国产硅藻土结构的研究

系统地研究了硅藻土结构, 发现除浙江白土表面具有双生的硅羟基外, 其它只有连生的与孤立的硅羟基; 经IR谱证明, 其内部尚有Si-O与Al-O振动, 酸洗或焙烧都能使硅藻体的孔径、孔径分布和结构发生改变; 经焙烧后, 结构均发生改变, 其自由水消失, 束缚水逐渐减少; 焙烧达1150℃时, 原组成无定形二氧化硅则晶化为α-方石英, 除吉林土具有一级孔洞, 云南土具有三级孔洞外, 本文中其它硅藻土均有二级孔洞。     

Thermogravimetric study of uranium phosphates

The thermal decomposition of UO₂NH₄PO₄ · 3H₂O and UO₂HPO₄ · 4H₂O was studied in the temperature range 25–1600?C. Both compounds gave U₂O₃P₂O₇ around 900?C after a two step dehydration and an orthophosphate-pyrophosphate transformation. UO₂NH₄PO₄ · 3H₂O did not form any pure intermediates, but (UO₂)₂P₂O₇ could be prepared from UO₂HPO₄ · 4H₂O. In air, U₂O₃P₂O₇ lost phosphorus above 1250?C. In argon, (UO)₂P₂O₇ was first formed between 1000 and 1290?C and this product only lost phosphorus at still higher temperatures. (UO)₂P₂O₇ was also obtained by reduction of (UO₂)₂P₂O₇ or U₂O₃P₂O₇ at 700?C in H₂ or with carbon black in argon above 1000?C. It oxidised in air above 250?C with the formation of U₂O₃P₂O₇.     

Thermogravimetric study of uranium phosphates

The thermal decomposition of (UO₂)₃(PO₄)₂ and U(HPO₄)₂ ·xH₂O in the temperature range 25–1600?, was investigated. (UO₂)₃(PO₄)₂ decomposed first to 1/3[U₃O₈ + 3U₂O₃P₂O₇] and then to U₃O₅P₂O₇ before a loss of phosphorus was observed above 1350?. Decomposition in air and in inert atmospheres was nearly identical. Reduction with H₂ or with carbon black in argon gave U₃O₅P₂O₇ and [UO₂ + + (UO)₂P₂O₇] before pure UO₂ was formed. U(HPO₄)₂ ·xH₂O decomposed to UP₂O₇ in argon. It oxidized partly in air before the same product was obtained. The high temperature stability of UP₂O₇ and U₃(PO₄)₄ was also investigated.     

Thermogravimetric study about PVC-polyaniline blends

By dissolution of PVC and polyaniline in dimethylformamide, a series of blends PVC-polyaniline were produced which were studied by scanning electron microscopy and thermogravimetry. Special attention is focused on the kinetic study of the thermal degradation steps by using non-isothermal thermogravimetric data. The results show that the thermal stability of the synthesized blend is decreased as the total amount of polyaniline is enhanced. Furthermore, the Brřnsted acid doped blend is more stable than the corresponding undoped one. PVC and the PVC-polyaniline blends exhibit two mass loss steps which activation energy values are in the range from 176 to 283 kJ mol^-1 and 306 to 322 kJ mol^-1, respectively. This revised version was published online in August 2006 with corrections to the Cover Date.     

Thermogravimetric study of rubber waste-polyurethane composites

Granulated rubber obtained from used tyres, below 1.5 mm granularity (fine rubber) and polyurethane prepolymers (Chemolan M, Chemolan M50 and Chemolan B3) were used for the synthesis of rubber waste-polyurethane composites, containing 90, 85, 80, 75 and 70% w/w of fine rubber. The influence of the kind of polyurethane resin on hardness, elasticity, glass transition temperature and thermal stability of composites was studied. Kinetic parameters of the thermal degradation process of composites were calculated from thermogravimetric analysis (TG) data.This work has been financially supported by the State Committee for Scientific Research, Poland (research project-grant no. 3 T09B 043 19).     

Thermogravimetric study of some disperse dyestuffs

Two disperse dyestuffs, though exhibiting similar behaviour upon TG-DTG-DTA, have different dyeing properties. Thermoanalytical investigations are not sufficient to predict dyeing characteristics and fastness.

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Zusammenfassung Zwei Dispersionsfarbstoffe, die sich bei der TG-DTG-DTA ähnlich verhalten, zeigen unterschiedliche Färbeeigenschaften. Thermoanalytische Untersuchungen sind nicht ausreichend, um Färbeeigenschaften und die Farbechteheit vorherzusagen.

