Crystallization of glasses in the system SiO2-Li2O-TiO2-Al2O3, investigated in situ at high temperature by XRD and DTA methods

The processes of crystallization of fibres (diameter 10–15m) and coarse powders (grain size 500–1000m) with four compositions in the system SiO₂-Li₂O-TiO₂-Al₂O₃ were studied by conventional and in situ high-temperature XRD, DTA, SEM and optical microscopy. Activation energies of crystallization and morphological indices were deduced from the kinetic curves obtained by recording the high-temperature XRD peak intensity as a function of time. The glass-ceramic fibres drawn from compositions which exhibit glass-inglass phase separation show prevailing not-oriented bulk crystallization, whereas prevailing surface crystallization was found for single-phase glass fibres. Homogeneously-dispersed crystallization was obtained on heating fibres of these compositions. The partially cocrystallized glass fibres of eutectic composition between Li-metasilicate and-spodumene gave rise to a very fine and homogeneously-dispersed sub-microstructure.

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Zusammenfassung Die Prozesse der Kristallisation von Fasern (Durchmesser 10–15m) und groben Pulvern (Korngröße 500–1000m) von SiO₂-LiO₂-TiO₂-Al₂O₃ in vier verschiedenen Zusammensetzungen wurden mittels herkömmlicher und in situ XRD, DTA, SEM und optischer Mikroskopie untersucht. Aktivierungsenergien der Kristallisation und morphologische Indices wurden aus den durch Registrierung der Intensität der Hochtemperatur-XRT-Peaks in Abhängigkeit von der Zeit erhaltenen kinetischen Kurven ermittelt. Die aus Gemischen einer die Glas-in-Glas-Phasentrennung bedingenden Zusammensetzung gezogenen Glas-Keramik-Fasern zeigen vorwiegend eine nicht-orientierte Bulk-Kristallisation, während vorherrschend Oberflächenkristallisation bei Einphasen-Glasfasern festgestellt wurde. Eine homogen verteilte Kristallisation wurde beim Erhitzen der Fasern dieser Zusammensetzungen erhalten. Bei partiell ko-kristallisierten Glasfasern einer eutektischen Mischung von Li-Metasilikat und (-Spodumen liegt eine sehr feine und homogen-disperse Submikrostruktur vor.

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( 10–15 ) ( 500–1000 ) SiO₂-Li₂O-iO₂AL₂O₃ , , . , - . , --, ë, - . - . — - - - .

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This work was supported by the Italian C. N. R., Progetto Finalizzato Chimica Fine e Secondaria — Sottoprogetto Metodologie.

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We are indebted to Dr. B. Locardi of Stazione Sperimentale del Vetro, Murano (Venice) for furnishing the initial glasses and fibres.

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We are also indebted to the G. Giacomello Institute (C. N. R., Rome) for furnishing the computer programme for the unit cell parameter refinement. Assistance by M. Pistolato and F. Venuda in the experimental work is gratefully acknowledged.     

Hydrocondensation of CO2: Reaction of CO2(CO)/H2 on CuO/ZnO contact masses

The hydrocondensation of CO₂ and CO with and without added MeOH, HCHO and (CH₃)₂CHOH has been studied on CuO/ZnO contact masses in a static reactor at different pressures and reaction times.

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CO₂ CO MeOH, HCHO (CH₃)₂CHOH CuO/ZnO .

     

Kinetics of isotope exchange of dioxygen with a powdered high-temperature superconducting material Ba2YCu3O7?x

It has been found that the rate of isotope exchange in Ba₂YCu₃O_7–x–O₂ system is high. Its kinetics is exponential, first order with respect to dioxygen and the exchange is of the mixed first/third type.

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Ba₂YCu₃O_7–x–O₂ . -, -, - .

     

ERS spectrum of methyl radicals on ZnO surface

The established formation of methyl radicals on the ZnO surface due to the interaction of methane with photoinduced hole centers O_s indicates that their formation and thermal destruction occur without participation of surface electron centers Zn_s.

