9). The oil blends were thermally oxidized by Rancimat (temperature 100, 110, 120, and 130 °C; airflow rate 20 L h⁻¹) for estimating the induction period (IP) and kinetic rate constant (k) of lipid oxidation. The oils were exhaustively characterized for thermal stability by thermogravimetry and differential scanning calorimetry. The temperature-dependent kinetics of lipid oxidation was described using Arrhenius equation (lnk vs. 1/T) and activated complex theory (lnk/T vs. 1/T). The calculated kinetic parameters, viz. activation energies, activation enthalpies, and entropies varied from 90.80 to 99.17, 87.58 to 95.94, − 33.28 to − 4.78 J mol⁻¹ K⁻¹, respectively (R²> 0.90, p < 0.05). The optimized blend (OB) consisted of 50.8 and 49.2% of SO and SEO, respectively, and showed the highest synergism (115%) and IP (100 °C) than SO (13.2 vs. 6.1 h). This could be attributed to lignans (6304 vs. 5289 mg kg⁻¹)-induced thermal stability and effective retention of tocopherols (270 vs. 197 mg kg⁻¹). OB possesses balanced composition of ω-fatty acids (ω-9, 34.5 vs. 28.7%; ω-6, 49 vs. 52%) and superior thermal stability (onset temperature, 387 vs. 212 °C; oil induction time, 21.6 vs. 15.7 min) than SO. It could be recommended over SO for culinary applications while ensuing thermal stability and nutritional benefits.

     

Sorption of radioactive cobalt onto nano calcium silicate/CuO composite modified by humic acid

The sorption process of Co(II) onto nanoparticles of calcium silicate doped with 5% CuO treated by humic acid was evaluated using batch technique. This process follows the second order kinetic model. Equilibrium isotherm models of Co(II) sorption onto the modified composite was 208.91 mg/g. Negative value of free energy change (ΔG⁰), confirms the spontaneous sorption of Co(II) ions onto the modified composite. The removal efficiency (R%) reached 96.9% using 0.5 g of the modified composite. Therefore, the composite could be used for treatment of radioactive waste containing ⁶⁰Co.

     

The electrochemical behaviour of butyltrimethylammonium bis(trifluoromethylsulfonyl)imide at negatively polarised aluminium electrode studied by in situ soft X-ray photoelectron spectroscopy,electrochemical impedance spectroscopy and cyclic voltammetry techniques

The in situ X-ray photoelectron spectroscopy data indicate that butyltrimethylammonium bis(trifluoromethylsulfonyl)imide (N4111(TFSI)) adsorbs strongly within the potential range −3.25 V < E < −2.25 V and specifically at E < −3.25 V (vs. Ag-QRE) at the Al electrode. Strong adsorption of the intermediates of N4111(TFSI) electrochemical decomposition was observed in electrochemical impedance spectroscopy and cyclic voltammetry measurements. At E < −4.25 V (vs. Ag-QRE), very intensive electrochemical reduction of N4111(TFSI) took place at the Al electrode giving gaseous products. In the potential range from − 2.25 to 0.00 V (vs. Ag-QRE), non-specific adsorption of N4111(TFSI) exists et al. surface.

     

Sorptive removal of cobalt, strontium and cesium onto manganese and iron oxide-coated montmorillonite from groundwater

