A study on martensitic transformation in Ti50−x/2Ni50−x/2Cu x alloys with X≤10 at%

The effect of Cu additions on the martensitic transformation sequence and temperature in Ti_50–x/2Ni_50–x/2Cu _x alloys with x: 1–10 at% are investigated by ER, DSC, X-ray and IF measurements. Experimental results show that the transformation sequence of Ti_50–x/2Ni_50–x/2Cu _x alloys with x: 1–4 at% proceeding as two-stage B2RB19 transformation on cooling and Ti_50–x/2Ni_50–x/2Cu _x alloys with x=5, 10 at% have no martensitic transformation. The addition of Cu in Ti_50–x/2Ni_50–x/2Cu _x alloys assists the formation of R-phase, a behaviour which is quite different from that in Ti₅₀Ni_50–x Cu _x alloys. Both the Ms and T _R temperatures decrease rapidly with increasing Cu addition in Ti_50–x/2Ni_50–x/2Cu _x alloys with x: 1–4 at%. It is proposed that the Cu+Ni effects on the Ms temperature in Ti_50–x/2Ni_50–x/2Cu _x alloys is similar as Cu +Ni effects in Ti₅₀Ni_50–x Cu _x alloys and as Ni effects in as-quenched Ni-rich TiNi alloys.     

600°C Section of the Fe–FeS–NiS–Ni Phase Diagram

The 600°C section of the Fe–FeS–NiS–Ni phase diagram was studied by optical and electron microscopy techniques, x-ray diffraction, and electron probe x-ray microanalysis. The results agree with the most reliable data available in the literature. The solid-solution regions identified are those of (Fe _z Ni_{1 – z} )_{3 ±} S₂(high-temperature heazlewoodite structure), (Fe _z Ni_{1 – z} )S_{1 +} , (Fe _z Ni_{1 – z} )_{9 +} S₈(pentlandite structure), -(Fe,Ni), and -(Fe,Ni). The section also contains seven two-phase and three three-phase regions. The S content of the monosulfide solid solution attains 50.8 at. % at Ni : (Ni + Fe) = 0.6 and 54.0 at. % at Ni : (Ni + Fe) = 0.2. The heazlewoodite solid solution contains up to 26 at. % Fe (at 44.3 at. % S). The highest Ni content of the pentlandite solid solution is 22.5 at. % at 47.5 at. % S and 32.0 at. % at 46.2 at. % S.     

Electrical conductivity study of oxidation process in manganese-substituted magnetites

During oxidation in air of finely-grained manganese-substituted magnetites (Mn _0.8x ²⁺ Fe _1–0.8x ³⁺ )_A– (Fe _1+0.6x ³⁺ Fe _1–0.8x ²⁺ Mn _0.2x ³⁺ )_BO ₄ ^2– (A=tetrahedral, B=octahedral) the temperature dependence of the electrical conductivity over a temperature range of 100 to 700° C was investigated. Below 500° C the evolution of electrical conductivity might be closely associated with the position and nature of cations in the spinel lattice. The profile of the =f(t) curves show that the mechanism of electrical conduction in the temperature range 150 to 300° C can be explained in terms of the oxidation of Fe²⁺ to Fe³⁺ ions at octahedral sites. For the temperature range 300 to 400° C the conductivity involves the hopping of electrons from tetrahedral-site Mn²⁺ ions to tetrahedral-site Mn³⁺ ions. Above 500° C the oxidation of Mn²⁺ ions leads to an increase in conductivity with the generation of new phases of -Fe₂O₃, Mn₂O₃ and -(MnFe)₂O₃.     

Oxygen Stoichiometry and Phase Transitions of SrCo1– xFexO3 – δ

The oxygen stoichiometry of SrCo_{1 – x} Fe _x O_{3 –} (0.1 x 0.9) solid solutions was determined by solid-electrolyte coulometry as a function of temperature (20–1000°C) and oxygen partial pressure (1–100 Pa). The results, together with X-ray diffraction studies between 400 and 900°C, indicated a sequence of phase transitions: perovskite brownmillerite high-temperature perovskite. The composition stability region of the parent perovskite structure was shown to be 0.2 <x 1.0. The Co-rich samples (x 0.2) consisted of perovskite and hexagonal phases.     

Measurements of the A ⇄ B transition in a magnetic field for superfluid3He near the polycritical point

Measurements of both AB and BA transitions have been made as a function of magnetic field up to 100 G at temperatures and pressures close to the polycritical point (PCP). Forms for the specific heat differenceC _A–C _B=C ₀ (P)–(P)(T _c –T)/T _c and for the magnetization differenceM _A–M _B=H(T _c –T)/T _c fit the data satisfactorily except very nearT _c , where some other mechanism, thought to be a free energy difference due to residual heat flows, tends to stabilize the A phase. The pressure of the PCP, taken to be that at whichC ₀ =0, is found to be 21.22±0.02 bar.Work supported by the U.S. Energy Research and Development Administration under contract number E(04-3)-34, P.A. 143.     