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ZnO O _s ^– . , Zn _s ⁺ .

     

Thermal properties of the clathrate compounds of binary cyanides

The stoichiometry of thermal decomposition of a particular group of clathrate compounds, of the type Cd(en)Pd(CN)₄·2G, with the same coordination component but different clathrate-enclosed components, was investigated. Irrespective of the experimental conditions, the liberation of the enclosed component G always proceeded in one step. Thermal investigation of the decomposition stoichiometry under identical experimental conditions showed that the temperature intervals in which the enclosed components are given off shift to lower temperatures in the order C₆H₅OH=> C₆H₆ > > C₄H₅N > C₄H₄S. Diffraction measurements indicated a considerable change in the structures of the original clathrate compounds after thermal release of the enclosed componentG.

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Zusammenfassung Die Stöchiometrie der thermischen Zersetzung einer bestimmten Gruppe von Klathratverbindungen vom Typ Cd(en)Pd(CN)₄·2G mit der gleichen Koordinationskomponente und verschiedenen Klathrat-Einschlußkomponenten wurde in dieser Studie untersucht. Ungeachtet der Versuchsbedingungen vollzieht sich die Freisetzung der eingeschlossenen KomponenteG stets in einer Stufe. Die unter gleichen Versuchsbedingungen durchgeführte thermische Untersuchung der Zersetzungsstöchiometrie zeigte, daß die Temperaturbereiche, in denen die eingeschlossenen Komponenten freigesetzt werden in der Reihenfolge C₆H₅OH > C₆H₆ > C₄H₅N > C₄H₄S in Richtung der niedrigeren Temperaturwerte verschoben werden. Die Diffraktionsmessungen weisen darauf hin, daß eine beträchtliche Änderung der Struktur der ursprünglichen Klathratverbindung nach thermischer Freisetzung der eingeschlossenen KomponenteG sichtbar wird.

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Résumé Dans cette étude on a établi la stoechiométrie de la décomposition thermique d'un groupe particulier de clathrates du type Cd(en)Pd(CN)₄·2G, avec le même composant de coordination et différents composants occlus. Indépendamment des conditions d'expériences, la libération du composant occlusG s'effectue toujours en une étape. L'étude thermique de la stoechiométrie de la décomposition effectuée dans les mêmes conditions d'expériences, a montré que les intervalles des températures dans lesquels les composants occlus sont libérés, se déplacent vers les températures plus faibles dans l'ordre suivant: C₆H₅OH > C₆H₆ > > C₄H₅N > C₄H₄S. Les mesures de diffraction indiquent qu'après la libération thermique du composant occlusG, une variation considérable de la structure initiale des clathrates originaux apparaît.

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Cd(en)Pd(CN)₄. 2G . , G . , , , ] ₆₅>₆₆>C₄H₆N>C₄H₄S. - , G.

     

Heterogeneous reactions of solid nickel(II) complexes, IV

The decomposition heats (H) for complexes of the type Ni(NCS)₂L₂ were studied by means of a differential scanning calorimeter. From the decreasing values ofH the following order has been established:a) for pseudooctahedral complexes: py >-pic > > Q; andb) for square-planar complexes: 2,6-lut > Q >-pic. The results obtained are compared with the data from the TG, DTG, and DTA curves.

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Zusammenfassung Es erfolgte die Bestimmung der Zersetzungswärmen (H) der Komplexe vom Typ Ni(NCS)₂L₂ durch die Differential Scanning Calorimetrie. Mit abnehmendenH Werten ergab sich die Reihenfolge:a) Pseudooktaedrische Komplexe: Py >ß-Pic > Q;b) Quadratische Komplexe: 2,6-Lut. > Q >-Pic. Ergebnisse mit aus den DTA, TG und DTG-Kurven gewonnenen Resultaten wurden verglichen.

