Thermogravimetric analysis of calcium montmorillonite treated with hexamethylene diisocyanate

The product of the reaction between calcium montmorillonite and hexamethylene diisocyanate in acetone, catalyzed with dibutyltin dilaurate, was studied by thermogravimetry to determine the amount of polymer produced. The method developed to determine polymer content in the clay possessed excellent accuracy and precision, and produced more consistent results than traditional gravimetric methods.This research originated as a portion of the author's Master's degree research undertaken at California State Polytechnic University Pomona, and conducted at the Getty Conservation Institute (GCI). The author is indebted to the following colleagues at the GCI for providing advice and direction: Neville Agnew, Charles Selwitz, Dusan Stulik, James Druzik, David Scott and William Ginell. Consolidated adobe samples were prepared at the GCI by Richard Coffman, and by Dr. Michael Geis, department of Chemistry, Loyola University. Much valuable information and technical assistance was provided by Dr. Hans Wiedemann and Genia Paul, both of Mettler Instrument Corporation.     

Thermogravimetric studies on poly(methyl methacrylate), poly(tetrahydrofuran) and their blends

TG studies are given for PMMA prepared by radical polymerization, PTHF prepared by cationic polymerization, and their blends. A procedure is proposed for determining the activation energy, frequency factor, and the order of events corresponding to the respective stages of the multistage TG curves. The order of the initial event of PMMA is not the 1st. It is shown for this discussion that the relationship between mass loss and time of the 2nd order reaction is similar to that of the depolymerization including the vaporization process at the earlier times. Some of TG curves of PTHF are not dependent on the heating rate. This independence depends on the size of sample. The order of event of PTHF, which is obtained from TG curves dependent on the heating rate, is the 0th. The event order equal to the 0th reflects major contribution of vaporization in the event. The TG behaviors shown by the procedure mentioned above for the PMMA/PTHF blends with the smaller PMMA or PTHF contents cancel those of PMMA or PTHF. This revised version was published online in July 2006 with corrections to the Cover Date.     

Are kinetic parameters of non-isothermal thermogravimetric degradation of polymers unequivocal?

Due to the complex character of the thermal degradation of polymers as a solid-gas chain reaction, an unequivocal kinetic characteirzation is possible only for stationary states of both radical concentration and reaction mechanism. These conditions are hardly realizable in non-isothermal thermogravimetry. Additional the weight losses are depedent on the volatility of the reaction products. That is not always certain in polymer degradation. As a consequence the deduced ‘kinetic parameters’ are not unequivocal. They are conversion and heating rate dependent and may be influenced by sample shape and size. Thus the ‘kinetic parameters’ are in fact from the point of view of mathematics the fitting parameters of a ‘rate equation’ like relation, specific for the used reaction conditions only. From the point of view of chemical kinetics they are neither attributable to a determined reaction mechanism nor can they be used for predictions. Dedicated to the 70^th Anniversary of Dr. Jo Flynn     

Thermogravimetric analysis of chitins of different origin

In this work the thermal properties of chitins of different origin were compared using a thermogravimetric technique. The α_s-α_r method, which makes possible a comparison of the thermal resistances of materials with similar thermostability, was used. The basic range of thermal conversion was determined. In this range, the thermal resistance depends on the chitin origin. The value of activation energy was calculated. No influence on the average molecular mass, crystallinity and the degree of acetylation on the thermal resistance was observed. On the other hand, it was found that the thermal stability depends on the size and perfection of crystallites as well as on the crystalline form of the chitin.     

