Thermal decompositions of formates. Part VII. Thermal decomposition of yttrium formate dihydrate

The thermal dehydration of yttrium formate dihydrate and decomposition of yttrium formate anhydride were studied in flowing nitrogen and carbon dioxide atmospheres by means of TG and DTA.The dehydration reaction was not affected by the atmospheric condition and took place successively without any intermediate hydrate. The mechanism of the dehydration reaction was found to be a phase boundary controlled interface reaction.The decomposition of yttrium formate occurred in three stages, and yttrium oxyformate and yttrium oxycarbonate were formed as the intermediate products.In a carbon dioxide atmosphere, the decomposition took place at a higher temperature than in a nitrogen atmosphere.The anhydrous salt melted during the main stage of the decomposition and the kinetic behaviour of this stage was characteristic of a homogeneous first order reaction.     

ICP-AES analysis of aluminum isopropoxide,yttrium, and neodymium oxide nanopowders

A technique has been developed for analysis of impurities in precursors of the optic ceramics: aluminum isopropoxide, yttrium and neodium oxide nanopowders (weight fraction of Nd ≤5%) by atomic-emission spectroscopy with inductively coupled plasma. In the case of aluminum isopropoxide, the effect of matrix is compensated by applying Bi as an internal standard. The detection limits of impurities were found to be 10^?5–10^–6 wt.%.     

Synthesis of aluminum nitride in transferred arc plasma furnaces

Ultrafine particles of aluminum tnitride (AIN) arc produced by a transferred an plasma. Two devices are used: a transferred arc plasma on aluminum natal in nitrogen or nitrogenlammonia atmospheres, and a item concept of transferred arc plasma when, DC anode and cathode ares are coupled together above an alumintun melt. Equilibrium chemical compositions mere calculated. The temperature distributions in the plasma are measured hr emission spectroscopy Flit, powder, made from 99.8%, aluminum ingot, it as analyzed and confirmed to be 99.3%, of hexagonal phase aluminum nitride. In othertests, from 99.99% aluminum ingot, a translucent AIN vinter was obtained. The densification behavior was assessed by hot pressing and by pressureless sintering, with and without additives. The thermal conductivities are given.     

Synthesis of an aluminum nitride–yttria (AlN–Y2O3) composite from nano-sized porous AlN and YCl3

In order to enhance the thermal conductivity of aluminum nitride (AlN) with sintering additives including yttria (Y₂O₃), it is necessary to form yttrium aluminate garnet (YAG) and secondary phases both within and around the boundaries of AIN drains. Nano-sized porous AlN particles were produced to form YAG and secondary phases within AlN grains, after which a AlN–Y₂O₃ nano–nano composite was formed from AlN and amorphous Y₂O₃. Porous AlN powders were first successfully synthesized by the chemical vapor synthesis (CVS) method. Highly crystalline and nano-sized porous AlN powders were synthesized at 1,200 °C. Brunauer–Emmett–Teller (BET) analysis showed that these powders had very large surface areas, suggesting that the particles approached nano-scale sizes with very small pores. To form composites of Y₂O₃ and AlN, we prepared a yttrium source solution that infiltrated the nano-sized pores of the AlN particles. Such an infiltration of AlN with amorphous Y₂O₃ was expected to effectively reduce the residual oxygen content by facilitating the formation of YAG and secondary phases during the sintering process. We characterized the composite powders of AlN–Y₂O₃ and the sintered bodies using BET, XRD, SEM, TEM, and thermal conductivity analyses.

