Thermogravimetry

The rate and kinetics of the thermal decomposition of potassium iodate (KIO 3) has been studied as a function of particle size, in the range 63-150 lm, by isothermal thermogravimetry at different temperatures, 790, 795, 800 and 805 K in nitrogen atmosphere. The theoretical and experimental mass loss data are in good agreement for the thermal decomposition of all samples of KIO 3 at all temperatures studied. The isothermal decomposition of all samples of KIO 3 was subjected to both model-fitting and model-free (isoconversional) kinetic methods of analysis. It has been observed that the activation energy values are independent of the particle size. Isothermal model-fitting analysis shows that the thermal decomposition kinetics of all the samples of KIO 3 studied can be best described by the contracting cube equation.

Objective: Biodegradable polycaprolactone/starch composites can be used for bone tissue engineering applications. The effect of the ratio of components on composite properties is of tremendous importance. Methods: Polycaprolactone/starch composite of 80/20 and 70/30 ratios were fabricated by dissolving them in chloroform followed by evaporation of the solvent. Results: The composites were characterized by fourier transform infrared spectroscopy. Their bioactivity was evaluated by studying the apatite formation ability after immersing the specimens in simulated body fluid. The results of compressive test on samples showed that the composite's modulus and strength approximated that of human trabecular bone. Mass loss in distilled water and starch degradation rate in PBS was evaluated, which showed that the starch ratio was effective in composite degradation. MTT analysis and alkaline phosphatase levels showed that this composite had no toxicity and could increase G-299 cell line osteoblastic activities. Conclusion: The increase in cellular osteoblastic activities and the ability for apatite formation on the composite surface, in addition to the polycaprolactone/starch samples' mechanical properties shows their capability to be used as substitutes for bone. Because this composite degradation rate is controlled by changing the starch ratio, it has the potential for use in bone tissue engineering applications. Samples that have a 70/30 ratio are considered optimal due to their enhanced cellular response and better mechanical properties.

The growing petroleum deficit requires the development of alternative fuel sources. Biodiesel is a good alternative, as it is a biodegradable and renewable product, which obeys the carbon cycle. In this work, the biodiesel from babassu was synthesized using the methanol route, and characterized by physico-chemical analyses in order to make able the investigated biodiesel to fulfill with its properties the requirements of Brazilian National Agency for Petroleum, Natural Gas and Biofuel (ANP). Besides gas chromatography, IR spectroscopy experiments and thermoanalytical measurements in air and in nitrogen were done to determine the main thermal decomposition processes and calorimetric events. The evaporation temperature of babassu biodiesel was similar in both atmospheres, started around 52 in air and around 60°C in nitrogen.

To explore the potential fate and transport of perfluorochemicals in the thermal treatment of sludge, perfluorooctanesulfonate (PFOS), a perfluorochemical species commonly dominant in wastewater sludge, was mixed with hydrated lime (Ca(OH) 2 ) to quantitatively observe their interaction under different temperatures. The phase compositions of the mixtures after the reactions were qualitatively identified and quantitatively determined using X-ray diffraction technique. The results of the thermogravimetry and differential scanning calorimetry analyses indicate that PFOS gasified directly during the thermal treatment process when the temperature was increased to around 425 • C. However, the formation of CaF 2 at 350 • C suggests that the presence of Ca(OH) 2 in the mixture can lead to the decomposition of PFOS at 350 • C, which is lower than the decomposition temperature of PFOS alone (425 • C). The increase of temperature promoted a solid state reaction between PFOS and Ca(OH) 2 , and also enhanced the interaction between the gaseous products of PFOS and CaO (or Ca(OH) 2 ). The preferred Ca/F molar ratio to achieve fluorine stabilization by Ca(OH) 2 was above 1:1 in the experiment involving 400 • C and 600 • C treatment. It also showed that equilibrium efficiency is achieved within 5 min at 400 • C and within 1 min above 600 • C.

The performance of copper/nickel oxide catalysts supported on ceramic monoliths of ␥-alumina/silicate, for the selective catalytic reduction (SCR) of nitrogen oxides in flue gas from nitric acid plants ([NO]/[NO x ] = 0.7) has been studied. The monoliths prepared were characterised by thermogravimetry, nitrogen adsorption-desorption, mercury intrusion porosimetry (MIP), X-ray diffraction (XRD), electron probe microanalysis wavelength dispersion spectroscopy (EPMA-WDS) and their mechanical strengths were measured. The support composition and heat-treatment temperature was optimised to obtain monolithic structures with satisfactory mechanical and textural properties. Thus, a monolith with a ␥-alumina/silicate weight ratio of 2/3 was selected to give the best combination of textual and mechanical properties. The influence of active phase (CuO/NiO) content and operating conditions (residence time, [NH 3 ]/[NO x ] ratio) on the NO x conversion and ammonia slip was studied at laboratory scale to determine the optimum conditions for operation at pilot-plant scale. The maximum catalytic activity was achieved for a catalyst with CuO content of 6.3 wt.%. At higher active phase concentration a decrease in the catalytic activity was observed, related to the formation of copper oxides crystals detected by XRD. The presence of these species increase the reaction rate of the competitive ammonia oxidation reaction and thus, reduce the ammonia concentration in the outlet. The selected monolithic catalyst was tested at pilot-plant scale with real gases from a nitric acid production plant achieving NO x conversions of around 90 vol.%, with ammonia emissions lower than 10 ppm, at 230 • C and GSHV (NTP) of 10,600 h −1 .

