Synthesis hexagonal ZrW2O8 and its thermal properties

ZrW₂O₈ as the typical negative thermal expansion (NTE) material has attracted much attention for the potential applications in various fields such as tailored coefficient of thermal expansion (CTE) composites. The hexagonal ZrW₂O₈ (h-ZrW₂O₈), with the combination of ZrO₂ and WO₃ in a composite, was synthesized at a pressure of 2 GPa and the temperature between 600°C and 700°C. We found h-ZrW₂O₈ decomposes to ZrO₂+WO₃ oxides that start from 500°C and end at 800°C, and determined the CTE of h-ZrW₂O₈ is?16.3×10^?6°C^?1 in the temperature range from 150°C to 450°C. The results show that ZrW₂O₈ with a hexagonal structure is metastable and exhibits high NTE property like its cubic structure.     

Corrosion products on steel 20 in aerated hydrazine solutions: Mössbauer study

Composition of corrosion layers on steel 20 in aerated solutions with hydrazine concentrations less than 11 ppm was studied at 50, 60, and 80°C in dynamic conditions by transmission Mössbauer spectroscopy and X-ray diffraction as supplementary technique. Corrosion rates were determined by gravimetric method. A comparison with corrosion in water at 80°C was made. The observed layers have not any protective character. For 0.1 m/s linear velocity, they are composed by nonstoichiometric magnetite, (Fe_3?x O₄,x=0.02–0.04) with lepidocrocite (γ-FeOOH) as secondary phase at 50°C. Haematite (α-Fe₂O₃) is observed at 60 and 80°C with a 19 nm particle size. It becomes smaller for higher velocity (0.7 m/s).     

New polymorphs of alumina: Part II μ and λ alumina

Abstract

We had reported observation of polymorphs of alumina having rare earth sesquioxide type structures in xerogel γ alumina (XGA) at high pressures and temperatures (High Pressure Research, 1998). In this paper we report observation of two additional phases at somewhat different pressures and temperatures. The XGA quenched from 5.2 GPa and 1450°C showed, besides α Al₂O₃, a new hexagonal metastable polymorph μAl₂O₃. Over a period of 10 to 12 weeks μ A1₂O₃ transforms to a stable hexagonal phase λ Al₂O₃. The cell parameters of λ Al₂O₃ are comparable with those of k Al₂O₃ found by Saalfield on dehydration of gibbsite A1₂O₃3H₂O in air at 800°C. The XGA containing 1 wt% of Cr₂O₃ yielded similar results at 4.56GPa and 1100°C. Further the XGA containing Cr showed complete transformation to n Al₂O₃ at 5.2 GPa and 1520°C.     

Nano-polycrystalline diamond synthesized through the decomposition of stearic acid

ABSTRACT

Here we report a novel route for synthesizing nano-polycrystalline diamond (NPD) using stearic acid (C₁₈H₃₆O₂) as a starting material under high pressure and high temperature. The obtained NPD shows a transparent dark-yellowish color similar to the standard NPD synthesized from graphite and consists of extremely fine diamond grains (～10?nm). The temperature required for the present synthesis of pure transparent NPD is as low as 1000°C at 13 and 17?GPa, which is surprisingly lower than that for conventional NPD synthesis (1800–2000°C). The amorphous-like, extremely poorly crystalline graphite produced by the thermal decomposition of stearic acid likely provides preferential nucleation sites for diamond and significantly lower the activation energy. The removal of volatile components such as H₂O generated through the decomposition from the system is a key to obtain pore-free transparent NPD. Magnesite, MgCO₃ and periclase, MgO can be used as an efficient H₂O remover through the hydration reaction.     

Surface oxidation control of nanosized magnetite and Mössbauer measurements

Selected highly homogeneous powders of Fe₃O₄ with different particle size on the nanometer scale (10?±?2 and 3?±?2 nm) obtained by soft-chemical methods were studied by Mössbauer spectroscopy. The study shows clearly the powerful possibilities of Mössbauer spectroscopy to analyze the surface oxidation of nanostructured powders of magnetite. On the other hand, it is shown that for very small superparamagnetic particles the spectrum of magnetite might be quite similar to that of maghemite, making it difficult to distinguish between both phases.     

