On the thermal degradation of cellulose in cotton fibers

Thermal decomposition of cellulose has been widely studied for the past several years. It has been reported that the source of cellulose and its composition greatly affect its pyrolysis. One of the most widely used analytical tools for the study of cellulose pyrolysis is thermogravimetric (TG) analysis. Several model-fitting methods have been employed to study cellulose pyrolysis kinetics. An alternative to the model-fitting approach is the so-called model-free method developed by Vyazovkin. This isoconversional technique calculates the activation energy as a function of the degree of the conversion. In this article, the pyrolysis of cellulose in cotton fibers compared to microcrystalline cellulose (Avicel, PH 105) was investigated. TG curves were acquired as a function of the heating rates (4, 5, 8, 10, and 16 °C min^?1) and the model-free method was used to analyze the data. Activation energies of cotton fibers and Avicel were obtained, and compared to the data reported in the literature. In addition, models for isothermal decomposition were calculated and compared with experimental data at the same temperature.     

The effect of metal ions on thermal oxidative degradation of cotton cellulose ammonium phosphate

The thermal oxidative degradation of cellulose, and of cellulose ammonium phosphate and its metal complexes products were studied by thermal analysis, infrared spectroscopy and elemental analysis. The temperature of decomposition was lower for metal complexes of cellulose ammonium phosphate than those samples untreated by metal ions and the values of char yield were greater for treated cellulose than those untreated. This indicates the metal ions can catalyze the reaction of degradation and form more char. This revised version was published online in August 2006 with corrections to the Cover Date.     

Application of infrared spectroscopy and thermal analysis to the examination of the degradation of cotton fibers

The potential of infrared spectroscopy and thermal analysis when determining the degree of damage of historical textiles was investigated. Model samples of artificially aged cotton were used. The results obtained by the two instrumental methods were correlated with the mean degree of polymerization of cellulose and with their tensile strength. Neither of the two instrumental methods on its own was found suitable for the determination of the degree of damage of cellulose-based textile materials. They should be combined with other methods serving to determine the extent of damage of cellulose-based textile materials, e.g. via the degree of polymerization of cellulose.     

The potential of ferric pyrophosphate for influencing the thermal degradation of cotton fabrics

Ferric pyrophosphate (FePP) was used as additive to study its synergistic effect of thermal degradation on cotton fabrics. The microscale combustion calorimetry (MCC), thermogravimetric analysis (TG), Raman spectroscopy and Real Time Fourier transform infrared spectroscopy (RT-FTIR) were utilized to evaluate the synergistic effects of FePP on cotton/DIA. The MCC results revealed that cotton/DIA/FePP generated less combustion heat during heating than that of cotton/DIA. TG results showed that presence of FePP improved the thermal stability of materials. The Raman spectroscopy test showed that FePP can ameliorate the structural organization level of the carbon and the graphitization degree of the char. RT-FTIR data revealed the mechanism of the influence of FePP, which can catalyze the break of the flame retardant as well as promote the char forming.     

Boundary effect on the thermal degradation of copolymers

The mechanism of thermal degradation of vinyl-type copolymers at high temperatures was investigated theoretically and experimentally. A parameter β was proposed to account for the boundary effect. Values of β for acrylonitrile–styrene and methyl methacrylate–styrene copolymers were determined experimentally. It was ascertained that the value of β was independent of the distribution of monomer sequence lengths in a copolymer, but dependent on the pyrolysis temperature and on the nature of the copolymer. The boundary effect is attributed to differences in the dissociation energies of C? C bonds connecting terminal monomer units to adjacent monomer units in copolymer chain radicals.     

The effect of fullerene on the resistance to thermal degradation of polymers with different degradation processes

Investigations were made about the effect of fullerene (C₆₀) on the resistance to thermal degradation of high density polyethylene (HDPE), polypropylene (PP), polymethyl methacrylate (PMMA), and bisphenol A polycarbonate (PC) matrix by using thermogravimetric analysis coupled to Fourier transform infrared spectroscopy. The results showed that the influences of C₆₀ on the resistance to the thermal degradation of different polymers were dependent on their thermal degradation mechanism. The resistance to the thermal degradation of HDPE, PP, and PMMA were improved with the addition of C₆₀, especially for HDPE matrix, which indicated that the radical trapping played a dominant role. PP and PMMA released more gaseous products at high temperature by the random scission of C–C backbone; owing to the lower bond dissociation energy of C–C in the backbone for the existence of side chains. Meanwhile, the steric hindrance of side chains also made the radicals hard to recombine with each other and accelerated the random scission, leading to the less effect on the resistance to the thermal degradation of PP and PMMA. However, few changes of resistance to the thermal degradation were found in PC matrix with the addition of C₆₀ for its non-radical degradation mechanism.     