S2 TABLE S1. Results of TGA analyses of sorbent hydrated after CO 2 cycles a CaO carbonated (%) Sample CaO sulphated (%) Before After CaO hydrated (%) CaO unreacted (%) KR37 (75-150 μm) 29.77 4.69 10.44 50.66 9.13 KR38 (300-425 μm) 28.09 4.08 8.72 53.98 9.21 KR39 (600-750 μm) 26.59 4.86 9.60 55.76 8.05 KR40 (75-150 μm) 0.00 19.31 24.80 68.74 6.46 KR41 (300-425 μm) 0.00 14.60 18.98 70.74 10.28 KR42 (600-750 μm) 0.00 16.46 20.76 70.55 8.68 a The values of CaO sulphated were calculated on the basis of mass increment at end of sulphation step and represent the CaSO 4 /totalCaO molar ratio. The values of CaO hydrated and carbonated were calculated on the basis of mass loss in the TGA experiments, which correspond to the Ca(OH) 2 and CaCO 3 decomposition and represent the Ca(OH) 2 /totalCaO and CaCO 3 /totalCaO molar ratio, respectively. The values of CaO unreacted are calculated by difference.

The 6-year-old term 'Sample Controlled Thermal Analysis' (SCTA) designates the branch of thermal analysis where a feedback from the sample is used to control its heating or cooling. In this method , it is therefore the sample itself which determines its own heating and cooling conditions as the name implies. This approach can be considered as a real breakthrough in the field of thermal analysis. It has indeed the advantage, as compared with conventional thermal analysis, of providing: elimination of uncertainties due to thermal effects in the sample container, improved resolution, accurate determination of reaction temperatures and accurate kinetic data. SCTA has since its introduction in the early seventies been used in many studies both on inorganic and to a certain extent organic (polymers) compounds with the aim to study the temperature, the type and the kinetics of reactions taking place during heating and cooling: in the case of ceramics and adsorbents SCTA has even been used in synthesis of materials with specific properties. These techniques are now also available in commercial TA instruments. A new book in the series Hot Topics in Thermal Analysis and Calorimetry (edited by Judit Simon, Hungary) was announced at the workshop. The title is: Sample Controlled Thermal Analysis: Origin, Goals, Multiple Forms, Applications and Future. The editors are Ole Toft Sørensen (Denmark) and Jean Rouquerol (France). This book is expected to be published by Kluwer during the spring 2003. • Kinetic studies, J.

The azo-ester compounds containing an acryloyloxy group were derived from phenol and 2,6-dimethylphenol; first azobenzene derivatives were prepared by reacting substituted benzenediazonium salts with phenol and 2,6-dimethylphenol then their acryloyloxy derivatives were synthesized in a SchotteneBauman-type reaction. The characterisation of the synthesized azo-ester dye has been described by IR, UVevis, 1 H NMR, 13 C NMR spectroscopic techniques, and elemental analysis. The influence of the substituents and acryloyloxy group on the spectral data of the synthesized compounds has been described. The thermal behaviour of the present compounds has been determined by means of differential thermal analysis (DTA) and thermogravimetry (TG) techniques.

Progesterone rapidly dissolves in an aqueous solution containing hydroxypropyl-b-cyclodextrin (HPBCD) at 1:2 molar ratio, forming a soluble inclusion complex. After filtration and freeze-drying of the final solution, the final powder was examined by SEM, DSC, TGA, XRD, Raman, and FTIR spectroscopy. Experimental results confirm that an inclusion complex exists in the solid state and possible structure of the complex is briefly discussed. ß

The dehydration/desolvation of two hydrate solvates of the pharmaceutically important compound finasteride (namely, bisfinasteride monohydrate monotetrahydrofuran and bisfinasteride monohydrate mono-1,4-dioxane) has been studied by solid-state nuclear magnetic resonance, powder X-ray diffraction, thermogravimetric analysis (including coupling with mass spectrometry) and dynamic vapour sorption. The structure is unusual in that water holds the host finasteride molecules together by hydrogen bonding to form channels in which the solvent is sited. Whilst the solvent guest molecules are not strongly bound to the host, their presence is essential for structural stability. Desolvation is not found to occur at a well-defined temperature or even to consistently produce the same anhydrous form (form I vs. form II), but is instead highly dependent on the physical environment and, therefore, on the technique used. This behaviour complicates investigations, but the combination of complementary methods does allow the desolvation to be understood. Water and solvent are shown to be lost simultaneously, with no evidence of an intermediate form or increased mobility of the hydrogen-bonded water molecules. The results are consistent with a model in which structural collapse and rearrangement follows the loss of a small fraction of the solvent molecules from the channel structure, with the final form produced being very sensitive to the presence of water vapour during desolvation.