Microstructural Evolution of Fe2O3 and ZnFe2O4 during Sonochemical Synthesis of Zinc Ferrite

The microstructural evolution of Fe₂O₃ and ZnFe₂O₄ during high-temperature (600–800°C) sonochemical synthesis of zinc ferrite is studied by x-ray diffraction analysis. The results are used to develop a qualitative model for ultrasonically activated solid-state reactions A _s +B _s C _s.     

Structure of Mo2.0 – x Ni1.0 + x P (x = 0.2) and Some Crystal-Chemical Features of Ternary Phases in the Mo–Ni–P System

The crystal structure of Mo_{2.0 – x} Ni_{1.0 + x} P (x= 0.2) is determined by powder x-ray diffraction (monoclinic symmetry, new structure type, sp. gr. Im, a = 1.04036(5) nm, b= 0.84055(4) nm, c= 0.47357(2) nm, = 91.538(3)°; R _int = 0.094, R _prof = 0.197). The 850°C section of the Mo–Ni–P phase diagram is studied in detail, and the crystal-chemical features of molybdenum nickel phosphides are discussed.     

Electrical properties of Si4+ substituted copper ferrite

The electrical resistivity, , and Seebeck coefficient, , for the system Cu_1+xSi_xFe_2–2xO₄ (where x = 0.05, 0.1, 0.15, 0.2 and 0.3) have been studied as a function of temperature. Temperature variation of the resistivity exhibits two breaks. Each break is associated with a change in activation energy. The conduction process at low temperature is governed by the reaction Cu _A ¹⁺ + Cu _A ²⁺ Cu _A ²⁺ + Cu _A ¹⁺ . However, at higher temperature, it is due to intersite cation exchange and reoxidation such as Cu _A ²⁺ + Fe _B ³⁺ Cu _B ²⁺ + Fe _A ³⁺ . Measurement of the Seebeck coefficient, , from room temperature to 800 K reveals n-type conduction for the sample with x= 0.05, while the measurements for other samples show p-type conduction for lower temperatures and n-type conduction at higher temperatures. The activation energies in the paramagnetic region are found to be less than those in the ferrimagnetic region.     

A Mössbauer study of the oxidation of Fe-Ni alloys at 535 and 635°C

Fe⁵⁷ transmission Mössbauer spectroscopy, supported by metallography, SEM and X-ray diffraction analysis, has been employed to study the oxidation of Fe-Ni alloys at 535 and 635° C in 1 atm. of air. With increasing Ni content of the alloy, the composition of the scale changed and the oxidation rate decreased. For an alloy containing 0.9% Ni, the oxide scale produced at 535° C was Fe₃O₄ covered by a thin outer layer of-Fe₂O₃, while at 635° C FeO was additionally present as a major phase. The scale formed on a 10% Ni alloy at both 535 and 635° C was similar to that observed for the 0.9% Ni alloy oxidized at 535° C (i.e. of Fe₃O₄ and-Fe₂O₃), although the-Fe₂O₃ layer tended to be relatively thicker. For a 49% Ni alloy, the scale at both 535 and 635° C comprised an inner layer of Ni _x Fe_3–x O₄ (withx0.5, on average) and an outer layer of-Fe₂O₃, of similar thickness. Finally, on an 83% Ni alloy oxidized at 635° C, the scale consisted of roughly equally thick layers of NiO (next to the metal) and NiFe₂O₄, and a thin outer covering of-Fe₂O₃. The decrease in oxidation rate with increasing Ni content of the alloy is discussed briefly in relation to the changing composition of the scale and diffusion in the alloy.     

Structural,transport and infrared studies of oxidic spinels Zn1−xNixFeCrO4

X-ray, electrical conductivity and IR studies for the system Zn_1–x Ni _x FeCrO₄ were carried out. All the compounds, 0 x 1 showed cubic symmetry. X-ray intensity calculations and IR studies indicate the presence of Zn²⁺ at tetrahedral sites, Ni²⁺ and Cr³⁺ at octahedral sites, and Fe³⁺ ions are equally distributed at both the sites. Activation energy and thermoelectric coefficient decreases with the increasing values ofX. All the compounds exhibit P-type semiconductivity which may be due to transfer of Fe³⁺ ions from B-site to A-site creating holes. The electrical resistivity temperature behaviour obeys the relation= ₀ exp (E/KT). The mobility of holes as calculated from IR and conductivity data is of the order of 10^–9 cm² V sec^–1. The probable ionic configuration for the system is suggested to be Zn _1–x ²⁺ Fe _x ³⁺ [Fe _1–x ³⁺ Ni _x ²⁺ Cr³⁺] O ₄ ^2– .     