The effect of zinc stearate on thermal degradation of paraffin wax

In this research, the effects of zinc stearate addition on paraffin wax degradation were investigated by differential scanning calorimetry (DSC) and thermogravimetry (TG). The apparent activation energies of wax decomposition in nitrogen and air atmospheres were determined as 76 and 37 kJ mol⁻¹, respectively applying Kissinger method to TG data. The degradation rate constants of paraffin containing zinc stearate (0.1–0.5%) were found to be almost two times greater than that of paraffin only in air atmosphere. However, zinc stearate did not affect the rate constants in nitrogen significantly.     

The effect of ammonium polyphosphate on the mechanism of thermal degradation of polyureas

The thermal decomposition of structurally related N–H and N,N′-disubstituted polyureas (Table I) and their mixtures with ammonium polyphosphate (APP) was investigated by thermogravimetry (TG) and direct pyrolysis in a mass spectrometer (MS). The N–H polyureas (IV–VI) undergo a quantitative depolymerization process with the formation of oligomers with amine and isocyanate end groups. In contrast, the thermal degradation of the N,N′-disubstituted polyureas (I–III) proceeds by a different mechanism as a function of their chemical structure. The addition of APP lowers the thermal stability of the N,N′-disubstituted polyureas, whereas that of the N–H polyureas is unaltered. However, our data show that APP does not change the nature of the pyrolytic products. The destabilizing effect of the additive can be attributed to the catalytic action of the acid species formed by its thermal decomposition.     

The effect of the chemical structure of chain ends on the thermal degradation of polystyrene

A set of polystyrenes of comparable molecular weight around 4000, prepared by anionic polymerisation, were end-capped with various structures. Their thermal degradation behaviour (weight loss kinetics, nature and amount of volatile by-products) is governed by the nature of the chain ends. Some features of the degradation mechanisms are discussed.     

The effect of zinc bromide on the thermal degradation of poly(vinyl acetate)

PVA normally degrades under vacuum at an appreciable rate at temperatures above 230°C. PVA and zinc bromide, unlike most polymer-additive systems, are compatible, giving transparent cast films from acetone solution. Even at a molar ratio of one ZnBr₂ molecule to ten VA units in the polymer, there is a considerable destabilisation of PVA, the threshold for acetic acid production being reduced to just over 100°C. Blends with various molar ratios have been studied, the maximum effect being observed at a 1:1 ratio of the components. No new degradation products are observed and it is concluded that the observed increase in the rate of deacetylation is due to weakening of the CO bonds attaching acetate groups to the polymer backbone as a result of complex formation between the carbonyl groups and zinc bromide. The mechanism of degradation of PVA is further discussed: this study provides additional support for the view that acetate radicals are involved.     

The effect of tin stabilizers on the thermal degradation of poly(vinyl chloride)

Simultaneous HCl evolution and spin-generation measurements were made on poly(vinyl chloride) (PVC) samples containing stabilizers of the type R_x Sn Y_4-x. It was found that tetrabutyltin and tributyltin laurate were better stabilizers than dibutyltin dilaurate. On the basis of the results, a mechanism for the stabilization of PVC by this class of compounds is proposed.     

Kinetic compensation effect in the thermal degradation of polymers

The kinetic study of thermal degradation takes into account the validity of the Arrhenius equation. From TG data, the activation energy,E _a and pre-exponential factor,A, are evaluated. These results are interpreted by using the kinetic compensation effect as basis. A linear correlation between In(A) andE _a is obtained in all cases studied. However, in a plot of the logarithm of the rate constant as a function of reciprocal temperature for the same series of reactions, the thermal oxidative degradations of Nylon-6 and PVC display a point of concurrence and one isokinetic temperature, whereas those of HIPS and PC do not. Therefore, in the thermal oxidative degradations of Nylon-6 and PVC a true compensation effect occurs, which could be related to the bulk properties of metal oxides, such as different valence states, whereas for other polymers it displays only an apparent compensation effect. This means that degradation is largely independent of the bulk properties of oxides, but may be related to the distribution of different kinds of active links in the polymer surface having different activation energies.     