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Thermogravimetric study of the pyrolysis of waste wood

A thermogravimetric study of the pyrolysis of three different types of waste wood (forest wood, old furniture and used pallets) is carried out in a TGA equipment using dynamic and isothermal techniques. Isothermal runs were carried out at two temperature levels, one between 225° and 325°C (low range) and the other, between 700° and 900°C (high range). Results show a good agreement between the kinetic parameters obtained from either dynamic or isothermal techniques. It must be remarked that the own chemical composition of each type of wood together with the compounds added to the wood for each application, play a fundamental role in the kinetic behavior of their thermal decomposition.     

Bulgarian natural diatomites: modification and characterization

Natural Bulgarian diatomite modified by oxidation with sulfuric acid and H₂O₂ or by coating with manganese oxide was characterized considering its chemical composition, surface area, pore volume, and structure. Modified diatomites displayed larger surface area and pore volumes in comparison with untreated natural diatomite, which favored their sorption behavior. Sorption properties of diatomites towards Fe³⁺, Pb²⁺, Cu²⁺, Cd²⁺, Mn²⁺, Ni²⁺, Co²⁺, Cr³⁺, Pd²⁺, Ca²⁺, and Mg²⁺ were investigated and their sorption capacities were determined. Sorption properties of manganese oxide-modified diatomite were superior to those of diatomite modified by oxidation. Owing to its high sorption capacity towards Co²⁺, Ni²⁺, Pb²⁺, Cr³⁺, Fe²⁺, Cu²⁺, and Cd²⁺, the manganese oxide-modified diatomite is a promising low-cost sorbent for selective removal of milligram amounts of these toxic metal ions from contaminated water.     

Thermogravimetric study of polyacrylamide with evolved gas analysis

Dried samples of polyacrylamide in an He atmosphere have been subjected to thermogravimetric analysis in the 30–600°C range, and the evolved gases were monitored by FTIR. Water, ammonia, and small quantities of carbon dioxide are released in the first stages of decomposition (220–340°C), where the polymer chains remain intact and the reaction occurs on the pendant amide groups. In the second stage of decomposition (340–440°C), the majority of the weight loss occurs, and main chain breakdown occurs, releasing carbon dioxide, water, nitrile compounds, and imides. Trapping of the gases in this stage and analysis by GC–FTIR and GC–MS reveals the presence of more than 20 decomposition products, and confirms that a large proportion of these can be assigned to glutarimide and its substituted analogs. Imidization and dehydration reactions on the amide groups, as well as free radical breakdown of the main chains, with inter- and intramolecular hydrogen transfer, can account for many of the products of the decomposition. © 1993 John Wiley & Sons, Inc.     

Thermogravimetric study of magnetite reduction at low temperature

Results on hydrogen reduction of pure magnetite to iron at low temperature are reported as part of research on ammonia synthesis catalyst. Experimental work was carried out by thermogravimetry and by electron microscopy.The reduction has a typical S-shaped kinetic curve, with a poorly reproducible induction period. The slope of the reduction curve at 50% conversion (k _0.5) was found to depend on sample mass (2–50 mg), particle size, temperature (220–280C) and presence of moisture in the hydrogen .The results suggest both interparticle and intraparticle (through iron ash) diffusion to be slow. Morphological examinations of the sample at various reduction degrees support this interpretation.

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Zusammenfassung Die Ergebnisse der Reduktion von reinem Magnetit zu Eisen durch Wasserstoff bei niedrigen Temperaturen werden als Teil einer Forschungsarbeit über Katalysatoren zur Ammoniak-Synthese mitgeteilt. Die Versuche wurden mittels Thermogravimetrie und Elektronenmikroskopie durchgeführt.Die Reduktion verläuft nach einer typisch S-förmigen kinetischen Kurve, mit einer schlecht reproduzierbaren Induktionsperiode. Es wurde festgestellt, daß die Steile der Kurve bei 50% Konversion (k _0.5) von der Probenmenge (2–50 mg), der Teilchengröße, der Temperatur (220 bis 280) und der Feuchtigkeit des Wasserstoffes abhängt.Diese Ergebnisse lassen darauf schliessen, daß sowohl die interpartikuläre als auch die intrapartikuläre Diffusion (durch die Eisen-Asche) langsam ist. Diese Deutung wird durch morphologische Prüfung des Musters bei verschiedenen Reduktionsstufen unterstützt.