Thermogravimetric analysis of composites obtained from sintering of rice husk-scrap tire mixtures

Summary The disposal of used automotive tires has caused many environmental and economical problems to most countries. We propose the use of rice husk as filler for increasing the value of recycled tire rubber. Thermal degradation of both components and their sintering mixtures is presented in this paper. Thermal decomposition of rice husk occurs in various steps in the temperature range between 150 and 550°C. This complex process is the result of the overlapping of thermal decomposition of the three major constituents common in all lignocellulosic materials, i.e., hemicellulose, lignin and cellulose. Hemicellulose is degraded at temperatures between 150 and 350°C, cellulose from 275 to 380°C and lignin from 250 to 550°C. The degradation process of major constituents of scrap tires or their composites is observed at temperatures between 150 and 550°C. For composites, the addition of rice husk (maximum 25%) produces an increase in the mass loss rate. This effect is higher as the amount of rice husk increases. However, the degradation initial temperature of elastomeric matrix is not affected with addition of rice husk. Apparent kinetic parameters were also studied by the isoconversional Friedman method. We observed that the addition of rice husk produces a decrease in apparent activation energy for low conversions (up to 0.6). For higher conversions this decrease was not so clearly observed.     

Thermogravimetric investigation

Ion-exchange of transition metal ions into montmorillonite was investigated using two different ion-exchange procedures. Performing ion-exchange from aqueous solution of the respective metal ion leads to material possessing measurable BrØnsted acidity, while the solid-state exchange materials show predominantly Lewis acidity.Measurements by means of a derivatograph allowed us to construct a feasible reaction mechanism for solid-state ion exchange. Satisfactory correlation was found between the results calculated from the reaction steps assumed and the measurements by means of a derivatograph.Financial support by the Hungarian Research Fund (OTKA T014275) is gratefully acknowledged. The skilful technical assistance of Kati Barna is highly appreciated.     

Effect of Chlorination Treatment on the Thermogravimetric Behaviour of Wool Fibres

The thermal behaviour of wool, untreated and chlorinated to various extents, was investigated. The kinetic parameters of the water loss and pyrolysis processes were computed and, based on their values, the way chlorination treatment affects wool fibre is discussed. As it appears, the chlorination process affects the fibre only superficially and not its internal chemical composition, as the values of the kinetic parameters of the thermal decomposition of wool fibre do not seem to be influenced at all by the treatment.This revised version was published online in November 2005 with corrections to the Cover Date.     

Thermal analysis of the polymerization process on the surface of inorganic fillers

The thermal polymerization of pentabromobenzyl (mono)acrylate (PBB-MA) on the surface of the inorganic fillers Mg(OH)₂ and CaCO₃ was studied. FTIR spectroscopy and extraction of the polymer in bromobenzene show that polypentabromobenzyl acrylate (PBB-PA) was mostly grafted on the surface of Mg(OH)₂. Thermal analysis (TG, DSC, isothermal DSC (IDSC)) demonstrated an increase in polymerization starting temperature, and differences in polymerization enthalpy and apparent activation energy when an inorganic filler is added. These differences depend on the chemical composition of the filler used.The authors acknowledge valuable discussions with Prof. S. Yariv. The authors are also grateful to Berecha Foundation (Geneva) for the financial support of this work.     

Calorimetric study of supramolecular structure formation in the course of linear epoxide-amine polycondensation. Epoxy-amine catenate polymers

The formation of linear epoxy-amine polymers has been studied using the calorimetry method. Catenate polymer (olympic gel) is produced in the course of linear polycondensation of aniline with resorcinol diglycidyl ether. A relation was found to exist between the kinetics of the processes and the glassy state transition temperatures for the samples obtained in the reaction. A model of glassy state formation is proposed, In accordance with latter the polymeric glasses are considered to have the dissipative structure resulting from a kinetically controlled phase transition.Deceased April 8, 1991.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 889–895, May, 1993.The authors are grateful to Prof. Z. Rigbi (Izrael) for help and support and to V. A. Rosniatovskii for participation in the discussion of results     

Thermogravimetric analysis of polymers for assessing thermal degradation

Experimental techniques and theoretical analyses of thermogravimetry as applied to the thermal decomposition of polymers are reviewed. It is concluded that little useful mechanistic information can be derived simply by measuring weight loss during heating. Stability assessments can be based on apparent A and E values determined by isothermal analysis. However, such parameters will apply only within the temperature range defined by the conditions of data collection.     

