Thermal reactions of inorganic hydroxy-compounds under applied electric fields

The effect of electric fields on the thermal dehydration of amorphous hydrated iron(III) oxide under oxidizing, inert and reducing atmospheres was studied by X-ray diffractometry. In oxidizing and inert atmospheres, the transformation to-Fe₂O₃ was enhanced by electric fields, especially at the negative electrode. The crystallite size of the product was also greatest at the negative electrode. Both results are explained in terms of the migration of protons to the negative electrode, where they subsequently form water which acts as a nucleating agent for the crystalline phase. In reducing atmospheres the formation of Fe₃O₄ and FeO at the expense of Fe₂O₃ is facilitated by electric fields, particularly at the negative electrode. Possible reaction mechanisms are considered, and the role of protons in stabilizing defect-spinel intermediates and products is discussed.

---

Zusammenfassung Der Einfluß eines elektrischen Feldes auf die thermische Dehydratisierung des amorphen hydratisierten Eisen(III)oxids in oxidierenden, inerten und reduzierenden Atmosphären wurde durch Röntgendiffraktometrie untersucht. In oxidierenden und inerten Atmosphären wurde die Umwandlung zu -Fe₂O₃ durch elektrische Felder gefördert, besonders an der negativen Elektrode. Die Form der Kristallite des Produkts war ebenfalls an der negativen Elektrode am größten. Beide Ergebnisse werden durch die Proteinwanderung zur negativen Elektrode erklärt, wo diese Wasser bilden, das für die kristalline Phase als Keimbildner fungiert. In reduzierenden Atmosphären wird die Bildung von Fe₃O₄ und FeO auf Kosten von Fe₂O₃ durch elektrische Felder besonders an der negativen Elektrode erleichtert. Mögliche Reaktionsmechanismen werden erörtert und die Rolle der Protonen bei der Stabilisierung defekt-spineller Zwischenstufen und Produkte besprochen.

---

Résumé L'effet d'un champ électrique sur la déshydratation thermique de l'oxyde de fer(III) hydraté amorphe a été étudié par diffractométrie des rayons X, dans des atmosphères oxydante, inerte et réductrice. En atmosphères oxydante et inerte, le champ électrique facilite la transformation en -Fe₂O₃, en particulier à l'électrode négative. La taille des cristaux formés est également plus élevée à l'électrode négative où il se forme de l'eau qui agit comme agent de nucléation de la phase cristalline. En atmosphère réductrice, le champ électrique facilite la formation de Fe₃O₄ et FeO, aux dépens de Fe₂O₃, en particulier à l'électrode négative. On considère les mécanismes de réaction possibles et on discute le rôle des protons sur la stabilisation des produits et des intermédiaires défauts-spinelles.

---

- (III) , . -Fe₂O₃ , , . , , . Fe₃O₄ FeO Fe₂O₃ . , .

---

---

The author is indebted to P. J. Melling for assistance with the measurements in H₂/N₂ atmospheres.     

Nondestructive compositional depth profiling using variable‐kinetic energy hard X‐ray photoelectron spectroscopy and maximum entropy regularization

We discuss the calculation of nondestructive compositional depth profiles from regularization of variable kinetic energy hard X‐ray photoelectron spectroscopy (VKE‐XPS) data, adapting techniques developed for angle‐resolved XPS. Simulated TiO₂/Si film structures are analyzed to demonstrate the applicability of regularization techniques to the VKE‐XPS data and to determine the optimum choice of regularization function and the number of data points. We find that using a maximum entropy‐like method, when the initial model/prior thickness is similar to the simulated film thickness, provides the best results for cases where prior knowledge of the sample exists. For the simple structures analyzed, we find that only five kinetic energy spectra are necessary to provide a good fit to the data, although in general, the number of spectra will depend on the sample structure and noisiness of the data. The maximum entropy‐like algorithm is then applied to two physical films of TiO₂ deposited on Si. Results suggest interfacial intermixing. Published 2014. This article is a U.S. Government work and is in the public domain in the USA.     

