Reaktion von Kaolinit mit Kaliumhydroxid

The reaction of kaolinite with potassium hydroxide (1 to 9N) was investigated between 70 and 90°C. During a first period of the reaction the content of Si and Al in solution increased and reached a maximum in 100 to 240 minutes, depending on KOH concentration and temperature; then an amorphous aluminosilicate gel formed. After an induction period, again depending on KOH concentration and temperature, the concentrations of Si and Al decreased rapidly, due to the formation of a crystalline potassium aluminosilicate.     

Characterization of the aluminum/potassium chlorate mixtures by simultaneous TG-DTA

Thermogravimetry (TG) and differential thermal analysis (DTA) in the non-isothermal mode have been used to examine the thermal behaviour of the micron sized aluminum (Al) powder/potassium chlorate pyrotechnic systems in air, in relation to the behaviour of the individual constituents. The effects of different parameters of Al powder, such as particle size and its content in the mixtures, on their thermal property were investigated. The results showed that, the reactivity of Al powder in air increases as the particle size decreases. Also, it was found that neat Al with 5 μm particle sizes (Al₅) has a fusion temperature of about 647°C, that for 18 μm powder (Al₁₈) is 660°C. Pure potassium chlorate has a fusion temperature around 356°C and decomposes at 472°C. DTA curves for Al₅/KClO₃ (30:70) mixture showed a maximum peak temperature for the ignition of mixture at 485°C. Also, by increasing the particle size of Al powder, the ignition temperature of the mixture increased. On the other hand, the oxidation temperature increased by enhancing the Al content of the mixtures. In this particular study, we observed that the width of reaction peak for the mixtures corresponds to their Al contents of samples.     

Thermal study of naphthylammonium- and naphthylazonaphthylammonium-montmorillonite

The blue organo-clay color pigment (OCCP) naphthylazonaphthylammonium-montmorillonite was synthesized from the white naphthylammonium-montmorillonite by treating with NaNO₂, the azo colorant being located in the interlayer space. The following effects on the basal spacing of naphthylazonaphthylammonium-and naphthylammonium-clay were investigated: (1) the amount of naphthylammonium loading the clay, (2) the amount of NaNO₂ used for the staining, (3) aging of the preparation suspension and (4) thermal treatment. Samples were heated at 120, 180, 240, 300 and 360°C and diffracted by X-ray. During aging, some of the dye decomposed. Samples, after one day aging, were investigated by DTA. During the dehydration stage both organo-clays gradually decomposed, the naphthylammonium-clay at 120°C and the OCCP at 180°C. That fraction of organic matter, which did not escape, was air-oxidized at above 200°C and charcoal was obtained. The appearance and size of the DTA exothermic peaks depended on the amount of organic matter, which did not escape and this depended on the total amount of organic matter in the DTA cell. DTA proved that naphthylammonium reacted with NaNO₂ to form OCCP.     

Novel test method to estimate bound rubber formation of silica-filled solution styrene-butadiene rubber compounds

Bound rubber formation was investigated in detail by applying various extraction temperatures (at room temperature, 90°C, and 180°C) and novel treatment methods (ammonia bubbling and sonication). Bound rubbers could be divided into three major components of core shell, primary layer including tightly primary layer and occluded rubber, and secondary layer including connecting filament. Bound rubber content of the core shell was measured by four successive procedures of extraction at room temperature, ammonia bubbling, extraction at 180°C and sonication. Bound rubber content of the tightly primary layer was measured by three successive procedures of extraction at 90°C, ammonia bubbling and sonication. Bound rubber content of the primary layer was measured by two successive procedures of extraction at 90°C and sonication.     

Kristallstruktur,Phasenumwandlung und Kaliumionenleitfähigkeit von Kaliumtrifluormethylsulfonat

