Effect of ferrite powder fineness on the structure and properties of ceramic materials

Comprehensive study of the structure and properties of ferrite materials prepared from powders with different specific surface (0.4 m²/g<S_sp<1.2 m²/g) shows that the optimum specific surface of manganese—zinc ferrite powders is about 0.6 m²/g. With an increase in the specific surface of nickel—zinc and barium ferrite powders the porous crystalline structure of sintered specimens and most of the main electromagnetic properties of ferrite articles are improved.     

Finely dispersed Si3N4−SiC powders and materials based on them

The objectives of the present research were to investigate the preparation of homogeneous ultrafine composite Si₃N₄−SiC powders by a plasmochemical process and the properties of ceramics produced from them. The chemical and phase compositions of the powders depended on the particle size of the initial powder, silicon input rate, and ratio of ammonium and hydrocarbon flow rates. The particle size and specific surface area of the compounds depended on the concentration of particles in the gas jet, and the cooling rate of the products. Composite powders containing from a few up to 90 mass % SiC, with specific surface areas of 24–80 m²/g and free silicon and carbon content less than 0.5 mass % were obtained. The main phases present were α-Si₃N₄, β-Si₃N₄, β-SiC, and X-ray amorphous Si₃N₄. Dense materials were prepared both by hot pressing at 1800°C under a load of 30 MPa and gas-pressure sintering at 1600–1900°C under a pressure of 0.5 MPa nitrogen. The plasmochemical composites had smaller pore sizes, were finer grained, and densified more rapidly than materials sintered from commercial powders. Institute of Inorganic Chemistry, Latvian Academy of Sciences, Salaspils. Translated from Poroshkovaya Metallurgiya, Nos. 1–2(405), pp. 7–12, January–February, 1999.     

Nitride Formation and Excess Nitrogen Uptake After Nitriding Ferritic Fe-Ti-Cr Alloys

The microstructure of the nitrided zone of Fe-Ti-Cr alloys, containing a total of 0.30 at. pct (Ti + Cr) alloying elements, with varying Ti/Cr atomic ratio (0.45, 0.87, and 1.90), was investigated by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The stable TiN and CrN nitrides did not precipitate after nitriding. Instead, ultrafine, metastable, mixed Ti_1–x Cr _x N nitride precipitates developed in the nitrided zone: The precipitates were of platelet morphology (length ≤30 nm and thickness ≤3 nm) and of cubic, rock-salt, crystal-structure type. The misfit strain around the nitride platelets in the ferrite matrix increases with increasing Ti/Cr atomic ratio. As a consequence, most pronouncedly for the highest Ti/Cr atomic ratio, a tetragonally distorted ferrite matrix surrounds the precipitates, as evidenced both by XRD and TEM. The amount of nitrogen taken up was determined quantitatively by measuring the so-called nitrogen-absorption isotherms. It follows that the absorbed amount of so-called excess nitrogen dissolved in the matrix and adsorbed at the nitride-platelet faces increases distinctly with increasing Ti/Cr atomic ratio. The results were discussed in terms of the dependence of misfit strain on the Ti/Cr atomic ratio and the higher chemical affinity of Ti for N than of Cr for N.     

Microstructures and properties of nanocomposites obtained through SPTS consolidation of powders

The microstructures and properties of copper- and aluminum-based nanocomposites processed through severe plastic torsional straining (SPTS) consolidation of metallic micrometer powders and ceramic nanopowders were investigated by transmission electron microscopy (TEM), X-ray diffraction (XRD), microhardness and electrical resistivity measurements, and mechanical tests. It was shown that the SPTS consolidation of powders is an effective technique for fabricating metal-ceramic nanocomposites with a high density, ultrafine grain size, and high strength. Copper samples processed under a high pressure of 6 GPa exhibited high failure strength and strain as well as unusual strain hardening. Superplastic-like behavior was found in Al-Al₂O₃ nanocomposite samples. This article is based on a presentation made in the symposium “Mechanical Behavior of Bulk Nanocrystalline Solids,” presented at the 1997 Fall TMS Meeting and Materials Week, September 14–18, 1997, in Indianapolis, Indiana, under the auspices of the Mechanical Metallurgy (SMD), Powder Materials (MDMD), and Chemistry and Physics of Materials (EMPMD/SMD) Committees.     