Thermal reactions of inorganic hydroxy-compounds under applied electric fields,III

The energy level separation in symmetrical and unsymmetrical double minimum potentials in the presence of electric fields is calculated by first-order perturbation theory, from which the tunnelling probability of protons is obtained for both perturbed and unperturbed potentials. Tunnelling probability is slightly increased by fields of about 10⁵ V/m, but a greater increase in tunnelling probability occurs when a symmetric potential becomes unsymmetric. The tunnelling process is too rapid to account for observed differences in dehydroxylation behaviour of Al(OH)₃, Mg(OH)₂ and kaolinite under electrolysis. Estimates, from indirect evidence, of the rates of anion defect generation and annihilation support the theory that the rate-determining field-dependent process is the surmounting of anionic lattice vacancies by oxygen-containing species.

---

Zusammenfassung Die Trennung des Energieniveaus in symmetrischen und unsymmetrischen doppelten Minimumpotentialen in Gegenwart von elektrischen Feldern wird mittels einer Störungstheorie erster Ordnung berechnet, aus welcher die Wahrscheinlichkeit der Tunnelbildung von Protonen für gestörte sowie ungestörte Potentiale erhalten wird. Felder von 10⁵V/m erhöhen die Wahrscheinlichkeit der Tunnelbildung in geringem Maße, eine bedeutendere Zunahme der Wahrscheinlichkeit der Tunnelbildung tritt jedoch auf, wenn ein symmetrisches Potential unsymmetrisch wird. Der Vorgang der Tunnelbildung ist zu schnell um die Unterschiede des Verhaltens von Al(OH)₃, Mg(OH)₂ und Kaolinit bei der elektrolytischen Dehydroxylierung zu erklären. Schätzungen der Geschwindigkeiten der Anionen-Defektbildung und -Vernichtung aus indirekten Angaben unterstützen die Theorie, daß der geschwindigkeitsbestimmende, feldbedingte Vorgang die Überdeckung der Lücken im Anionengitter durch sauerstoffhaltige Arten ist.

---

Résumé La séparation des niveaux d'énergie des potentiels à minimum double, symétrique et asymétrique, se calcule à l'aide de la théorie des perturbations du premier ordre, à partir de quoi la probabilité de l'effet tunnel des protons s'obtient aussi bien pour les potentiels perturbés que pour les non perturbés. La probabilité de l'effet tunnel augmente quelque peu sous l'influence de champs d'environ 10⁵ V/m, mais une augmentation plus notable de cette probabilité apparaît quand un potentiel symétrique devient asymétrique. Le processus de l'effet tunnel est trop rapide pour rendre compte des différences de comportement observées pour Al(OH)₃, Mg(OH)₂ et la kaolinite lors de l'électrolyse déshydroxylante. Des estimations faites à partir de données indirectes pour connaître les vitesses d'apparition des défauts anioniques et celles de leur disparition, viennent à l'appui de la théorie suivant laquelle le processus dépendant du champ et déterminant la vitesse est celui de l'occultation des lacunes du réseau anionique par des espèces contenant de l'oxygène.

---

. , . 10⁵V/; , . , Al(OH)₃, Mg(OH)₂ . , , .

---

---

Part of this work was carried out under an S.R.C. research grant. The author is indebted to Dr. J.P.M. Bailey for advice on the quantum-mechanical calculations, Dr. W.T. Raines and Dr. P.G. Rouxhet for helpful discussion. and to Mrs. F. Jackson for the computing.     

Thermal reactions of inorganic hydroxy-compounds under applied electric fields,I

A method which has been developed for thermogravimetric study of solids in the presence of applied electric fields has been used in a study of kaolinite dehydroxylation in a controlled inert atmosphere. Electric fields of 10⁵ V/m lower the initiation temperature for dehydroxylation by as much as 60 in some cases; the activation energy for dehydroxylation is reduced by 3–12 kcal/mole. The rate constants for electrolysed samples (based arbitrarily on a first-order law) are increased by electrolysis but this effect falls off at higher temperatures as the normal thermal processes begin to predominate. The effect of the field on the various processes of ionic migration in the lattice is discussed.

