Co-firing of biomass with coals

The combustion of coal and coal/fir (Abies bornmulleriana) wood blends at the proper ratio (20, 40, 50 wt%) was investigated with thermogravimetric analysis (TG). The influence of biomass blends on thermal and kinetic behavior of coal was studied under non-isothermal conditions. The activation energy of the samples was evaluated with the Ozawa–Flynn–Wall model which compares the combustion of these biowastes with coal under non-isothermal conditions. Our research found that blending influences activation energy of coal; moreover, activation energy related to 50 wt% blend was more similar to pure wood combustion than to coal combustion. Therefore, the activation energy profile shifted from 80.6 to 169.3 kJ/mol. The average reaction order of the samples ranged from 0.13 to 0.35.     

Thermal characterization of solid lipid nanoparticles containing praziquantel

Solid lipid nanoparticles (SLNs), loaded and unloaded with praziquantel (PRZ-load SLN and PRZ-unload SLN) were prepared by two different procedures: (a) oil-in-water hot microemulsion method, obtaining at 70 °C an optically transparent blend composed of surfactant, co-surfactant, and water; and (b) oil-in-water microemulsion method, dissolving the lipid in an immiscible organic solvent, emulsified in water containing surfactants and co-surfactant, and then evaporated under reduced pressure at 50 °C. The mean diameter, polydispersity index (PdI), and zeta potential were 187 to 665 nm, 0.300 to 0.655, and −25 to −28 mV respectively, depending on the preparation method. The components, binary mixture, SLNs loaded and unloaded with PRZ, and physical mixture were evaluated by differential scanning calorimetry (DSC) and thermogravimetry (TG). The non-isothermal isoconversional Flynn-Wall–Ozawa method was used to determine the kinetic parameters associated with the thermal decomposition of the samples. The experimental data indicated a linear relationship between the apparent activation energy E and the pre-exponential factor A, also called the kinetic compensation effect (KCE), allowing us to determine the stability with respect to the preparation method. Loading with PRZ increased the thermal stability of the SLNs.     

Applicability of bi-pseudo component separated-stage model for decomposition of lignocellulosic materials in air at multiple heating rates

In our previous research (Liu et al., J Anal Appl Pyrol 63:303–325, 2002), the pseudo bi-component separated-stage model (PBSM) was suggested for the kinetic analysis on the decomposition of lignocellulosic materials in air at relatively lower heating rates. As a continuing work, this paper is intended to investigate the applicability of PBSM at different heating rates by experimental analyses. Decomposition of oil tea wood has been studied by means of non-isothermal thermogravimetric analysis in air atmosphere at 10–25 K min⁻¹ heating rates. A two-step parallel reaction kinetic model is used to optimize the kinetic parameters of these materials in air. Meanwhile, an improved PBSM is developed to describe the thermal degradation process of oil tea wood. Furthermore, a comparison between the kinetic results of parallel model and PBSM reveals realistic applicability of PBSM. It is concluded that the PBSM has relatively high accuracy for the first decomposition step in the lower temperature range, while fails to predict the thermal decomposition behavior in the char oxidative process which occurs in the higher temperature range.     

Phase distribution of the products of radiation and postradiation distillation of cellulose

A comparison of the postradiation dry distillation of cellulose and its distillation in the mode of electron-beam radiation heating has shown that irradiation reduces the yield of char and water. Preirradiation of cellulose at doses of 0.2–2.2 MGy stimulates a monotonic increase in the proportion of total organic products in the condensate distilled off during postradiation dry distillation, reducing the proportion of water by one third. Effective distillation of cellulose in the radiation heating mode is observed at a dose rate above ∼1 kGy/s. The condensate distilled off at 1.5–2.5 kGy/s is composed of organic compounds by ∼90% and is characterized by a high density (up to 1.33 g/cm³) and a high refractive index (up to 1.4690).     