     

Thermal decomposition of barium oxalate hemihydrate BaC2O4·0.5H2O

The thermal behaviour of BaC₂O₄sd0.5H₂O and BaCO₃ in carbon dioxide and nitrogen atmospheres is investigated as part of a study about the thermal decomposition of barium trioxalatoaluminate. For this purpose thermogravimetry, differential thermal analysis, differential scanning calorimetry and high temperature X-ray diffraction were used. An infrared absorption spectrum of BaC₂O₄·0.5H₂O was scanned at room temperature.At increasing temperature, in dry nitrogen, the hydrate water of BaC₂O₄· 0.5H₂O is split off, followed by the oxalate decomposition. A part of the evolved carbon monoxide disproportionates, leaving carbon behind. At higher temperatures the latter reacts with barium carbonate, previously formed. Finally the residual solid barium carbonate decomposes into barium oxide and carbon dioxide.In dry carbon dioxide atmosphere an analogous dehydration occurs, followed by oxalate decomposition. Under these conditions the carbon formation is fully suppressed, and as a consequence no secondary reaction occurs. The barium carbonate decomposition is shifted to much higher temperatures, at a low rate in the solid phase, a strongly accelerated one at the onset of melting, and a moderated one when the melt is saturated with barium carbonate. The two phase transitions of BaCO₃ are detectable in both atmospheres mentioned.     

Ordered mesoporous alumina-supported metal oxides

The one-pot synthesis of alumina-supported metal oxides via self-assembly of a metal precursor and aluminum isopropoxide in the presence of triblock copolymer (as a structure directing agent) is described in detail for nickel oxide. The resulting mesoporous mixed metal oxides possess p6 mm hexagonal symmetry, well-developed mesoporosity, relatively high BET surface area, large pore widths, and crystalline pore walls. In comparison to pure alumina, nickel aluminum oxide samples exhibited larger mesopores and improved thermal stability. Also, long-range ordering of the aforementioned samples was observed for nickel molar percentages as high as 20%. The generality of the recipe used for the synthesis of mesoporous nickel aluminum oxide was demonstrated by preparation of other alumina-supported metal oxides such as MgO, CaO, TiO 2, and Cr 2O 3. This method represents an important step toward the facile and reproducible synthesis of ordered mesoporous alumina-supported materials for various applications where large and accessible pores with high loading of catalytically active metal oxides are needed.     

Paracyanogen reexamined

Samples of paracyanogen were prepared by the pyrolysis of silver cyanide, the photolysis of cyanogen, and by sputtering a carbon electrode in a nitrogen plasma. This work was undertaken to establish whether these materials are alike and to derive structural information on the basis of FT-IR, ¹³C-MAS—NMR, and through temperature-programmed thermal decomposition. Paracyanogen derived from the above sources is indeed alike spectrally and thermally. Paracyanogen is a polymer that incorporates carbon, mostly sp², and nitrogen in a disordered structure. Cyanogen is the main volatile component released in the thermal decomposition of paracyanogen. The cyanogen released was identified by FT-IR and MS. The rate of release reaches a maximum at ca. 700°C. Paracyanogen is not an appropriate carbon nitride precursor because of its limited thermal stability. © 1993 John Wiley & Sons, Inc.     

New ceramic-carbon composites for electrodes for electrochemical capacitors

A new class of composite materials is introduced. Fine powders of silica, titania, Y-modified zirconia, and three types of alumina were pressed and sintered to form porous monoliths with relatively uniform pore structure. Carbon was then deposited in the pores of such monoliths by thermal decomposition of dichloromethane, cyclohexene, and glucose. The structure of the carbon deposit was studied by low-temperature nitrogen adsorption and by thermal analysis. The composite materials were used as electrodes in electrochemical capacitors with 1-ethyl-3-methylimidazolium trifluoromethylsulfonate (a low-temperature ionic liquid) as the electrolyte. High capacitances were observed for glucose-derived materials, which had high specific surface areas.     

Diol—Based Sol–Gel as a Novel Binder for Barium Titanate Ceramics

The relative merits of using a diol-based sol–gel precursor as a binder in the fabrication of barium titanate ceramics made by die-pressing a mixed oxide starting powder have been investigated. The characteristics of powder compacts were compared to samples prepared using a conventional PVB organic binder. The green strength of pellets with the PVB binder was higher than for samples containing the gel, but strength after binder burnout from gel samples was double that of pellets made with PVB. The gel led to improvements in densification during sintering, but these were most noticeable at low sintering temperatures and at intermediate stages of densification. After sintering for 2 h at 1150C, the gel-containing samples reached 75% of theoretical density, some 5% more than for the organic polymer binder. Sintering at 1300C for 2 h, gave a sintered density of ~96% of theoretical density using the gel additive, which was only 2% higher than for the conventional PVB binder system. The decomposition characteristics of the gel were investigated by TGA, FTIR and GC-MS techniques.     