---

Zusammenfassung Eine zur thermogravimetrischen Analyse von Festkörpern unter Anwendung elektrischer Felder entwickelte Methode wurde zum Studium der Dehydroxylierung von Kaolinit in einer geregelten inerten Atmosphäre herangezogen. Elektrische Feldstärken von etwa 10⁵ V/m setzten die Anfangstemperatur der Dehydroxylierung in einigen Fällen sogar um 60 C herab; die Aktivierungsenergie der Dehydroxylierung wird um 3 bis 12 kcal/mol herabgesetzt. Die — willkürlich aufgrund einer Gesetzmäßigkeit erster Ordnung berechneten — Geschwindigkeitskonstanten der elektrolysierten Proben werden durch die Elektrolyse erhöht, doch fällt dieser Effekt bei höheren Temperaturen, wo er von den normalen thermischen Vorgängen überlagert wird, weg.Die Wirkung des elektrischen Feldes auf die verschiedenen Vorgänge der Ionenwanderung im Gitter wird erörtert.

---

Résumé On a mis au point une méthode pour l'étude thermogravimétrique des solides sous l'action d'un champ électrique et on l'a utilisée pour suivre la déshydroxylation de la kaolinite en atmosphère inerte contrÔlée. L'application de champs électriques d'environ 10⁵ V/m abaisse la température initiale de la déshydroxylation de 60 C dans certains cas et l'énergie d'activation est réduite de 3 à 12 kcal/mol. On observe l'augmentation des constantes de vitesse des échantillons soumis à l'action du champ électrique (par rapport à une loi choisie arbitrairement du 1^er ordre) mais cet effet cesse aux températures élevées où les processus thermiques normaux deviennent prédominants.On discute l'influence du champ électrique sur les processus de migration d'ions dans la grille.

---

. , 10⁵ V/m, , 60C; 3–12 /. ( ) , , .

---

---

This work was supported by an S.R.C. Research Grant. The author is indebted to Dr W.T. Raines and Dr G. M. Fryer for helpful discussion.     

Thermal reactions of inorganic hydroxy-compounds under applied electric fields,II

The effect of electric fields on the thermal dehydroxylation of Mg(OH)₂ (brucite) and Al(OH)₃ (gibbsite) have been studied by thermogravimetry in a controlled inert atmosphere. Electric fields exert no beneficial effect on the reaction of gibbsite; in some cases the reaction is slightly retarded. By contrast, a small but significant beneficial effect is observed in brucite, in which the initiation temperature and activation energy is lowered at field strengths of about 10⁵ V/m. The difference in behaviour of the two hydroxides is attributed to differences in the mobility of anionic defects and oxygen-containing “proton-transfer complexes”. The transport of the various protonbearing species in an electric field is discussed.     

Synthesis of organic‐inorganic hybrid gels by means of thiol‐ene and azide‐alkene reactions

Organic–inorganic hybrid gels have been synthesized from a multi‐vinyl functional cyclic siloxane, 1,3,5,7‐tetravinyltetramethylcyclotetrasiloxane (TVMCTS), or a cubic silsesquioxane, octavinyloctasilasesquioxane (PVOSS), and α,ω‐dithiol compounds, 1,6‐hexanedithiol (HDT), 1,10‐decanedithiol (DDT), using thiol‐ene reaction in toluene. The network structure of the resulting gels, mesh size and mesh size distribution, was quantitatively characterized by means of a scanning microscopic light scattering (SMILS). The gels obtained from TVMCTS‐HDT formed homogeneous network structure with 1.5–1.6 nm mesh. Relaxation peaks derived from large clusters and/or micro gels were detected in the SMILS analysis of the TVMCTS‐DDT, PVOSS‐HDT, and PVOSS‐DDT gels besides those from the small meshes. The organic–inorganic hybrid gels were also synthesized from TVMCTS, PVOSS with α,ω‐diazide compounds, 1,6‐hexanediazide (HDA), 1,10‐decanediazide (DDA), using azide‐alkene reaction in toluene. All the gels obtained with the azide‐alkene reaction formed the homogeneous network structure. Enthalpy relaxation at the glass transition of the dried samples was detected by differential scanning calorimetry to study the network uniformity of the original gels. The gels synthesized by the azide‐alkene reaction showed larger enthalpy than the gels synthesized by the thiol‐ene reaction, indicating homogeneous network structure in the former gels. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2229–2238     

Isothermal kinetic calorimeter applied to emulsion polymerization

A method for the direct measurement, by means of the heat of reaction, of essentially instantaneous polymerization rates is described. The polymerization is carried out isothermally, and the evolved heat is measured electrically over short time intervals. Applied to emulsion polymerization, the technique reveals several previously unobserved features.     