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Résumé On communique les résultats obtenus en réduisant par l'hydrogène à basse température la magnétite pure en fer, travail faisant partie de recherches sur les catalyseurs pour la synthèse de l'ammoniac. Les expériences ont été effectuées par thermogravimétrie et par microscopic électronique.La courbe cinétique de la réduction présente la forme en S type, avec une période d'induction peu reproductible. Il est apparu que la pente de la courbe de réduction, pour un taux de conversion de 50% (k _0.5) dépendait de la prise d'essai (2–50 mg), de la dimension des particules, de la température (220 à 280) et de la présence d'humidité dans l'hydrogène .Ces résultats permettent de conclure que les processus de diffusion sont lents, qu'ils soient de type interparticule ou intraparticule. L'examen morphologique des échantillons pour divers degrés de réduction a confirmé cette interprétation.

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Thermogravimetric study of alcohol adsorption on active charcoal

Interest of using the Mac Bain thermogravimetric balance in order to characterize alcohol adsorption or desorption on various active charcoal is developed. Precautions and peculiarities of proposed method are indicated. They result from very good precision and reproducibility in the thermal range of 273.15 to 313.5 K, and in the pressure range of 666.6 Nm⁻² to 26664 Nm⁻².Some results are given to illustrate the statics, and kinetics of adsorption desorption process of alcohol on various active charcoals.These results are important to develop and optimize refrigerating machines, or heat pumps, or physico-chemical storage using these systems.     

Thermogravimetric study of the reduction of basic lead sulphate

In this paper, the results of the study of the reduction of basic lead sulphate with a gas (CO + CO₂) mixture are presented. This is a secondary reaction during the reduction of lead sulphate. The change in the both lead and PbS content in the reaction products, depending on the process temperature and the composition of the gaseous phase, was established. The comparison of the rate of the reduction reaction of lead sulphate and basic lead sulphate shows that the process proceeding with a higher output is the reduction of basic lead sulphate.     

Thermogravimetric study on perovskite-like oxygen permeation ceramic membranes

The oxygen permeation properties of mixed-conducting ceramics SrFeCo_0.5O_3−δ (SFCO), Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCFO), La_0.2Sr_0.8Co_0.8Fe_0.2O_3−δ (LSCFO) and Ba_0.95Ca_0.05Co_0.8Fe_0.2O_3−δ (BCCFO) were studied by thermogravimetric method in the temperature range 600–900 °C. The results show that the oxygen adsorption rate constants k_a of all material are larger than oxygen desorption rate constants k_d and both k_a and k_d are not strongly dependent on temperature in the studied temperature range. The oxygen vacancy contents δ(N₂) and δ(O₂) in nitrogen and oxygen and their difference Δδ = δ(N₂) − δ(O₂) play an important role in determining the temperature behavior of oxygen permeation flux J_O2.     

Thermogravimetric study of the oxidation behaviour of uranium dicarbide

Systematic studies were carried out on the oxidation behaviour of uranium dicarbide in air in the temperature range 25 °C to 700 °C employing thermogravimetry, evolved gas detection X-ray diffraction and chemical analysis. The mechanistic aspects were investigated and the oxidation was found to proceed through reaction processes involving oxidation of uranium to-UO₃ with release of chemically bound carbon, reaction of released carbon leading to the formation of CO₂ which gets liberated stepwise, decomposition of-UO₃ to U₃O₈ and oxidation of free carbon to CO₂. Examination of the thermoanalytical behaviour of sintered graphite, UO₃, mixtures of graphite with UO₃ and with U₃O₈ supported the above findings.

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Zusammenfassung Das Oxydationsverhalten von Urandikarbid in Luft im Temperaturbereich zwischen 25 und 700 °C wurde mittels Thermogravimetrie, Gasprodukteanalyse, Röntgendiffraktion und chemischer Analyse systematisch untersucht. Studien des Mechanismus ergaben, daß die Oxydation über Teilschritte abläuft, die folgende Schritte beinhalten: Oxydation von Uran zu-UO₃ unter Freisetzung chemisch gebundenen Kohlenstoffes, Reaktion des freigesetzten Kohlenstoffes unter Bildung von CO₂, das schrittweise entweicht, Zerfall von-UO₃ zu U₃O₈ und Oxydation von freiem Kohlenstoff zu CO₂. Diese Feststellungen wurden durch Untersuchung des thermoanalytischen Verhaltens gesinterter Graphit- und UO₃-Proben sowie Mischproben von Graphit mit UO₃ bzw. U₃O₈ bekräftigt.

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, , 25–700°. , , -UO₃ , , , -UO₃ U₃O₈ . ë , UO₃, UO₃ U₃O₈ .

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The authors wish to thank Dr. M. K. Ahmed for his help in O/U measurements and Dr. P. R. Vasudeva Rao for useful advices during the course of the work.     