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Résumé Détermination par analyse enthalpique différentielle des chaleurs de décomposition (H) des complexes de formule générale Ni(SCN)₂L₂. Le classement des valeurs deH par ordre décroissant montre que pour les complexes pseudo-octaédriques py >gb-pic > Q et que pour les complexes plans carrés lut-2,6 > Q >-pic. Comparaison de ces résultats avec les données des courbes TG, TGD et ATD.

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(H) Ni(NCS)₂L₂. H : ) >-pic > Q; ) 2,6 lut > Q >-Pic. , , .

     

Quantum chemical calculations on the catalytic dehydration of 2-propanol

The charge on atoms and the bond strengths in CH₃CHOHCH₃, CH₃ CH₃, CH₃CHOHCH ₂ ^– , CH₃ CH ₂ ^– and CH₃ CH₃...O(H)CH(CH₃)₂ have been calculated by the CNDO/2 method. The results are in agreement with published experimental observations on catalytic dehydration. A modified mechanism of anti-elimination on solid catalysts is proposed.

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CH₃CHOHCH₃, CH₃ CH₃, CH₃CHOHCH ₂ ^– , CH₃ CH ₂ ^– CH₃ CH₃...O(H)CH(CH₃)₂, CNDO/2. . .

     

Phenothiazine cation radical formation on silica, silica-alumina and alumina

The solution of phenothiazine in benzene produces phenothiazine cation radicals on the surface of silica, alumina and silica-alumina catalysts.

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- SiO₂, Al₂O₃ .

     

Design and application of a liquid-flow adsorption micro calorimeter based on the Calvet-type DAK 1-1 microcalorimeter (USSR)

The construction and the properties of a liquid-flow adsorption microcalorimeter are described. The calorimeter is based on the commercially available Calvet-type DAK 1-1 microcalorimeter (USSR), which has been equipped with a flow system consisting of a pump, several sets of heat exchangers and an adsorption cell. The minimum detectable heat effect is 1W up to a flow rate of 30 cm³/h.Results on the application of the calorimeter to adsorption and desorption processes of nonionic (Triton X-100) and anionic (styrene phosphonic acid) surfactant solutions in water at an-Al₂O₃ surface are presented and discussed.

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Zusammenfassung Konstruktion und Eigenschaften eines Flüssigkeits-Strömungs-Adsorptions-Mikrokalorimeters werden beschrieben. Das Kalorimeter wurde weiterentwickelt aus dem Calvet-Mikrokalorimeter DAK 1-1 (USSR), das mit einem Strömungssystem aus einer Pumpe, verschiedenen Wärmeaustauschern und einer Adsorptionszelle ausgestattet wurde. Der kleinste nachweisbare Wärmeeffekt liegt bei 1W bis zu einer Durchflussgeschwindigkeit von 30 cm³ h^–1. Mit dem Kalorimeter erhaltene Messergebnisse zur Adsorption und Desorption wässeriger Lösungen von nichtionischen (Triton X-100) und anionischen (Styrenphosphonsäuren) Tensiden an-Al₂O₃ werden dargestellt und diskutiert.

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, 1-1 (), , , . 1 30 ³/. ( X–100) (- ) -l₂₃.

     

ESR studies of photoinduced centers on weakly reduced anatase

The paramagnetic centers of reduced anatase (g₁=1.999, g₂=1.984, g₃=1.979) and (g₁=2.046, g₂=2.008), assigned to the stabilization of photoinduced holes near anion vacancies, have been studied. For the reduced oxide a new type of O₂ photoadsorption at h >1 eV due to the generation of only electron surface centers has been discovered.

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, : (g₁=1,999, g₂=1,984, g₃=1,979) (g₁=2,046, g₂=2,008), . O₂ h>1 , .