Crystal Structure, Phase Transition, and Potassium Ion Conductivity of Potassium Trifluoromethanesulfonate According to the results of temperature dependent powder diffractometry (Guinier‐Simon‐technique) potassium trifluoromethanesulfonate is dimorphic. The phase transition occurs between –63 °C and –45 °C. The low‐temperature modification crystallizes monoclinic with a = 10.300(3) Å, b = 6.052(1) Å, c = 14.710(4) Å, β = 111.83(2)° (–120 °C) and the room‐temperature modification with a = 10.679(5) Å, b = 5.963(2) Å, c = 14.624(5) Å, β = 111.57(3)°, Z = 6, P2₁. According to single crystal structure determination, potassium trifluoromethanesulfonate consists of three different potassium‐oxygen‐coordination polyhedra, linked by sulfur atoms of the trifluoromethanesulfonate groups. This results in a channel structure with all lipophilic trifluoromethane groups pointing into these channels. By means of DSC, the transition temperature and enthalpy have been determined to be –33 °C and 0.93 ± 0.03 kJ/mol, respectively. The enthalpy of melting (237 °C) for potassium trifluoromethanesulfonate is 13.59 kJ/mol, the potassium ionic conductivity is 3.68 · 10^–6 Scm^–1 at 205 °C.     

Polybutylene terephthalate reactive blending with polymethylhydrosiloxane by ruthenium‐catalyzed carbonyl hydrosilylation reaction

Carbonyl hydrosilylation reaction was developed to prepare reactive blending between PBT and polymethylhydrosiloxane (PMHS). It focused on the addition reaction of Si–H groups from PMHS onto carbonyl groups from PBT catalyzed by triruthenium dodecacarbonyl (Ru₃(CO)₁₂). An approach on PBT model compounds was carried out and investigated by NMR spectroscopy to evidence the potentiality and efficiency of carbonyl hydrosilylation reaction. At temperatures up to 100 °C, the hydrosilylation reaction can reach 33 mol% conversion in a few hours. Side reactions were also highlighted. Such side reactions can reach more than 23 mol% of the final products when temperature increases to 180 °C. Then hydrosilylation reaction was extended to PBT modification with a molar ratio of ester group/SiH = 3.5 and viscosity ratio polysiloxane/PBT = 4.0 × 10^?5. The reaction was carried out in an internal mixer at 220 °C and followed through the evolution of the torque of the reactional medium. Samples for different processing times were investigated by SEM and rheology. From these analyses, the dispersion of PMHS was promoted with diameters of few micrometers. The elastic behavior of final material was characteristic of solid or gel‐like structures, suggesting a network structure formation consistent with the gel fraction increase from 0 to 0.55. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 1855–1868     

Ultrathin cobalt silicide film formation on Si(100)

The interfacial reaction between ultrathin Co film and substrate Si(100) was studied by in situ XPS using monochromatized Al Kα. When the Co is deposited on Si(100) at room temperature, CoSi₂ is formed during the initial stage of Co deposition and then metallic Co starts to grow sequentially. For 8 ML Co deposition on Si(100) the interfacial reaction layer is relatively thin compared with the pure Co overlayer, which is not involved in the interfacial reaction in depth. The Co layers change rapidly to CoSi layers after annealing at 270°C, and then CoSi₂ layers form after annealing at 540°C for 2 min. The CoSi₂ layers are changed to CoSi₂ islands by post‐annealing at >650°C. Copyright © 2003 John Wiley & Sons, Ltd.     

Reconstructive and displacive transformations of tectosilicates

By using the thermally induced phase transformation initial zeolites were converted into pure carnegieite, stuffed derivative of cristobalite. The polymorphs obtained from Na-LTA are stoichiometric (NaAlSiO₄), since those obtained from Na-FAU zeolite are non-stoichiometric (Na_1-xAl_1-xSi_1+xO₄). Stoichiometric carnegieite have cubic structure, while non-stoichiometric carnegieite crystallized in cubic and orthorhombic forms. ²⁹Si MAS NMR spectra show a very large but expecting difference between stoichiometric and non-stoichiometric carnegieite. The spectrum of stoichiometric carnegieite has only one peak Si(4Al), while the spectrum of non-stoichiometric carnegieite consist few superimposed peaks assigned to Si(4Al), Si(3Al), Si(2Al), Si(1Al) and Si(0Al). DTA study indicates the occurrence of displacive phase transition of all synthesized carnegieite. The transition temperature is depending on silicon aluminum order: T _m=690°C for stoichiometric, T _m=565 and 660°C for non-stoichiometric, low-temperature and high-temperature carnegieite, respectively. This revised version was published online in July 2006 with corrections to the Cover Date.     

