Showing papers in "Journal of Thermal Analysis and Calorimetry in 2000"

Kinetic Analysis Using Multivariate Non-linear Regression. I. Basic concepts

Abstract: In principle, the kinetic analysis of thermal effects has limitations when based on a single measurement. Using a simulated example and the dehydration of Ca(OH)2 , it will be shown that, through the simultaneous application of non-linear regression to several measurements run at different heating rates (multivariate non-linear regression), the difficult problem of determining the probable reaction type can be reliably solved.

Thermal Methods of Organic Matter Maturation Monitoring During a Composting Process

Abstract: The possibility to use thermal analysis for a quick characterisation of chemical changes in the organic matter of composted materials was tested. Nine samples were taken at progressive stages of maturation from the same trench of a fully automated composting plant. DSC and TG were simultaneously performed in static air conditions on whole ground composts. Progressive stages in the composting process yielded samples whose DSC traces revealed appreciable modifications in thermal patterns that agreed well with quantitative data obtained from TG measurements. The ratio between the mass losses associated with the two main exothermic reactions (R1) showed a good sensitivity in detecting the changes in the level of stabilisation during the composting process. Thermal methods seem to be a valid comparative method in evaluating the level of bio-transformation of materials during a composting process.

Determination of Activation Energy for Glass Transition of an Epoxy Adhesive Using Dynamic Mechanical Analysis

Abstract: The activation energy associated with the glass transition relaxation of an epoxy system has been determined by using the three-point bending clamp provided in the recently introduced TA Instruments DMA 2980 dynamic mechanical analyzer. A mathematical expression showing the dependency of modulus measurements on the sample properties and test conditions has also been derived. The experimental results showed that the evaluation of activation energy is affected by the heating rate and test frequency, as well as the criterion by which the glass transition temperature (Tg) is established. It has been found that the activation energy based on the loss tangent (tanδ) peak is more reliable than on the loss modulus (E2) peak, as long as the dynamic test conditions do not cause excessive thermal lags.

The Accuracy of Senum and Yang's Approximations to the Arrhenius Integral

Abstract: The accuracy of the integral of the Arrhenius equation, as determined from the 1st to the 4th degree rational approximation proposed by Senum and Yang, has been calculated. The precision of the 5th to 8th rational approximations, here proposed for the first time, has also been analyzed. It has been concluded that the accuracy increases by increasing the order of the rational approximation. It has been shown that these approximations to the Arrhenius equation integral would allow an accuracy better than 10−8 % in the E/RT range generally observed for solid state reactions. Moreover, it has been demonstrated that errors closed to 10−2 % can be obtained even for E/RT=1, provided that high enough degrees of rational approximation have been used. Thus, it would be reasonable to assume that high degree rational approximations for the Arrhenius integral could be used for the kinetic analysis of processes, like adsorption or desorption of gases on solid surfaces, which can take place at low temperatures with very low values of E/RT.

Applications of Successive Self-Nucleation and Annealing (SSA) to Polymer Characterization

Abstract: A new technique to thermally fractionate polymers using DSC has been recently developed in our laboratory. The applications of the novel successive self-nucleation and annealing (SSA) technique to characterize polyolefins with very dissimilar molecular structures are presented as well as the optimum conditions to thermally fractionate any suitable polymer sample with SSA. For ethylene/α-olefin copolymers, the SSA technique can give information on the distribution of short chain branching and lamellar thickness. In the case of functionalized polyolefins, detailed examinations of SSA results can help to establish possible insertion sites of grafted molecules. The application of the technique to characterize crosslinked polyethylene and crystallizable blocks within ABC triblock copolymers is also presented.

Magnetic Suspension Balance For Simultaneous Measurement of a Sample and the Density of the Measuring Fluid

Abstract: This paper deals with gravimetric measurements of adsorption equilibria of gases on the surface of porous solids with a new type of magnetic suspension balance. Items discussed include the measurement of adsorption data at high pressure and temperature as well as the simultaneous measurement of adsorption and the density of the adsorptive gas using only one magnetic suspension balance.

Glass and Structural Transitions Measured at Polymer Surfaces on the Nanoscale

Abstract: This paper reviews our recent progress in determining the surface glass transition temperature, Tg, of free and substrate confined amorphous polymer films. We will introduce novel instrumental approaches and discuss surface and bulk concepts of Tg. The Tg of surfaces will be compared to the bulk, and we will discuss the effect of interfacial interactions (confinements), surface energy, disentanglement, adhesion forces, viscosity and structural changes on the glass transition. Measurements have been conducted with scanning force microscopy in two different shear modes: dynamic friction force mode and locally static shear modulation mode. The applicability of these two nano-contact modes to Tg will be discussed.

