Efecto de solvente sobre la descomposición térmica de trans-3,6-dimetil-3,6-difenil-1,2,4,5-tetraoxaciclohexano en solución

The thermal decomposition reaction of trans-3,6-dimethyl-3,6-diphenyl-1,2,4,5-tetraoxacyclohexane (acetophenone cyclic diperoxide, DPAF), in different solvents (methanol, 1,4-dioxane, acetonitrile and 2-propanol/benzene mixtures) in the initial concentration and temperature ranges of (4.2-10.5) x 10-3 M and 140.0 to 185.0 ºC, respectively, follows a pseudo first order kinetic law up to at least 70% DPAF conversion. An important solvent effect on the rate constant values, activation parameters (DH# and DS#) and reaction products obtained in different solvents is detected, showing that the reaction is accelerated in alcohols.

Decomposição térmica de complexos de Zn e Cd com isomaleonitriladitiolato (imnt)

Thermal decomposition of [Bu4N]2[Zn(imnt)2] and [M(NH3)2(imnt)] complexes with M = Zn and Cd, and imnt = (bis 1,1-dicyanoethylene-2,2 dithiolate) in inert atmosphere was investigated by thermogravimetric analysis (TG) and differential scanning calorimetry (DSC). Pyrolysis studies at different temperatures, 300, 400, 500, and 600 ºC, in N2 atmosphere were performed and the products were characterized by X-ray diffraction (XRD), infrared and Raman spectroscopy, and scanning electron microscopy (SEM). The products were identified as sulfide sub-micron particles, along with amorphous carbon. Particle sizes estimated by SEM were ca. 50 nm for the cationic complexes and 500 nm for the neutral complexes.

Caracterização dos produtos líquidos e do carvão da pirólise de serragem de eucalipto

This study proposes the low temperature pyrolysis as an alternative conversion process for residual biomass and for obtaining gaseous, liquid and solid chemical feedstocks. Using a bench electrical pyrolysis oven, four product fractions from eucalyptus sawdust were obtained: a gaseous one, two liquid (aqueous and oily), and a solid residue (char). These products were characterized by different analytical methods. The liquid fractions showed themselves as potential sources for input chemicals. The residual char revealed appreciable adsorption capability. The process demonstrated good efficiency, generating at least two fractions of great industrial interest: bio oil and char.

Análise térmica aplicada ao estudo de materiais energéticos

This paper shows different aspects related to the application of different thermal analysis techniques in the study of energetic materials. The criteria used to choose the best technique and an exact approach to adjust the experimental data with a proper model are here discussed. The paper shows how to use the different thermal analysis results to help develop new compounds, to study the stability of some energetic materials and their compatibility, and the conditions necessary for a secure storing environment.

Decomposição térmica de espumas de poliuretano para fabricação de vitrocerâmica celular de Li2O-ZrO2-SiO2-Al2O3 (LZSA)

Characterization of the thermal decomposition of polyurethane (PUR) foams was performed by Fourier-transformed infrared (FT-IR) spectroscopy and thermogravimetric analysis (TGA). Three main weight loss paths were observed by TGA, the residue being lower than 3 wt.% for 3 different PUR foams analyzed. FT-IR spectra indicated CO2, CO, NH3 and isocyanides as main decomposition products. PUR foams of different cell sizes were immersed in a slurry of the parent glass ceramic of composition Li2O-ZrO2-SiO2-Al 2O3 (LZSA) and submitted to heat treatment. The LZSA cellular glass ceramics obtained after sintering and crystallization resembled the original morphology of the PUR foams.

Biomateriais: deposição de hidroxiapatita sobre superfície de Ti-cp modificada por aspersão térmica

The osseointegrated titanium implants are reliable and safe alternatives to treatments for long periods of time. For surface modification, thermal aspersion of TiO2 was used. The samples with and without TiO2 were treated with NaOH and SBF in order to obtain a layer of HA. Characterization was done by SEM and FTIR. The images of HA obtained by SEM show a uniform morphology and a porous structure with spherical particles. The IR spectra show that the surface of Ticp/ TiO2 is more favorable for the HA deposit, as can be seen by the increase of the crystalline structure and the very intense and defined bands of the OH group of HA that is verified about 3571 and 630 cm-1. Thus the Ticp/ TiO2 surface presents a satisfactory nucleation of HA when compared to Ticp.

Estudo da decomposição térmica de propelente sólido compósito de baixa emissão de fumaça

The thermal decomposition of hydroxyl-terminated polybutadiene (HTPB)/ammonium nitrate (AN) based propellants, so called smokeless formulations, and raw materials were investigated by differential scanning calorimetry (DSC) and thermogravimetry (TG). The thermoanalytical profile of different components and of propellant were evaluated and the Arrhenius parameters for the thermal decomposition of the propellant sample were determined by the Ozawa method. The kinetic parameters of the thermal decomposition of propellant samples were determined by DSC measurements. The values obtained for activation energy (Ea) and pre-exponential factor were 163 kJ mol-1 and 1.94x10(6) min-1.

A pirólise como técnica analítica

In this paper historical aspects of analytical pyrolysis, the equipment used, the fundamentals and the mechanisms of pyrolysis of different polymeric materials are discussed. The latest work on analytical pyrolysis applied to various types of synthetic and natural samples is reviewed. Current applications of this technique that are discussed include identification of microorganisms, analysis of trace compounds by forensic laboratories, investigation of food and agricultural products, study of the chemical composition of wood, authentication and conservation of artworks, and the study of environmental and geochemical samples.