     

Silane-silanol condensation catalyzed by organotin compounds

The rate of condensation of H–SiR₂–(OSiR₂)_n–H (n=2, 3 or 4 and R=CH₃) and HO-SiRR–(OSiRR)₃–OH (R=C₆H₅) in xylene at 100 °C, catalyzed by dibutyltin diacetate, dilaurate and di-(2-ethyl)hexanoate, has been studied by infrared spectroscopy. The kinetic law is first order in each reactant and the reaction is accompanied by autocondensation of the silanol. The mecha nism involves complexation of the silanol with the catalyst, followed by the attack of a silane or silanol molecule.

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H–SiR₂–(OSiR₂)_n–H ( n=2,3 4 R=CH₃) HO–SiRR–(OSiRR)₃–OH ( R=C₆H₅) 100° C, , -(2-) , . . .

     

Thermal and photochemical stability of polystyrene and its blends with polyvinyl chloride

The influence of some irregularities in polystyrene (PS) and polyvinyl chloride (PVC) chains on their thermal stability was investigated. UV irradiation caused an increase in the content of these irregularities in the polymers. It was found that the presence of carbonyl groups and crosslinking of the polymer chains hamper the thermal dehydrochlorination of PVC and the total decomposition of both polymers. On the other hand, weak peroxy linkages (which facilitate degradation processes) and conjugated double bonds decrease the temperature of total decomposition of PS and PVC blends.

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Zusammenfassung Es wurde der Einfluß von Unregmlmäßigkeiten in Polystyrol (PS)- und Polyvinylchlorid (PVC)-Ketten auf deren thermische Stabilität untersucht. UV-Bestrahlung verursacht ein Ansteigen des Gehaltes an Unregelmäßigkeiten in den Polymeren. Es wurde festgestellt, daß die Gegenwart von Carbonylgruppen und Querverbindungen der Polymerketten die thermische Dehydrochlorierung von PVC und eine vollständige Zersetzung beider Polymere verhindern. Andererseits senken Peroxidverknüpfungen (die die Degradierungsvorgänge erleichtern) und konjugierte Doppelbindungen die Temperatur für eine vollständige Zersetzung von PS und PVC Gemischen.

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. - . , . , , , .

     

Influence of sodium salt addition on the morphological and catalytic properties (ethane hydrogenolysis) of aluminasupported cobalt

NaNO₃ addition to Co/Al₂O₃ results in an increase in the reducibility, in a smaller dispersity of the metal and in a decrease in the ethane hydrogenolysis rate due to a decorative effect.

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NaNO₃ Co/Al₂O₃ ,

     

The thermometric and enthalpimetric determination of organic compounds

Two main parameters determine the methods for the assay of organic compounds in industrial systems; these are the rates of reaction of the molecular organic and often non-aqueous systems which differ from those in ionic and aqueous systems, and secondly, the fact that in most organic systems an organic functional group is required to be determined by a general method applicable to the functional group in a variety of chemical environments. In pharmaceutical products it is desired to determine the functional groups without prior separation from excipients of various kinds and to obtain rapid assays, often with precision much lower than those normally required in inorganic systems. These methods are discussed with examples taken from the foodstuff industry, the pharmaceutical industry, etc.

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: , . , - , . . , . , , .

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Partly presented at the II. Seminar Thermometric Analysis, Budapest, September 2–7, 1980.     

Acidity and cyclohexene isomerization activity of aluminas from sodium aluminate

The relationship between the catalytic activity of aluminas and the pH of precipitation of the corresponding aluminium hydroxides and the Na₂O/Al₂O₃ molar ratio of sodium aluminate is shown. The precipitation agent exerts a strong effect on the catalytic activity of the aluminas.

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pH , Na₂ O/Al₂O₃ . .

     

A rapid method for catalyst testing. Zeolite catalysts for methanol conversion to hydrocarbon

A rapid method for testing catalysts is suggested, which permits a 30-fold reduction in the time of their examination. The method is recommended for studying catalytic processes taking place with either evolution or absorption of heat.

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- , Qj 30 . , .

     

Methods for finding steady-state solutions of mathematical models for chemico-technological schemes

Gradient and Newton methods are suggested for searching for steady-state solutions of chemico-technological schemes to obtain synthetic fuels.

