Thermogravimetric Fourier Transform Infrared Spectroscopy of Hydrocarbon Fuel Residues

Although thermogravimetric analysis (TG) has become an indispensable tool for the analysis and characterization of materials, its scope is limited as no information is obtained about the qualitative aspects of the evolved gases during the thermal decomposition. For processes involving mass loss, a powerful technique to provide this missing information is Fourier transform infrared spectroscopy (FT-IR) in combination with TG. It supplies a comprehensive understanding of thermal events in a reliable and meaningful way as data are obtained from a single sample under the same conditions. The coupling TG/FT-IR is used in fuel analysis for the identification of residual volatiles, to determine their sequence of release and to resolve thermogravimetric curves. In this work, the usefulness of TG/FT-IR for characterizing middle distillate fuel residues is illustrated with some typical examples of recent application. A Bio-Rad FTS 25 FT-IR spectrometer coupled with a TA Instruments TGA 2950 thermogravimetric analyzer was used for data aquisition. The results obtained demonstrate the utility of this combined technique in determining the decomposition pathway of tarry materials at various stages of pyrolysis, thereby allowing new insights into the complex thermal behaviour of hydrocarbon residual systems. This revised version was published online in August 2006 with corrections to the Cover Date.     

Assessing the transfer of pesticides to the atmosphere during and after application. Development of a multiresidue method using adsorption on Tenax and thermal desorption-GC/MS

An air sampling and analytical method based on adsorption on porous polymer (Tenax TA) followed by automatic thermal desorption (ATD) and GC/MS analysis was developed for ten pesticides commonly used on major crops in Britanny and some of their metabolites in air (from spray drift and volatilisation transfer processes): alachlor, atrazine (and two major degradation products: deethylatrazine and deisopropylatrazine), carbofuran, cyprodinil, epoxyconazole, iprodione (and 3,5-dichloroaniline), lindane (and -HCH, its isomer), metolachlor, terbuconazole and trifluralin. This method was established with special consideration for optimal thermal desorption conditions, linear ranges, limits of detection and quantification. Moreover, collection efficiencies of Tenax TA at room temperature were examined. This method was then applied to the determination of ambient pesticide levels during the spraying season at a rural area. The method was also applied to determine the vertical gradient of alachlor concentrations on a treated maize parcel to evaluate volatilisation fluxes.     

Density functional theory investigation of the phonon instability, thermal equation of state and melting curve of Mo

The phonon instability and thermal equation of state of Mo are extensively investigated using density functional theory. The calculated phonon dispersion curves agree well with experiments. Under compression, we captured a large softening in the transverse acoustic (TA) branches of body-centred cubic Mo. When the pressure is raised to 716 GPa, the frequencies along Γ-N in the TA branches soften to imaginary frequencies, indicating structural instability. For face-centred cubic Mo, the phonon calculations predicted the stability by promoting the frequencies from imaginary to real. Within quasi-harmonic approximation, we predicted the thermal equation of state and some other properties including the thermal expansion coefficient α, product αK(T), heat capacity C(V), entropy S, Grüneisen parameter γ and Debye temperature Θ(D). The melting curves of Mo were also obtained successfully.     

Optimizing fitting parameters in thermogravimetry

This study presents an alternative to simple estimation of parametric fitting models used in thermal analysis. The addressed problem consists in performing an alternative optimization method to fit thermal analysis curves, specifically TG curves and their first derivatives. This proposal consists in estimating the optimal parameters corresponding to fitting kinetic models applied to thermogravimetric (TG) curves, using evolutionary algorithms: differential evolution (DE), simulated annealing and covariance matrix adapting evolutionary strategy. This procedure does not need to include a vector with the initial values of the parameters, as is currently required. Despite their potential benefits, the application of these methods is by no means usual in the context of thermal analysis curve’s estimation. Simulated TG curves are obtained and fitted using a generalized logistic mixture model, where each logistic component represents a thermal degradation process. The simulation of TG curves in four different scenarios taking into account the extent of processes overlapping allows us to evaluate the final results and thus to validate the proposed procedure: two degradation processes non-overlapped simulated using two generalized logistics, two processes overlapped, four processes non-overlapped and four processes overlapped two by two. The mean square error function is chosen as objective function and the above algorithms have been applied separately and together, i.e., taking the final solution of the DE algorithm is the initial solution of the remaining. The results show that the evolutionary algorithms provide a good solution for adjusting simulated TG curves, better than that provided by traditional methods.     