Applicability of montmorillonite, manganese oxide-coated montmorillonite (MOCM) and iron oxide-coated montmorillonite (IOCM) as backfill materials in permeable reactive barrier (PRB) to remediate contaminated groundwater was investigated. Single- and bi-solute competitive sorptions of Co, Sr and Cs were conducted. The Freundlich, Langmuir and Dubinin-Radushkevich models fitted the single-solute sorption data well (R ² > 0.95). Maximum sorption capacities (q _mL) of Co and Sr predicted by the Langmuir model were in the order of MOCM (0.37 mmol/g for Co and 0.28 mmol/g for Sr) > montmorillonite (0.27 mmol/g for Co and 0.19 mmol/g for Sr) ≈ IOCM (0.23 mmol/g for Co and 0.21 mmol/g for Sr), while those of Cs were in the order of montmorillonite (1.11 mmol/g) > MOCM (0.68 mmol/g) > IOCM (0.62 mmol/g). In the bi-solute sorptions, the sorbed amount of one solute decreased due to the presence of the other competing metal ion. Langmuir model parameters for single-solute (q _mL and b _L) and bi-solute ( q_\textmL^* q_{\text{mL}}^{*} and b_\textL ^* b_{\text{L}}^{ *} ) sorptions were compared to analyze the effect of competition between the metal ions. The competitive Langmuir (R ² > 0.81) and P-factor (R ² > 0.82) models predicted the bi-solute competitive sorption data well but not the SRS model (0.003 < R ² < 0.97).     

Thermodynamic study of triclosan adsorption from aqueous solutions on activated carbon

The change in the thermodynamic properties of triclosan adsorption on three activated carbons with the different surface chemistry was studied through immersion calorimetry and equilibrium data; the amount adsorbed of triclosan (Q) during calorimetry was determined and correlated with the energy associated with adsorbate–adsorbent interactions in the adsorption process. It was noted that triclosan adsorption capacity decreases with an increase in oxygenated surface groups. For an activated carbon oxidized with HNO₃ (OxAC), the amount adsorbed was 8.50?×?10^?3 mmol g^?1, for a activated carbon without modification (GAC) Q?=?10.3?×?10^?3 mmol g^?1 and for a activated carbon heated at 1073 K (RAC1073) Q?=?11.4?×?10^?3 mmol g^?1. The adsorbed amounts were determined by adjusting the isotherms to the Sips model. For the activated carbon RAC1073, the immersion enthalpy (ΔH_imm) was greater than those of the other two activated carbons due to the formation of interactions with the solvent (ΔH_immOxAC?=?? 27.3 J g^?1?<?ΔH_immGAC?=?? 40.0 J g^?1?<?ΔH_imm RAC1073?=???60.7 J g^?1). The changes in the interaction enthalpy and Gibbs energy are associated with adsorbate–adsorbent interactions and side interactions such as the adsorbate–adsorbate and adsorbate–solvent interactions.

     

Investigation of Sr uptake by birnessite-type sorbents from seawater

Sorption of micro- and microamounts of Sr from seawater has been studied using granulated Na-birnessite. Distribution coefficients of ⁹⁰Sr in the natural seawater are 0.8–1.2?×?10³ ml g^?1, in the model seawater they are 1.6–1.8?×?10³ ml g^?1. Application of Na-birnessite was shown to be prospective in sorption–desorption–regeneration regime. In dynamic sorption conditions, over 150 bed volumes of seawater can be purified till 5% breakthrough occurs at feed rate 10 BV h^?1. Na-birnessite can be used for ⁹⁰Sr radionuclide removal from liquid radioactive wastes containing seawater.

     

The role of phosphate released from Na–Al–P glass under repository conditions in speciation and transport of americium

The uptake of natural radioactivity by pasture-grass collected from seven different grasslands of Digor was calculated. The activities of ²²⁶Ra, ²³²Th and ⁴⁰K in pasture-grass were in the range of 21.8 ± 6.3–49.6 ± 13.4, 51.9 ± 13.2–127.7 ± 23.8 and 309.5 ± 33.5–807.3 ± 64.4 Bq kg⁻¹, respectively. The soil to pasture-grass transfer factors were evaluated and determined to be in the range from 0.26 ± 0.13 to 0.69 ± 0.34, 0.64 ± 0.27 to 1.99 ± 0.40 and 0.64 ± 0.014 to 1.40 ± 0.032 for ²²⁶Ra, ²³²Th and ⁴⁰K, respectively. The distribution of ²²⁶Ra and ²³²Th in different parts of pasture-grass indicated a decreasing tendency in order of root > stem > leaf. ⁴⁰K mainly accumulated in stem of pasture-grass and is followed by declining trend stem > leaf > root.