Al-5%Mg alloy at low oxygen pressure. The oxidation of a liquid Al-5%Mg alloy was studied by isothermal (700°C) and isobaric thermogravimetry, under controlled oxygen partial pressure (lower than 50hPa). At low oxygen pressure, the reaction proceeds in the gaseous phase, due to the evaporation of magnesium from the alloy. A model exists in the literature to describe such reactions ; we verified experimentally that the assumptions of this model could be made for our reacting system; consequently, the variations of the oxidation rate with oxygen partial pressure were accounted for.

The paper reviews the pyrolysis of biomass constituents and possible secondary reactions. Biomass pyrolysis yields mostly liquid and solid fuel, easy to store and transport. Relevant working conditions for experiments and large-scale operation are: (i) biomass particles < 200 mm, (ii) a particle heating rate of at least about 80 K min À1 and (iii) a reactor environment where the internal resistance to heat penetration is smaller than the external resistance to heat transfer (Biot-number, Bi < 1). The circumstances of TGA and DSC experiments meet these requirements and fully determine the reaction kinetics and endothermicity of the pyrolysis reaction. The reaction rate constant and the heat of reaction are essential parameters in the design of a pyrolysis reactor. For most of the biomass species tested, the first order reaction rate constant is large and >0.5 s À1. The heat of reaction ranges from 207 to 434 kJ kg À1. All results tie in with literature data, although the reader is cautioned in using literature data since experiments were not always performed under relevant testing conditions.

The hybrid material copper (II) tetrachloro-bis(phenyl ethyl ammonium) (C 6 H 5 CH 2 CH 2 NH 3 ) 2 CuCl 4 , or PEACuCl, has been investigated by temperature-dependent spectroscopic absorption experiments. The absorption bands observed in the near-infrared region (1.3-1.9 eV) generally exhibit redshifts with increasing temperature. The temperature-induced energy shifts of the spectral components are shown to be consistently related to temperature-induced Cu-Cl bond length changes. Additionally, the thermochromic color change is caused by a charge transfer band edge redshifting (in the visible region 2.0-2.8 eV) with increasing temperature. By comparison with similar Cu-based systems, it is suggested that this shift is caused by broadening and strengthening of the band.

a b s t r a c t Nanometric inorganic pigments are widely used as fillers for hybrid composite materials. However, these nanometric powders are hydrophilic in nature and their surface must be functionalized before use. In this work, titanium dioxide (TiO 2 ) nanoparticles were coated using silane coupling agents with alkyl functionality. A supercritical carbon dioxide (scCO 2 ) method was used for surface silanization. Five alkylalkoxysilanes with different alkyl chain length and structure were studied: methyltrimethoxy, isobutyltriethoxy, octyltriethoxy, octyldimethylmethoxy and octadecyltrimethoxysilane. The microstructure and thermal stability of deposited monolayers were characterized using thermogravimetric analysis, ATR-IR spectroscopy, transmission electron microscopy, wettability characterization and low-temperature N 2 adsorption/desorption analysis. The use of scCO 2 as a solvent provided an effective approach to functionalize individual inorganic nanoparticles due to the enhanced diffusivity of the solution molecules in the aggregates interparticle voids. The trifunctional silanes employed here yielded surfaces with better thermal stabilities and greater hydrophobicities than the used monofunctional silane.

Thermogravimetry with Fourier Transform Infrared Analysis (TG-FTIR) has been used to measure the organic oxygen content in a suite of coals of differing rank and compare these with the values determined by difference according to ASTM D3176-89. Two coking coals, one Cretaceous and one Carboniferous, were oxidized at 50 jC to simulate natural weathering and analyzed for their oxygen content by both techniques. Results indicate that the pyrolysis technique is reliable and rapid and is free of the large possible errors inherent in the determination of organic oxygen content by difference. D (J.A. MacPhee), mohammed _ [email protected] (M.A. Khan). www.elsevier.com/locate/fuproc Fuel Processing Technology 81 (2003) 211 -221