Isothermal transformations in an Fe-9 pct Ni alloy

Isothermal transformation from austenite in an Fe-9.14 pct Ni alloy has been studied by optical metallography and examination by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). In the temperature range 565 °C and 545 °C, massive ferrite (α _q ) forms first at prior austenite grain boundaries, followed by Widmanst?tten ferrite (α _W ) growing from this grain boundary ferrite. Between 495 °C and 535 °C, Widmanst?tten ferrite is thought to grow directly from the austenite grain boundaries. Both these transformations do not go to completion and reasons for this are discussed. These composition invariant transformations occur below T ₀ in the two-phase field (α+γ). Previous work on the same alloy showed that transformation occurred to α _q > and α _W on furnace cooling, while analytical TEM showed an increase of Ni at the massive ferrite grain boundaries, indicating local partitioning of Ni at the transformation interface. An Fe-3.47 pct Ni alloy transformed to equiaxed ferrite at 707 °C ±5 °C inside the single-phase field on air cooling. This is in agreement with data from other sources, although equiaxed ferrite in Fe-C alloys forms in the two-phase region. The application of theories of growth of two types of massive transformation by Hillert and his colleagues are discussed. This article is based on a presentation made at the symposium entitled “The Mechanisms of the Massive Transformation,” a part of the Fall 2000 TMS Meeting held October 16–19, 2000, in St. Louis, Missouri, under the auspices of the ASM Phase Transformations Committee.     

Overall kinetics and morphology of the products of austenite decomposition in a Fe-0.46 Pct C-5.2 Pct Cr alloy transformed isothermally above the bay

The overall transformation kinetics of austenite isothermal decomposition above the bay of the time-temperature-transformation (TTT) curve and the eutectoid morphology of the resulting products have been studied in a Fe-0.46 pct C-5.2 pct Cr alloy. Classical lamellar pearlite was formed at high temperatures while complex ferrite plus carbide morphologies, sometimes described as spiky pearlite, arborescent structures, or nonclassical decompositions products of austenite in Fe-Cr-C alloys, formed at low temperatures. While X-ray diffraction of extracted carbides and selected area diffraction-transmission electron microscopy (TEM) showed evidence for a mixture of M₃C and M₇C₃ carbides, thermodynamic calculations results obtained only M₇C₃ as the equilibrium carbide at the temperatures studied. A tentative explanation for the arborescent morphology is presented, based on the hypothesis of the existence of a drag force or free energy dissipation term that is locally relaxed by the partition of Cr into the carbides at the reaction front, consequently removing Cr from the interface. This article is based on a presentation made in the “Hillert Symposium on Thermodynamics & Kinetics of Migrating Interfaces in Steels and Other Complex Alloys,” December 2–3, 2004, organized by The Royal Institute of Technology in Stockholm, Sweden.     

Thermodynamics of Arsenic in FeOx-CaO-SiO<Subscript>2</Subscript> Slags

The distribution of arsenic between calcium ferrite slag and liquid silver (wt pct As in slag/ wt pct As in liquid silver) with 22 wt pct CaO and between iron silicate slag with 24 wt pct SiO₂ and calcium iron silicate slags was measured at 1573 K (1300 °C) under a controlled CO-CO₂-Ar atmosphere. For the calcium ferrite slags, a broad range of oxygen partial pressure (10^–11 to 0.21 atm) was covered, whereas for the silicate slags, the oxygen partial pressure was varied from 10^–9 to 3.1 × 10^–7 atm. The measured relations between the distribution ratio of As and the oxygen partial pressure indicates that the oxidation state of arsenic in these slags is predominantly As³⁺ or AsO_1.5. The measured distribution ratio of arsenic between the calcium ferrite slag and the liquid silver was about an order of magnitude higher than that of the iron silicate slag. In addition, an increasing concentration of SiO₂ in the calcium-ferrite-based melts resulted in decreases in the distribution of arsenic into the slag. Through the use of measured equilibrium data on the arsenic content of the metal and slag in conjunction with the composition dependent on the activity of arsenic in the metal, the activity of AsO_1.5 in the slags was deduced. These activity data on AsO_1.5 show a negative deviation from the ideal behavior in these slags.     