Application of the Šesták-Berggren Equation to Organic and Inorganic Materials of Practical Interest

Abstract: Reactions that have an initial acceleratory period are common in both organic and inorganic systems. The Sestak-Berggren equation, dx/dt= -kxn(1-x)m[-ln(x)]p, with p set to zero (also called the extended Prout-Tompkins (PT) equation) is an excellent empirical kinetic law for many of these systems. In this work, it is shown to fit both isothermal and constant heating rate pyrolysis data for a well-preserved algal kerogen in a petroleum source rock and two synthetic polymers (polycarbonate and poly-ether-etherketone), dehydration of calcium oxalate monohydrate, decomposition of ammonium percholorate, and diffusive release of gas implanted in materials. Activation energies derived by non-linear regression to multiple experiments are consistent with those derived by simple isoconversional methods. Errors caused by misapplication of first-order kinetics to single-heating-rate data are discussed briefly.

Thermodynamic Analysis of DSC Data for Acetaminophen Polymorphs

Abstract: This article provides a thermodynamic analysis of DSC data for acetaminophen polymorphic forms I and II by measurement of heat capacity. Form I is found to have lower heat capacity and free energy and hence better stability than Form II down to at least –30°C. The transition temperature below which Form II becomes more stable was determined to be less than –120°C. Form I is more stable than Form II as a consequence of its higher entropy, since its crystallographic packing arrangement is of larger energy.

Influence of the degree of dehydroxylation of kaolinite on the properties of aluminosilicate glasses

Abstract: The degree of dehydroxylation of kaolinite, DTG and DIR, respectively, is characterized by thermogravimetric analysis (TG) and Fourier transform infrared spectroscopy (FTIR). The relation between DTG and DIR based on the infrared absorptions at 3600–3700, 915, 810, and 540 cm−1 is established. Three regions can clearly be distinguished: the dehydroxylation region (DTG<0.9), the metakaolinite region (0.9

Thermodynamic Aspects of the Vaterite-Calcite Phase Transition

Abstract: Although vaterite is the least stable anhydrous calcium carbonate polymorph, it is formed as a metastable phase in some normal and pathological biomineralisation processes. In this work, thermodynamic aspects of the vaterite-calcite phase transition were comprehensively studied. Vaterite samples were prepared by different methods and characterised for the composition, crystal structure, specific surface and grain size. All products were identified to be pure vaterite by careful X-ray diffraction measurements. The enthalpy and Gibbs energy of transition were determined by precise calorimetric and potentiometric measurements. The reliability of the thermodynamic data for the vaterite-calcite phase transition derived from this work was shown by the use of different calorimetric methods to determine the enthalpy of transition and the independent measurements of heat capacity and entropy of vaterite. Our recommended values are ΔtrsG* = -2.9 ± 0.2 kJ mol-1, ΔtrsH* = -3.4 ± 0.2 kJ mol-1 and ΔtrsS* = -1.7 ± 0.9 J K-1 mol-1, where the uncertainties are given as twice the standard deviations.

Structural and Mechanical Properties of Crosslinked Drawn Gelatin Films

Abstract: Differential scanning calorimetry and high angle X-ray diffraction analyses were performed on gelatin films, air dried at different values of constant elongation, crosslinked with glutaraldehyde and examined at constant relative humidity of 75%. Drawing induces a preferential orientation of the chain segments of gelatin parallel to the stretching direction, and a linear increase of the renaturation level, calculated as the ratio between the denaturation enthalpy of gelatin films and that of tendon collagen. The comparison with the results previously obtained on the mechanical properties of the films, puts into evidence the different contributions of orientation and renaturation on the improvement of the mechanical parameters on drawing. The results offer important information on the role of glutaraldehyde (GTA) crosslinking on the stability of collagenous materials.

Mechanism of Thermal Decomposition of d-metals Nitrates Hydrates

Abstract: A series of six nitrates(V) hydrates of 4d-metals as well as mercury and cadmium thermal decomposition was examined by DTA, TG and EGA techniques. It was found that thermal decomposition of d-metals nitrate(V) hydrates proceeds in three stages: partial dehydration, oxo-nitrates and hydroxide nitrates formation and metal oxides formation. General chemical equations for all decomposition stages were proposed. It was found that dehydration of hydrated salts is accompanied by partial decomposition of nitrate(V) groups.