Sulfonamide antibiotics are persistent pollutants of aquatic bodies, known to induce high levels of bacterial resistance. We investigated the adsorption of sulfadiazine, sulfamethazine, and sulfachloropyridazine sulfonamides into a highly dealuminated faujasite zeolite (Y) with cage window sizes comparable to sulfonamide dimensions. At maximal solubility the antibiotics were almost completely (>90%) and quickly (t < 1 min) removed from the water by zeolite. The maximal amount of sulfonamides adsorbed was 18-26% DW of dry zeolite weight, as evidenced by thermogravimetric analyses and accounted for about one antibiotic molecule per zeolitic cage. The presence of this organic inside the cage was revealed by unit cell parameter variations and structural deformations obtained by X-ray structure analyses carried out using the Rietveld method on exhausted zeolite. The most evident deformation effects were the lowering of the Fd-3m real symmetry in the parent zeolite to Fd-3 and the remarkable deformations which occurred in the 12-membered ring cage window after sulfadiazine or sulfachloropyridazine adsorption. After sulfamethazine adsorption, zeolite deformation caused a lowering in symmetry up to the monoclinic P2/m space group. The effective and irreversible adsorption of sulfonamides into organophylic Y zeolite makes this cheap and environmentally friendly material a suitable candidate for removing sulfonamides from water.

. New catalysts based on hydrotalcite-like precursors Mg-Fe and Mg-Al-Fe were synthesized. The structure of catalyst precursors was confirmed by XRD, FT-IR and TG. Appearance of separate brucite phase was observed for Mg-Fe Ž . precursors with excess of Mg, while for Mg-Al-Fe precursors, increase in Al content led to a formation of MgAl OH 2 8

Blends of poly(1-caprolactone) (PCL) with chitosan and a whey-protein-isolate (WPI) were prepared by solution mixing and ®lm casting. The purpose was to increase the water vapour resistivity of chitosan and whey by blending them with a hydrophobic biodegradable polymer. The water vapour transmission rate was determined by a standard technique and by a new technique based on microcalorimetry. The blends were characterised by scanning electron microscopy (SEM), density measurements and thermogravimetry. Oxygen permeability was measured on the pure components and on some of the blends. The incorporation of PCL yielded a pronounced decrease in water vapour transmission rate of both chitosan and the WPI measured at a relative humidity gradient of 11 to 0%. A volume content of 17±18% of PCL lowered the water vapour transmission rate by 70±90%. It was found that the majority of the PCL particles were ellipsoidal in chitosan and ®brous in the WPI and the data indicated that the particle shape had an important in¯uence on the water vapour transmission rate. The large decrease in water vapour transmission rate was also due to a reduction in water solubility because of limited swelling of the constrained chitosan or WPI matrix in the presence of PCL. SEM revealed that the miscibility/compatibility between PCL and the matrices was good. The water vapour transmission rate of the ®lms decreased with increasing vacuum-drying time of the chitosan and WPI solutions. Microcalorimetry provided accurate estimates of water vapour transmission rate. Furthermore, this technique proved to be very¯exible and the water vapour transmission rate could be determined over a broad range of relative humidities in a single experiment. q

Commercial humic acid was dialyzed and characterized by infrared, UV/vis spectroscopy, 13 C NMR spectrometry, thermogravimetry, and elemental analysis. The dialyzed humic acid was titrated with HNO 3 and NaOH in order to obtain the buffer capacity value (β). The humic acid presented buffer behavior by base and acid addition, and moreover, an excellent buffer capacity by addition of NaOH. Humic acid showed buffer action between pH 5.5 and 8.0, and a maximum buffer capacity at pH 6.0. The same study was followed calorimetrically to determinate the enthalpy of interaction between H + /OH − and buffer, which resulted in a maximum enthalpy of −38.49 kJ mol −1 at pH 6.0. This value suggests that the buffer activity is based on chemisorption of proton and hydroxyl.

We prepared hydrazine-reduced materials from both graphite oxide (GO) particles, which were not exfoliated, and completely exfoliated individual graphene oxide platelets, and then analyzed their chemical and structural properties by elemental analysis, XPS, TGA, XRD, and SEM. Both reduced materials showed distinctly different chemical and structural properties from one another. While hydrazine reduction of graphene oxide platelets produced agglomerates of exfoliated platelets, the reduction of GO particles produced particles that were not exfoliated. The degree of chemical reduction of reduced GO particles was lower than that of reduced graphene oxide and the BET surface area of reduced GO was much lower than that of reduced graphene oxide.

A new nonlinear optical material tetrakis thiourea nickel chloride (TTNC) was synthesized and single crystals were grown from mixed solvent of water and isopropanol by both slow evaporation and slow cooling methods. The grown crystals were characterized by powder X-ray diffraction analyses to confirm the crystal structure. The presence of functional groups and the coordination of metal ions to thiourea were confirmed by FTIR and Raman spectroscopy analyses. UV-VIS spectrum was recorded to study the optical transparency of the grown crystals. Thermal properties of the crystals have been by investigated using thermo gravimetric (TG) and differential thermal analyses (DTA), which indicate that the material does not decompose before melting. The second order nonlinear optical property of the grown crystal was examined by Kurtz powder technique and mechanical behavior was studied by Vicker's microhardness test.