Damage‐depth profiling of ion‐irradiated polyimide films with a variable‐energy positron beam

Various polyimide layers [2.2–2.6 μm of hexafluoroisopropylidene bis(phthalic anhydride‐oxydianiline), pyromellitic dianhydride‐oxydianiline, and 3,3′‐4,4′‐biphenyltetracarboxylic dianhydride‐p‐phenylenediamine] spin‐coated on silicon substrates were studied with a variable‐energy positron beam in combination with a Doppler‐broadened annihilation radiation technique. From the experiments, the thickness of the layers was estimated with the VEPFIT routine. These values corresponded well to the values determined from interferometry and ellipsometry. Irradiation of the polyimides with 1 × 10¹⁵ boron ions/cm² at an energy of 180 keV led to a strong chemical modification of the irradiated top layer. This caused the inhibition of positronium formation in the irradiated layer, which was observed as a lowering of the annihilation line S parameter. The thickness of the modified layer was estimated to be 700–800 nm. This value did not agree with the ellipsometric measurements but corresponded to the maximum implantation depth of boron ions calculated with TRIM (Transport of Ions in Matter) code. The positron results appeared somewhat larger than the TRIM estimates. Reasons for these relations are discussed. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 3062–3069, 2000     

Application of variable-temperature kinetic experiments to oxidative addition reactions of dimethylplatinum(II) complexes with alkyl halides

Rate constants and activation parameters of oxidative addition reactions of [PtMe₂(2,2′-bipyridine)] with EtI and [Pt(p-MeC₆H₄)₂ (2,2′-bipyridine)] with MeI in solvents acetone and benzene have been obtained very easily and with good accuracy from variable-temperature spectrophotometric kinetic data using a method based on nonisothermal analysis. The results are compared with those obtained by the traditional isothermal method. It is shown that there are significant advantages to measuring the reaction rates under variable-temperature kinetic conditions, as compared to the constant-temperature kinetic method.     

Biospecific interaction analysis using surface plasmon resonance detection applied to kinetic, binding site and concentration analysis.

A system for real-time biospecific interaction analysis using biosensor technology based on the optical phenomenon surface plasmon resonance is described. The biospecific interface is a sensor chip covered with a hydrogel matrix. One component of the interaction to be studied is immobilized covalently to the hydrogel and other interactants are passed over the chip in solution. The mass change at the sensor surface, reflecting the progress of the interaction studied, is monitored in real time. The technique, which does not require molecular labels for detection, can measure mass changes down to 10 pg/mm2. Repeated analyses can be performed on the same sensor chip. Applications shown include kinetic measurements, binding site analysis and concentration determination.     

Solution route to inorganic nanobelt‐conducting organic polymer core‐shell nanocomposites

A facile and versatile solution‐based approach was developed to prepare semiconductor metal oxide nanobelt‐conducting organic polymer core‐shell nanocomposites. Well‐defined nanobelts of several types of oxide nanobelts were combined with conducting polymer [polypyrrole (PPy) and polyaniline (PANi)] via in situ polymerization in aqueous solution to obtain a new type of inorganic–organic composite nanostructure. Samples were characterized by using X‐ray diffraction, scanning electron microscopy, transmission electron microscopy, Fourier transform infrared, electron energy loss spectra, high‐resolution transmission electron microscopy, and ultraviolet–visible techniques. Electron energy loss spectra revealed the existence of C?C and C? N bonds in coating layers to prove the encapsulation of PPy or PANi. The red‐shift of absorption band at high‐energy was observed for PPy‐encapsulated composites via ultraviolet–visible spectroscopy, and significant absorption band shifts were also encountered to PANi‐encapsulated composites, which suggest possibilities of band‐gap tuning of such metal oxide‐conducting polymer composites to be applied especially in solar cell devices. However, the sacrifice of nanobelts‐core led to hollow structures of PPy and PANi, which expands the synthetic strategies to prepare conducting polymer nanotubes. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2892–2900, 2005     

Free‐radical copolymerization of styrene and itaconic acid studied by 1H NMR kinetic experiments