Nucleating Agents in Polypropylene

Abstract: The effects of nucleating agents such as dibenzylidene sorbitol (DBS) (a derivative of sorbitol), pine crystal 1500, sodium and potassium benzoates in commercial grade isotactic polypropylene iPP are studied using differential scanning calorimetry (DSC). Isothermal crystallization kinetics of polypropylene to the alpha phase have been analyzed using Avrami's model. Results indicate that dibenzylidene sorbitol and pine crystal are very effective in increasing the crystallization temperature of the polymer and number of nuclei formed during crystallization.

Starch Gelatinization Kinetics in Bread Dough. DSC investigations on 'simulated' baking processes

Abstract: Starch gelatinization in wheat flour dough of various moisture contents was quantitatively evaluated by means of DSC. The experimental records were worked out in the form of excess heat capacity vs. T traces which were deconvoluted to single out the contribution of starch gelatinization from that of the decomposition of amylose-lipid complexes. The quantitative procedure used put into evidence that a third endothermic process would take place in the dough with a poor moisture content. DSC runs carried out with sealed pans (i.e., at constant moisture level) and open pans (from which some water was free to evaporate) allow simulation of two extreme conditions of a real baking process, namely that relevant to the central core and to superficial layer of a dough loaf, respectively. The extent of starch gelatinization occurred in these conditions was quantitatively assessed. These data were collected at various heating rates and used to define temperature-time-transformation(TTT) diagrams which are useful tools to predict the progress of baking for any given thermal history of the system.

Thermal Decompositions of Pure and Mixed Manganese Carbonate and Ammonium Molybdate Tetrahydrate

Abstract: The thermal decompositions of pure and mixed manganese carbonate and ammonium molybdate tetrahydrate in molar ratios of 3:1, 1:1 and1:3 were studied by DTA and TG techniques. The prepared mixed solid samples were calcined in air at 500, 750 or 1000°C and then investigated by means of an XRD technique. The results revealed that manganese carbonate decomposed in the range 300–1000°C, within termediate formation of MnO2, Mn2O3 andMn3O4. Ammonium molybdate tetrahydrate first lost its water of crystallization on heating, and then decomposed, yielding water and ammonia. At 340°C,MoO3 was the final product, which melts at 790°C. The thermal treatment of the mixed solids at 500, 750 or 1000°C led to solid-solid interactions between the produced oxides, with the formation of manganese molybdate. At 1000°C, Mn2O3 and MoO3 were detected, due to the mutual stabilization effect of these oxides at this temperature.

The use of thermogravimetry in the study of rubber devulcanization

Abstract: Thermogravimetry was employed to study the changes occurring in rubber vulcanizates during devulcanization carried out by microwave treatment, a new promising method of recycling rubber waste. The thermogravimetric parameters Ti, T5 and Tp and the compositions of devulcanizates in comparison with vulcanizates were determined. The results obtained allowed estimation of the degree of destruction of the polymer chains in response to microwave treatment and permitted establishment of the most advantageous conditions of devulcanization in order to obtain the best properties of rubber devulcanizates for reuse in rubber processing. The results demonstrated that thermogravimetry is a very useful method for investigation and control of the microwave devulcanization process.

Thermal studies on lanthanide nitrate complexes of 4-N-(2'-furfurylidene)aminoantipyrine

Abstract: The kinetics and mechanism of thermal decomposition of nitrate complexes of lanthanides with the Schiff base4-N-(2′-furfurylidene) aminoantipyrine (abbreviated as FAA) have been studied by TG and DTG techniques. The kinetic data for the first stage of decomposition were calculated using the Coats-Redfern equation. The rate-controlling process obeys Mampel model representing random nucleation, with one nucleus on each particle. It is observed that there is no gradation in the values of the kinetic parameters of decomposition of the complexes.

KINETIC STUDY ON PYROLYSIS OF EXTRACTED OIL PALM FIBER Isothermal and non-isothermal conditions

Abstract: Pyrolysis of extracted oil palm fibers under isothermal and non-isothermal conditions was carried out in a thermogravimetric analyzer. Isothermal curves showed that increasing pyrolysis temperature resulted in a faster pyrolysis and a higher conversion of oil palm fibers into gaseous products. Raw material sizes (below 1.0 mm) had insignificant effects on the isothermal pyrolysis, but the fibers with a size fraction of 1.0 to 2.0 mm resulted in a lesser conversion. Two-step reactions were found in the non-isothermal pyrolysis as evidenced by the presence of two peaks in the derivative thermogravimetry curves. Raw material sizes had no obvious effects on the temperature at which the maximum rate of pyrolysis occurred, but affected the rate of sample mass loss. For the low and high temperature regimes, a three-dimensional diffusion mechanism and a first-order of reaction mechanism respectively were used to describe the non-isothermal pyrolysis kinetics of extracted oil palm fibers.