Thermal stability of acrylonitrile/chlorosulphonated polyethylene rubber blend

The properties of chlorosulphonated polyethylene (CSM) rubber, acrylonitrile rubber (NBR) and their blend (50/50 w/w) were studied. Fourier transform infrared (FTIR) studies supported that CSM/NBR rubber blend is self curable, when cross-linking takes place between acrylonitrile groups of NBR and –SO₂Cl groups or in situ generated allyl chloride moieties of CSM. The thermal stability of vulcanizates was analyzed in nitrogen by thermogravimetry. It was found that the initial degradation temperature of elastomer based on CSM rubber is lower than of pure NBR rubber. By adding NBR to CSM rubbers, the degradation temperature of crosslinked material increased, indicating higher thermal stability. The activation energy for the degradation are determined using the Arrhenius equation The activation energies for the rubber blends are higher than for elastomers based on pure rubbers. It was found that the mass loss of the blends at any temperature was between those of the pure rubbers. The differential scanning calorimetry (DSC) was used for the glass transition temperature determination. It is estimated thermodynamic immiscibility of NBR/CSM blend based on noticed two different glass transition temperatures, corresponding to CSM and NBR rubbers.     

Thermal Degradation of Natural Polymers

The thermal degradation of sodium hyaluronate, xanthan and methylcellulose was evaluated by thermogravimetric and infrared analysis. Kinetic parameters such as activation energy and pre-exponential factor were determined considering the Ozawa and Freeman–Carroll methods. The results suggest changes in the degradation mechanism with the fraction of mass loss for both the studied polysaccharides. The activation energy values determined by the Freeman–Carroll method are higher than those obtained by the Ozawa method under the same conditions, probably because in the first method a first order reaction was assumed and the thermal history effects were eliminated since only one TG curve was used to determine the kinetic parameters. Low thermal stability was observed for polyanions e.g. sodium hyaluronate (Na-Hy) and xanthan(XT) in comparison with methylcellulose (MC) which is a neutral polysaccharide. By infrared spectroscopy, it was observed that at low temperatures there occured only the scission of the exocyclic groups for both polysaccharides and that the scission of strong links in the backbone occurred at high temperatures, in agreement with the kinetic parameters determined for the degradation reaction. This revised version was published online in July 2006 with corrections to the Cover Date.     

Effect of starting xylose concentration on the microaerobic metabolism of Debaryomyces hansenii: the use of carbon material balances

Xylitol production by Debaryomyces hansenii NRRL Y-7426 was performed on synthetic medium varying the initial xylose concentration between 50 and 300 g/L. The experimental results of these tests were used to investigate the effect of substrate level on xylose consumption by this yeast. Satisfactory values of product yield on substrate (0.74–0.83 g/g) as well as volumetric productivity (0.481–0.694 g/L·h) were obtained over a wide range of xylose levels (90–200 g/L), while a worsening of kinetic parameters took place at higher concentration, likely due to a substrate inhibition phenomenon. The metabolic behavior of D. hansenii was studied, under these conditions, through a carbon material balance to estimate the fractions of xylose consumed by the cell for different activities (xylitol production, biomass growth, and respiration) during the lag, exponential, and stationary phases.     

Study of Kinetic Parameters of Reject/Clay/Composites by Thermal Analysis

Thermal degradation of granite and marble industry reject (GMIR), a red clay (RC)and their composites were studied by non-isothermal thermogravimetry (TG/DTG) in nitrogen atmosphere, differential thermal analysis (DTA) and derivative thermogravimetry(DTG) in air atmosphere. Measurements were made in the temperature range of 25–1000,25–1200 and 25–1400°C. The kinetic parameters were determined by Flynn–Wall and Kissinger's methods. The results indicate the absent dominance of one mechanism of reaction, and the composites show smaller values of kinetic parameters than GMIR or RC. This revised version was published online in July 2006 with corrections to the Cover Date.     