Síntese, caracterização e análise térmica dos sais de lítio, sódio e potássio do ácido palmítico e do seu éster etílico

Alkaline salts of the palmitic acid were synthesized and characterized from aqueous and ethanolic medium. The salts were characterized by elemental analysis (EA) and infrared spectroscopy (IR). EA and IR, being its synthesis comproved, also characterized the ethyl palmitate. All the salts and the ester were submitted to thermal analysis using thermogravimetry (TG), and differential thermal analysis (DTA) in the temperature ranging from room to 700 ºC under air dynamic atmosphere. Differential scanning calorimetry (DSC) measurements were taken from -90 ºC up to temperatures close to the starting of the decomposition temperature, determined by thermogravimetry, using heating and cooling cycles.

Determinação da relação siringila/guaiacila da lignina em madeiras de eucalipto por pirólise acoplada à cromatografia gasosa e espectrometria de massas (PI CG/EM)

The use of analytical pyrolysis combined with gas chromatography/mass spectrometry (Py-GC/MS) to determine the syringyl/guaiacyl ratio (S/G) in lignins from Eucalyptus spp woods was investigated. Sample of E. grandis and "E. urograndis" wood, with and without extractives, were subjected to pyrolysis from 300 ºC to 600 ºC. The products that results from pyrolysis were identified by mass spectrometry and the S/G ratio was determined based on the areas of the peaks corresponding to the guaiacyl and syringyl derivatives. The best S/G estimation is achieved when pyrolysis is carried out at 550 ºC. Extractives and carbohydrate present in the woods do not interfere with the results.

Estudo cinético da decomposição térmica do pentaeretritol-tetranitrado (PETN)

The pentaerythritol-tetranitrate (PETN) is a nitroether used in explosives and propellant formulations. Due to its suitable properties, PETN is used in booster manufacture. Knowing the thermal decomposition behavior of an energetic material is very important for storage and manipulation, and the purpose of this work is to study the kinetic parameters of the decomposition of PETN, compare the results with literature data and to study the decomposition activation energy differences between two crystalline forms of PETN (tetragonal and needle) by means of differential scanning calorimetry (DSC). Fourier transform infrared spectroscopy (FT-IR) is used to study the two crystalline forms.

Uso da cinza da casca do arroz (CCA) obtida da geração de energia térmica como adsorvente de Zn(II) em soluções aquosas

The removal study was conducted using 1.00 g of the rice husk ash (RHA) and 20.0 mL solution with concentrations in the range of 10-1000 mg/L of Zn(II). The influence of contact time, initial metal concentration, agitation and pH of the removal process was investigated. Superior removals to 95% were obtained at the end of 24 h of contact. The agitation increased in 20% the removal of Zn(II), being needed only 5 min to reach the equilibrium. The adsorption process was studied by the models of isotherms of Langmuir, Freundlich and BET, obtaining results of R L and 1/n for a process favorable of adsorption. BET isotherm best represents the equilibrium adsorption. The results showed that the RHA has the largest capacity and affinity for the removal of Zn(II).

Argilas como catalisadores verdes na esterificação do colesterol: caracterização espectroscópica e identificação de polimorfos por métodos de análise térmica. Uma proposta laboratorial interdisciplinar para o 1º ciclo universitário

A laboratory experiment that enables the professor to introduce the problematic of sustainable development in pharmaceutical chemistry to undergraduate students is proposed, using a simple synthetic procedure. Cholesteryl acetate is prepared by the esterification of cholesterol using Montmorillonite K10 as heterogeneous catalyst. Cholesterol and cholesteryl acetate are characterized by spectroscopic (¹H RMN, 13C RMN, FTIR) and thermal analysis techniques. The thermal methods are used to introduce the concepts of polymorphism and the nature of mesophases.

Avaliação de biocombustível derivado do bio-óleo obtido por pirólise rápida de biomassa lignocelulósica como aditivo para gasolina

A biofuel was prepared from acid aqueous fraction (pH = 2) of bio-oil produced by fast pyrolysis (Bioware Technology) of lignocellulosic biomass (sugar cane residue) and tested in blends (2, 5, 10 e 20% v/v) with gasoline type C (common) marketed in Brazil. The specification tests made in the Refinery President Getúlio Vargas (PETROBRAS) showed increasing in the octane number (MON) and antiknock index (AKI) with reduction in the residue generation during the combustion. The physicochemical characteristics of the biofuel were similar that combustible alcohol allowing its use as gasoline additive.

Análise térmica aplicada à caracterização da sinvastatina em formulações farmacêuticas

Thermogravimetry (TG) and differential scanning calorimetry (DSC) are used in pharmaceutical studies for drugs characterization, purity, formulations compatibility, polymorphism identification, stability evaluation, and thermal decomposition of drugs and pharmaceutical formulations. Simvastatin showed fusion at 138.5 ºC and thermal stability up to 248 ºC. Simvastatin was incompatible with preservative excipient butylhydroxyanisole (BHA) performing a process of crystal amorphization. The drug showed morphological polymorphism, where it has the same unit cell but with different crystal habits according to the recrystallization solvent.