The thermolysis behavior of Ag/PAMAMs nanocomposites

Ag/polyamidoamine (PAMAM) nanocomposites were produced by photoreduction of relevant metallic salts in different generations of PAMAM (PAMAMs) methanol solutions under room temperature and ambient pressure. The obtained Ag nanoparticles were quite uniform in size with a diameter of about 15 nm. Thermogravimetric analysis (TGA) results showed that the amount of Ag nanoparticles could well affect the thermal stability of PAMAMs. As the mass ratio of Ag nanoparticles to PAMAMs increased, the weight-losing ratios decreased. Meanwhile, TGA curves also indicated that the thermal behavior of Ag/PAMAMs was greatly different in the two stages of low (130~280 °C) and high temperature (280~450 °C) range; the loading of Ag nanoparticles mainly influences the thermal stability of PAMAMs in high temperature region (280~450 °C). Moreover, the multistage decomposition profile of derivative thermal gravimetry curves suggested that there might contain some intermediate Ag/PAMAMs type of composites.     

Changes induced in the thermal properties of Galizian soils by the heating in laboratory conditions

The soil properties can be strongly affected by wildfires, causing direct effects on ecosystem productivity and sustainability. These effects depend, among other things, on the soil type and on the temperature reached during the fire. The variations of thermal properties of several Galizian soils heated in an oven in laboratory conditions at different temperatures (200–500 °C) during 15 min have been examined in this study. The measured properties are heat of combustion of soil organic matter, ignition temperature, specific heat and mass loss, determined using DSC 2920 TA Instruments and a TGA 7 Perkin Elmer under dry air gas flow. In agreement with other authors, this study establishes three temperature intervals with different effects on the soil: up to 200 °C, low intensity heating, with no significant changes in thermal properties; between 200 and 350 °C, medium intensity heating, with losses of organic matter up to 50%; and high intensity heating to temperature higher than 350 °C, with harmful effects on the soil organic matter. On the other hand and taking into account that the sampled soils had been affected by forest fires, the variations of thermal soil properties with the laboratory heating temperatures allowed for an estimation of the temperature reached by the soil in the real fire.     

Application of dilatometric analysis to the study of autoclaved calcium silicate materials

The process of shrinkage of calcium silicate hydrate was investigated by dilatometry up to 350 °C. The properties of this material are based on the formation of C–S–H phases during the reaction at temperatures between 180 and 205 °C and water vapor pressure lower than 16 bars. The main C–S–H phases are 11.3 Å tobermorite and xonotlite. 11.3 Å tobermorite converts to 9.3 Å tobermorite on air at temperatures around 300 °C. The hydrosilicate materials were prepared from quicklime and finely ground sand with different CaO/SiO₂ ratios under different hydrothermal conditions. The reaction time was 24 h. Materials based on xonotlite and tobermorite were produced, and the calcium silicate phases were characterized by XRD and TG/DTA methods. Dilatometry measurements were used to study the effect of heating conditions on sample shrinkage. Dehydration of hydrated calcium silicate minerals occurred during heating. The results show that sample shrinkage is dependent on the type and amount of C–S–H phases, the amount of bound water and formation of 9.3 Å tobermorite. All samples showed shrinkage after heating up to 350 °C, but this change was not irreversible for all samples after cooling to room temperature.

     

Influence of thermal process on microstructural and physical properties of ambient pressure dried hydrophobic silica aerogel monoliths

The experimental results of thermal process on the microstructural and physical properties of ambient pressure dried hydrophobic silica aerogel monoliths are reported and discussed. With sodium silicate as precursor, ethanol/hexamethyldisiloxane/hydrochloric acid as surface modification agent, the crack-free and high hydrophobic silica aerogel monoliths was obtained possessing the properties as low density (0.096 g/cm³), high surface area (651 m²/g), high hydrophobicity (~147°) and low thermal conductivity (0.0217 Wm/K). Silica aerogels maintained hydrophobic behavior up to 430 °C. After a thermal process changing from room temperature to 300 °C, the hydrophobicity remained unchanged (~128°), of which the porosity was 95.69% and specific density about 0.094 g/cm³. After high temperature treatment (300–500 °C), the density of final product decreased from 0.094 to 0.089 g/cm³ and porosity increased to 96.33%. With surface area of 466 m²/g, porosity of 91.21% and density about 0.113 g/cm³, silica aerogels were at a good state at 800 °C. Thermal conductivities at desired temperatures were analyzed by the transient plane heat source method. Thermal conductivity coefficients of silica aerogel monoliths changed from 0.0217 to 0.0981 Wm/K as temperature increased to 800 °C, revealed an excellent heat insulation effect during thermal process.     

