Thermal decomposition products of cellulose

Untreated and flame-retardant-treated cellulose were thermally decomposed under vacuum and the products were quantitatively analyzed by gas chromatography. An unidentified product at a retention index of 2270 (between 5-methylfurfural and 5-hydroxymethylfurfural), α- and β-D -glucose, and a group of “dimers” that have not been reported previously were found in this study. The identification of this unknown product should assist in studies on the thermal decomposition of cellulose and further the understanding of the mechanism of flame retardancy.     

Thermal decomposition of cellulose ethers

The thermostability and thermal decomposition kinetics of methyl cellulose (MC), ethyl cellulose (EC), carboxymethyl cellulose (CMC), hydroxyethyl cellulose (HEC), and hydroxypropyl–methyl cellulose (HPMC) were characterized in nitrogen and air by thermogravimetry (TG). Various methods of kinetic analysis were compared in case of thermal degradation of the five cellulose ethers. The initial decomposition temperature (T_d), temperature at the maximum decomposition rate (T_dm), activation energy (E), decomposition reaction order (n), and pre-exponential factor (Z) of the five cellulose ethers were evaluated from common TG curves and high-resolution TG curves obtained experimentally. The decomposition reactions in nitrogen were found to be of first order for MC, EC, and HPMC with the average E and ln Z values of 135 kJ/mol and 25 min⁻¹, although there were slight differences depending on the analytical methods used. The thermostability of cellulose ethers in air is substantially lower than in nitrogen, and the decomposition mechanism is more complex. The respective average E, n, ln Z values for HEC in nitrogen/air were found to be 105/50 kJ/mol, 2.7/0.5, and 22/8.3 min⁻¹, from constant heating rate TG method. The respective average E, n, and ln Z values for three cellulose ethers (EC/MC/HPMC) in air are 123/144/147 kJ/mol, 2.0/1.8/2.2, 24/28/28 min⁻¹ by using high-resolution TG technique. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2927–2936, 1999     

Thermal decomposition and combustion of biofuels

The results concerning the thermal decomposition and combustion of hydrolytic lignin, spruce, and the organic components of wood in a fixed-bed reactor are reported. Data on the emitted gas components and fine particles were acquired. The formation of gas components from spruce exhibited a maximum in a temperature range of 430–450°C. This temperature range corresponds to the completion of the release of volatile substances and to the char oxidation. For the different test materials, the thermal decomposition and combustion processes were accompanied by the formation of a large amount of particles. Nanoparticles having a diameter below 0.1 μm dominate.     

Thermal decomposition behavior of miscible cellulose/synthetic polymer blends

The thermal decomposition behavior of the miscible cellulosic blends cellulose(Cell)/poly(N-vinyl-2-pyrrolidone) (PVP), Cell/poly(ethylene glycol) (PEG), and Cell/poly(vinyl alcohol) (PVA) was investigated by thermogravimetry. The thermal stability of Cell in the Cell/PVP blends decreased but that of Cell in the Cell/PEG and Cell/PVA blends was hardly influenced. The thermal stability of synthetic polymers in the blends was little affected. The difference in thermal decomposition behavior was correlated to the difference in miscibility. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2133–2137, 1998     

Thermal degradation of cellulose and cellulose esters

Cellulose, cellulose diacetate (CDA), cellulose triacetate (CTA), cellulose nitrate (CN), and cellulose phosphate (CP) were subjected to dynamic thermogravimetry in nitrogen and air. The thermostability of the cellulose and its esters was estimated, taking into account the values of initial thermal degradation temperature T_d, the temperature at the maximum degradation rate T_dm, and char yield at 400°C. The results show that these polymers may be arranged in the following order of increasing thermostability: CN < CP < regenerated cellulose < filter cotton < CDA < CTA. The activation energy (E), order (n), and frequency factor (Z) of their degradation reactions were obtained following the Friedman, Chang, Coats–Redfern, Freeman–Carroll, and Kissinger methods. The dependence of T_d, T_dm, E, n, Ln Z, and char yield at 400°C on molecular weight and test atmosphere is also discussed. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68:293–304, 1998     

Thermal chemistry and decomposition behaviors of energetic materials with trimerizing furoxan skeleton