50 keV H+ ion beam irradiation of Al doped ZnO thin films: Studies of radiation stability for device applications

Thin films of Al doped ZnO (Al:ZnO) were deposited on two substrates (Si and glass) at room temperature and 300°C using DC magnetron sputtering. These films were bombarded with 50 keV H⁺ beam at several fluences. The pristine and ion beam irradiated films were analysed by X‐ray diffraction, Raman spectroscopy, scanning electron microscopy, and UV‐Vis spectroscopy. The X‐ray diffraction analysis, Hall measurements, Raman and UV‐Vis spectroscopy confirm that the structural and transport properties of Al:ZnO films do not change substantially with beam irradiation at chosen fluences. However, in comparison to film deposited at room temperature, the Al:ZnO thin film deposited at 300°C shows increased transmittance (from 70% to approximately 90%) with ion beam irradiation at highest fluence. The studies of surface morphology by scanning electron microscopy reveal that the ion irradiation yields smoothening of the films, which also increases with ion fluences. The films deposited at elevated temperature are smoother than those deposited at room temperature. In the paper, we discuss the interaction of 50 keV H⁺ ions with Al:ZnO films in terms of radiation stability in devices.     

Redox behavior of high Si/Al ratio Cu-ZSM5 in NO decomposition

Commercial H-ZSM5 zeolites with a Si/Al ratio equal to 25 and 75 have been exchanged using copper acetate aqueous solutions with different concentrations. Copper saturation is reached at the 130 and 230% level of Cu exchange for Si/Al equal to 25 and 75, respectively, although FTIR spectra showed that a fraction of Al-OH exchange positions is still available. Catalytic activity experiments of NO decomposition have been carried out at 450°C in a fixed bed reactor. Catalysts have been characterized with H₂ TPR and NO adsorption experiments at 120°C. All samples are partially reduced upon thermal treatment under inert flow (He) leading to the formation of Cu⁺-containing sites in addition to a fraction of differently reduced copper species. The Cu⁺-containing sites, also responsible for NO adsorption and subsequent production of N₂O at 120°C, have been proposed to be the active centers. A quantitative estimation of these species, likely having multi-ionic structure, has been provided.     

Mechanism of dehydration of magnesium oxalate dihydrate

The isothermal dehydration of magnesium oxalate dihydrate has been studied at various temperatures between 190 and 260°C in the presence of air. The isothermal dehydration curves show the usual sigmoidal character and display an induction period which is highest at 190°C. The dehydration velocity constant (k) values (obtained by the application of Mampel's equation) plotted vs. 1/T according to the Arrhenius equation gave a plot in which two linear sections intersect at ～215°C with activation energies of 12.3 and 18.3 kcal mole^?1 for the lower- and higher-temperature sections, respectively. This behaviour is tentatively explained in terms of a change in the mechanism of dehydration, and not the formation of some new phase other than the dihydrate and the anhydrous oxalate phases present in both the original crystalline oxalate and the sample heated at 200°C for 120 min. X-Ray patterns of the heated oxalate sample left for a few days at room temperature showed a marked sensitivity for rehydration of the anhydrous oxalate phase.     

Surface chemistry and diffusion of trace and alloying elements during in vacuum thermal deoxidation of stainless steel

Removal of the native surface oxide from steel is an important initial step during vacuum brazing. Trace and alloying elements in steel, such as Mn, Si, and Ni, can diffuse to the surface and influence the deoxidation process. The detailed surface chemical composition and grain morphology of the common stainless-steel grade 316L is imaged and spectroscopically analyzed at several stages of in-vacuum annealing from room temperature up to 850°C. Measurements are performed using synchrotron-based X-ray photoemission and low-energy electron microscopy (XPEEM/LEEM). The initial native Cr surface oxide is amorphous and unaffected by the underlying Fe grain morphology. After annealing to ~700°C, the grain morphology is seen at the surface, persisting also after the complete oxygen removal at 850°C. The surface concentration of first Mn and then Si increases significantly when annealing to 500°C and 700°C, respectively, while Ni and Cr concentrations do not change. Mn and Si are not located only in grain boundaries or clusters but are distributed across over the surface. Both Mn and Si appear as oxides, while Cr oxide becomes metallic Cr. Annealing from 500°C up to 850°C leads to the removal of first the Mn and then Si oxides from the surface, while Cr and Fe are completely reduced to metals. Deoxidation of Cr occurs faster at the grain boundaries, and the final Cr metal surface content varies between the grains. The findings are summarized in a general qualitative model, relevant for austenite steels.     