Thermodynamic performance of automobile air conditioners working with R430A as a drop-in substitute to R134a

The refrigerant R134a is to be phasing out soon in automobile air conditioning applications due to its high global warming potential of 1430. Hence, it is essential to identify a sustainable alternative refrigerant to phase out R134a in automobile air conditioners. This paper presents the experimental thermodynamic performance of R430A (composed of R152a and R600a, in the ratio of 76:24, by mass) as a drop-in substitute to replace R134a in automobile air conditioners. The experiments were carried out in an automobile air conditioner test setup equipped with a variable frequency drive electrical motor. During experimentation, the ambient temperature and ambient relative humidity were maintained at 35?±?1 °C and 65?±?5%, respectively. The compressor speed was varied in the range between 1000 and 3000 rpm. The results showed that the coefficient of performance of an automobile air conditioner working with R430A was found to be 12–20% higher with 6–11% reduced compressor power consumption when compared to R134a. The R430A has 2–6 °C higher compressor discharge temperature when compared to R134a. The physical stability of the lubricant used in the compressor was retained while operating with R430A. The maximum exergy destruction occurs in the compressor (0.28 kW for R134a and 0.24 kW for R430A) followed by evaporator (0.16 kW for R134a and 0.14 kW for R430A), condenser (0.14 for R134a and 0.12 kW for R430A) and expansion valve (0.043 kW for R134a and 0.039 kW for R430A) at a compressor speed of 1000?±?10 rpm. The exergy destruction of the system operating with R430A was found to be 12–28% lower when compared to R134a systems due to its favorable thermo-physical properties. The total equivalent warming impact of R430A was found to be lower when compared to R134a by about 47.3%, 35% and 32.4% for LPG, petrol and diesel vehicles, respectively. The results confirmed that R430A is a good drop-in substitute to replace R134a in existing automobile air conditioning systems.

     

Experimental study of the ignition temperatures of low-rank coals using TGA under oxygen-deficient conditions

The factors affecting the ignition temperatures of two low-rank coals were experimentally studied using thermogravimetric analysis. The experiments were conducted with coal powders of four different particle size distributions. The thermogravimetric analyzer was operated at three heating rates, 10, 20, and 30 °C min^?1 and four oxygen concentrations of 3, 6, 9, and 12%. The results showed that the ignition temperature decreased by about 25 °C as the oxygen concentration increased from 3% to 12%. The standard deviation of the activation energy was 16.75% at a conversion degree of less than 0.4, and it decreased to 1.35% at the end of the combustion process. At a heating rate of 10 °C min^?1, the ignition temperature increased by about 8 °C as the coal particle size increased by 100 μm. At a heating rate of 30 °C min^?1, the effect of the particle size on the ignition temperature was enhanced and the ignition temperature increased to 15 °C.

     

Recrystallization of Zeolite Y to Analcime and Zeolite P with <SC>d</SC>‐Methionine as Structure‐Directing Agent (SDA)

In this study, the synthesis of template free zeolite Y and its recrystallization to two types of pure zeolite P and analcime in the presence of the amino acid d‐methionine as structure‐directing agent were investigated. The recrystallization occurred solely when specific heating cycles were applyed. A completely crystallized phase of zeolite Y for the mixture of zeolite P and analcime was observed in the presence of d‐methionine at a concentration of 0.015 <SC>m</SC>. The effect of different Si/Al ratios (2.3–9.3), crystallization temperatures (40–160 °C), and crystallization times (28–96 hours) on the achievement of two different zeolite types were studied as well. Pure zeolite P was obtained during conventional heating to 100 °C for 42 hours, whereas pure analcime zeolite was achieved by heating the mixture to 160 °C for 96 hours. The products were characterized by X‐ray diffraction, scanning electron microscopy, and IR spectroscopy.     

The melting behaviour of poly(3-hydroxybutyrate) by DSC. Reproducibility study

This work is concerned with the melting behaviour and accuracy of differential scanning calorimeter (DSC) analyses of poly(3-hydroxybutyrate) (PHB), a semi-crystalline thermoplastic polymer completely biodegradable and biocompatible, and obtained from renewable resources. Melting parameters of PHB were determined for the first fusion event applying standard experimental procedures for thermal analysis, using heating rates ranging between 1 °C/min and 20 °C/min. The analyses of DSC energy flow scans showed a complex melting peak that may be resolved into three elementary peaks having different intensities at different melting temperatures. Peak temperatures depend on heating rate, while the total crystallinity detected was independent of the rate. A study of 24 DSC runs showed good temperature reproducibility (±0.5 °C), but poor reproducibility of mass crystallinity (±10%).     