Magnetic nanoparticles based on iron coated carbon produced from the reaction of Fe2O3 with CH4: a Mössbauer study

In this work, it was investigated the production of magnetic nanoparticles encapsulated with carbon by the reaction of hematite and methane by Temperature Programmed Reaction up to 950°C. XRD and Mössbauer analyses showed that the materials prepared at 600°C and 700°C are mainly composed of magnetite and small amounts of hematite α -Fe₂O₃ with particle size of 30–40 nm. At higher temperatures, the spectra also display two central doublets corresponding to wüstite phase (Fe_1???x O). The materials were also characterized by magnetization measurements, BET surface area, thermal analysis (TG) and SEM. These materials can be prepared by a simple and low cost process and show great potential to be used as adsorbents and catalyst support.     

Reduction of hematite with ethanol to produce magnetic nanoparticles of Fe3O4, Fe1 − x O or Fe0 coated with carbon

The production of magnetic nanoparticles of Fe₃O₄ or Fe⁰ coated with carbon and carbon nanotubes was investigated by the reduction of hematite with ethanol in a Temperature Programmed Reaction up to 950°C. XRD and Mössbauer measurements showed after reaction at 350°C the partial reduction of hematite to magnetite. At 600°C the hematite is completely reduced to magnetite (59%), wüstite (39%) and metallic iron (7%). At higher temperatures, carbide and metallic iron are the only phases present. TG weight losses suggested the formation of 3–56 wt.% carbon deposits after reaction with ethanol. It was observed by SEM images a high concentration of nanometric carbon filaments on the material surface. BET analyses showed a slight increase in the surface area after reaction. These materials have potential application as catalyst support and removal of spilled oil contaminants.     

Preparation of (As x Co3−x O4)(x=0–0.024) nanoparticles by rheological phase reaction method

Nanoparticles of a series of arsenic–cobalt mixed valency spinel oxides of theoretical formula As _x Co_3?x O₄, (x=0, 0.005, 0.01, 0.015, 0.024) have been successfully prepared by the rheological phase reaction and the pyrolysis method. The products were characterized by X-ray powder diffraction, scanning electron microscope, thermogravimetric analysis and simultaneous differential thermal analysis. Calcination of the precursor at 500 ^°C resulted in the formation of arsenic-doped cobalt oxide nanoparticles of 48 nm in crystal size. The effect of the calcination temperature on the crystal size of arsenic-doped Co₃O₄ was discussed.     

Spin‐dependent‐magnetoresistance control by regulation of heat treatment temperature for magnetite nano‐particle sinter

The control of spin‐dependent‐magnetoresistance by regulation of the heat treatment (HT) temperature for magnetite (Fe₃O₃) nano‐particle sinter (MNPS) has been studied. The average nano‐particle size in the MNPS is 30nm and the HT was carried out from 400°C to 800°C. The HT of the MNPS varies the coupling form between adjacent magnetite nano‐particles and the crystallinity of that. The measurements on electrical resistance (ER), magnetoresistance (MR) and magnetization were performed between 4K and 300K. The behavior of the ER and MR considerably changes at the HT temperature of ～600°C. Below ～600°C the ER indicates the variable‐range‐hopping conduction behavior and the MR shows the large intensity in a wide temperature region. Above ～600°C the ER shows the indication of the Verwey transition near 110K like a bulk single crystal and the MR designates the smaller intensity. We consider that below ～600°C the ER and MR are dominated by the grain‐boundary conduction and above ～600°C those are determined by the inter‐grain conduction. The magnetic field application to the grain‐boundary region is inferred to cause the large enhancement of the MR.     