Trimerizing furoxans are ideal molecular skeletons for the construction of high energetic substances due to their compact structures and high enthalpy of formations. To explore and compare the thermal behaviors of energetic materials with tandem trimerizing furoxan molecular skeleton, we reported the first systematic research on the thermochemical behaviors and decomposition mechanism of 3,4-bis(3-fluorodinitromethylfuroxan-4-yl)furoxan (BFTF), 3,4-bis(3-cyanofurazan)furazan oxide (BCTFO) and benzotrifuroxan (BTF). According to the research results of the DSC-TG experiments, both the substituted furoxan based energetic compounds (BCTFO and BFTF) exhibited low melting points and complicated thermal decomposition behaviors around 240 °C, while the melting point of unsubstituted furoxan (BTF) was much higher. Their detailed decomposition mechanisms were proposed based on the experimental results through tandem techniques including in-situ FTIR spectroscopy method and DSC-TG-FTIR-MS quadruple technology, which indicated that the cleavage of substituent would trigger the decompositions of BFTF and the decomposition of trimerizing furoxan skeletons almost synchronous occurrence with substituents in BCTFO. The self-oxidation-reduction of the linear and annular trimerizing furoxans lead to similar decomposition fragmented small molecule products.     

Thermal and mechanical properties of polypropylene nanocomposite materials reinforced with cellulose nano whiskers

We use polypropylene (PP, an apolar polymer) and cellulose nano whiskers (CNW, a polar material) to produce nano polymer composites with enhanced mechanical and thermal properties. To improve compatibility, maleic anhydride grafted PP has also been used as a coupling agent. To enhance the uniform distribution of CNW in the composite, the matrix polymer is dissolved in toluene, and sonification and magnetic stirring are applied. Good film transparency indicates uniform CNW dispersion, but CNW domains in the composite film observed under an scanning electron microscope may indicate slight agglomeration of CNW in the composite film. The tensile strength of the composite compared with neat PP improves by 70–80% with the addition of CNW. The crystallinity has also been improved by about 50% in the CNW reinforced samples. As the content of CNW increases, the composite exhibits higher thermal degradation temperature, higher hydrophilicity, and higher thermal conductivity. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Thermal degradation studies of cellulose phosphates and cellulose thiophosphates

The thermal degradation of cellulose, cellulose phosphates, and cellulose thiophosphates was studied by differential thermal analysis, dynamic thermogravimetry, and derivative thermogravimetry from ambient temperature up to 750°C. Various thermodynamic parameters for different stages of thermal degradation of cellulose and its derivatives have been obtained following the methods of Broido, and Freeman and Carroll. Infrared spectra of thermally degraded samples were obtained. The data were analyzed in an effort to obtain more information concerning the flame-retardant mechanisms of cellulose phosphates and cellulose thiophosphates. Lower values of decomposition temperatures and activation energies of decomposition and higher char yields of cellulose phosphates as compared to cellulose lead to the conclusion that cellulose phosphorus esters are good flame retardants, and this property is retained even when these esters were subjected to ion exchange by Na⁺ and K⁺ ions. However, with the introduction of sulphur atoms, there was some decrease in this property.     

A comparative study of the thermal decomposition of cellulose and cellulose triacetate

Conclusions A comparative study has been made of the thermal decomposition of cellulose and of cellulose acetates having various degrees of polymerization, and also of specimens regenerated from nonaqueous solutions.The effect of the solvent on reducing the effective energy of activation of thermal decomposition on transition from the starting samples of cellulose and its derivatives to specimens regenerated from nonaqueous solutions has been revealed.It has been found that the degree of polymerization exerts no significant effect on the temperature of thermal decomposition.Translated from Khimicheskie Volokna, No. 4, pp. 28–29, July–August, 1986.     

Thermal decomposition of polystyrene

Kinetic studies on the decomposition of polystyrene samples with molecular weights ranging from 900 to 1.8 × 10⁶ have been carried out making use of the differential thermogravimetric and differential scanning calorimetric techniques. Changes in molecular weight distributions with decomposition, at different temperatures or times, have been studied by gel permeation chromatography. This technique was likewise used to carry out component splitting of the undecomposed polymer samples. These components have been shown to break down statistically primarily by a process of random scissions yielding lower molecular weight products. The major portion of the observed weight loss, by the volatilization of small chain segments, is attributed to a rapid and complete depolymerization of chains. These interpretations are based on changes in polydispersity occurring during the decompositions. Similar components, decomposing in a different manner but under identical operating conditions, are suspected of being different stereoregular forms of the polymer. The order of reaction as computed from the method of Freeman and Carroll has been found to be zero for random scissions and one for the process of depolymerization. The activation energy computed by the method of Coats and Redfern was found to increase with molecular weight reaching a maximum value in the 10⁵ molecular weight range.     