Isolation,Purification, and Properties of a Novel Small Heat Shock Protein from the Hyperthermophile <Emphasis Type="Italic">Sulfolobus solfataricus</Emphasis>

The isolation, purification, and properties of a putative small heat shock protein (sHsp), named SsHSP14.1, from the hyperthermophilic archaeon Sulfolobus solfataricus have been investigated. The sHsp was successfully expressed and purified from Escherichia coli. In vivo chaperone function of SsHSP14.1 for preventing aggregation of proteins during heating was investigated. It was found that recombinant SsHSP14.1 with a molecular mass of 17.8 kDa prevented E. coli proteins from aggregating in vivo at 50 °C. This result suggested that SsHSP14.1 confers a survival advantage on mesophilic bacteria by preventing protein aggregation at supraoptimal temperatures. In vitro, the purified SsHSP14.1 protein was able to prevent Candida antarctica lipase B from aggregation for up to 60 min at 80 °C. Moreover, the SsHSP14.1 enhanced thermostability of bromelain extending its half-life at 55 °C by 67%.     

An investigation of the effect of microwave treatment on the structure and unfolding pathways of β-lactoglobulin using FTIR spectroscopy with the application of two-dimensional correlation spectroscopy (2D-COS)

Microwave treatment of β-lactoglobulin (β-Lg) in D₂O solution under various conditions was monitored by Fourier transform mid infrared (mid-FTIR) spectroscopy. At sub-ambient temperatures, no microwave-induced changes in the conformation of the protein were detected. Microwave heating of the β-Lg solutions to temperatures in the range of 40–60 °C resulted in a marked increase in the rate of hydrogen–deuterium (H–D) exchange as compared to conventional heating at the same temperature. At heating temperatures in the range of 70–90 °C, the microwave-heated solutions exhibited more extensive protein aggregation than conventionally heated solutions. Application of two-dimensional (2D) correlation analysis to the Fourier self-deconvolved FTIR spectra recorded as a function of number of cycles of microwave or conventional heating revealed that the unfolding pathway of β-Lg was different in these two temperature ranges (40–60 °C versus 70–90 °C) but was similar in both microwave – treated and conventionally heated samples. Nevertheless, within the temperature range of 70–90 °C microwave treatment accelerated the unfolding of β-lactoglobulin.     

Comparison of two digestion procedures for the determination of lead in lichens by electrothermal atomic absorption spectrometry

The efficiency of two procedures for the digestion of lichen was investigated using a heating block and a microwave oven. In the open vessels, concentrated nitric acid was added to the samples, left for 1 h, and the addition of 30% (v / v) hydrogen peroxide completed the digestion. In the closed system, the complete digestion was performed using concentrated nitric acid and hydrogen peroxide, reducing the amount of chemicals, time and contamination risk. Both digestion methods gave comparable results, and recoveries were statistically not different. For a lichen sample spiked with 10 μg Pb, the recovery was 111% and 110% using microwave and heating block digestion, respectively, while it was 100% and 103% for a 100 μg Pb spike. For the determination by electrothermal atomic absorption spectrometry samples were diluted 20 times with water and a volume of 20 μL was injected into the graphite furnace without chemical modifier. Pyrolysis and atomization temperatures of 700 °C and 1500 °C, respectively, were used. The characteristic mass was 8.4 ± 0.6 pg for aqueous calibration solutions and 8.9 ± 0.8 pg for samples. Calibration was against matrix matched standards. The recovery test showed some contamination problem with the lowest concentrations in both procedures. The detection limits were 4.4 μg L^− 1 with microwave oven and 5.4 μg L^− 1 with the heating block in the undiluted blank.     

Evaluation of the porous structure development of chars from pyrolysis of rice straw: Effects of pyrolysis temperature and heating rate

The effects of pyrolysis temperature and heating rate on the porous structure characteristics of rice straw chars were investigated. The pyrolysis was done at atmospheric pressure and at temperatures ranging from 600 to 1000 °C under low heating rate (LHR) and high heating rates (HHR) conditions. The chars were characterized by ultimate analysis, field emission scanning electron microscope (FESEM), helium density measurement and N₂ physisorption method. The results showed that temperature had obvious influence on the char porous characteristics. The char yield decreased by approximately 16% with increasing temperature from 600 to 1000 °C. The carbon structure shrinkage and pore narrowing occurred above 600 °C. The shrinkage of carbon skeleton increased by more than 22% with temperatures rising from 600 to 1000 °C. At HHR condition, progressive increases in porosity development with increasing pyrolysis temperature occurred, whereas a maximum porosity development appeared at 900 °C. The total surface area (S_total) and micropore surface area (S_micro) reached maximum values of 30.94 and 21.81 m²/g at 900 °C and decreased slightly at higher temperatures. The influence of heating rate on S_total and S_micro was less significant than that of pyrolysis temperature. The pore surface fractal dimension and average pore diameter showed a good linear relationship.     