Microstructure and mechanical properties of ternary intermetallic compound dispersed P/M Al-Mn-X-Zr (x=Cu,Ni) alloys

Heat-resistant aluminum alloys are generally developed by dispersing stable intermetallic compounds by adding transition metals (TM) whose diffusion coefficient in aluminum alloys is low even at high temperatures. Commonly used intermetallic compounds include Al-TM binary intermetallic compounds, for example, Al₆Fe, Al₃Ti and Al₃Ni. By contrast, multicomponent intermetallic compounds are hardly used. The present study focuses on Al-Mn-Cu and Al-Mn-Ni ternary intermetallic compounds, and by finely dispersing these intermetallic compounds, attempts to develop heat-resistant alloys. Through the atomization method, Al-(4.96–5.96)Mn-(6.82–7.53)Cu-0.4Zr and Al-(5.48–8.76)Mn-(2.23–4.32)Ni-0.4Zr (in mass%) powders were fabricated, and by degassing these powders at 773 K, intermetallic compounds were precipitated. These powders were then solidified into extrudates by hot extrusion at 773 K. The microstructural characterization of powders and exrudates was carried out by XRD analysis, SEM/EDX and TEM. The mechanical properties of extrudates were determined at room temperature, 523 K and 573 K. In Al-Mn-Cu alloys, while a small amount of Al₂Cu was crystallized, precipitated Al₂₀Mn₃Cu₂ intermetallic compounds were mainly dispersed. In Al-Mn-Ni alloys, while a small amount of Al₆Mn intermetallic compounds was precipitated, the precipitated A₆₀Mn₁₁Ni₄ intermetallic compounds were mainly dispersed. Both ternary intermetallic compounds were about 200 nm in size. The compounds were elliptical, and their longitudinal direction was oriented along the extrusion direction. In the Al-Mn-Cu alloys, since the work hardening at room temperature was high, the tensile strength became 569 MPa. At elevated temperatures, since hardly any work hardening was observed, the tensile strength decreased markedly. However, in Al-Mn-Ni alloys, since the work hardening is low even at room temperature, the roomtemperature strength is not high. Thus, the decrease in tensile strength at elevated temperatures is relatively small and a high strength was obtained at 523 K and 573 K: 276 MPa and 207 MPa, respectively.     

Liquidus Temperatures in the “Cu<Subscript>2</Subscript>O”-FeO-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-CaO System at Molten Metallic Copper Saturation

Calcium ferrite slags, which are represented by the “Cu₂O”-FeO-Fe₂O₃-CaO system at copper saturation, have been applied successfully to existing copper-converting processes. Because of the industrial importance of this system, the characterization of the effects of oxygen partial pressure and silica on the phase equilibria is necessary to improve the control of process parameters, which include fluxing and operating temperatures. In the current study, experimental methods, which use the equilibration/quenching/electron probe X-ray microanalysis (EPMA) techniques with primary phase substrate support, were subsequently developed to incorporate fixed oxygen partial pressure experiments. Experiments were carried out at 1200 °C and 1250 °C both with and without silica additions; both liquidus and solidus data were reported for the primary phase field of spinel and dicalcium ferrite between the oxygen partial pressures of 10^−5.0 and 10^−6.5 atm. The analyzed compositions of the liquid and solid phases are used to construct the phase diagram of the pseudoternary “Cu₂O”-“Fe₂O₃”-CaO system in equilibrium with metallic copper at fixed oxygen partial pressures and with additions of silica. The maximum solubility of silica within the liquid slag phase, prior to dicalcium silicate precipitation, was measured at specific conditions. Two empirical equations used for the calculation of the copper oxide concentration in calcium ferrite slag are evaluated with the new experimental data defined in the current study.     

Combustion synthesis of α-Si3N4-(MgO, Y2O3) composites

The possibility of obtaining composite powders of α-Si₃N₄-Y₂O₃ and α-Si₃N₄-MgO by self-propagating high-temperature synthesis (SHS) is studied. It is established that the α → β phase transformation starts at temperatures lower than the melting points of the corresponding eutectics. Metastable composite powders based on α-Si₃N₄ with a high rate of phase transition are obtained. The composite powders (α-Si₃N₄-Y₂O₃, α-Si₃N₄-MgO) are used in hot pressing technology. __________ Translated from Poroshkovaya Metallurgiya, Vol. 46, No. 1–2(453), pp. 10–14, 2007.     