Effect of atmospheric nitrogen on the oxidation mechanism of aluminum alloys with rare-earth metals

Interaction (25–620°C) of aluminum and its alloys with an atmosphere saturated with nitrogen was studied to determine the role played by rare-earth metals in the mechanism by which nitride phases are formed in oxidation of Al + REM alloys in air. The ellipsometric method and Auger electron spectroscopy were used to determine that, under the given experimental conditions, metallic aluminum is subjected to the greatest extent to the nitridation process, which is competing with the oxidation process. The process is initiated by the conversion of the amorphous oxide film to γ-Al₂O₃. The surface of Al + REM alloys interacts with nitrogen at the outer part of the oxide layer. The rare-earth metal actively reacts with impurity oxygen present in the atmosphere under study and hinders formation of nitride/oxynitride layers.     

Study on thermal degradation of cattlehide collagen fibers by simultaneous TG–MS–FTIR

Leather was useful materials since dawn of human history for excellent properties, but thermal degradation mechanism was not very clear yet. In this paper, much progress has been made in elucidating the thermal stability and thermal degradation mechanism by thermoanalytical study in argon. Thermogravimetric analysis simultaneously coupled with mass spectrometry and Fourier transform infrared spectrometry was employed to study the thermal degradation of cattlehide collagen fibers through in-depth analysis of the evolved gas. Thermogravimetry analyses carried out on sample, deprived from any residual catalyst and highlighted a two-step thermal degradation. New evidence demonstrates that the process during temperature range from 373 to 513 K was phase transformation. Photographs of polarizing microscope confirmed the conclusion. The decomposition of cattlehide collagen fibers starts at about 523 K. The cattlehide collagen fibers may undergo the process of melting, oxidation and decomposition. In decomposition, more than three steps take place. The mass spectra and Fourier transform infrared spectrometry stated clearly that double bond of carbon to oxygen, carbon to sulfur and carbon to nitrogen were destroyed firstly because the carbon dioxide, carbon monoxide and ammonia evolved simultaneously. The second peak of carbon monoxide in mass spectra indicated that some organic fragments were decomposed above 1073 K which confirmed that thermal degradation of leather is more than three steps.     

Coating of polyamide 12 by sol–gel methodology

The combination of sol–gel methodology with rapid prototyping (RP) produces functionalized 3D structures with potential applications in various fields. However, this combination has been little explored. In this paper, we used the sol–gel method to deposit vanadium isopropoxide onto polyamide (PA12) constructed by RP and pretreated with acetic acid, to obtain a functionalized substrate with new thermal, physical, and chemical properties. Vanadium isopropoxide (one, five, or ten layers) was deposited onto the PA12 piece by dip-coating. We characterized the coated PA12 by thermal analyses, X-ray diffraction, and infrared spectroscopy, which revealed that V=O and Si–O–Si groups exist on the PA12 surface. PA12 coating with vanadium isopropoxide enhanced the decomposition temperature. Differential scanning calorimetry revealed increased fusion and decomposition enthalpy as a function of the PA12 coating. Therefore, deposition of vanadium isopropoxide onto PA12 pretreated with acetic acid improves the thermal stability of PA12 prepared by RP.     