The comparison of differences in flammability and thermal degradation between cotton fabrics treated with phosphoramidate derivatives

The effectiveness of a phosphoramidate tetraethyl piperazine‐1,4‐diyldiphosphoramidate (TEPP) as a flame retardant on cotton twill fabrics was compared with that of a previously studied diethyl 4‐methylpiperazin‐1‐ylphosphoramidate (DEPP). TEPP was formed in a reaction between two phosphonates and a piperazine then cotton twill fabrics were treated with TEPP at different levels of add‐on (2–19 wt%) and characterized using vertical flammability, limiting oxygen index, microscale combustion calorimetry, and thermogravimetric analysis methods. The results showed better flame retardancy and thermal behavior for TEPP fabrics when compared with DEPP fabrics. When the morphological structure of the formed char from the burned areas was examined by scanning electron microscopy, the results revealed a fairly insignificant difference in the mode of action between the two types of fabric. Copyright © 2014 John Wiley & Sons, Ltd.     

Investigation of water influence on coal based on thermal oxidative degradation kinetics

Journal of Thermal Analysis and Calorimetry - In order to further understand the effect of the water content on spontaneous combustion of coal, the thermal oxidative degradation kinetics of coals...     

A hint on the correlation between cellulose fibers polymerization degree and their thermal and thermo-oxidative degradation

The degree of polymerization is one of the main parameters reflecting cellulose ageing. Viscometry is a method frequently used for determination of cellulose fibers polymerization degree, however, sample preparation and viscosity measurement are demanding, time consuming and do not provide reproducible results. In this study, the relationship between polymerization degree of cellulose fibers obtained by viscosity measurement and their degradation parameters obtained by thermal analysis were investigated. Differential scanning calorimetry provided values of effective combustion heat and thermogravimetry (TG) was used for the determination of temperatures and associated mass losses during the cellulose degradation. Effective combustion heat did not show any correlation with degree of polymerization of investigated cotton fabrics. In contrast, results from TG suggested several promising nonlinear correlations which could be used as a hint to develop a method useful for quick determination of cotton fabrics polymerization degree. The most promising correlations with cellulose polymerization degree were found for both rates of thermal and thermo-oxidative degradations.     

The effect of water vapour pressure on the thermal dehydration of yttrium formate dihydrate

The kinetics of the thermal dehydration of yttrium formate dihydrate was studied by means of isothermal gravimetry under various water vapour pressures from 5×10^–4 to 8 torr. On the whole, the dehydration was described as the three dimensional phase boundary reaction, R₃. An unusual dependence of the rate of dehydration on the atmospheric water vapour pressure was observed: with increasing water vapour pressure, the rate increased at first, passed through a maximum, and then decreased gradually to a constant value. These phenomena were similar to the Smith-Topley effect. The mechanism of the phenomena can be described on the basis of the crystallinity of the dehydrated product phase.The authors wish to thank Mr. H. Minagawa of the Analytical Instrument Laboratory of Niigata University, for the X-ray diffraction measurements at high temperatures, and Mr. K. Hirata for help in the experimental work.     

Chemiluminescence during thermal degradation of sodium persulfate in the presence of terbium sulfate: 2. The effect of water of crystallization

An abnormally strong influence of water of crystallization on the intensity of chemiluminescence (CL) in the thermal degradation reaction of sodium persulfate in the presence of terbium(III) sulfate was revealed. As the water is driven off terbium sulfate Tb₂(SO₄)₃ · nH₂O (n= 8–0), the luminescence intensity and light sum increase. The maximum CL intensity for the completely dehydrated sample is 20 times higher and the light sum is two orders of magnitude greater than those of the crystal hydrate containing eight water molecules. It was found that the rise in the CL yield is due to an increase in the yield of excitation of the emitter *Tb(III), rather than the yield of its emission, with a change in the coordination environment.     

Study on the thermal degradation of high performance fibers by TG/FTIR and Py-GC/MS

The thermal degradation behaviors of Kevlar 49, Kevlar 129 (Poly(p-phenylene terephthamide), Nomex (polyisophthaloyl metaphenylene diamine), and PBO(poly(p-phenylene benzobisoxazole)) fibers were measured by TG/FTIR and Py-GC/MS. The characteristic temperatures of the fibers in air were obtained by TG. It indicated that the initial degradation temperature of the PBO is the highest. The initial degradation temperature of Nomex fiber is the lowest, but the end decomposition temperature of Nomex is the highest. The gases released by the pyrolysis in air were mainly CO₂, CO, H₂O, NO, and HCN, also containing a small amount of NH₃, and the absorption peaks of CO₂ were the strongest. The results of Py-GC/MS showed that CO₂ and benzene were the most pyrolysis fragment. With the change of pyrolysis temperature, the chromatogram and mass spectra results take a large variety. The pyrolysates can help us to study the pyrolysis process of high performance fibers.