The mechanism of ferrite formation from iron sulfides during zinc roasting

The formation of zinc ferrite (ZnFe₂O₄) during the fluidized-bed roasting of zinc concentrates presents subsequent processing difficulties both for zinc recovery and for iron separation and disposal. A major source of iron in these concentrates is from the iron sulfides — pyrite and pyrrhotite. This study examined the changes undergone by these iron minerals when roasted together with sphalerite at 1223 K in a fluidizing gas mixture of 3 pct oxygen and 97 pct nitrogen. Optical microscopy and electron microprobe analysis were employed to identify the three stages that lead to ferrite formation and to examine the processes that occur within each stage. The first stage is oxidation of the sulfides to highly vesicular, amorphous magnetite particles containing small amounts of zinc. The second stage involves both densification of these particles by sintering and counterdiffusion of iron and zinc cations to form a continuous phase of homogeneous zinc-rich spinel and a precipitate of hematite. In the third stage, continuation of cation diffusion and increasingPo ₂ results in the formation of stoichiometric zinc ferrite. These observations have been interpreted by reference to the established phase relationships that occur in the Zn-Fe-O system, and a detailed, solid state reaction mechanism for the formation of zinc ferrite has been proposed.     

Sol-Gel Derived Nanocrystalline Fluoridated Hydroxyapatite Powders and Nanostructured Coatings for Tissue Engineering Applications

Nanocrystalline fluoridated hydroxyapatite (FHA) powders and coatings with a chemical composition of Ca₁₀(PO₄)₆OH_2–x F _x (where x values were selected equal to 0.0 ,0.5, 1.0, 1.5, and 2.0) were prepared through a modified simple sol-gel technique in comparison with conventional alkoxide-based sol-gel route. X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), fourier transform infrared (FTIR) spectroscopy, pF-meter with a fluorine-sensitive electrode, and inductively coupled plasma–optical emission spectroscopy (ICP-OES) analysis techniques were employed in order to evaluate phase composition, particle size distribution, morphology, functional groups, fluorine content, and purity of prepared FHA nanopowders, respectively. SEM analysis was used to study the surface morphology and cross section of the FHA coatings, deposited on 316L stainless steel substrate. Results indicated that single-phase and homogeneous FHA nanopowders with carbonate peaks in the FTIR spectrum were synthesized through the modified sol-gel technique. TEM analysis revealed that fluorapatite (FA) powder was composed of nanosized particles, ~25 nm in size, with polyhedron shape and straight corners. In the modified sol-gel technique, polymerization and gelation kinetic of the sol were significantly improved without any need to use additives or pH control. Uniform, dense, well-adhered, and compacted FHA coatings were formed on the 316L stainless steel substrate after 24 hours of aging.     

Oxidation of porous nanocrystalline titanium nitride. II. Scale structure and composition

We have used x-ray phase analysis to study the composition of the products of reaction between oxygen and nanocrystalline powders with particle sizes 15, 40, 55, and 80 nm, and also specimens pressed (and sintered) from them. The powders were oxidized in air at 100°C (400 h) to 500°C (5 min), while the sintered specimens were oxidized at 600–900°C for 15, 120, and 240 min. In all cases, in the initial oxidation step the oxynitride Ti(O_xN_y) is formed, which over time is oxidized to TiO, Ti₂O₃, Ti₃O₅, TiO₂ (anatase) and TiO₂ (rutile). In the range 600–800°C, formation of a continuous oxide layer and conversion of anatase to rutile slows down diffusion of oxygen in the scale. We have established that at 900°C, the growth rate of the scale thickness increases and so the reflections from the oxynitride are barely noticeable on the diffraction patterns taken from the surface of the oxidized specimen. In these diffraction patterns, along with strong reflections from the rutile, we also observed weak reflections from lower oxides and anatase, which may be due to reaction between oxygen and the titanium ions diffused to the scale surface. We have concluded that at T > 850°C, the mechanism for oxidation of TiN changes. This is due to superposition of counterdiffusion of titanium ions on the diffusion of oxygen. __________ Translated from Poroshkovaya Metallurgiya, Nos. 3–4(448), pp. 72–78, March–April, 2006.     