High-temperature Study of Phase Equilibria in the Systems CsCl-LnCl3 (Ln=Ce,Nd) by Knudsen Effusion Mass Spectrometry

Pulse thermal analysis (PTA) is based on the injection of a specific amount of gaseous reactant into a carrier gas stream. PTA provides the following advantages compared to conventional TA: (i) quantitative calibration of the mass spectrometric signals allows increasing the sensitivity of TA measurements; (ii) monitoring of gas-solid processes with defined extent of reaction i.e. the reaction can be stopped at any point between pulses, enabling elucidation of the relationship between the composition of the solid and the reaction progress; (iii) simultaneous monitoring of changes in mass, thermal effects, composition and amount of gaseous reactants and products under pulse conditions. This revised version was published online in August 2006 with corrections to the Cover Date.     

Pyrolysis of flame retardants and fire protected polymers

The simultaneously working combination of thermal analysis and mass spectrometry (TA/MS) is a very useful method for studying the degradation process of polymeric materials during thermal treatment [1–7]. Beside the thermal effects, as recorded from thermogravimetry (TG) or differential thermal analysis (DTA) the evolved degradation products can be determined and identified by the on - line coupled mass spectrometer. Additional their temperature depending abundance can be registrated. Combustion of polymers in horizontal (BIS) or vertical (VCI) furnaces and subsequent off line high resolution GC/MS analysis of pyrolysis products is suitable for the simulation of burning processes     

Thermal behavior of five free anthraquinones from rhubarb

The thermal behavior of five free anthraquinones (chrysophanol, emodin, physcion, aloe-emodin, and rhein) from rhubarb had been investigated using TG, DTG and DTA technique. The results show that all the free anthraquinones have the similar TG and DTG curve shapes, however, due to the substituted groups attached on the skeleton of 1,8-dihydroxy anthraquinone are different, every anthraquinone has different mass loss features. Moreover, all the DTA curves of these free anthraquinones have two obviously characteristic peaks, but with special curvilinear types, peak location and peak values. Therefore, thermal analysis (TA) characteristics of anthraquinones above mentioned could be established, and it is possible to easily distinguish these anthraquinones by using TA technique.     

Electrostatic Interaction and Reaction Behavior of a 1, 2,4‐Triazole Mixture with Dinitrobenzene

The electrostatic interactions between gas generating agent and organic electron withdrawing additives were studied to understand how the interaction affects the reactions of their thermal behavior. To explore the electronic interaction and its effect, the thermal behavior of a mixture of dinitrobenzene isomers [p‐dinitrobenzene (pDNB) and m‐dinitrobenzene (mDNB)] and 1, 2,4‐triazole (TA) was analyzed. Density functional calculations and electron density analysis proved that both pDNB and mDNB in a 1:1 ratio withdraw electrons from TA. The analysis of pyrolysis behavior showed that TA and dinitrobenzene mixtures (TA/pDNB or TA/mDNB) react at lower temperatures than each precursor. Gas chromatography mass analysis and UV/Vis spectroscopy showed reasonable results that suggested that pDNB and TA make condensed products in the initial stage of the reaction according to the differential scanning calorimetry measurement. When the mixtures were ignited under pressurized conditions, TA/pDNB burned easily while TA/mDNB burned only partially. These results suggested that the interaction between triazole and dinitrobenzene affects the pyrolysis and combustion behavior of a TA/dinitrobenzene mixture.     

The stability of Tenax TA thermal desorption tubes in simulated field conditions on the HAPSITE® ER

Due to the growing need to monitor aircraft cabin, cockpit and breathing-line air quality, functional assessment of sampling equipment for the specialised field conditions of flight need to be established for both in-flight and ground safety. In this article, we assess the reliability of Tenax TA thermal desorption tubes to perform under various relevant field sampling conditions, such as storage temperature, loading temperature, vibrational velocity, gravitational force (G Force) and altitude pressure with semi-real-time gas chromatograph-mass spectrometer (GC-MS) analysis on the field portable HAPSITE^® ER (Hazardous Air Pollutants on Site Extended Range) instrument. First, we show that Tenax TA thermal desorption tubes can handle storage under extreme environmental conditions, 4–77°C, over numerous analytical test cycles. Next, we confirm that extreme loading temperature, both hot (77°C) and cold (4°C), does not affect the analytical reliability of Tenax TA thermal desorption tubes. Then, we illustrate that G Force may have a significant (p ≤ 0.0364) effect on Tenax TA performance while vibrational velocity (p ≤ 0.7265) and low ambient air pressure (p ≤ 0.1753), such as that found at high altitude, do not. Finally, several Tenax TA thermal desorption tubes were flight-tested, demonstrating that the durability of these tubes maybe insufficient for use on military cargo aircraft (p = 0.0107). The results presented here provide a rationale for additional testing of Tenax TA thermal desorption tubes for flight suitability.     