M?ssbauer study of carbon coated iron magnetic nanoparticles produced by simultaneous reduction/pyrolysis

Magnetic iron nanoparticles immersed in a carbon matrix were produced by a combined process of controlled dispersion of Fe^3?+? ions in sucrose, thermal decomposition with simultaneous reduction of iron cores and the formation of the porous carbonaceous matrix. The materials were prepared with iron contents of 1, 4 and 8 in %wt in sucrose and heated at 400, 600 and 800°. The samples were analyzed by XRD, Mössbauer spectroscopy, magnetization measurements, TG, SEM and TEM. The materials prepared at 400° are composed essentially of Fe₃O₄ particles and carbon, while treatments at higher temperatures, e.g. 600 and 800° produced as main phases Fe⁰ and Fe₃C. The Mössbauer spectra of samples heated at 400° showed two sextets characteristic of a magnetite phase and other contributions compatible with Fe^3?+? and Fe^2?+? phases in a carbonaceous matrix. Samples treated at temperatures above 600° showed the presence of metallic iron with concentrations between 16?C43%. The samples heated at 800° produced higher amounts of Fe₃C (between 20% and 58%). SEM showed for the iron 8% sample treated at 600?C800°C particle sizes smaller than 50 nm. Due to the presence of Fe⁰ particles in the carbonaceous porous matrix the materials have great potential for application as magnetic adsorbents.     

Influence of heat treatment on structure and some physical properties of lithium boro-niobate glass

The glass composition (90?mol% Li₂B₄O₇–10?mol% Nb₂O₅) was prepared by the melt quenching technique. The quenched sample was heat treated at 480°C, 545°C and 630°C for 5?h and heat treated at 780°C with different time. The times were 5, 10, 15, 20, 28, and 36?h. The glass and glass ceramics were studied by differential thermal analysis (DTA), X-ray diffraction (XRD), and dc conductivity as a function of temperature. Lithium niobate (LiNbO₃) and lithium diborate (Li₂B₄O₇) were the main phases in glass ceramic addition to traces from LiNb₃O₈. Crystallite size of the main phases determined from the X-ray diffraction peaks are in the range <100?nm. The fraction of crystalline (LiNbO₃) phase increases with increase the heat treatment temperature and time. The relation between physical properties and structure were studied.     

Identification of iron oxide phases in thin films grown on Al2O3(0 0 0 1) by Raman spectroscopy and X-ray diffraction

We report on the identification of Fe₃O₄ (magnetite) and α-Fe₂O₃ (hematite) in iron oxide thin films grown on α-Al₂O₃(0 0 0 1) by evaporation of Fe in an O₂-atmosphere with a thickness of a few unit cells. The phases were observed by Raman spectroscopy and confirmed by X-ray diffraction (XRD). Magnetite appeared independently from the substrate temperature and could not be completely removed by post-annealing in an oxygen atmosphere as observed by X-ray diffraction. In the temperature range between 400 °C and 500 °C the X-ray diffraction shows that predominantly hematite is formed, the Raman spectrum shows a mixture of magnetite and hematite. At both lower and higher substrate temperatures (300 °C and 600 °C) only magnetite was observed. After post-annealing in an O₂-atmosphere of 5 × 10^?5 mbar only hematite was detectable in the Raman spectrum.     

Synthesis and characterization of hollow ��-Fe2O3 sub-micron spheres prepared by sol�Cgel

In this work we report the preparation of magnetic hematite hollow sub-micron spheres (??-Fe₂O₃) by colloidal suspensions of ferric nitrate nine-hydrate (Fe(NO₃)₃·9H₂O) particles in citric acid solution by following the sol?Cgel method. After the gel formation, the samples were annealed at different temperatures in an oxidizing atmosphere. Annealing at 180°C resulted in an amorphous phase, without iron oxide formation. Annealing at 250°C resulted in coexisting phases of hematite, maghemite and magnetite, whereas at 400°C, only hematite and maghemite were found. Pure hematite hollow sub-micron spheres with porous shells were formed after annealing at 600°C. The characterization was performed by X-ray diffraction (XRD), Mössbauer spectroscopy (MS) and scanning electron microscopy (SEM).     