Preparation and phase transition characterization of VO2 thin film on single crystal Si (100) substrate by sol–gel process

Vanadium dioxide (VO₂) thin films were fabricated on single crystal Si (100) substrates by sol–gel method, including a process of annealing a vanadium pentoxide (V₂O₅) gel precursor at different temperatures. The crystalline structure and morphology of the films were investigated by XRD, FE-SEM and AFM, indicating that the films underwent the grain growth, agglomeration and grain refinement process with increased annealing temperatures. The film annealed at 500 °C exhibits the formation of VO₂ phase with a strong (011) preferred orientation and high crystallinity, the surface of the film is uniform and compact with a grain size of about 120 nm. Meanwhile, the film exhibits excellent phase transition properties, with a decrease of transmittance from 35.5 to 2.5% at λ = 25 μm and more than 3 orders of resistivity magnitude variation bellow and above the phase transition temperature. The phase transition temperature is evaluated at 60.4 °C in the heating transition and 55.8 °C in the cooling transition. Furthermore, the phase transition property of the VO₂ film appears to be able to remain stable over repetitive cycles 100 times.     

Kinetics of Lime Pretreatment of Sugarcane Bagasse to Enhance Enzymatic Hydrolysis

The objective of this work was to determine the optimum conditions of sugarcane bagasse pretreatment with lime to increase the enzymatic hydrolysis of the polysaccharide component and to study the delignification kinetics. The first stage was an evaluation of the influence of temperature, reaction time, and lime concentration in the pretreatment performance measured as glucose release after hydrolysis using a 2³ central composite design and response surface methodology. The maximum glucose yield was 228.45 mg/g raw biomass, corresponding to 409.9 mg/g raw biomass of total reducing sugars, with the pretreatment performed at 90°C, for 90 h, and with a lime loading of 0.4 g/g dry biomass. The enzymes loading was 5.0 FPU/dry pretreated biomass of cellulase and 1.0 CBU/dry pretreated biomass of β-glucosidase. Kinetic data of the pretreatment were evaluated at different temperatures (60°C, 70°C, 80°C, and 90°C), and a kinetic model for bagasse delignification with lime as a function of temperature was determined. Bagasse composition (cellulose, hemicellulose, and lignin) was measured, and the study has shown that 50% of the original material was solubilized, lignin and hemicellulose were selectively removed, but cellulose was not affected by lime pretreatment in mild temperatures (60–90°C). The delignification was highly dependent on temperature and duration of pretreatment.     

Flour starch thermal characteristics Modulated scanning calorimetric study

Thermal characteristics of refined wheat flour blend made with 90% Ohio soft red winter wheat and 10% Canadian Hard Red Winter Wheat are explored using a series of modulated differential scanning calorimeter conditions. Influences of pan type, period, amplitude of the thermal modulation, and underlying thermal heating rate on flour starch thermal transitions are presented. Wheat flour was blend 1:1 with water, and then heated at various heating rates while the amplitude and period of the instantaneous heating rate was modulated between ±0.5 and ±1.0 °C amplitude and 60 s to 80 s period. Study shows faster heating rates favor increased total heat flow and results in proportional increases in both reversing and non-reversing thermokinetic events of recrystallization. Slower overall heating rates (e.g., 2.5 °C min⁻¹) produced better resolution of thermal events related to preexisting structural phases, but allowed more time for creation of new events such as recrystallization, annealing.     

Reflective and transparent cellulose-based passive radiative coolers

Radiative cooling passively removes heat from objects via emission of thermal radiation to cold space. Suitable radiative cooling materials absorb infrared light while they avoid solar heating by either reflecting or transmitting solar radiation, depending on the application. Here, we demonstrate a reflective radiative cooler and a transparent radiative cooler solely based on cellulose derivatives manufactured via electrospinning and casting, respectively. By modifying the microstructure of cellulose materials, we control the solar light interaction from highly reflective (>?90%, porous structure) to highly transparent (≈ 90%, homogenous structure). Both cellulose materials show high thermal emissivity and minimal solar absorption, making them suitable for daytime radiative cooling. Used as coatings on silicon samples exposed to sun light at daytime, the reflective and transparent cellulose coolers could passively reduce sample temperatures by up to 15 °C and 5 °C, respectively.