Thermal decomposition of tricaproin

Tricaproin was used as model system to study thermal decomposition of simple triglycerides. The tricaproin samples were pyrolyzed under three different conditions: at 250 C for 1 hr, 270 C for 1 hr and 270 C for 15 hr. Hydrocarbons, acrolein, methyl hexanoate, hexanal, hexanoic acid, 6-undecanone, 2-oxoheptyl hexanoate, propanediol dicaproate, propenediol dicaproate, oxopropanediol dicaproate and dicaproin were identified. Mechanisms involving both free radical and nonfree radical reactions were proposed for the formation of these compounds.     

Thermal decomposition of asphaltenes

The thermal decomposition of Athabasca asphaltene at relatively low (< 350 °C) temperatures is believed to proceed by elimination of groups situated on peripheral sites of the asphaltene. More severe degradation of the asphaltene structure does not occur until elevated (> 350 °C) temperatures are attained.     

Acid decomposition of highly substituted cellulose xanthate

The acid decomposition of cellulose xanthate was studied spectrophotometrically with a stopped-flow technique. The reactivity of the xanthate groups was found to decrease with an increase in the viscose γ number. This was explained by the occurrence of stabilizing interactions exerted between closely spaced xanthate groups. With uniformly substituted xanthates this effect began to be noticeable at γ numbers above 50. At higher γ numbers partial decomposition by acid resulted in an uneven distribution of xanthate groups along the chain molecules. Another feature of cellulose xanthate is that the degree of dissociation at constant acid concentration decreases with an increase in the γ number. This can be ascribed to variations in the dielectric constant inside the macromolecules.     

Pyrolysis and combustion of cellulose. VII. Thermal analysis of the phosphorylation of cellulose and model carbohydrates during pyrolsis in the presence of aromatic phosphates and phosphoramides

Thermal gravimetric analysis, differential scanning calorimetry, and derivative thermal gravimetric analysis were utilized to characterize the thermal interactions between cellulose, 1-6, anhydro β-D-glucopyranoside, and D-glucose and model phosphate and phosphoramide flame retardants. The phosphoramides induced higher char yields than the phosphates during the pyrolysis of the mixtures of carbohydrates and organophosphorus compounds. Exothermic reactions attributed to phosphorylation and char formation were observed with each of the phosphoramide/carbohydrate mixtures and were absent with the phosphates. The individual phosphorus compounds studied showed similar thermal behavior with each of the carbohydrates indicating that the mode of interaction for these mixtures was similar. Isothermal gravimetric analysis of the organophosphorus/carbohydrate mixtures was used to measure the rate of decomposition weight loss from isothermal conditions. This weight loss was used as an indication of rate of fuel formation. The kinetics observed for these measurements indicated that the phosphoramide mixtures underwent a rapid weight loss to a final char with an effective E_act of about 55 kcal/mol while the phosphate mixtures exhibited effective E_act′s for decomposition lower than those observed for the pure carbohydrates. Mixtures of glucose with selcted arylphosphoramide esters were pyrolysed in order to determine the effect of lability of the leaving group on char formation. Gas chromatographic analysis of the pyrolysis products indicated that phenol was the favored leaving group in comparison with aniline units, but char promotion appeared to be dependent on the number of P-N bonds present in the original phosphoramide. Electron spectroscopy for chemical analysis indicated that chemically similar chars were obtained from the different organophosphorus/carbohydrate combinations.     

Thermal decomposition and ignition of coal

A study of the thermal decomposition and ignition of coal as functions of pelletizing pressure and dwell time has revealed that: (1) ignition and thermal behaviour are related to the apparent density of the pelletized coal; (2) for a given apparent density of pelletized coal, the ignition temperature is related to the rate constants of thermal decomposition. Isothermal decomposition in air at 550 °C has been shown to fit the Avrami-Erofeev equation for three-dimensional growth of nuclei.