Partial thermal reduction of ammonium paratungstate tetrahydrate

Thermal decomposition of ammonium paratungstate tetrahydrate, (NH₄)₁₀[H₂W₁₂O₄₂]·4H₂O has been followed by simultaneous TG/DTA and online evolved gas analysis (TG/DTA-MS) in flowing 10% H₂/Ar directly up to 900°C. Solid intermediate products have been structurally evaluated by FTIR spectroscopy and powder X-ray diffraction (XRD). A previously unexplained exothermic heat effect has been detected at 700–750°C. On the basis of TG/DTA as well as H₂O and NH₃ evolution curves and XRD patterns, it has been assigned to the formation and crystallization heat of γ-tungsten-oxide (WO_2.72/W₁₈O₄₉) from β-tungsten-oxide (WO_2.9/W₂₀O₅₈) and residual ammonium tungsten bronze.     

Thermochemical decomposition of cobalt doped ammonium paratungstate precursor

The calcination is one of the important steps in the preparation of nanostructured WC and WC–Co powders from chemically co-precipitated W–Co precursors. In the present paper, the processing of the precursor prepared by co-precipitation from cobalt(II) hydroxide and ammonium paratungstate is reported. The precursor was calcined at different temperatures under various atmospheres. The resulting powders were investigated using scanning electron microscopy, X-ray diffraction, thermogravimetric analysis (TGA), differential TGA, BET, and mass spectrographic analysis techniques. The results showed that the precursor decomposes differently by calcination under different atmospheres, i.e. nitrogen, air, and helium–5% oxygen. Different decomposition behaviour was observed when the calcination was carried out at medium temperature in flowing and non-flowing air. Nanostructured powders with particle size of around 90 nm can be obtained after calcination. The precursor decomposes into CoWO₄ and WO₃ oxides at 520 °C in air after a weight loss of 10.3%.     

The measurement of crystallite size in ultrahigh-modulus polyethylene

Crystal length determinations have been undertaken on ultrahigh-modulus linear polyethylene fibers by dark-field electron microscopy. There is good agreement between the results and those obtained from wide-angle x-ray diffraction line broadening. The crystal length distributions from the dark-field microscopy are also consistent with those determined by nitric acid etching. The significance of the present results is considered in the light of recent proposals for the structure of these materials and the achievement of high modulus.     

Influence of crystallite size on the oxidation kinetics of magnetite

The oxidation of magnetite yields the lacunar phase γ-Fe₂O₃, for sizes less than 5000 Å and the rhombohedral phase, α-Fe₂O₃, for sizes above 10 000 Å. For intermediate sizes, oxidation kinetics and X-ray analysis have confirmed that the γ-Fe₂O₃ phase forms at the beginning of the reaction, followed by phase α-Fe₂O₃ forming from γ-Fe₂O₃ and then directly from the still-unoxidized magnetite. Influence of size could be accounted for in terms of structure and stresses at the crystal lattice level.     

The effect of crystallite shape on small-angle X-ray scattering

Summary Diffraction by a linear crystallite system was calculated to explain different shapes of small-angle reflections. The calculations show that various SAXS patterns observed can be obtained theoretically if the shape of certain crystallites are accounted for. Various reflection shapes can be explained chiefly by the changes in the crystallite shape and size. Dash, four-point and two-point reflections are associated with rectangular and oblique crystallite of small lateral dimensions. In the case of radial reflections the crystallite represents a plate and the fibril — a stack of plates. Structural changes in oriented samples with planar crystallite texture caused by shrinkage were studied. The principal process of shrinkage consists in the growth of lateral (with respect to the texture axis) crystallite dimensions and in their transformation into plates. Simultaneously the rotation of the macromolecule axis takes place. At the second stage of the shrinkage the layers twist around an axis perpendicular to the film plane. Then isotropic structure is formed. Transition between the two kinds of reflections are typical of various processes taking place in the course of polymer deformation and shrinkage.