Paromomycin (PM) is an aminoglycoside antibiotic, first isolated in the 1950s, and approved in 2006 for treatment of visceral leishmaniasis. Although isolated six decades back, sufficient information essential for development of pharmaceutical formulation is not available for PM.

Ambroxol theophylline-7-acetate (ACE) is the salt obtained by reaction of equimolar amounts of ambroxol (AMB), a drug showing mucolytic and expectorant properties, and theophylline-7-acetic acid (TAA), a xanthine derivative with specific bronchodilator activity. ACE is used for the treatment of bronchial and pulmonary diseases (bronchitis, asthma, emphysema, chronic obstructive disease). Recrystallization experiments of ACE resulted in the isolation of two polymorphs (monotropically related) and four solvated forms. X-ray diffractometry, DSC, TGA, and HSM techniques were used to investigate the forms that are obtained by thermal desolvation of the solvates. The phase diagram of the TAA-AMB binary system was constructed by performing thermal analyses on mixtures of TAA-AMB and of each component plus the interaction compound (TAA-ACE and ACE-AMB). The Schroeder-Van Laar equation proved to be a very useful tool for checking the consistency between the experimental data and the theoretical model related to the general system, showing complete miscibility in the liquid phase and complete immiscibility in the solid phase.

Leather industries which promote hide stabilization by the conventional chrome-tanning process are a major source of pollution because of the resultant chromium-rich wastes. In this work, an extensive characterization of such a chromium-rich waste sludge is presented, regarding its chemical composition (XRF), crystalline phase contents (XRD), organic carbon content (TOC), thermal behavior by thermogravimetry (TG) and differential scanning calorimetry (DSC), as well as its stability under chemical attack (the concentration of important ions in the leachates being determined by capillary electrophoresis) and when submitted to temperatures as high as 1100 8C, in air. The material showed the tendency to produce some undesirable, and previously non-detected hexavalent chromium when exposed to high temperatures, but after washing off the soluble salts and the elimination of the organic matter by firing, the resultant material was succesfully tested as a ceramic pigment in a conventional glaze composition usually employed in the ceramic tile industry.

Sonochemical synthesis followed by supercritical drying was used to prepare MgO nanoparticles from Mg(OCH 3 ) 2 and Mg(OC 2 H 5 ) 2 . Their physicochemical properties were examined by means of X-ray diffraction (XRD), simultaneous thermal analysis (DTA, TG, EGA), specific surface area measurement, scanning and transmission electron microscopy. The dehydrated MgO oxides were free of -OCH 3 groups. The highest values of specific surface area (1236 m 2 g À 1 ) have been obtained by hydrolysis of magnesium methoxide using toluene as solvent agent. D

Rare earth phosphate powders (Re=La, Ce or Y) were synthesized from an aqueous precipitation method. The effect of temperature, pH, ripening time and Re/P mole ratio of the initial reagents was investigated. Elementary analysis, surface area and bulk density measurements, FT-infrared spectroscopy, X-ray diffraction and SEM observations were performed to characterize the precipitates. All the powders of hydrated form (La, Ce or Y)PO 4 Á nH 2 O were single phase. They exhibited a Re/P mole ratio smaller than 1 due to residual H 3 PO 4 adsorbed at their surface. A unit formula could be written as RePO 4 Á nH 2 O Á (H 3 PO 4 ) x with nE0:5 (for Re=La or Ce) or n ¼ 2 (for Re=Y) and xo0:1: High-temperature thermogravimetry was necessary to detect these residuals and insure the purity of the powders. The precipitation of lanthanum or cerium phosphates was slow, resulting in powders with a high specific surface. The precipitation of yttrium phosphate was faster and significant crystal growth occurred during the ripening, which resulted in a whisker-like morphology and a very low specific surface.

Thermal decomposition processes were investigated for Bacillus Gram-positive spores. Thermogravimetry analysis (TGA) experiments at 200 K min −1 produced a temporal evolution of biochemicals from the spores. Qualitative and quantitative aspects such as peak resolution, peak ratios, peak positions, and temperature maxima are compared and contrasted in the thermal weight loss and differential thermogravimetry (DTG) curves for different Bacillus bacterial spores. The TGA experimental data were used to generate the activation energy and frequency factor Arrhenius equation parameters. These parameters were used to produce TGA and the negative of the first derivative of the TGA (−DTG) decomposition model curves, and the latter are compared to their respective bacterial experimental TGA and −DTG profiles for validation and modeling purposes. The thermal decomposition model is also shown to have application in the prediction of weight loss profiles at significantly higher heating rates than that from the laboratory TGA system. The model thermal decomposition profiles are applied in comparisons to the total ion chromatograms of Bacillus atrophaeus bacterial spores generated by an outdoors fielded pyrolysis-gas chromatography-ion mobility spectrometry (Py-GC-IMS) bioaerosol detection system. Pyrolysis at a high heating rate of 3300 K min −1 was used. The bioaerosol detection system provides very similar qualitative information to the TGA and −DTG experimental and model profiles.