Chromium determination in sea water by electrothermal atomic absorption spectrometry using Zeeman effect background correction and a multi-injection technique

Electrothermal atomic absorption spectrometry (ETAAS) applying a Zeeman effect background correction system (ZEBC) and a tranverse heated atomizer was used to directly determine chromium in sea water. Calcium chloride (at a concentration of 20 mg L^–1) was applied as chemical modifier with optimum charring and atomization temperatures of 1600°C and 2000°C, respectively. The detection limit was 0.2 μg L^–1, by injecting 20 μL aliquot of sea water sample. This detection limit could be reduced further to 0.05 μg L^–1, using multiple injections (injection of five 20 μL aliquot of sea water). The accuracy of the methods developed were confirmed by analyses of different certified reference materials. Finally, interferences from major and minor components of sea water are studied. Received: 20 February 1997 / Revised: 26 May 1997 / Accepted: 8 June 1997     

Study on the pyrolysis of Moroccan oil shale with poly (ethylene terephthalate)

Investigations into the pyrolytic behaviours of oil shale, poly (ethylene terephthalate) (PET) and their mixture have been conducted using a thermogravimetric analyzer. Experiments were carried out dynamically by increasing the temperature from 298 to 1,273 K with heating rates of 2–100 K/min under a nitrogen atmosphere. Discrepancies between the experimental and calculated TG/DTG profiles were considered as a measurement of the extent of interactions occurring on co-pyrolysis. The maximum degradation temperature of each component in the mixture was higher than those the individual components; thus an increase in thermal stability was expected. The kinetic processing of thermogravimetric data was carried out using Flynn–Wall–Ozawa (FWO) method.     

Synthesis of mesoporous hydrophobic silica microspheres through a modified sol–emulsion–gel process

Mesoporous silica microspheres were synthesised through a sol–emulsion–gel process using Span 80 as the surfactant in silica sol/n-hexane water in oil emulsion system. Surface modification of the microspheres was done with trimethylchlorosilane to obtain hydrophobic silica microspheres. Various parameters related to the synthesis of microspheres, including concentration of surfactant and viscosities of sol were studied. The hydrophobicity (wettability), thermal stability, porosity, and morphological features were also investigated.     

Thermogravimetric Analysis and Thermal Ageing of Crosslinked Nitrile Rubber/Poly(ethylene-co-vinyl Acetate) Blends

The thermal behaviour of nitrile rubber (NBR)/poly(ethylene-co-vinyl acetate) (EVA) blends was studied by thermogravimetry. The effects of blend ratio, different crosslinking systems (sulphur, peroxide and mixed), various fillers (silica, clay and carbon black) and filler loading on the thermal properties were evaluated. It was found that the initial decomposition temperature increased with the addition of NBR to EVA. Among the various crosslinking systems studied, the peroxide cured system showed the highest initial decomposition temperature. This is associated with the high bond dissociation energy of C–C linkages. The addition of fillers improved the thermal stability of the blend. The mass loss at different temperatures and activation energy of degradation were also studied. The thermal ageing of these blends was carried out at 50 and 100°C for 72 h. It was seen that the properties are not affected by the mild ageing condition. Also, the peroxide cured system was found to exhibit better retention in properties, than other crosslinking systems. This revised version was published online in August 2006 with corrections to the Cover Date.     

Interpenetrating polymer network microspheres of hydroxy propyl methyl cellulose/poly (vinyl alcohol) for control release of ciprofloxacin hydrochloride

Hydroxypropylmethylcellulose and Poly (vinyl alcohol) blend microspheres were prepared by water in oil emulsion method and Ciprofloxacin Hydrochloride (CFHcl) was loaded into the interpenetrating polymer network (IPN) microspheres that are crosslinked with glutaraldehyde (GA). Blend microspheres were characterized using Fourier transform infrared Spectroscopy (FT-IR), Scanning electron microscopy, X-ray diffraction and Differential scanning Calorimetry. FTIR spectra results confirmed crosslinking reaction between –OH groups of Poly (vinyl alcohol) and –CHO groups of glutaraldehyde. Scanning electron micrograph showed the formation of plain, uniform and smooth microspheres. X-ray diffraction and thermal studies of plain and drug loaded microspheres indicates that the drug is dispersed at the molecular level in the IPN matrix. In vitro dissolution experiments were performed in pH 7.4 buffer medium at 35 °C which indicates a sustained and controlled release of ciprofloxacin hydrochloride (CFHcl) from the IPN microspheres up to 10 h.     