The effect of side chain association on thermal and viscoelastic properties: Cellulose acetate based polycaprolactones

Abstract: Cellulose acetate-based polycaprolactones (CAPCL's) were synthesized by the polymerization of e-caprolactone which was initiated by non-substituted OH group in cellulose acetate. The CL/OH (mol mol−1) ratios of the CAPCL's were changed from 2 to 20. Thermal and viscoelastic properties of the CAPCL sheets were studied by differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). Glass transition, cold crystallization and melting were determined by DSC. Dynamic modules (E'), dynamic loss modules (E'') and tanδ were measured in a temperature range from −150 to 50°C by DMA. Apparent activation energy of a dispersion was calculated from the frequency dependency of E'' peak temperature. It was found that the main chain motion of both CA and PCL is observed in a CL/OH ratio from 0 to 10 mol mol−1. However, when CL/OH ratio exceeds 10 mol mol−1, the crystalline region which is rearranged by the PCL chain association is observed and only the main chain motion of PCL can be detected.

Solid-state Decompositions — Stagnation or Progress?

Abstract: An appraisal of the trends discerned in the recent literature concerned with solid-state decompositions suggests that this research area lacks a general theoretical framework and, hence, order in the subject is difficult to recognize. There have been surprisingly few reviews of the field. Many of the continuing flow of research publications may be of individual value, but most do not contribute to the overall development of the topic. For example, in many studies of reversible dissociations the sensitivity of rate characteristics to prevailing conditions is not discussed so that the fit of data to rate equations and the magnitudes of calculated Arrhenius parameters may be of empirical value only. Some studies report kinetic results without mechanistic discussions supported by complementary observations. Progress forward from an apparent state of stagnation depends upon more critical examination of the existing literature, coupled with better designed experiments to establish the reproducibility and reliability of kinetic conclusions. Techniques capable of providing insights into the bond redistribution steps that occur during reactions in crystals are also urgently needed.

Hydration of Cement Slurry in The Presence of Spent Cracking Catalyst

Abstract: The physicochemical properties of spent fluidized bed cracking catalyst and its influence on hydration process of cement slurry were studied. The samples were cement slurries prepared with water/solid=0.5 and additions of used catalyst amounted to 0, 5, 10, 15, 20 and 25%with resp. to the solid. After definite time they were subjected to thermogravimetric analysis (TG, DTG, DTA) and, in order to determine the progress of reaction with water, the heat of hydration was measured by means of isotherm calorimetry. The studies disclosed that the spent cracking catalyst is not merely an inactive filler in cement slurries, but it modifies the course of the hydration process. The spent catalyst is a pozzolana additive and its presence leads to a decrease of calcium hydroxide contents in the system. The spent catalyst affect on the heat of cement hydration. Small amounts additive accelerate the process of binding.

Society as a Many-Particle System

Abstract: Statistics: Order-disorder problems in many-particle statistics may be solved by the Lagrange principle: L=TlogP+E→maximum!

New Physico-chemical Properties of Water Induced by Mechanical Treatments. A calorimetric study at 25°C

Abstract: An extensive thermodynamic study has been carried out on aqueous solutions, obtained through the iteration of two processes: a dilution 1:100 in mass and a succussion. The iteration is repeated until extreme dilutions are reached (less than 1⋅10–5 mol kg–1 ) to the point that we may call the resulting solution an 'extremely diluted solution'. We conducted a calorimetric study, at 25°C, of the interaction of those solutions with acids or bases. Namely, we measured the heats of mixing of acid or basic solutions with bidistilled water and compared them with the analogous heats of mixing obtained using the 'extremely diluted solutions'. Despite the extreme dilution of the latter solutions, we found a relevant exothermic excess heat of mixing, excess with respects to the corresponding heat of mixing with the untreated solvent. Such an excess has been found in about the totality of measurements, and of a magnitude being well beyond one that could arise any issue of sensibility of the instrumental apparatus. Here we thus show that successive dilutions and succussions can permanently alter the physico-chemical properties of the solvent water. The nature of the phenomena here described still remains unexplained, nevertheless some significant experimental results were obtained.