The free‐radical copolymerization of itaconic acid (IA) and styrene in solutions of dimethylformamide and d₆‐dimethyl sulfoxide (50 wt %) has been studied by ¹H NMR kinetic experiments. Monomer conversion versus time data were used to estimate the ratio k_p · k_t^−0.5 for various comonomer mixture compositions. The ratio k_p · k_t^−0.5 varies from 5.2 · 10⁻² for pure styrene to 2.0 · 10⁻² mol^0.5 L^−0.5 s^−0.5 for pure IA, indicating a significant decrease in the rate of polymerization. Individual monomer conversion versus time traces were used to map out the comonomer mixture–composition drift up to overall monomer conversions of 60%. Within this conversion range, a slight but significant depletion of styrene in the monomer feed can be observed. This depletion becomes more pronounced at higher levels of IA in the initial comonomer mixture. The kinetic information is supplemented by molecular weight data for IA/styrene copolymers obtained by variation of the comonomer mixture composition. A significant decrease in molecular weight of a factor of 2 can be observed when increasing the mole fraction of IA in the initial reaction mixture from 0 to 0.5. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 656–664, 2001     

Coupled membrane process applied to fruit juice concentration

A coupled membrane process of membrane distillation and osmotic evaporation, where the solutions were thermostated separately at different temperatures, was developed. Enhanced water flux was obtained since the total driving force of the coupled process was higher than the sum of the driving forces of single processes. Apple, raspberry, sour cherry, red, and black currant juices were concentrated by the novel, mild technique. Presented at the 33rd International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 22–26 May 2006.     

A variable‐temperature study of 1,2‐bis(dimethylamino)‐1,2‐bis(2,6‐dimethylanilino)diborane

The title compound, C₂₀H₃₂B₂N₄, is monoclinic at ambient temperature but triclinic (pseudo‐monoclinic) below 150 K. The structures of the two phases, determined at 200 and 120 K, respectively, are very similar, the molecular symmetry being crystallographic C₂ and approximate (local) C₂, respectively. There is significant π conjugation within each N—B—N moiety, but none between them or between the N—B—N and arene moieties.     

Facile synthesis of core‐shell organic–inorganic hybrid nanoparticles with amphiphilic polymer shell by one‐step sol–gel reactions

Organic–inorganic hybrid core‐shell nanoparticles with diameters ranging from 100 to 1000 nm were prepared by a one‐pot synthesis based on base catalyzed sol–gel reactions using tetraethoxysilane and a triethoxysilane‐terminated polyethylene‐b‐poly(ethylene glycol) as reactants. Data from TEM, TGA, and solid‐state NMR analysis are in agreement with the formation of core‐shell nanoparticles with an inorganic‐rich core and an external shell consisting of an amphiphilic block copolymer monolayer. The influence of the organic–inorganic ratio, solution concentration, and postcuring temperature on core and shell dimensions of the nanospheres were investigated by TEM microscopy. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1699–1709, 2008     

Configuration-specific kinetic theory applied to an ideal binary gas mixture

This paper is the second in a two-part series dealing with the configuration-specific analyses for molecular collision events of hard, spherical molecules at thermal equilibrium. The first paper analyzed a single-component system, and the reader is referred to it for the fundamental concepts. In this paper, the expressions for the configuration-specific collision frequencies and the average line-of-centers collision angles and speeds are derived for an ideal binary gas mixture. The analyses show that the average line-of-centers quantities are all dependent upon the ratio of the masses of the two components, but not upon molecular size. Of course, the configuration-specific collision frequencies do depend on molecular size. The expression for the overall binary collision frequency is a simple sum of the configuration-specific collision frequencies and is identical to the conventional expression.     

Non-isothermal kinetic applied to thermal decomposition of commercial alkyd varnish

Summary PHB polyester poly(3-hydroxybutyrate) is an interesting biodegradable polymer and intensively investigated as cast and sheet films with applications in food industry or in medicine. The films obtained are typically brittle and many scientists have attempted to reduce this brittleness by blending with other polymers. PHB from Usina da Pedra was blended with PEG poly(ethyleneglycol) 300 resulting in blend 1 and blend 2. The two mixtures were melted at 200 and quenched at 0°C. TG curves showed that the thermal stability of the blends and the PHB are identical. For these blends the crystallization temperature decreased compared to the pure PHB, which is probably due to the lower nucleation density.     

Kinetics of reactions in solution: Method for the treatment of data from non-isothermal chemical kinetic experiments

A new method is proposed for the treatment of kinetic data derived from non-isothermal kinetic experiments for the determination of the parameters of the Arrhenius equation. The results obtained from its application show the excellent precision of this method.

---

. , , .