Thermogravimetric examination of polyalcohol-formate binary systems

Mixtures of trimethylolpropane (TMP) or pentaerythritol (PER) with sodium or calcium formate (SF or CF) were investigated all over their composition range. Complete additivity was found to occur in the case of the TMP-SF and TMP-CF systems which renders it possible to determine the contents of both TMP and the given formate from in-dependent signals of weight loss over the entire range of quantitative composition of the mixtures under investigation. Additivity was found not to occur in the PER-SF system in the entire range of quantitative composition; SF content could only be determined from the ash weight. In the PER-CF system, additivity was absent at some signals; CF content could be determined in the full range from three independent signals, PER could be determined independently only at its content up to 50% by weight.     

Synthesis, Structure and Photoluminescence of Two Zinc Carboxyl－ate Polymers with Different Coordination Architectures

The hydrothermal reaction of ZnO with benzene‐1,4‐dicarboxylic add gave Zn·BDC·2H₂O (1) and Zn‐BDC·H₂O (2) (BDC = benzene‐1, 4‐dicarboxylate), respectively. Polymer 1 (C₄H₄O₃ZH_0.5) shows a one‐dimensional zigzag chain structure built up from the alternate connection of tetrahedral ZnO₄ and BDC units. Polymer 2 (C₄H₃O_2.5Zn_0.5) possesses a three‐dimensional framework containing infinite zigzag Zn·Zn·Zn pseudochains generated by five‐coordinate zinc centers and a rectangular channel system including three groups of different straight channels along the [001], [010] and [60–1] directions. The two metal‐organic polymeric compounds exhibit strong photoluminescent emission bands at 402 nm (λ_ex = 260 nm) (for 1) and at 344 nm and 385 nm (λ_ex = 279 nm) (for 2) in the solid state at room temperature.     

Hydrothermal synthesis and crystal structure of two new lanthanide coordination polymers with 1,2-phenylenediacetate

Two new compounds {[Ln₂(1,2-pda)₃(H₂O)₂]·?2H₂O} _n (1,2-H₂pda?=?1,2-phenylenediacetic acid, Ln?=?Tb, 1; Ho, 2) were prepared by hydrothermal reaction and characterized by X-ray crystallography. The Ln³⁺ is nine-coordinate by eight oxygen atoms of six 1,2-pda ligands and one oxygen of water. Ln³⁺ ions are bridged by 1,2-pda ligands via bridging/chelating-bridging pentadentate and chelating-bridging/chelating-bridging hexadentate coordination to form 3-D framework structures. Complex 1 emits strong green fluorescence corresponding to ⁵D₄???⁷F_j (j?=?6–3) transitions of the Tb³⁺.     

On the flexibility of cyclochain polymers

Conformational parameters for a wide variety of aromatic cyclochain polymers have been computed assuming free rotation about virtual bonds. The flexibility with free rotation is shown to be determined by the geometry of the repeat unit and can vary over a wide range (15–1500 Å). Experimental values of the Kuhn segment length A are calculated from literature data on the hydrodynamic behavior of polymeric macromolecules of this class in solution. For most polymers A_fr for free rotation is equal to the experimental A_exp, and hindered rotation is mainly due to bulky substituents. © 1993 John Wiley & Sons, Inc.     

Polymer analysis: Molecular structure and properties of industrial polymers

Low density polyethylenes made by the known high pressure processes show significantly different molecular structures. The physical and technological properties are closely related to molecular structure and morphology. For example, the adhesive strength of a laminate consisting of an ozone treated low density polyethylene film and an aluminum foil depends strongly on the synthesis conditions. The molecular structures and dilute solution properties of many fully aromatic thermotropic liquid crystalline copolyesters can now be determined using the new solvent 3,5-bis(trifluoromethyl)phenol. A typical random copolyester was fractionated by precipitation from solution, and the fractions were studied in detail by viscometry, integrated and dynamic light scattering, and size exclusion chromatography. From the structure data thus obtained the molecular mass distribution and the persistence length were calculated. Polymer blends, block copolymers, and graft copolymers can be characterized by fractionation procedures using demixing solvents in an ultracentrifuge and subsequent analysis of the fractions.     