Determination of activation energies of the U(Mo)/Si and U(Mo)/Al solid state reaction using in-situ X-ray diffraction and Kissinger analysis

The solid state reaction between U(Mo) and Si, leading to the formation of silicides, has been studied using in-situ X-ray Diffraction. Samples were prepared by sputter depositing Si in thin layers on U(Mo) substrates (8 wt% Mo) and vice versa. In a similar way the reaction between U(Mo) and Al has been studied using U(Mo) substrates covered with a thin layer of Al. The samples were heated to temperatures up to 950 °C in a static purified helium atmosphere. Even though the measurements were hampered by the undesired oxidation of uranium, the formation of various silicides and aluminides could be observed. Kissinger analysis on ramp anneals with ramp rates of 0.2, 0.5, 1 and 3 °C/s have been performed to investigate the kinetics of the formed silicides. Using this method, the apparent activation energy for the different silicide formation reactions was deduced. Using the effective heat of formation rule, a prediction was made on the first phase formed and the subsequent phase sequence. A good agreement was found between the measurements and prediction.     

Influence of temperature and humidity on the degradation process of ascorbic acid in vitamin C chewable tablets

Ascorbic acid (AA) is the active ingredient of vitamin C chewable tablets. It is unstable even at room temperature, and increased temperature and humidity rapidly increase its degradation. To protect the active substance, we made its coating with polymers ethyl cellulose that provides its thermal protection and protection from moisture. We bet each particle of AA with a layer of polymer by the method of fluidization. Extra protection against thermal effects and penetration of moisture and oxygen provides the packaging. By using four kinds of packaging: polypropylene container for tablets, strips of aluminum and polyvinyl chloride Al/PVC strips, glass bottles, and strips of aluminum and polyethylene (Al.PE/PE.Al) of 3, of 6 months and of 12 months. One of the tablets are stored at room temperature (25 ± 2 °C/60% RH ± 5%), and the rest in terms of accelerated aging or increased temperature and humidity (30 ± 2 °C/65% RH ± 5% and 40 ± 2 °C/75% RH ± 5%). The speed of degradation of unprotected AA usually get doubled when there is increasing of the temperature for every 10 °C. Experimentally the concentration of AA was monitored, its oxidation product-dehydroascorbic acid and its degradation product-diketogulonic acid.     

The thermal behavior of k-exchanged forms of natrolite

A series of K-exchanged forms of natrolite are easily obtained by treatment with KCl solution at room temperature for 1–62 days. The maximum degree of exchange of K is 91.94%. The thermal behavior of the exchanged forms is studied by DTA-TG and high temperature X-ray powder diffraction. The DTA curve of the exchanged form of the 91.94% sample exhibits a single large endotherm at 150°C due to a one-step dehydration, showing the remarkable decrease in dehydration temperature compared with natrolite. The dehydrated phase of natrolite collapses at about 800°C, while destruction of the dehydrated K-form occurs above 1000°C. It is well recognized that the thermal stability of natrolite is increased by Na-K exchange.     

Water sorption heats on silica-alumina-based composites for interseasonal heat storage

CaCl₂-containing composites have been prepared by depositing the hydrated salt (by incipient wetness impregnation) on three different silica-aluminas with various Si/Al ratios. The surface area and porosity of all the samples were determined by N₂-adsorption at ?196 °C, and their water sorption properties were investigated by thermogravimetry linked to differential scanning calorimetry (TG–DSC) in order to determine the quantity of adsorbed/desorbed water and the related heats. The heat released and the quantity of adsorbed water were found to depend on parameters such as the silica-alumina pore diameters, the Si/Al ratio, and the presence of accessible CaCl₂ active phase. The short-term stability of both supports and composites has been also checked by performing successive hydration–dehydration cycles. The sample with the lower Si/Al ratio provided the highest heat per surface area of material, and the heat released per mol of water increased with the amount of Al₂O₃ present in the samples. The deposition of CaCl₂ positively acted on the quantity of heat released during the water sorption, and the composite with the higher alumina content (75 mass% Al) showed the largest heat released per m² of material (2.4 J m^?2) compared to those containing 25 and 13 mass% Al (1.4 and 1.2 J m^?2, respectively).     