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Zusammenfassung Die Röntgen-Beugung eines Systems aus linearen Kristalliten wurde berechnet, um verschiedene Formen von Kleinwinkelreflexionen zu erklären. Die Berechnungen zeigen, daß die beobachteten verschiedenen SAX-Beugungsbilder theoretisch erhalten werden können, wenn die Form der verschiedenen Kristallite in geeigneter Weise gewählt wird. Verschiedene Beugung kann im wesentlichen mit Änderungen von Kristallitgestalt und -große gedeutet werden. Strich-, 2-Punkt- und 4-Punkt-Beugung sind mit rechteckigen und plättchenförmigen Kristalliten von kleinen lateralen Dimensionen verknüpft. Im Fall von radialen Reflektionen ist der einzelne Kristallit ein Plättchen, und eine Fibrille ist ein Stapel von Plättchen. Strukturänderungen in orientierten Proben mit planarer Kristallittextur, erzeugt durch Schrumpfung, wurden studiert. Der Hauptvorgang bei Schrumpfung besteht im Wachsen der lateralen (mit Hinblick auf die Texturachse) Kristallit-dimensionen und in ihrer Überführung in Plättchen. Gleichzeitig findet eine Drehung der Achsen der Makromoleküle statt. Im 2. Stadium der Schrumpfung schrauben sich die Schichten um eine Achse senkrecht zur Filmebene. Dann bildet sich die isotrope Struktur. Der Übergang zwischen den beiden Arten von Beugungen ist für die verschiedenen Prozesse typisch, die im Laufe einer Deformation und einer Schrumpfung von Polymeren stattfinden.

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Dedicated to Prof.R. Hosemann on the occasion of his 60th birthday     

Preparation and characterization of WO3 from ammonium paratungstate via hydrothermal method

Tungsten trioxide powder has been prepared from ammonium paratungstate via hydrothermal method using orthogonal and mono-level design of experiments. The effects of preparation process on particle size, specific surface area, crystal form and crystalline morphology of the tungsten trioxide was investigated by TEM and XRD etc. It was found that the optimum conditions of the preparation are hydrothermal crystallization for 8 h at 180°C, followed by vacuum drying at 45°C and calcination at 500°C for 2 h. The blank reference experiment shows that hydrothermal crystallization treatment favors the formation of hexagonal tungsten trioxide, and the tungsten trioxide powder sample prepared by this method has a high degree of crystallinity. __________ Translated from Chinese Journal of Applied Chemistry, 2005, 22(8) (in Chinese)     

共沉淀分离-氢化物发生-原子荧光光谱法测定高纯偏钨酸铵中痕量铋

提出了以氢氧化镧为共沉淀剂,对高纯偏钨酸铵中痕量杂质元素铋进行共沉淀分离富集后以HG-AFS进行测定的方法。在强碱性环境中进行两次共沉淀,能使铋元素定量分离回收,偏钨酸铵残留量降至很低水平。选择了适宜的反应条件以及仪器的最佳工作条件,考察了钨基体对被测元素的干扰。铋的检出限0.020 ng/mL,测定下限0.012μg/g,相对标准偏差4.6%,回收率在92.8%~108.4%之间,方法适用于高纯偏钨酸铵中痕量铋的测定。     

Thermal decomposition of native cellulose: Influence on crystallite size

The thermal degradation behavior of crystalline cellulose has been investigated using thermogravimetry, differential thermal analysis, and derivative thermogravimetry in a nitrogen atmosphere. Three cellulose samples, Halocynthia, cotton, and commercial microcrystalline cellulose Funacel, were used in this study to analyze the influence on crystallite size. They all belongs to cellulose I_β type and those crystallite sizes calculated from the X-ray diffractometry profiles by Scherrer equation were very different in the order Halocynthia > cotton > Funacel. The thermal decomposition of cellulose shifted to higher temperatures with increasing crystallite size. However, activation energies for the thermal degradation were the almost the same among the samples: 159-166 kJ mol⁻¹. These results indicated that the crystal structure does not affect the activation energy of the thermal degradation but the crystallite size affects the thermal degradation temperature.     