Adsorption–desorption phenomena of water vapor on a superabsorbent polymer partially crosslinked with potassium

The objective of this article is to study an amorphous superabsorbent polymer, which is able to absorb up to 300 times its weight of water. Adsorption–desorption phenomena of water vapor on the polymer as a function of temperature showed a reversibility of the adsorption–desorption phenomena. The thermal stability of the polymer at atmospheric pressure was also studied. The kinetic study of the desorption phenomena of water vapor on the polymer according to certain physicochemical parameters was discussed. The results showed that the kinetic regime governing the desorption phenomena of water vapor on the polymer is a process limited by a mono-dimensional diffusion for low masses and by a three-dimensional diffusion for high masses.     

Determination of Organophosphorus Pesticides in Soybean Oil, Peanut Oil and Sesame Oil by Low-Temperature Extraction and GC-FPD

A low-temperature clean-up method for residue determination was developed and validated for 14 organophosphorus pesticides in soybean oil, peanut oil and sesame oil by gas chromatography with flame photometric detector (GC-FPD). A different matrix influenced the response and retention time of pesticides. Hence matrix-matched calibration standards were used to counteract the matrix effect. The pesticide responses in blank samples of soybean oil, peanut oil and sesame oil were within the linear range of 0.02–1 mg kg⁻¹ and the correlation coefficients were higher than 0.9989. Average recoveries obtained from different oil samples at three fortified levels were higher than 50% with relative standard deviations (RSDs) of less than 15%. The limit of detections (LODs) of studied pesticides ranged from 2 to 5 μg kg⁻¹. Thirty-nine commercial samples were analyzed, and the results were confirmed by gas chromatography–mass spectrometry (GC–MS) in selective ion monitoring (SIM) mode.     

Development of novel elastomeric blends derived from chlorinated nitrile rubber and chlorinated ethylene propylene diene rubber

Chlorinated nitrile rubber (Cl-NBR) has been blended with chlorinated ethylene propylene diene rubber (Cl-EPDM) in different ratios by a conventional mill mixing method. The effect of the blend ratio on processing characteristics, mechanical properties (such as tensile and tear strength, elongation at break, hardness, abrasion resistance, heat build-up and resilience), structure, morphology, glass transition temperature (Tg), thermal stability, flame retardancy, oil resistance, AC conductivity, dielectric properties and transport behavior of petrol, diesel and kerosene were investigated. The shift in absorption bands of blends studied from FTIR spectra, single Tg from DSC analysis and decrease in amorphous nature from XRD showed the molecular miscibility in Cl-NBR/Cl-EPDM blends. SEM images showed the uniform mixing of both Cl-NBR and Cl-EPDM in a 50/50 blend ratio. The TGA curves indicated the better thermal stability of the polymer blend. The elongation at break, heat build-up, resilience and hardness of the polymer blend decreases with an increase in Cl-NBR content in the blend whereas the flame and oil resistance were increased with increase in Cl-NBR content. Among the polymer blends, the maximum torque, tensile strength, tear and abrasion resistance was obtained for the 50/50 blend ratio because of the effective interfacial interactions between the blend components. AC conductivity and dielectric properties of polymer blend increased with increase in the ratio of Cl-NBR in the blend. Different transport properties such as diffusion, permeation and sorption coefficient were measured with respect to nature of solvent and different blend ratios. Temperature dependence of diffusion was used to estimate the activation parameters and the mechanism of transport found to be anomalous.     