Study of thermal decomposition of ammonium cerium sulphate

Thermal decomposition of ammonium cerium sulphate has been studied by differential scanning calorimetry and thermogravimetry. The results show that the material decomposes in five steps in the temperature region 364–1116 K in oxygen. Based on the thermal data, elemental analysis and magnetic susceptibility measurements, sequence of decomposition has been established. The final product has been identified as CeO₂ by X-ray diffractometry. Ammonium cerium sulphate and the products of the first and the final transitions contain cerium ion in 4+ oxidation state, while the three intermediate phases have cerium ion in 3+ oxidation state. From the non-isothermal DSC studies, kinetic parameters have been computed. The isothermal data show that the dehydration process follows Ginstling-Brounshtein mechanism, while the next three steps are governed by Mampel's unimolecular law of random nucleation.

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Zusammenfassung Mittels DSC und TG wurde die thermische Zersetzung von Ammoniumzersulfat untersucht. Die Ergebnisse zeigen in Sauerstoff einen fünfstufigen Zersetzungsprozeß im Temperaturbereich 364–1116 K. Ausgehend von den thermoanalytischen Angaben, der Elementaranalyse und den Messungen der magnetischen Suszeptibilität wurde eine Sequenz für die Zersetzung erstellt. Das Endprodukt wurde mittels Röntgendiffraktion als CeO₂ identifiziert. Ammoniumzersulfat und die Produkte des ersten und des letzten Überganges enthalten Zerionen mit der Oxydationsstufe +4, während in den drei Zwischenschritten Zerionen mit der Oxydationsstufe +3 vorkommen. Anhand der nichtisothermen DSC-Untersuchungen wurden die kinetischen Parameter berechnet. Die isothermen Angaben zeigen, daß der Dehydratationsprozeß einem Ginstling-Brounstein Mechanismus folgt, während die folgenden drei Schritte durch das Mampelsche unimolekulare Gesetz der Randomkeimbildung bestimmt werden.

     

Thermogravimetric Analysis of Polynitro Arenes

Attention was paid to seventeen samples of polynitro arenes. Stability of these nitrocompounds was specified by means of non-isothermal thermogravimetric analysis (TG). Linear relationships were specified between the positions of TG-onsets and the mass of the samples. The relation of slopes of the mentioned relationships to the rate constants of the thermal decomposition under condition of Russian manometric method (SMM) was confirmed and solved for studied polynitro arenes. These arene derivatives were classified into several groups in the sense of this relation. The classification was interpreted by dominating influence of intermolecular interaction factors on the corresponding TG-onsets positions. The found relations can be used for the TG results conversion to the parameters, which are comparable with SMM outputs. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermogravimetric Analysis of Aromatic Polyamides with Benzimidazolyl Side Group

The TG studies are presented for isomers of benzimidazolyl-substituted polyamides (BIPA). The TG data are compared with those polyamides (PA) of identical backbones without substitution, in view of the mechanism of thermal degradation. The TG mass loss curves divided to three temperature ranges reflect the decomposition reactions in the respective temperature ranges: (1) cleavage of single bonds of nitrogen to aromatic ring, (2) random scission of single bonds, (3) condensation of the remained rings. Liberation of benzimidazole rings occurs in the temperature range (2). The final product, char, contains benzimidazole rings. Terephthaloyl-rich BIPA's retard liberation of benzimidazole from the decomposed polymer. This revised version was published online in August 2006 with corrections to the Cover Date.     

Determination of degradation apparent activation energy values of polymers

The isothermal degradation of three aromatic polyetherketones was studied in an inert environment at various temperatures in the range 683-803 K. In the first degradation stage (mass loss D￡20%) a linear increase of D as a function of heating time (t) was observed and the corresponding kinetic D=D _o+bt equations at various temperatures were directly drawn by smoothing the experimental TG data. The b values, which represent the mass loss rates during degradation, increased as a function of temperature according to Arrhenius-type equations, from which degradation E _a values were determined, which appear in agreement with those from literature methods. Some differences observed were discussed and interpreted. This revised version was published online in July 2006 with corrections to the Cover Date.