The kinetics of solid‐state reactions toward consensus—Part I: Uncertainties,failures, and successes of conventional methods

An account of conventional dynamic thermal analysis (TA) with respect to uncertainties, failures, successes, and limitations as applied to solid‐state (s‐s) processes is discussed. A review of some controversial aspects of TA is presented. The scope is to discuss in three parts the adequate understanding of TA and to open a controversy about the dynamic methods and about the necessity of stimulating a consensus between scientists for a better TA. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 343–353, 2001     

Thermal characteristics of mixtures of cyclonite and nitroglycerine or diazidonitrazapentane

The thermal characteristics of mixtures of cyclonite (RDX) and nitroglycerine (NG) and of RDX and diazidonitrazapentane (DIANP) were studied. The thermal decomposition processes of NG and RDX are not synchronous with those of RDX/NG mixtures. The DSC curves show two obviously exothermic peaks, one at 203°C for NG and other at 240°C for RDX. However, there is only a single exothermic peak in the DSC curves of RDX/DIANP mixtures within certain ratio limits, due to the coincidence of the exothermic decomposition peaks for both RDX and DIANP and their mutual dissolution. The effects of the different thermal characteristics of different explosives on the combustion performance are also discussed.     

Differential thermal analysis of some fibers containing chlorine

The differential thermal analysis curves of four fibers containing chlorine (Saran, Cordelan, Teklan and Kanekalon), and their blends, are influenced by experimental conditions, although not to the same extent as those of poly(vinyl chloride) resin in powder form. The curves were determined using two different (Du Pont) cells, and are discussed in terms of sample holder geometry and material composition. The importance of procedural variables in “fingerprint” applications of thermal analysis for routine fiber identification is re-emphasised.     

Assessment of collagen-based materials which are supports of cultural and historical objects

The thermal degradation of collagen-based materials, viz. collagen, recently manufactured parchments and tanned leathers, a heritage parchment and patrimonial (historical) leathers, was investigated by thermal analysis methods. With progressive heating, all these materials exhibit three main successive processes, associated with dehydration, protein denaturation and pyrolysis/oxidation. The analysis of both denaturation and thermo-oxidation revealed significant differences between aged leather, collagen, recently manufactured parchments and tanned leathers in terms of the number of overlapping processes (reflected in the number of peaks recorded at denaturation) and of the oxidative degradation rates, given by the normalised curves of differential thermal gravimetry (DTG). The various observations are proposed as qualitative indices for assessing the age and storage conditions of leather. A three-phase model was used for explaining the results. This consists of crystalline collagen filaments that are embedded in an amorphous matrix with an interface zone between the crystalline and amorphous regions. Solid-state ¹H NMR investigations corroborate the thermal analysis results and enhance the understanding of the ageing processes.     

Thermovoltaic detection. III. Thermal decomposition of some amino acids

The thermal dissociation reactions of selected amino acids were studied by thermovoltaic detection (TVD), TG and DSC. All of the TVD curves except L-arginine contained a broad EMF output peak in the 200–300°C temperature range. The leading edges of the peak maxima were reproducible to within ± 1–2% while the trailing edges were reproducible to ± 20% or so. The latter was related to the irreproducible nature of the electrode-decomposition products interface. The TVD curves were not unique in that they yielded thermal analysis curves that were not inherently different from other TA techniques.     

Thermal Treatment of Iron-Copper Metastable Alloys

Mechanical alloying is a versatile technique for the solid state synthesis of many materials, including alloys such as iron-copper where the elements are immiscible under equilibrium conditions. The structural and magnetic state of these alloys, and their thermal stability, have been investigated by means of thermomagnetometry, DSC, X-ray diffraction and Mössbauer spectroscopy. Comparison of the thermomagnetometry curves for the various alloys together with analysis of intermediate reaction products enabled the individual thermal processes to be identified. The Curie temperature of the alloys was measured, and it was found that on heating the metastable alloys underwent phase segregation between 300-400°C.     