Size effects in monodomain magnetite based ferrofluids

Ferrofluids based on two types of hybrid particles Fe₃O₄/β-cyclodextrin were prepared: Using monodomain (below 60 nm) magnetite nanoparticles with (A) non-superparamagnetic (non-SPM) behaviour and (B) with superparamagnetic (SPM) behaviour. We found a strong dependence of the hybrid particles’ magnetic properties on their size and homogeneity. In both types of ferrofluids we observed hyperthermia upon applying an ac electromagnetic field with frequency 40 kHz and amplitude 30 kA/m. The maximal ΔТ upon irradiation with duration of about 12 min for the non-SPM particles was 12 °C, while for the SPM ones it was 3.5 °C.     

Mössbauer study of Cu1−xZnxFe2O4 catalytic materials

In the present work, we have synthesized and characterized magnetic nanoparticles of maghemite γ-Fe₂O₃ to study their structural and magnetic properties. For the preparation, magnetite precursor, were oxidized by adjusting the pH = 3.5 at about 80 °C in an acid medium, The mean size of the maghemite particles calculated from the X-ray diffractogram was around 5.7 nm. Mössbauer spectroscopy measurements at room temperature show their superparamagnetic behavior. Furhermore, Mössbauer measurements were carried out at 77 K and 4.2 K in order to find the typical hyperfine fields of the maghemite. Magnetite phase was not found. FC and ZFC magnetization curves measured at 500 Oe indicate a blocking temperature of 105.3 K. The magnetization measurements also show almost zero coercivity at RT. TEM images show nanoparticles with diameter smaller than 10 nm, which are in good agreement with the X-ray pattern and the fitting of the magnetization data.     

The Massachusetts Toxics Use Reduction Act: a model for nanomaterials regulation?

Polyvinylimidazole (PVIm)-grafted superparamagnetic iron oxide nanoparticles (SPION) (Si-PVIm-grafted Fe₃O₄ NPs) were prepared by grafting of telomere of PVIm on the SPION. The product identified as magnetite, which has an average crystallite size of 9?±?2?nm as estimated from X-ray line profile fitting. Particle size was estimated as 10.0?±?0.5?nm from TEM micrographs. Mean particle size is found as 8.4?±?1.0?nm which agrees well with the values calculated from XRD patterns (9?±?2?nm). Vibrating Sample Magnetometer (VSM) analysis explained the superparamagnetic nature of the nanocomposite. Thermogravimetric analysis showed that the Si-Imi is 25?% of the Si-PVIm-grafted SPION, which means an inorganic content is about 75?%. Detailed electrical and dielectric properties of the properties of the product are also presented. The conductivity of the sample increases significantly with temperature and has the value in the range of 1.14?×?10^?7?C1.78?×?10^?4?S?cm^?1. Analysis of the real and imaginary parts of the permittivities indicated temperature and frequency dependency representing interfacial polarization and temperature-assisted reorganization effects.     

An investigation of the synthesis and conductivities of La-Ge-O based systems

Recently apatite-type phases (e.g. La_10?x(Si/Ge)₆O_26±z) have been attracting significant interest due to their high oxide ion conduction. In the case of the Ge based systems there is some uncertainty regarding the nature of the conducting phase, whether it is indeed apatite based or cation deficient La₂GeO₅-type. In this paper we report a detailed investigation of the phase with composition La_9.33Ge₆O₂₆. We show that for synthesis temperatures in the range 1150–1300 °C, the hexagonal apatite-type structure is obtained (a=b=9.913(4), c=7.282(4) Å), but heating to higher temperatures (>1300 °C) leads to the occurrence of extra peaks in the XRD pattern around the apatite peaks. Attempts to refine the extra peaks on a monoclinic apatite-type cell have so far proved unsuccessful, and the exact nature of this system is not clear, although the XRD pattern appears to resemble that of an apatite-type phase more closely than that of La₂GeO₅. In addition to the change in the XRD pattern, there is also a significant change in the oxide ion conductivity. Specifically the activation energy for samples prepared/sintered at high temperatures (1500 °C) is significantly higher than for those prepared/sintered at lower temperatures (1150 °C). The changes observed appear to be due to loss of Ge, and if the sample is heated at high temperature (1500 °C) for several days, the formation of La₂GeO₅ becomes apparent. This loss of Ge is a significant problem for the possible use of these materials in SOFCs. In addition to the data on La_9.33Ge₆O₂₆, we also present conductivity data for La₂GeO₅ and La₄GeO₈ for comparison.     