Fungicidal and bactericidal activity of metal diethyldithiocarbamate fungicides

Copper diethyldithiocarbamate, cadmium diethyldithiocarbamate, lead diethyldithiocarbamate, nickel diethyldithiocarbamate and zinc diethyldithiocarbamate have been synthesized. They have been characterized using TG, DTA, IR spectroscopy, X-ray and atomic absorption spectrophotometry. The thermal conversion of the compounds is 54.36–88% at 1000°C. Their solubility in sodium hydroxide, mineral acids, organic solvents, distilled water and salts solution has been measured. Fungicidal activity of the dithiocarbamates has been tested by well or cup diffusion method using five fungi species. Their activity has also been tested by broth dilution method using six bacterial species. Minimum Inhibitory Concentration (bactericidal) is 6.25–25.00 μg mL⁻¹.     

生物质与废轮胎共热解催化热解油蒸发过程及其动力学研究

采用热重微商(TG-DTG)法考察生物质稻壳与废轮胎共热解经催化与非催化热解油的热失重行为,并同0#柴油的热失重行为进行了比较;同时采用Achar微分法和Coats-Redfern积分法对热解油热失重蒸发过程的蒸发热进行了计算,并结合Satava和Bagchi法确定了热失重蒸发过程的机理函数, 建立了0#柴油和在催化与非催化条件下得到的热解油蒸发过程的动力学方程,得出了在催化与非催化条件下热解油热失重过程的机理函数,其动力学方程为dα/dt=Ae-△vapH/RT(1-TBX〗α)2;而0#柴油的热失重蒸发过程动力学方程为dα/dt=1.5Ae-△vapH/RT(1-α)2/3\[1-(1-α)1/3\]-1。蒸发热的顺序由大到小依次为,柴油＞非催化热解油＞SBA-15热解油＞MCM-41热解油。结果表明,通过建立的模型函数得到的蒸发热与实验值非常接近。催化剂SBA-15和MCM-41的存在对降低高沸点馏分的物质具有一定作用,而SBA-15催化作用强于MCM-41。     

Characterization and kinetic study of sunflower oil and biodiesel

In this study, the physico-chemistry characterization and kinetic study of the thermal decomposition of sunflower oil and its biodiesel were carried out. Sunflower biodiesel was synthesized by the methanol route and basic homogeneous catalysis. The physicochemical characterization of the sunflower oil and biodiesel were performed according to standards set out in the ANP resolution, and both are in accordance to the specifications. The chromatographic analysis was obtained by GC-FID. The yield of conversion of 97.4 wt% of sunflower oil in methyl esters confirms the efficiency of the conversion of the fatty acids into esters. The thermal analysis was performed on a thermobalance, using heating rates of 5, 10, and 20 °C min⁻¹. In these three rates, we observed a single well-defined step of mass loss that describes the volatilization and decomposition of the sunflower oil and the biodiesel. The kinetic study was performed using equations of approximation and integration methods such as Coats–Redfern, Van Krevelen, and Horowitz–Metzger. The kinetic parameters reaction order (n) and apparent activation energy (E _a), obtained by applying these method were correlated.     

Thermal behaviourof complexes of antipyrine derivatives Part III.

The thermal behaviour of the mixed-ligand complexes of cobalt(II) and copper(I) ions with antipyrine derivatives of 1,2-ethanediamine or piperazine (BAMP and TAMEN), with water and with 2-mercapto-benzothiazole (Hmbt) was investigated. The complexes contain 2-mercaptobenzothiazole (Hmbt, in the case of cobalt(II) ion) or dimercaptobenzothiazine (mbt–mbt, in the case of copper(I) ion) molecules as ligands and perchlorate (ClO₄^–) or thiocyanate (SCN – ) ion as counterion. By heating, water and ligands release the solid phase at lower temperature. At higher temperatures process of different organic reactions of ligands (e.g. polymerization, polycondensation) could be suggested to interpret the relative high final mass values.