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- .

     

The consistency of repeated H2?O2 titration cycles on supported Pt catalysts

H₂ and O₂ uptakes at 296 K on a Pt/Al₂O₃ catalyst remained constant during repeated H₂–O₂ titration cycles conducted in a high vacuum adsorption system. Previously reported variations in these uptakes are attributed to adsorption of contaminants during desorption conditions. Also, it was found that nearly 40% of the H₂ adsorbed could be removed by degassing at 296 K for 1 hr.

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H₂ O₂ 296 Pt/Al/₂O₃ H₂–O₂, . . , 40% H₂ 1 296 .

     

The relationship between the structures of Cu(II) complexes and their chemical transformations

The paper presents the results of a study of the course of thermal decomposition of complexes Cu(NCO)₂L₂ and Cu(LNCO)₂, withL=pyrazole, 3,5-dimethylpyrazole, 3,4,5-trimethylpyrazole and indazole. The DTA curves of Cu(NCO)₂L₂ show exothermic excursions somewhat below the decomposition temperatures, corresponding to an inner complex nucleophilic addition of a carbon atom (from an NCO group) to the imine nitrogen atom of a pyrazole ligand. In this reaction the carbamoylpyrazolate anion is formed, coordinated to Cu(II). For these reactions the DSC method yielded the followingH values: –12.80 kJ mol^–1 (L=pyrazole), –8.15 kJ mol^–1 (L=3,5-dimethylpyrazole), –19.49 kJ mol^–1 (L=3,4,5-trimethylpyrazole) and –11.59 kJ mol^–1 (L=indazole). The course of thermal decomposition for Cu(NCO)₂L₂ after the nucleophilic addition is the same as for Cu(LNCO)₂. The structure differences between the distortion isomers of Cu(NCO)₂L₂ and Cu(LNCO)₂ were manifested in the decomposition temperatures and, in some cases, also in the stoichiometry of the decomposition reactions.

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Zusammenfassung Der Verlauf der thermischen Zersetzung der Komplexe Cu(NCO)₂L₂ und Cu(LNCO)₂ mitL= Pyrazol, 3,5-Dimethylpyrazol, 3,4,5-Trimethylpyrazol und Indazol wurde untersucht. Die DTA-Kurven von Cu(NCO)₂L₂ zeigen etwas unterhalb der Zersetzungstemperaturen exotherme Effekte, die einer inneren komplexen nukleophilen Addition eines Kohlenstoffatoms (von einer NCO-Gruppe) an das Iminstickstoffatom eines Pyrazol-Liganden entsprechen. In dieser Reaktion wird das an Cu(II) koordinativ gebundene Carbamoylpyrazolat-Anion gebildet. Für diese Reaktionen wurden mit der DSC-Methode folgendeH-Werte erhalten: –12,80 kJ· mol^–1 (L= Pyrazol), –8,15 kJ·mol^–1 (L= 3,5-Dimethylpyrazol), –19,49 kJ·mol^–1 (L=3,4,5-Trimethylpyrazol) und –11,59 kJ·mol^–1 (L= Indazol). Nach der nukleophilen Addition zeigt Cu(NCO)₂L₂ den gleichen thermischen Zersetzungsverlauf wie Cu(LNCO)₂. Die Strukturunterschiede zwischen den Distortionsisomeren von Cu(NCO)₂L₂ und Cu(LNCO)₂ manifestieren sich in der Zersetzungstemperatur und, in einigen Fällen, auch in der Stöchiometrie der Zersetzungsreaktion.

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Cu(NCO₂L₂ Cu(LNCO)₂, L=, 3,5- , 3,4,5- . Cu(NCO)₂L₂ , ( NCO) . -, . H: : –12,80 /, 3,5- — –8,15 /, 3,4,5- –19,49 / — – 11,59 /. , Cu(LNCO)₂. — .