Effect of heat treatment on the dispersity of Sn(IV)—Sb—O powders and the porosity of thick-film gas sensors based on them

A study is made of how the granulometric composition and porosity of powders of solid solutions in the system Sn(IV)−Sb−O is affected by the conditions of precipitation of mixtures of tin hydroxide and antimony hydroxide and the heat-treatment temperature. Powders of tin and antimony hydroxides have a microporous structure and a high (≥200 m ²/g) specific surface. Heat treatment above 870 K forms Sn_1−xSb_xO₂ solid solutions, this being accompanied by an increase in the size of the particles and transformation of the microporous structure to a mesoporous structure. An increase in the antimony content of the solid solutions helps form finer powders. A examination is made of the parameters of the pore structure of bulk specimens of semiconductor gas sensors obtained by heat-treating mixtures of powders of solid solutions and ultrafine clay. Institute for Problems of Materials Science, Ukraine National Academy of Sciences, Kiev. Translated from Poroshkovaya Metallurgiya, Nos. 5–6(407), pp. 111–116, May–June, 1999.     

Reaction kinetics studies on Ti-Al-Cr-Nb-B intermetallics

In reaction synthesis (RS) route of powder metallurgy, heat of reaction between elemental powders is utilised to obtain intermetallic compounds. Prior to reaction synthesis of quaternary alloy Ti48Al2Cr2Nb (with 10 at. % B), reaction kinetics studies were carried out. Powder mixture was prepared and Differential Scanning Calorimetry (DSC) experiments were carried out at 3 different heating rates. Activation energy and Avrami Index ‘n’ are obtained by Johnson-Mehl-Avrami (JMA) equation. Formation of Al₃Ti was confirmed through X-ray diffraction (XRD). Reaction mechanisms are identified in accordance with ‘n’ values. In the temperature range of 1060–1150K, it proceeds as instantaneous nucleation and three dimensional growth with an activation energy of 176 kJ mole⁻¹.     

Properties and structure features of nanocomposite powders based on SiC

Features of the synthesis of SiC−Si₃N₄−Si₂N₂O composite powders are studied. The characteristics of the powders are examined on the basis of x-ray diffraction, transmission electron microscopy, and Raman spectroscopy. The structure features and mechanical properties of a ceramics formed on the basis of the synthesized powders are also studied. Institute for Problems of Materials Science, Ukraine National Academy of Sciences, Kiev. Traslated from Poroshkovaya Metallurgiya, Nos. 7–8(408), pp. 12–16, July–August, 1999.     

X-ray spectral investigation of the electronic structure and chemical bonding in ultradispersed powders and the fine-grained materials obtained from them. I. Titanium nitride

The dependence of the electron energy spectrum of ultradispersed TiN powders on particle size was studied by the method of ultrasoft x-ray spectroscopy. A relative narrowing of the x-ray TiL_α and NK_α emission bands (which reflect the energy distribution of valence Np- and Tid-states) depended on the specific surface area of the powders and charge states of the Ti and N atoms. It was shown that narrowing of these bands is due to localization of the Np- and Tid-orbitals of surface atoms as a result of breaking Ti−N bonds. Broadening of the NK_α and TiL_α bands in certain energy ranges was observed after compacting ultradispersed powders. This is a result of Tid and Np orbital splitting caused by the formation of Ti−N bonds between the surface atoms of neighboring particles brought into contact at high pressure and temperature. Institute for Problems of Materials Science, Ukraine National Academy of Sciences, Kiev. Translated from Poroshkovaya Metallurgiya, Nos. 7–8(408), pp. 75–85, July–August, 1999.     

Structure of a Fe-Cr-Mn-Mo-N alloy processed by mechanical alloying

Elemental Fe, Cr, Mn, and Mo powders were processed by mechanical alloying to develop a nanostructured Fe-18Cr-11Mn-5Mo alloy under a N₂ atmosphere. It was found that the nitrogen contents in the as-milled powder mixture increased up to 1.6 wt pct after 190 hours processing time. The as-milled powders were then annealed under vacuum at either 1173 or 1473 K to promote the formation of the resultant equilibrium phases. In the annealed powder mixtures, depending on the temperature and nitrogen content, the phases identified by X-ray diffraction were either austenite, ferrite, or chromium nitrides. Annealing at 1173 K promoted the development of γ-Fe, α-Fe, and Cr₂N for all the nitrogen contents considered (0.5 to 1.6 wt pct). The volume fractions of the various phases formed were found to be strongly influenced by the nitrogen content and annealing temperature. In addition, the levels of nitrogen absorbed during processing were retained after annealing. Finally, the outcome indicates that a fully austenitic structure can be obtained by annealing powder mixtures at 1473 K with maximum nitrogen contents of up to 1 wt pct.