     

Investigation of solution chemistry effects on sorption behavior of radionuclide <Superscript>64</Superscript>Cu(II) on illite

In this work, a series of batch experiments were carried out to investigate the effect of various environmental factors such as contact time, pH, ionic strength, coexisting electrolyte ions, humic substances and temperature on the sorption behavior of illite towards ⁶⁴Cu(II). The results indicated that ⁶⁴Cu(II) sorption on illite achieved equilibrium quickly. The pH- and ionic strength-dependent sorption suggested that ⁶⁴Cu(II) sorption on illite was dominated by ion exchange or outer-sphere surface complexation at pH < 7, whereas the pH-dependent and ionic strength-independent sorption indicated that the sorption process was mainly attributed to inner-sphere surface complexation at pH > 7. A positive effect of humic substances on ⁶⁴Cu(II) sorption was found at pH < 6.5, whereas a negative effect was observed at pH > 6.5. The Langmuir and Freundlich models were used to simulate the sorption isotherms of ⁶⁴Cu(II) at three different temperatures of 293, 313, and 333 K. The thermodynamic parameters (ΔH ⁰, ΔS ⁰, and ΔG ⁰) of ⁶⁴Cu(II) sorption on illite were calculated from the temperature dependent sorption isotherms, and the results indicated that the sorption of ⁶⁴Cu(II) on illite was endothermic and spontaneous. From the experimental results, it is possible to conclude that illite has good potentialities for cost-effective treatments of ⁶⁴Cu(II)-contaminated wastewaters.     

Densitometric high-performance thin-layer chromatography methods for the quantification of oleuropein in Olea europaea leaves and pharmaceutical preparation utilizing normal- and reversed-phase silica gel plates

Two validated, simple and precise densitometric high-performance thin-layer chromatography (HPTLC) quantification methods were proposed for both qualitative and quantitative estimation of oleuropein in Olea europaea leaves and a pharmaceutical product utilizing normal-phase and reversed-phase silica gel TLC plates. In method I, 10 × 20 cm glass plates coated with 0.2 mm thin layers of normal-phase silica gel 60 containing F₂₅₄ (E-Merck, Germany) and a mixture of ethyl acetate‒methanol‒water (8:1:0.5, V/V) were used as the stationary and the mobile phase, respectively. Method II utilized 10 × 20 cm glass-backed plates supporting 0.2 mm layers of RP-18 silica gel 60 containing F₂₅₄ (E-Merck, Germany) as the stationary phase and green solvents mixture composed of ethanol‒water (5.5:4.5, V/V) as the mobile phase. The two methods resulted in sharp, symmetrical, well-resolved peaks at R_F values of 0.47 ± 0.02 and 0.78 ± 0.03 with linearity ranges 200‒1400 ng/spot (r² = 0.9994) and 200‒1400 ng/spot (r² = 0.9996) for method I and method II, respectively. Spots corresponding to oleuropein were scanned at 200 nm. The two methods complied with the ICH guidelines for validation. Due to simplicity, low cost and short analysis time, the methods can be good alternatives for the quality control of different products containing olive leaves extract or pure oleuropein.

     

Separation of no-carrier-added radioactive scandium from neutron irradiated titanium

In this work, sorption of Ni(II) from aqueous solution to goethite as a function of various water quality parameters and temperature was investigated. The results indicated that the pseudo-second-order rate equation fitted the kinetic sorption well. The sorption of Ni(II) to goethite was strongly dependent on pH and ionic strength. A positive effect of HA/FA on Ni(II) sorption was found at pH < 8.0, whereas a negative effect was observed at pH > 8.0. The Langmuir, Freundlich, and D-R models were applied to simulate the sorption isotherms at three different temperatures of 293.15 K, 313.15 K and 333.15 K. The thermodynamic parameters (ΔH ⁰, ΔS ⁰ and ΔG ⁰) were calculated from the temperature dependent sorption, and the results indicated that the sorption was endothermic and spontaneous. At low pH, the sorption of Ni(II) was dominated by outer-sphere surface complexation or ion exchange with Na⁺/H⁺ on goethite surfaces, whereas inner-sphere surface complexation was the main sorption mechanism at high pH.     