With the aim to increase the recycling of fine sludge and dust disposed normally in landfill, cold bonded pelletizing of the sludge and dust using cement as binder was investigated in laboratory scale as well as in the pilot scale pelletizing plant. The influence of BF flue dust, BOF fine sludge and oily mill scale sludge on the cold strength, capacity and reduction degree of cold bond pellets was studied experimentally on the basis of a statistical procedure. With a coarser representative particle size, oily mill scale sludge has the greatest effect on the cold strength. BF flue dust has a negative effect for increasing both the cold strength and capacity for levels of over 25 % of the mixture. The BOF fine sludge has the positive effect on cold strength, while its interaction with BF flue dust has the negative effect on reduction degree. The results of pelletizing tests in pilot scale show that the maximum cold strength (TTH 94 %) and capacity (13-15 t/h) of products is obtained at the conditions given by the optimal mixture design and cure time. The industrial tests on charging cold bonded pellets as burden material in the BOF converter were described. The charging weight of cold bonded pellets varied from 0.5 to 2.5 tons. The results of industrial tests indicated that the converter process was not subject to any adverse disturbances due to the addition of 2.5 tons of cold bonded pellets.

The fate of levoglucosan after it forms during cellulose pyrolysis was investigated experimentally using time-resolved thermogravimetric analysis/differential scanning calorimetric combined with mass spectrometry measurements followed by high performance liquid chromatography and gel filtration chromatography of the pyrolysis residue. This study indicates that levoglucosan formed during cellulose pyrolysis is initially a liquid that undergoes two simultaneous, competing processes of evaporation and polymerization. Levoglucosan that evaporates escapes the high temperature pyrolysis zone while levoglucosan that polymerizes is trapped in the pyrolysis zone and dehydrates to low molecular weight volatile products and char. The oligosaccharides that form during polymerization are subject to two simultaneous reaction pathways: direct decomposition to low molecular weight products such as water, carbon dioxide, 5-hydroxymethylfurfural, furfural, furan and acetic acid, and formation of polysaccharides that eventually dehydrate to char and low molecular weight volatiles. Based on the experimental observations and quantitative measurements, a modified cellulose pyrolysis pathway involving levoglucosan as the major intermediate is proposed.

The use of silver(I)-2-[2-(2-methoxyethoxy)ethoxy]acetate, [AgO 2 C(CH 2 OCH 2 ) 3 H], and its application as an aqueous metal-organic decomposition (MOD) inkjet ink is reported. The chemical and physical properties of the silver carboxylate and the ink formulated thereof are discussed. The ink meets all requirements of piezo driven inkjet printing. The printed features were converted into electrically conducting silver patterns by thermal or photo-thermal treatment. The conversion of [AgO 2 C(CH 2 OCH 2 ) 3 H] to elemental silver follows a two-step decomposition as demonstrated by thermogravimetry-mass spectrometry (TG-MS) measurements. The measured conductivities of the printed features on glass and polyethylene-terephthalate (PET) are 2.7 × 10 7 S m −1 and 1.1 × 10 7 S m −1 , respectively, which correspond to 43% (glass) and 18% (PET) of the bulk silver conductivity.

The slow and fast pyrolysis of cherry seeds (CWS) and cherry seeds shells (CSS) was studied in fixed-bed and fluidized bed reactors at different pyrolysis temperatures. The effects of reactor type and temperature on the yields and composition of products were investigated. In the case of fast pyrolysis, the maximum bio-oil yield was found to be about 44 wt% at pyrolysis temperature of 500°C for both CWS and CSS, whereas the bio yields were of 21 and 15 wt% obtained at 500°C from slow pyrolysis of CWS and CSS, respectively. Both temperature and reactor type affected the composition of bio-oils. The results showed that bio-oils obtained from slow pyrolysis of CWS and CSS can be used as a fuel for combustion systems in industry and the bio-oil produced from fast pyrolysis can be evaluated as a chemical feedstock.