A conversion electron Mössbauer spectroscopy study of pulsed laser treatment at α-Fe2O3/H2O interface

Magnetite (Fe₃O₄) has been synthesized for the first time by using pulsed ruby laser induced reactive quenching process at α-Fe₂O₃/H₂O interface. Iron foils (99.99% pure) were oxidised at 450° C for four hours to form a thick layer of α-Fe₂O₃ on it. These oxidised samples were immersed in water and then treated with ruby laser pulses (λ=0.694 μm, pulse width = 30 ns, energy density = 10 J/cm²). The conversion electron Mössbauer spectroscopy (CEMS) has been used to characterize the laser induced surface modifications. It is shown that laser treated samples show the formation of Fe₃O₄ phase along with FeO. The stability of magnetite phase in laser treated sample against thermal treatment is also studied by investigating the changes in hyperfine interaction parameters upon vacuum annealing at 300° C.     

Chemical,optical, and electrical characterization of Ga2O3 thin films grown by plasma-enhanced atomic layer deposition

Thin Ga₂O₃ films were grown on Si (100) using trimethylgallium (TMG) and oxygen as the precursors through plasma-enhanced atomic layer deposition. The depositions were made over a temperature range of 80–250?°C with a growth per cycle of around 0.07 nm/cycle. Surface self-saturating growth was obtained with TMG pulse time ≥20?ms?at a temperature of 150?°C. The root mean square surface roughness of the obtained Ga₂O₃ films increased from 0.1?nm to 0.3?nm with increasing the growth temperature. Moreover, the x-ray photoelectron spectroscopy analysis indicated that the obtained film was Ga-rich with the chemical oxidation states Ga³⁺ and Ga¹⁺, and no carbon contamination was detected in the films after Ar⁺ sputtering. The electron density of films measured by x-ray reflectivity varied with the growth temperature, increasing from 4.72 to 5.80?g/cm³. The transmittance of Ga₂O₃ film deposited on a quartz substrate was obtained through ultraviolet visible (UV–Vis) spectroscopy. An obvious absorption in the deep UV region was demonstrated with a wide band gap of 4.6–4.8?eV. The spectroscopic ellipsometry analysis indicated that the average refractive index of the Ga₂O₃ film was 1.91?at 632.8?nm and increased with the growth temperature due to the dense structure of the films. Finally, the I-V and C-V characteristics proved that the Ga₂O₃ films prepared in this work had a low leakage current of 7.2?×?10^?11 A/cm² at 1.0?MV/cm and a high permittivity of 11.9, suitable to be gate dielectric.     

Phase transformation of strontium hexagonal ferrite

The phase transformation of strontium hexagonal ferrite (SrFe₁₂O₁₉) to magnetite (Fe₃O₄) as main phase and strontium carbonate (SrCO₃) as secondary phase is reported here. SrFe₁₂O₁₉ powder was obtained by a heat treatment at 250 °C under controlled oxygen flow. It was observed that the phase transformation occurred when the SrFe₁₂O₁₉ ferrite was heated up to 625 °C in confinement conditions. This transformation took place by a combination of three factors: the presence of stresses in the crystal lattice of SrFe₁₂O₁₉ due to a low synthesis temperature, the reduction of Fe³⁺ to Fe²⁺ during the heating up to 625 °C, and the similarity of the coordination spheres of the iron atoms present in the S-block of SrFe₁₂O₁₉ and Fe₃O₄. X-ray diffraction analysis confirmed the existence of strain and crystal deformation in SrFe₁₂O₁₉ and the absence of them in the material after the phase transformation. Dispersive X-ray absorption spectroscopy and Fe⁵⁷ Mössbauer spectroscopy provided evidences of the reduction of Fe³⁺ to Fe²⁺ in the SrFe₁₂O₁₉ crystal.