Formation and Thermal Decomposition of Indium Oxynitride Compounds

During the reactions of lithium oxide with indium nitride, lithium nitride with indium oxide, and lithium nitride with lithium indate LiInO2, the formation of a previously unknown crystalline phase, of composition Li4InNO2, was observed. The course of thermal decomposition of the new compound was determined. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal diffusivity measurement of ceramic materials used in spraying of TBC systems

The basic goal of this article was thermal diffusivity characterization of ceramic materials used in thermal barrier coating (TBC) systems for depositions of the insulation layer and characterization of the materials’ morphology and remanufacturing process. The base material was oxide 8YSZ (ZrO_2? ×?8Y₂O₃), which is usually dedicated to deposition of an insulating top layer in TBC systems. The data related to thermal properties such as thermal diffusivity and thermal conductivity are widely presented in the literature, but there is lack of information about the morphological form of investigated materials, and the presented results vary widely. Data on thermal properties based on the literature sources are inadequate for the real morphological form of materials used in the experiment (e.g., massive or single crystalline material vs. plasma-sprayed coatings), which consequently gives an unsatisfactory accuracy of the obtained numerical simulations by MES methods. This article presents the characterization of thermal diffusivity of the commercial 8YSZ ceramic material synthesized or remanufactured by different routes, which is investigated in the forms of pressed powder pellet (two commercial nano-sized powders with different morphologies), sintered pellets (one commercial powder, solid-state co-precipitated reacted powder of 8YSZ type), and a two-layered coating system of In625?+?NiCrAlY/8YSZ type. The range of analysis included morphological investigations of different types of powders in initial conditions and after remanufacturing (sintering, thermal spraying) as well as the thermal diffusivity analysis by the laser flash method. The obtained data were corrected by porosity factor and compared to each other. The best similarity for obtained thermal diffusivity data was found for commercial powers of HOSP^TM type after pressing and sintering processes and calculated (2-layered model) value of thermal diffusivity for two-layered system of In625/8YSZ TBS system. The results showed that there are significant differences in thermal diffusivity values for materials with different morphological forms.

     

Ultrafast shock compression and shock-induced decomposition of 1,3,5-triamino-2,4,6-trinitrobenzene subjected to a subnanosecond-duration shock: an analysis of decomposition products

Shock compression studies of pressed and confined ultrafine 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) powder were conducted using ultrashort ~300 ps, ~50 GPa shock waves. The recovered decomposition products were characterized using X-ray photoelectron spectroscopy, infrared spectroscopy, and Raman spectroscopy. A substantial amount of shock-related chemistry was observed. Approximately 75% of the nitrogen atoms were liberated as gas-phase species, along with ~33% of the oxygen atoms, as a result of the applied shock. Furthermore, we observe C 1s binding energies suggesting the formation of sp(3) hybridized amorphous carbon. For comparison, a carbon nitride material was also prepared and characterized by thermally pyrolizing TATB. The shock-compressed TATB and the thermally pyrolized TATB are qualitatively different, suggesting that, carbon nitrides, a possible indicator of nitrogen-rich heterocycles precursors, are not a major product class for strongly overdriven shock conditions. These experimental conditions were, however, not detonation conditions, and the possible formation of nitrogen-rich heterocycles in actual detonations still exists.     

Thermal transport and chemical effects of fillers on free-radical frontal polymerization

Frontal polymerization (FP) is a process in which a front propagates in a localized reaction zone, converting monomer into polymer through the coupling of thermal diffusion with the Arrhenius kinetics of an exothermic reaction. Fillers are added to control the rheological properties of the formulation and to enhance the mechanical properties of the product. However, the thermal and chemical effects of these fillers on the front propagation have not been thoroughly explored. Herein we report the thermal and chemical effects of fillers on free-radical frontal polymerization. It was found that fillers with high thermal diffusivities, such as milled carbon fiber and boron nitride increased the front velocity. Despite their high thermal diffusivities, fillers such as aluminum and alumina decreased the front velocity. This is likely due to the radical-scavenging ability of aluminum oxide, which was explored with clay minerals. It was found that the presence of water within clay fillers can also decrease the front velocity. To probe the chemical effects, acid-activated clay minerals were utilized. The results demonstrate that some fillers can increase front velocity through their high thermal diffusivities while others decrease it by acting as radical scavengers.     