A stoichiometric MgAl 2 O 4 spinel powder was synthesized by a microwave-assisted combustion synthesis (MWCS) route. For the purpose of comparison, another stoichiometric MgAl 2 O 4 spinel powder was also prepared following the conventional combustion synthesis (CCS) method. The batch size had a strong influence on the specific surface area of the material, which in turn is highly dependent on the preparation method adopted. The surface areas of these synthesized powders were found to decrease from 36.78 to 0.1 m 2 /g for MWCS and 126 to 8.06 m 2 /g for CCS samples, respectively, when the batch size was increased from 2 to 100 g. This could be attributed to sintering of the samples due to high adiabatic temperature generated as a result of increased heat accumulation with bigger batch quantities. Between the two powders synthesized by the two different routes, the powders obtained by MWCS and CCS routes were found to contain grains/crystals in range of 20-50 and 100-250 nm size, respectively. The thermogravimetry/differential thermal analysis (TG-DTA) and X-ray diffraction (XRD) studies reveal that microwave-assisted combustion synthesis route yields materials with higher degree of compositional stability and phase purity as compared to the conventional combustion synthesis method.

In this present work, barium ion was reacted with different ligands which are 5,7-dibromo, 5,7-dichloro, 7-iodo and 5-chloro-7-iodo-8-hydroxyquinoline, in acetone/ammonium hydroxide medium under constant stirring and the obtained compounds were as follows: (I) Ba[(C 9 H 4 ONBr 2 ) 2 ]·1.5H 2 O; (II) Ba[(C 9 H 4 ONCl 2 )(OH)]·1H 2 O; (III) Ba[(C 9 H 5 ONI) 2 ]·1H 2 O and (IV) Ba[(C 9 H 4 ONICl) 2 ]·5H 2 O, respectively. The compounds were characterized by elemental analysis, infrared absorption spectrum (IR), inductively coupled plasma spectrometry (ICP), simultaneous thermogravimetry-differential thermal analysis (TG-DTA) and differential scanning calorimeter (DSC).

The flame retardant effect of inorganic hydroxides, like aluminum hydroxide and magnesium hydroxide in ethylene vinyl acetate copolymer, was evaluated and compared with that of other inorganic fillers such as boehmite and hydrotalcite. The thermal decomposition of the fillers and the mixtures with EVA polymer were analysed by differential scanning calorimetry (DSC), Thermogravimetry (TG) and X-ray diffraction (XRD). The most significant flame retardant effects, observed using a mass loss calorimeter, indicated that the EVA polymer filled with 50 wt.% of hydrotalcite has the slowest heat release rate and the lowest evolved gas temperature. XRD data, combined with thermal analysis results, indicated that the layered structure of hydrotalcite may play a role in the degradation mechanism. The improved fire resistance of EVA filled with hydrotalcite also results from its intumescent behaviour. # (M. Braglia).

The thermal decomposition of potassium bromate (KBrO 3 ) has been studied as a function of particle size, in the range 53-150 lm, by isothermal thermogravimetry at different temperatures, viz. 668, 673, 678, and 683 K in static air atmosphere. The theoretical and experimental mass loss data are in good agreement for the thermal decomposition of all samples of KBrO 3 at all temperatures studied. The isothermal decomposition of all samples of KBrO 3 was subjected to both model fitting and model-free (isoconversional) kinetic methods of analysis. Isothermal model fitting analysis shows that the thermal decomposition kinetics of all the samples of KBrO 3 studied can be best described by the contracting square equation. Contrary to the expected increase in rate followed by a decrease with decrease in particle size, KBrO 3 shows a regular increase in rate with reduction in particle size, which, we suggest, is an impact of melting of this solid during decomposition.

The influence of platinum and barium precursors on the catalytic performance of monolithic Pt–Ba/Al2O3 NOx storage catalysts was studied. The precursors used in the preparation were: tetraammineplatinum nitrate [Pt(NH3)4(NO3)2] and hexachloroplatinic acid [H2Pt(Cl)6] for incorporation of platinum by adsorption from solution (ion exchange); and barium acetate [Ba(CH3–COO)2] and barium nitrate [Ba(NO3)2] for incorporation of barium by dry impregnation. The prepared samples were characterized by XRD, H2 chemisorption and thermogravimetry, to determine the distribution and dispersion of the metallic phases. The catalytic activity of the prepared monolithic catalysts was tested for lean/rich NOx storage and reduction in a flow reactor using hydrogen as reducing agent. The catalyst prepared from tetraammineplatinum nitrate and barium acetate was the most active in the NOx storage during the lean period. NOx storage capacity (NSC) and selectivity were dependent with temperature. The higher NSC was obtained at temperature 330–350 °C. About 80% selectivity to nitrogen was achieved with catalysts prepared from tetraammineplatinum nitrate, versus 70% when the platinum was incorporated from hexachloroplatinic acid.

Thermal behavior of four food dyes, i.e. tartrazine, crysoine, azorubine and amarant was studied under non-isothermal conditions, in dynamic air atmosphere and at heating rates of 5, 10, 15 and 20°C min -1 . The TG data were correlated to the FTIR spectra of each sample, before and after the thermal decomposition. Kinetic study by processing the TG data was performed. The main conclusion of this study is that the non-parametric kinetic method allows a separation of the steps of a complex process and that the values of the activation energy obtained by this method agree satisfactory with that of Flynn-Wall-Ozawa estimation.