Differential scanning microcalorimeter scal-1

Abstract: The paper describes the design and the principle of operation of the differential scanning microcalorimeter SCAL-1. This instrument serves to measure thermal parameters of protein or biopolymer solutions of low concentration (from0.1 mg ml−1) in the temperature range from −10 to 130°C using different rates. A distinctive feature of the microcalorimeter is that its calorimetric cell is made of glass, it is highly sensitive and measuring results can be easily and reliably reproduced.

Kinetics of Thermal Decomposition of Copper(II) Acetate Monohydrate

Abstract: The thermal decomposition of copper(II) acetate monohydrate was studied in air and nitrogen atmospheres by means of DTA-TG and SEM measurements. The kinetics of the thermal decomposition steps in air was studied by using isothermal and non-isothermal thermogravimetric techniques. The results are discussed in terms of various reaction interface models and different techniques of computational analysis of non-isothermal data. The activation parameters, calculated by using a composite method of integral analysis of non-isothermal data, revealed not only their independence from the heating rate and fractional reaction, but also a better correlation and agreement with the results obtained under isothermal conditions.

Mixed Ligand Complexes of 5-arylazo-8-hydroxyquinoline and α-amino Acids with Co(II), Ni(II) and Cu(II)

Abstract: Ten mixed ligand complexes of the type [M(X-QA)(aa)] and [Ni(X-QA)2(Haa)(H2O)],where X-HQA=5-arylazo-8-hydroxyquinoline derivatives, M=Co(II) orCu(II) and Haa=glycine (gly), alanine (ala) or methionine (met), have been prepared. The complexes have been characterized by elemental analysis, IR and electron spectra and thermal analysis. A tetrahedral structure has been proposed for the cobalt(II) and copper(II) complexes with bidentate coordination of amino acids. The nickel(II) complexes have been assigned an octahedral structure with the amino acids acting as monodentate ligands. The thermal behaviour of the complexes has been studied before and after γ-irradiation.

Application of Thermal Analysis in The Characterization of Anti-hypertensive Drugs

Abstract: The present work reports studies of the thermal behaviour of some anti-hypertensive drugs. Their purities were determined by DSC and specialized pharmacopeial methods. The thermogravimetric data allowed determination of the kinetic parameters: activation energy, frequency factor and reaction order. The activation energy values suggest the following sequence of stability: nifedipine>propanolol hydrochloride>captopril. Analysis of the DSC data indicated that the degrees of purity of nifedipine, captopril and propanolol hydrochloride were similar to those found by pharmacopeial methods BP 93 and USP 23. The simplicity, speed and low operational costs of thermal analysis justify its application in the quality control of pharmaceutical drugs.

Oxidation Behaviour of A Boron Carbide Based Material in Dry and Wet Oxygen

Abstract: The oxidation behaviour of a B4C based material was investigated in a dry atmosphere O2(20 vol.%)-CO2(5 vol.%)-He and also in the presence of moisture H2O (2.3 vol%) as boron oxide is very sensitive to water vapour. The mass changes of samples consisting of a chemical vapour deposit of B4C on silicon nitride substrates were continuously monitored in the range 500–1000°C during isothermal experiments of 20 h. The stability of boron oxide formed by oxidation of B4C was also studied in dry and wet atmospheres to explain the kinetic curves. In both atmospheres, oxidation is diffusion controlled at 700 and 800°C and enhanced by water vapour. At 900°C and higher temperatures, boron oxide volatilisation and consumption by reaction with water vapour modifies the properties of the oxide film and the material is no more protected. At 600°C, B4C oxidation is weak but the process remains diffusion controlled in dry conditions as boron oxide volatilisation is negligible. However, in the presence of water vapour, B2O3 consumption rate is significant and mass losses corresponding to this consumption and to the combustion of the excess carbon are observed.

Analysis of DSC Data Relating to Proteins Undergoing Irreversible Thermal Denaturation

Abstract: New approaches to the analysis of differential scanning calorimetry (DSC) data relating to proteins undergoing irreversible thermal denaturation have been demonstrated. The experimental approaches include obtaining a set of DSC curves at various scanning rates and protein concentrations, and also reheating experiments. The mathematical methods of analysis include construction of a linear anamorphosis and simultaneous fitting of a theoretical expression for the dependence of the excess heat capacity on temperature to a set of experimental DSC curves. Different kinetic models are discussed: the one-step irreversible model, the model including two consecutive irreversible steps, the Lumry and Eyring model with a fast equilibrating first step, and the whole kinetic Lumry and Eyring model.