Influence of crystallite size on acetone hydrogenation over copper catalysts

Acetone hydrogenation was studied over a family of Cu/SiO2 catalysts as well as UHP Cu powder and a Cu chromite catalyst. Oxygen chemisorption via dissociative N2O adsorption was used to count surface Cu atoms and calculate crystallite sizes, and a microwave absorption technique was used to measure the electrical conductivity of these Cu particles. Under differential reaction conditions at 423 K and 1 atm, all catalysts exhibited deactivation on stream and activities were typically 10-20% of their initial values after 3-4 h on stream. However, initial turnover frequencies (TOFs) varied from 0.056 s(-1) on the most highly dispersed Cu catalyst to 0.50 s(-1) on Cu powder, with the highest TOF of 2.4 s(-1) occurring on 110 nm crystallites. A similar trend with a broader (80-fold) variation was observed in the "steady-state" TOF values. Apparent activation energies varied between 11 and 14 kcal/mol. These initial TOF values are in good agreement with previous results, and a correlation exists between TOF and Cu crystallite size in this reaction, which appears to be structure sensitive. In addition, the electrical conductivity of these dispersed Cu nanoparticles, which was always less than that of bulk Cu, also increased with increasing Cu crystallite size; consequently, the change in this parameter may offer a possible explanation for the increase in TOF.     

Phase transformations of ammonium tungsten bronzes

This article discusses the formation and structure of ammonium tungsten bronzes, (NH₄) _x WO_3−y . As analytical tools, TG/DTA-MS, XRD, SEM, Raman, XPS, and ¹H-MAS NMR were used. The well-known α-hexagonal ammonium tungsten bronze (α-HATB, ICDD 42-0452) was thermally reduced and around 550 °C a hexagonal ammonium tungsten bronze formed, whose structure was similar to α-HATB, but the hexagonal channels were almost completely empty; thus, this phase was called reduced hexagonal (h-) WO₃. In contrast with earlier considerations, it was found that the oxidation state of W atoms influenced at least as much the cell parameters of α-HATB and h-WO₃, as the packing of the hexagonal channels. Between 600 and 650 °C reduced h-WO₃ transformed into another ammonium tungsten bronze, whose structure was disputed in the literature. It was found that the structure of this phase—called β-HATB, (NH₄)_0.001WO_2.79—was hexagonal.     

The effect of K+ ion exchange on the structure and thermal reduction of hexagonal ammonium tungsten bronze

This paper discusses the changes in the structure and thermal reduction of nanosize hexagonal ammonium tungsten bronze (HATB), (NH₄)_0.33−xWO_3−y, which were caused by K⁺ ion exchange (doping) and studied by XRD, XPS, ¹H-MAS NMR, FTIR, SEM and TG/DTA-MS. Comparison of the cell parameters of undoped and doped HATB revealed that both a and c cell parameters decreased after the ion exchange reaction, which showed that smaller K⁺ ions partly replaced the larger NH₄⁺ ions in the hexagonal channels of HATB. After the reaction, from the hexagonal channels less NH₃ evolved, which also supported the incorporation of K⁺ ions into the hexagonal channels.     

Influence of tungsten sources on the synthesis and properties of ammonium dioxothiotungstate

Ammonium dioxothiotungstate was synthesized using different tungsten sources and characterized in detail by powder X-ray diffraction, energy dispersive X-ray spectrometry, transmission electron microscopy, nitrogen adsorption, and temperature-programmed sulfidation. It was found that tungsten oxide nanobelts are superior to ammonium metatungstate as tungsten source for the synthesis of ammonium dioxothiotungstate due to a time-consuming aging step being excluded from the synthesis route. Moreover, detailed characteristic data reveal that, when tungsten oxide nanobelts are used, the physical and chemical properties of the resulting ammonium dioxothiotungstate including particles size, specific surface area, and sulfidation pattern were improved. Also, the hydrodesulfurization measurements showed higher catalytic activity and balanced selectivity of the resulting ammonium dioxothiotungstate.     

Effect of crystallite size on the thermal phase change and porous properties of boehmite

The effect of crystallite size on the thermal phase change and porous properties of boehmite was investigated using boehmites with crystallite sizes of 2.9 to 24.4 nm and boehmite gels prepared by precipitation and hydrothermal methods. The dehydroxylation temperature of boehmite increases, its phase transition temperature from gamma- to theta-Al(2)O(3) decreases and the theta- to alpha-Al(2)O(3) transition temperature increases as the crystallite size of the boehmite increases. Boehmite with a crystallite size of approximately 5 nm shows the highest specific surface area and greatest thermal stability. This boehmite contains pores of about 2-3 nm radius, suggested to be responsible for the superior porous properties and thermal stability.     