The dehydration reaction kinetics of tincal and borax decahydrate was investigated by thermogravimetry (TG) and differential thermal analysis (DTA). Various methods were used to analyze the TG and DTA data for determination of reaction kinetics. The activation energy, frequency factor, and order of reaction were calculated for both materials. The results obtained from different methods were generally in good agreement. The results of tincal and borax were also compatible.

Nanosized IrO 2 electrocatalysts (d * 7-9 nm) with specific surface area up to 100 m 2 g -1 were synthesized and characterized for the oxygen evolution reaction in a solid polymer electrolyte (SPE) electrolyzer. The catalysts were prepared by a colloidal method in aqueous solution and a subsequent thermal treatment. An iridium hydroxide hydrate precursor was obtained at *100°C, which was, successively, calcined at different temperatures from 200 to 500°C. The physico-chemical characterization was carried out by X-ray diffraction (XRD), thermogravimetry-differential scanning calorimetry (TG-DSC) and transmission electron microscopy (TEM). IrO 2 catalysts were sprayed onto a Nafion 115 membrane up to a loading of 3 mg cm -2 . A Pt catalyst was used at the cathode compartment with a loading of 0.6 mg cm -2 . The electrochemical activity for water electrolysis of the membrane-electrode assemblies (MEAs) was investigated in a single cell SPE electrolyzer by steadystate polarization curves, impedance spectroscopy and chrono-amperometric measurements. A maximum current density of 1.3 A cm -2 was obtained at 1.8 V and 80°C for the IrO 2 catalyst calcined at 400°C for 1 h. A stable performance was recorded in single cell for this anode catalyst at 80°C. The suitable catalytic activity and stability of the most performing catalyst were interpreted in terms of proper combination between nanostructure and suitable morphology.

Microencapsulation of Lippia sidoides essential oil was carried out by spray drying. Blends of maltodextrin and gum arabic were used as carrier. Spray dried microparticles were characterized using conventional (thermogravimetry, evolved gas analysis) and combined (thermogravimetry-mass spectrometry analysis) thermal analysis techniques in order to evaluate the abilities of carriers with different compositions in retaining and in releasing the core vs. dynamic heating. Thermal analysis was useful to evaluate the physico-chemical interactions between the core and carriers and to determine the protective effect of the carriers on the evaporation of essential oil.

The aim of this paper is the recovery of manganese and zinc from a mixture of zinc-carbon and alkaline spent batteries, containing 40.9% of Mn and 30.1% of Zn, after preliminary physical treatment followed by removal of mercury. Separation of the metals has been carried out on the basis of their different boiling points, being 357°C and 906°C the boiling point of mercury and zinc and 1564°C the melting point of Mn 2 O 3. Characterization by chemical analysis, TGA/DTA and X-ray powder diffraction of the mixture has been carried out after comminution sieving and shaking table treatment to remove the anodic collectors and most of chlorides contained in the mixture. The mixture has been roasted at various temperatures and resident times in a flow of air to set the best conditions to remove mercury that were 400°C and 10 min. After that, the flow of air has been turned into a nitrogen one (inert atmosphere) and the temperatures raised, thus permitting the zinc oxide to be reduced to metallic zinc by the carbon present in the original mixture and recovered after volatilization as a high grade concentrate, while manganese was left in the residue. The recovery and the grade of the two metals, at 1000°C and 30 min residence time, were 84% and 100% for zinc and 85% and 63% for manganese, respectively. The recovery of zinc increased to 99% with a grade of 97% at 1200°C and 30 min residence time, while the recovery and grade of manganese were 86% and 87%, respectively, at that temperature. Moreover, the chlorinated compounds that could form by the combustion of the plastics contained in the spent batteries, are destroyed at the temperature required by the process.

A pilot-scale dual fluidized bed combustion system was used for CO 2 capture using limestone sorbent with CaO-CaCO 3 looping. The sorbent was regenerated at high temperature using an air-or oxygen-fired fluidized bed calciner with flue gas recycle firing hardwood pellets. Two limestones were evaluated for CaO-CaCO 3 looping. Changes in the sorbent morphology during the tests were identified by scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDX). Changes in pore size distribution and sorbent surface area that occurred during reaction were determined by N 2 BET porosimetry. Thermogravimetric analysis (TGA) was used to determine the activity of the sorbent after processing in the dual fluidized bed combustion system. It was found that oxygenfired calcination with high CO 2 partial pressure reduced the effectiveness of the two limestone sorbents for CO 2 capture when compared to material calcined under oxygen-enhanced air combustion. A shell 1-2 lm thick, with reduced porosity, was formed around the sorbent particle and is believed to be responsible for reduced conversion of CaO to CaCO 3 . It is believed that ash deposition contributes to the formation of the shell.