Characterization of aerogel prepared high-surface-area alumina: in situ FTIR study of dehydroxylation and pyridine adsorption

Mesoporous high-surface-area alumina was prepared by a modified aerogel procedure. Specific surface areas between 530-685 m(2)g(-1) were obtained after heat treatment at 500 degrees C. Nitrogen adsorption studies have shown that surface areas and pore characteristics change upon decomposition of aluminum hydroxide to oxide as well as upon compaction of oxide powders. The surface area of aluminum hydroxide increased to a maximum, while the pore volume and diameter decreased as the hydroxide was heated to a temperature of 400 degrees C. Heating at higher temperatures resulted in sintering of the particles accompanied by a decline in the surface area. Compaction of activated alumina into pellets was accompanied by a relatively gradual change in the surface area and pore characteristics at pressures below 6.9 x 10(7) Pa, while severe changes took place at a pressure of 1.4 x 10(8) Pa. In situ IR studies of the dehydroxylation of the alumina surface, showed nu(OH) absorptions for isolated surface hydroxy groups centering at 3670, 3714, and 3765 cm(-1), which are shifted to lower frequencies than common literature values. Pyridine was found to adsorb on Al(3+) ions as well as through hydrogen bonding to relatively acidic surface OH groups, and IR spectra indicated the presence of strong Lewis acid sites.     

The effect of the sintering atmosphere on the densification of B4C ceramics

Densification of boron carbide during sintering may be improved by a two-stage process, namely heating to 2000°C under vacuum and sintering at 2190°C under argon. This sintering regime allows achieving a relative density of the ceramic bodies fabricated from a fine powder higher than 95%. The nitrogen treatment of the boron carbide phase at 1900°C leads to the formation of the BN phase and precipitation of graphite. Vacuum treatment of these samples at 2000°C leads to decomposition of the boron nitride phase. The liberated free boron may again react with graphite to form in situ boron carbide particles. The experimental investigations of the sintering behavior of the boron carbide phase under various atmospheres supported the thermodynamic predictions regarding the phase transformation. No evidence, however, was found for enhanced sintering under a nitrogen atmosphere.     

Formation of separating layers under conditions of the thermal aging of sorbents modified by fluorinated polyimide

Thermogravimetry, elemental analysis, low-temperature nitrogen adsorption, high-resolution electron microscopy, and gas chromatography are used to study the effect of the content of perfluorinated polyimide when used as a stationary phase for modifying Chromosorb P NAW diatomite supports and aluminum oxide, and the effect of thermal aging conditions on changes in their texture and chromatographic characteristics. It is shown that Chromosorb P NAW + 5 wt % of polyimide (PI) adsorbent thermally aged at 700°C in a flow of inert gas exhibits properties of carbon molecular sieves, while aluminum oxide impregnated with 10 wt % of PI and thermally aged at 250°C allows us to selectively separate permanent and organic gases, as well separate saturated and unsaturated hydrocarbons.     

Laser-induced breakdown spectroscopy measurements of uranium and thorium powders and uranium ore

Laser-induced breakdown spectroscopy (LIBS) was used to analyze depleted uranium and thorium oxide powders and uranium ore as a potential rapid in situ analysis technique in nuclear production facilities, environmental sampling, and in-field forensic applications. Material such as pressed pellets and metals, has been extensively studied using LIBS due to the high density of the material and more stable laser-induced plasma formation. Powders, on the other hand, are difficult to analyze using LIBS since ejection and removal of the powder occur in the laser interaction region. The capability of analyzing powders is important in allowing for rapid analysis of suspicious materials, environmental samples, or trace contamination on surfaces since it most closely represents field samples (soil, small particles, debris etc.). The rapid, in situ analysis of samples, including nuclear materials, also reduces costs in sample collection, transportation, sample preparation, and analysis time. Here we demonstrate the detection of actinides in oxide powders and within a uranium ore sample as both pressed pellets and powders on carbon adhesive discs for spectral comparison. The acquired LIBS spectra for both forms of the samples differ in overall intensity but yield a similar distribution of atomic emission spectral lines.