Cellulose polymorphy, crystallite size, and the Segal Crystallinity Index

The X-ray diffraction-based Segal Crystallinity Index (CI) was calculated for simulated different sizes of crystallites for cellulose Iβ and II. The Mercury software was used, and different crystallite sizes were based on different input peak widths at half of the maximum peak intensity (pwhm). The two cellulose polymorphs, Iβ and II, gave different CIs despite having the same pwhm values and perfect periodicity. The higher CIs for cellulose II were attributed to a greater distance between the major peaks that are closest to the recommended 2-θ value for assessing the amorphous content. That results in less peak overlap at the recommended 2-θ value. Patterns calculated with simulated preferred orientation had somewhat higher CIs for cellulose Iβ, whereas there was very little effect on the CIs for cellulose II.     

Determination of crystallite particle size distribution of polymers from WAXS

A method for the calculation of crystallite size distributions from the profile of wide-angle x-ray reflections is developed. The influence of lattice distortions on the profile is taken into account. The information about the lattice distortions is obtained from the measurement of the integral widths of a number of reflections. The method is applied to samples of (ethylen-1 hexen) copolymers. The change of crystallite size distributions in lateral directions with increasing temperature (20–121°C) is measured. Recrystallization processes at temperatures near the melting point are observed. © 1996 John Wiley & Sons, Inc.     

The effect of molecular weight and crystallite structure on yielding in ethylene copolymers

Nominal stress-strain curves of a series of random ethylene-hexene copolymers having narrow composition and most probable molecular weight distributions were investigated. A series of such molecular weight copolymers with a constant concentration of branches were crystallized under a variety of conditions. In each molecular weight series the level of crystallinity was approximately constant. Particular attention was focused on the yield region and the nature of the yielding process. It was found, quite surprisingly, that the yield stress was not solely dependent on the crystallinity level. Moreover, the shape of the force-elongation curve in the yield region was very dependent on the molecular weight and the crystallization mode. These changes in yielding correlated quite well with the overall crystallite structure that was characterized by thin section transmission electron microscopy. The orthorhombic unit cell of polyethylene was maintained in all the samples despite the changes that occurred in the overall crystallite structure. © 1997 John Wiley & Sons, Inc.     

Particle size effects on the oxidation of tungsten carbide nanopowders

The oxidation of tungsten carbide (WC) powders with the average particle size 〈D〉 from 20 to 6000 nm was studied by differential thermal and differential thermogravimetric analyses. WC powders are oxidized, irrespective of their dispersity, to higher oxide WO₃. The conclusion was drawn that at smaller particle sizes of WC powder, the oxidation rate increases, and the temperature of the peak of the exo effect decreases. The functional dependences of the temperature of the peak and the activation energy of oxidation on the particle size were determined.     

Effect of crystallite size on the intercalation pseudocapacitance of lithium nickel vanadate in aqueous electrolyte

This work describes lithium nickel vanadate (LiNiVO₄) as a pseudocapacitor electrode material for the first time. The micro and nano-sized LiNiVO₄ are synthesized via mechanochemical reaction and hydrothermal reaction followed by calcination, respectively. The phase purity, surface morphology and microstructure of the LiNiVO₄ synthesized by both methods are analysed by X-ray diffraction and scanning electron microscopy techniques. The lithium ion intercalation-extraction behaviour of the LiNiVO₄ electrode material is investigated in 1 M LiOH electrolyte solution. The results demonstrate an improved capacitive performance for nano-sized LiNiVO₄ electrode synthesized via hydrothermal reaction due to the collective effect of small size and additional redox sites. The nanocrystalline LiNiVO₄ electrode exhibits a high specific capacitance of 456.56 F g^?1 at a current density of 0.5 A g^?1. The cycle stability test reveals exceptional capacitance retention of 99.60% even after 1000 cycles owing to the unique structural feature which permit intercalation mechanism. These findings demonstrate the significance of lithium transition metal vanadate-based electrode material in the development of lithium ion intercalation pseudocapacitors.