     

Solvent swelling of Dictyonema oil shale: Low temperature heat-treatment caused changes in swelling extent

Equilibrium swelling experiments were used to gain insight into the structural changes of Dictyonema oil shale kerogen (baltoscandian basin black shale kerogen) during low-temperature heating. Room temperature volumetric swelling was measured for samples previously thermally pre-treated at different temperatures under an inert gas environment. The swelling capacity for heat-treated Dictyonema oil shale decreases with increasing pre-treatment temperature from about 150 °C to 380 °C, suggesting that cross-linking reactions occur during low-temperature heat treatment in the pre-pyrolysis temperature region. This behavior is consistent with that observed in non-softening low-tar yield coals.     

Studies on Immobilization and Partial Characterization of Lipases from Wheat Seeds (<Emphasis Type="Italic">Triticum aestivum</Emphasis>)

The objective of this study was to provide some features on immobilization and partial characterization of lipases from wheat seeds. The optimum pH and temperature were found to be 5.5 and 32–37 °C, respectively. The stability of the concentrated enzymatic extract to high temperatures (25, 35, 45, and 55 °C) showed that the incubation of the extract at 55 °C led to its complete inactivation. The concentrated enzymatic extract kept 90% of its hydrolytic and esterification activities until 70 and 40 days of storage at 4 °C, respectively. The extract presented higher hydrolytic specificity to substrates of medium and long chains and higher esterification affinity to fatty acids of short and medium chains and alcohols with two and three carbon atoms. After the immobilization process using activated coal and sodium alginate as supports, an enhancement of about threefold in lipase activity was observed. The development of the present work permitted us to point out some characteristics of lipases from wheat seeds necessary for the proposition of new future industrial applications for this important biocatalyst.     

Micro-pyrolysis of technical lignins in a new modular rig and product analysis by GC–MS/FID and GC × GC–TOFMS/FID

A new offline-pyrolysis rig has been designed to allow multifunctional experiments for preparative and analytical purposes. The system conditions can be set and monitored, e.g. temperature, its gradients and heat flux. Some special features include (1) high heating rates up to 120 °C/s with pyrolysis temperatures up to 850 °C at variable pyrolysis times and (2) the selection of different atmospheres during pyrolysis. A complete mass balance of products and reactants (gas, liquids and solids) by gravimetric methods and sequential chromatographic analyses was obtained.The pyrolytic behaviour and the decomposition products of lignin-related compounds were studied under different conditions: heating rates (from 2.6 °C/s up to 120 °C/s), pyrolysis temperatures at 500 °C and 800 °C in different atmospheres (N₂, H₂, and mixtures of N₂ and acetylene). Kraft lignin, soda lignin, organosolv lignin, pyrolytic lignin from pine bio-oil, residues from biomass hydrolysis and fermentation were studied.The obtained pyrolysis products were classified into three general groups: coke, liquid phase and gas phase (volatile organic compounds (VOC) and permanent gases). The liquid fraction was analysed by GC–MS/FID. In addition, comprehensive two-dimensional GC was applied to further characterise the liquid fraction. VOCs were semi-quantified by a modified headspace technique using GC–MS/FID analysis. The micro-pyrolysis rig proved to be an efficient and useful device for complex pyrolysis applications.     

Preparation of CuAlO<Subscript>2</Subscript> thin films with high transparency and low resistivity using sol–gel method

CuAlO₂ thin films were deposited on quartz substrates by sol–gel process using copper acetate monohydrate and aluminum nitrate nanohydrate as starting materials and isopropyl alcohol as solvent. The influence of annealing temperature on the film structure and the phase evolution of CuAlO₂ films were investigated, so as to obtain CuAlO₂ films with superior performance. The phase compositions of the films were dependent on the annealing temperature. The films annealed at temperatures below 400 °C were amorphous while those annealed above 400 °C were polycrystalline. The phases of CuO and CuAl₂O₄ appeared gradually with the increase of annealing temperature. When the heat treatment temperature was elevated to 900 °C, the uniform and dense films with single phase of CuAlO₂ were obtained, with a resistivity of 15 Ωcm. The transmittance of the 310 nm-thick CuAlO₂ film is 79% at 780 nm and the direct optical band gap is 3.43 eV.