Heterobimetallic complexes containing iron (II) and hexa-coordinated organosilicon

Heterobimetallic complexes of the type R₂Si(HL)Cl₂ and R₂SiL₂ (where R = Me, Et, Ph; L = ferrocenyl aroylhydrazone) have been synthesized at 40 °C to 50 °C and at room temperature (25 °C), respectively, and characterized by elemental analysis, molar conductance, infrared and NMR (¹H, ¹³C and ²⁹Si) spectral data. The ligands behave as bidentate, coordinating through the azomethine nitrogen and the oxygen in the amidic and the imidic acid forms of the ligand at low temperature and at room temperature, respectively. The ligands and their organosilicon complexes have been evaluated for the antifungal activity against Alternaria alternata, Fusarium oxysporum and Rhizoctonia solani, as well as antibacterial activity against gram negative, Escherichia coli and gram positive, Bacillus subtilis, at 28 °C. Organosilicon complexes of ferrocenyl aroylhydrazone were found to be more potent than the parent ligands.      

TMA and SEM characterization of the thermal dehydration of australian sedimentary opal

The dehydration of samples of a Coober Pedy, South Australian sedimentary white opal, displaying play of colour, was investigated using TMA by heating the samples of the specimen to a range of temperatures between room temperature and 1000 at 200°C intervals followed by cooling to room temperature. Etched fracture surfaces of the samples were then examined using SEM. The samples showed the typical expansion at low temperature up to 210°C before contraction was observed. The contraction of the opals was ascribed to both sintering, supported by morphological change observed in the SEM micrographs, and dehydroxylation of the silanol groups producing silicon-oxygen-silicon bridges resulting in a more dense silica network.     

State of titanium in supported titanium-magnesium catalysts for propylene polymerization

The oxidation state of titanium and the coordination state of Ti³⁺ ions in TiCl₄/D₁/MgCl₂ (D₁ is a phthalate) supported titanium-magnesium catalysts (TMCs) after the interaction with an AlEt₃/D₂ cocatalyst (D₂ is propyltrimethoxysilane or dicyclopentyldimethoxysilane) were studied by chemical analysis and EPR spectroscopy. Different oxidation state distributions of titanium ions were observed in the activated catalyst and mother liquor: Ti³⁺ and Ti²⁺ ions were predominant in the activated catalyst and mother liquor, respectively. The effects of interaction conditions (reaction temperature and time and Al/Ti and D₂/Ti molar ratios) of TMCs with the cocatalyst on the state of titanium in activated samples were studied. The interaction of TMCs with the cocatalyst decreased the titanium content and caused the appearance of aluminum in the activated sample, which was most clearly pronounced at a temperature of 25°C and occurred within the first 10 min of treatment. An increase in the temperature to 70°C and an increase in the interaction time to 60 min only slightly affected the concentrations of titanium and aluminum. The presence of D₂ as a cocatalyst constituent facilitated the removal of titanium compounds and restricted the adsorption of aluminum compounds on the catalyst surface. The main fraction of titanium consisted of Ti³⁺ ions (62–89%), and the rest was Ti⁴⁺ ions (22–35%) under mild interaction conditions (25°C; Si/Ti = 25) or Ti⁴⁺ (0–21%) and Ti²⁺ (9–21%) ions under more severe conditions (50 or 70°C; Si/Ti from 0 to 5). According to EPR-spectroscopic data, at D₂/Ti from 1 to 5, Ti³⁺ ions mainly occurred as associates, whereas they occurred as isolated ions at D₂/Ti = 25. The initial and activated catalysts were similar in activity in the reaction of propylene polymerization, and titanium compounds, which were removed from the catalyst upon interaction with AlEt₃/D₂, were inactive in this process.     

Morphology of polylactic acid crystallized during annealing after uniaxial deformation

Uniaxial deformation of amorphous L -polylactic acid films was performed at two different temperatures at which thermal degradation was minimal, 70 °C or T_g + 10 and 90 °C or T_g + 30. Samples were annealed postdeformation for long times (either 15 or 45 min) to approach equilibrium conditions. Samples deformed and annealed at 70 °C showed low crystallinity and poor crystalline order or crystal size, as determined by wide-angle X-ray diffraction. At 90 °C, high crystallinity and order parameters were observed. In addition, once the oriented chains had crystallized at this temperature, nonoriented chains also underwent crystallization, and a small fraction of nonordered crystal phase was therefore observed after long annealing times. These observations are explained on the basis of different morphologies in samples drawn at the two temperatures. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013