Newly selective electrochemical sensors for trace-level determination of Al(III) ions in drainage water,spiked tap water and pharmaceutical preparation samples

In this work, two newly sensitive and selective Al(III)-modified carbon paste electrodes (MCPEs) were developed based on diphenylcarbazone (DPC) modifier mixed with tricresyl phosphate plasticizer and either graphite powder (electrode I) or graphite powder mixed with graphene (electrode II). The potentiometric performance characteristics of the two electrodes were scrutinized and discussed. The proposed sensors showed a high electrochemical response in the linear concentration range of 1.0 × 10⁻⁶ to 1.0 × 10⁻² mol L⁻¹ with a good Nernstian slopes of 20.12 ± 0.30 mV decade⁻¹ and 20.63 ± 0.66 mV decade⁻¹ and limits of detection of 9.0 × 10⁻⁷ and 8.5 × 10⁻⁷ mol L⁻¹ for electrode (I) and electrode (II), respectively. Both electrodes showed a fast response time and reasonable thermal stability. The potentiometric response of the DPC-based electrodes was independent on the pH of the tested solutions in ranges of 2.5–5 and 2.5–5.5 for electrode (I) and electrode (II), respectively. The two electrodes can be also used in partially non-aqueous medium containing up to 20% (v/v) acetone or methanol with no significant changes in the working concentration ranges or the slopes. The proposed electrodes showed fairly good discriminating ability toward Al(III) ions in comparison with many other metal ions. The electrodes were applied successfully for Al(III) ions determination in drainage water, spiked tap water and pharmaceutical preparation samples. Furthermore, the electrode surfaces were characterized using energy-dispersive X-ray (EDX) and scanning electron microscopic (SEM) as surface characterization techniques and Fourier Transform Infrared (FT-IR) technique to confirm the interaction between Al(III) and DPC.

     

The preparation of PZS-OH/CNT composite and its adsorption of U(VI) in aqueous solutions

In this paper, polycyclotriphosphazene coated carbon nanotubes (PZS-OH/CNT) composite material has been synthesized via a facial method. The prepared PZS-OH/CNT was characterized by FTIR, BET, zeta potential and SEM. The material was investigated as an adsorbent for the adsorption towards U(VI) from aqueous solutions. Several parameters like solution pH, contact time and temperature were used to evaluate the sorption efficiency. The results indicated that the adsorption capacity of uranium on PZS-OH/CNT was improved from 41.48 mg g⁻¹ for CNT to 338.98 mg g⁻¹ due to the presence of functional groups on PZS-OH/CNT. The U(VI) sorption on PZS-OH/CNT was well fitted to the Langmuir adsorption isotherm and pseudo-second kinetics models. The thermodynamic parameters (ΔH, ΔS and ΔG) showed the U(VI) adsorption on CNT and PZS-OH/CNT was endothermic and spontaneous in nature.

     