Adsorption isotherms for benzene on diatomites from China

In this paper, benzene adsorption isotherm and their hysteresis on two important local diatomites were determined at 25℃, and their silicon hydroxyl group (SiOH) number was determined, their properties were reported, and the relationship between surface structure, surface SiOH number per nm2 and adsorption isotherm with hysteresis was discussed. The specific surface was also calculated from the isotherms, and pore-size distribution was determined.     

Thermogravimetric study of the C + SiO2 reaction

The kinetics of the reaction of one-to-one molar mixtures of crystalline silica and carbon powder were studied using thermogravimetric analysis. The resulting kinetic data was evaluated using simple kinetic and mass transport models. A two-stage reaction mechanism consisting of three stoichiometric reactions can adequately be used to describe the global reaction phenomena. Both the first and second stages of reaction were found to be influenced by diffusion mass transfer within the reacting bed of solids.

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Zusammenfassung Mittels Thermogravimetrie wurde die Reaktionskinetik der Reaktion von kristallinem Siliziumdioxid und Kohlenstoffpulver im Molverhältnis 11 untersucht. Die kinetischen Angaben wurden mittels einfachen kinetischen und Stofftransportmodellen ausgewertet. Zu einer adäquaten Beschreibung der gesamten Reaktionserscheinung kann ein Zweischrittereaktionsmechanismus bestehend aus drei stöchiometrischen Reaktionen benutzt werden. Sowohl der erste als auch der zweite Reaktionsschritt wird durch diffusiven Stofftransport innerhalb des Reaktionsbettes beeinflußt.

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This paper is based on the doctoral dissertation of the senior author.     

Thermogravimetric study of flame-retarding properties on phosphorylated beech sawdust

Beech sawdust (S) and samples containing 1% of H₃PO₄ (SP), (NaPO₃)_n (PS), P₂O₅ (POS), NaOH/P₂O₅ (SPS), NaOH (SS) or Na₂CO₃ (CS) were analysed using dynamic and isothermal thermogravimetry (TG) in nitrogen and oxygen environments. According to the results of dynamic experiments in nitrogen, the thermal resistance at 275 °C decreased in the order: S > SS > CS > SP> SPS > PS > POS, while in oxygen the order was: S > POS > SPS=CS=PS > SP > SS. The difference in residues obtained in nitrogen in comparison to oxygen environment reaches its maximum at temperatures from 300 to 325 °C and according to the decreasing values the following order could be listed: SS (300 °C/27%) > SP (325 °C/25%) > CS (300 °C/24%) > S (325 °C/23%) > SPS (300 °C/19%) > PS (300 °C/11%) > POS (275 °C/4%). This indicates that with a decreasing difference in residues formed in oxidative and inert environments the flame-retardant effect of the sample is increasing. The calculated initial rate constants of residue formation and gasification and the corresponding activation energies of the processes in nitrogen and oxygen from the isothermal experiments gave smaller values of rate constants for SPS than for S. For the SPS sample in comparison with S the activation energy of residue formation in nitrogen decreased while the three remaining values increased. The E_r* of PS in the oxygen is the biggest from all studied samples under the conditions used, while SPS gave the biggest E_g* in the oxygen environment. The phosphorus could be washed out with water from SP and SPS, while it remained in PS and POS. These last two samples also have the best flame-retarding properties according to TG analysis.     

Thermogravimetric study of silica with a chemically modified surface

Thermal methods were used to determine the thermal stability of organic groups introduced into the surface of silica precipitated following its reactions with dimethyl-dichlorosilane (DDS), methyltrichlorosilane (MTS) and methyltriethoxysilane (MTES).It was found that modification with MTS or DDS leads to a permanent hydrophobic film on the silica surface.

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Zusammenfassung Thermische Methoden wurden benutzt, um die thermische Stabilität von organischen Gruppen zu bestimmen, die auf die Oberfläche von ausgefällter Kieselsäure durch die Reaktion mit Dimethyldichlorsilan (DDS), Methyltrichlorsilan (MTS) und Methyltriäthoxysilan (MTES) eingebracht wurden. Die Modifizierung mit MTS oder DDS verursacht auf der Oberfläche der Kieselsäure eine permanente hydrophobe Schicht.

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Thermogravimetric study of some dichromates and molybdates of organic bases

A comparative study is made of the thermal and kinetic stabilities of the thermal decomposition of dichromates and molybdates of organic bases with formulae (BH)₂Cr₂O₇ and (BH)₄Mo₈O₂₆, respectively. The compounds show several steps of decomposition controlled by a random nucleation mechanism.