Studies on amidation and imidization processes of amine salts of aromatic tetracarboxylic acids and diamine

The amidation (A) and imidization (I) processes of several amine salts prepared from aromatic tetracarboxylic acids and diamine have been studied by means of thermal analysis (TG, DTA and DSC) and IR spectroscopy. The degrees of imidization (cyclization) of these salts, as estimated via thermal analysis under programmed heating, are 87–93%. The activation energies of these A–I processes, as determined from DSC curves, are 125 and 250 kJ mole⁻¹. From the thermal analysis curves and infrared absorption spectra, it appears that the amidation and imidization processes are superimposed, and the imidization process occurs before the completion of the amidation.     

Analysis of the thermal decomposition of commercial vegetable oils in air by simultaneous TG/DTA

This work presents a study of the thermal decomposition of commercial vegetable oils and of some of their thermal properties by termogravimetry (TG), derivative termogravimetry (DTG) and by differential thermal analysis (DTA). Canola, sunflower, corn, olive and soybean oils were studied. A simultaneous SDT 2960 TG/DTA from TA Instruments was used, with a heating rate of 10 K min^-1 from 30 to 700°C. A flow of 100 mL min^-1 of air as the purge gas was used in order to burnout the oils during analysis to estimate their heat of combustion. From the extrapolated decomposition onset temperatures obtained from TG curves, it can be seen that corn oil presents the highest thermal stability (306°C), followed by the sunflower one (304°C). Olive oil presents the lowest one (288°C). The heat of combustion of each oil was estimated from DTA curves, showing the highest value for the olive oil. Except for corn oil, which presents a significantly different thermal decomposition behavior than the other oils, a perfect linear correlation is observed, with negative slope, between the heat of combustion of an oil and its respective extrapolated onset temperature of decomposition in air. This revised version was published online in August 2006 with corrections to the Cover Date.     

Applications of thermal analysis in quality control of solidification processes

Summary Thermal analysis is widely used to determine solidification characteristics of metals and alloys in various metallurgical processes. Computer-Aided Cooling Curve Analysis (CA-CCA) is the most popular thermal analysis technique because of its ease of use and low cost. This paper discusses the principles of CA-CCA and zero curve calculations. The methods for calculating key solidification characteristics of metals from cooling curves are presented, and their importance in the quality control of manufacturing processes are demonstrated. Examples are presented for cast iron, copper and aluminum alloys.     

Thermal decomposition of basic lead carbonate

TG and DTA curves of the thermal decomposition of basic lead carbonate, 2PbCO₃ Pb(OH)₂, are presented and compared with the thermogram of normal lead carbonate PbCO₃. The appearance of different intermediate compounds at identical experimental conditions is ascribed to the degree of perfection of the carbonate crystals. Poorly developed basic lead carbonate crystals, formed in the presence of polyglutamic acid, give no recognizable intermediate compounds.     

Double Tetrametaphosphates Ca2-xMx IIP4O12

Abstract

The thermal synthesis of Ca₂-_xM_x ^IIP₄O₁₂ (M^II=Mn, Co; x=0,5 -1,5) starts from a mixture of carbonates of the respective metals and phosphoric acid. Formation of the products has been followed by TA (thermal analyses) under quasi-isothermal-isobaric conditions and compared with that of simple tetrametaphosphates at the same conditions (Refs 1,2). Distinct effect of water vapour pressure on the condensation reaction course is indicated; enhanced pressure retards the reactions and shifts them to higher temperatures, but it favours formation of the desired condensation intermediates and, especially, increases the yield of the double tetrametaphosphate. Monoclinic structure of the microcrystalline products obtained has been confirmed. The lattice parameters have been determined, and their shift to lower values with increasing x has been observed. The TA methods have been used to follow thermal stability of the products and to determine the temperatures of melting and of reversible transition to higher linear phosphates (polyphosphates). For these vitreous products we have determined their softening temperatures, and temperature, heat, and energy of the recrystallization connected with reverse formation of the double tetrametaphosphates. The reversible transition is also used for synthesis of the pure products (Ref. 3) which appear to be promissing as special inorganic pigments (Ref. 4).