Thermal and exergoeconomic analysis of a dairy food processing plant

The dairy processing industry in India, on an average basis, involves an extensive amount of thermal and electrical energy consumption, i.e. 2.51 × 10⁵ kW MT⁻¹ and 1.44 × 10⁵ kW MT⁻¹, respectively, for an installed milk food processing capacity of 1.21 × 10⁵ TPD. However, energy consumption spectrum depends upon the level of automation along with better utilisation of utility resources. The global ultra-high-temperature (UHT) pasteurised milk trade was valued at € 52.29 billion in 2012 and is expected to reach € 114.38 billion by 2019–2020. In the present work energy, exergy and exergoeconomic evaluation of ultra-high-temperature milk pasteurisation plant have been considered. The overall energy efficiency and efficiency pertaining to executable potential of energy in UHT Milk Processing Unit were reported to be 86.36% and 53.02%. The specific exergy destruction and specific exergy improvement potential were estimated to be 219.23 kJ kg⁻¹ and 137.60 kJ kg⁻¹, respectively. The highest possible retrievable exergy potential of the plant was associated with heating coil, i.e. 158.98 kW, followed by homogeniser (54.62 kW), which pinpointed towards the possibility of huge technical improvement. The processing cost was enumerated to be highest for heating coil (r_k: 38.35%) followed by regeneration-1 (r_k: 23.40%). Further, the total operating cost rate associated with thermodynamic deficiencies of subunits was estimated to be highest for heating coil (4859.82 € H⁻¹) followed by regenerator-2 (1264.88 € H⁻¹) and homogeniser (1187.14 € H⁻¹). The broad survey of thermoeconomic indices of subunits indicated that the level of exergetic destruction was far more on higher side.

     

High-performance thin-layer chromatography method for the quantification of quetiapine fumarate and its related genotoxic impurities using green solvents

A novel high-performance thin-layer chromatographic (HPTLC) analytical method has been developed and optimized for the quantification of quetiapine fumarate (QF) and its two genotoxic impurities in drug substance and drug product. The desired separation was achieved on 60F₂₅₄ pre-coated HPTLC plates using combination of green solvents, ethyl acetate‒ethanol‒n-heptane (5:1:4, V/V) as developing solvents. The detection wavelength used for quantification was 229 nm. QF and its two related genotoxic impurities, namely, 2-chloroaniline and 2-aminodiphenylsulfide, were well resolved from one another with retention factor values of 0.13 ± 0.02, 0.57 ± 0.02 and 0.76 ± 0.02, respectively. The optimized method was validated according to the guidelines laid down by the International Council for Harmonisation. The linearity was determined in the range of 100–600 ng/spot for QF and 10‒60 ng/spot for its two related genotoxic impurities; R² ≥ 0.993. The method exhibited precision along with good accuracy, where 0.51, 0.86 and 1.86. The percentage recoveries obtained for 2-chloroaniline and 2-aminodiphenylsulfide were 99.04‒101.04%. The developed method can be successfully used for the analysis of drug samples.

     

Sorption of 14C, 99Tc, 137Cs, 90Sr, 63Ni, and 241Am onto a rock and a fracture-filling material from the Wolsong low- and intermediate-level radioactive waste repository, Gyeongju, Korea

Sorption experiments for radionuclides such as ¹⁴C, ⁹⁹Tc, ¹³⁷Cs, ⁹⁰Sr, ⁶³Ni, and ²⁴¹Am were conducted using two different groundwaters (GM-1 and SS-5) and solid materials (granodiorite and fracture-filling material) sampled from the Wolsong low- and intermediate-level radioactive waste (LILW) repository, Gyeongju, Korea. The distribution coefficients of the radionuclides, K _d’s, were obtained and their sorption properties were discussed for each radionuclide. For all sorbing radionuclides, the K _d values for the fracture-filling material were observed to be higher than those for granodiorite regardless of the groundwater. The K _d values were increased in the sequence ⁹⁹Tc < ¹⁴C < ⁹⁰Sr < ¹³⁷Cs < ⁶³Ni < ²⁴¹Am regardless of sorbent types implying that the sorption of radionuclides onto geological media is affected by their chemical behavior in accordance with geochemical environments. Anionic radionuclides such as ¹⁴C and ⁹⁹Tc showed very low K _d values both for the granodiorite and fracture-filling material. The mineralogical composition of the geological media and groundwater conditions was also observed to be important in the sorption of sorbing radionuclides, especially in the case of strongly sorbing radionuclides.