The cubic autocatalator: The influence of the quadratic autocatalytic and the uncatalysed reactions

The proptotype chemical reaction scheme, the cubic autocatalator, A + 2B 3B; B C is taken in a closed system, with A formed from the precursor P by the simple step P A. The pooled chemical approximation is invoked whereby the concentration of P can be assumed to remain constant throughout. The effects of allowing the quadratic autocatalytic reaction A + B 2B and the uncatalysed reaction A B in the scheme are considered in detail. The full scheme is described by the non-dimensional parameters µ (measuring the reaction rate of the initiation step) ands andr (measuring the reaction rates of the quadratic autocatalytic and the uncatalysed steps respectively). It is shown, provided only thatr ors (or both) are non-zero, no matter how small, the solution remains bounded for all (positive) values of µ, whereas withr =s = 0 the solution is bounded only for µ > µ₀ (µ₀ = 0.900 32). It is shown that withr = 0 ands 0 the governing equations have a Hopf bifurcation at µ = 1 –s producing a stable limit cycle which exists for all µ in 0 < µ <1 –s. The behaviour of these limit cycles as µ 0 is also discussed.     

Reactive processing of nickel-aluminide intermetallic compounds

NiAl have been fabricated by reactive sintering compacts of ball-milled powder mixtures containing Ni and Al. The reaction mechanism, as well as phase and microstructural development, were investigated by analyzing compacts quenched from different temperatures during reactive hot compaction. It was found that the reaction process was strongly affected by pressure, heating rates, heat loss from the sample to the environment. The application of 50 MPa prior to the reaction resulted in the intermetallic-formation reaction initiating at a temperature (480°C) much lower than that (550°C) when no pressure was applied. At high heating rate (50°C/min), when the heat loss is small, the formation of NiAl occurs rapidly via combustion reaction. On the other hand, if the heat loss is significant as in slow heating rate (10°C/min), the reaction process is controlled by solid-state diffusion. The phase formation sequence for the slow solid-state reaction was determined to be: NiAl₃ Ni₂Al₃ NiAl NiAl (Al-rich) + Ni₃Al NiAl.     

Preparation of nickel and Ni-Zn ferrite films by thermal decomposition of metal acetylacetonates

Nickel and Ni-Zn ferrite (Ni_1–x Zn _x Fe₂O₄) films were prepared on various substrates (quartz glass, MgO single crystal, etc.) by thermal decomposition of metal acetylacetonates (Ni (acac)₂ · 2H₂O, Zn (acac)₂ · 2H₂O and Fe (acac)₃). Typical decomposition and heat treatment conditions for obtaining a single phase of NiFe₂O₄ film were as follows: evaporation temperature of Ni-Fe complexes: 230°C, the mole concentration of Fe (acac)₃,R (%) = Fe (acac)₃/(Fe (acac)₃ + Ni (acac)₂ · 2H₂O) = 33, substrate temperature: 330 to 550° C, and heat treatment of the as-grown film: 800 to 1000° C, 1 h. Ni_1–x Zn _x Fe₂O₄ films were obtained by controlling the compositionR in Ni-Fe complexes and the evaporation temperature of Zn (acac)₂ · 2H₂O. The Ni-Zn ferrite film at the compositionx = 0.37 (Ni_0.63Zn_0.37Fe₂O₄) gave the maximum saturation magnetization _s = 60 emu g^–1 and the coercive forceHc 25 Oe. These films showed a magnetic anisotropy which makes the magnetization easy parallel to film surface.     

Ab initio calculations of Fe–Ni clusters

The clusters of Fe, Ni, and Fe–Ni are investigated computationally using a density functional approach. The geometries of clusters are optimized under the constraint of well-defined point group symmetries at the UB3LYP/LanL2DZ level. The equilibrium geometries and binding energies are presented and discussed, together with natural populations and natural electron configurations. In addition, the binding energies of Fe_n−xNi_x clusters are found to generally decrease by successive substitutions of Ni atoms for Fe atoms. For Fe_n−xNi_x clusters, the comparisons on total energies between isomers indicate that Ni atoms energetically prefer clustering in the mixed Fe–Ni clusters. The calculations for Fe_n−xNi_x clusters show that the clustering leads to a segregation of Ni atoms from Fe atoms.     

Effect of Crystal Structure on the Electrical Properties of CaTi1 – xFexO3 – δ

The electrical conductivity of CaTi_{1 – x} Fe _x O_{3 –} (x= 0–0.5) was measured as a function of temperature and oxygen partial pressure. At 1000°C, the highest conductivity was observed at x= 0.2. The crystal structure of the materials with x= 0, 0.2, 0.25, and 0.3 was studied by x-ray powder diffraction and refined by the full-profile analysis method. The results were used to elucidate the mechanisms of the high-temperature (1000°C) formation, ordering, and transport of oxygen vacancies in CaTiO₃upon substitution of Fe³⁺for Ti⁴⁺. The composition dependences of ionic conductivity calculated for CaTi_{1 – x} Fe _x O_{3 –} agree well with experiment.     

Cu2+ ions in sodium fluoride-sodium borate glasses studied by EPR and optical absorption techniques

Electron paramagnetic resonance (EPR) and optical absorption spectra of Cu²⁺ ions in 80Na₂B₄O₇-(20 – x)NaF – xCuO (NFNB) glass system with 0 x 6 mol% have been studied. EPR spectra of all the glass samples exhibit resonance signals characteristic of Cu²⁺ ions. The values of spin-Hamiltonian parameters indicate that the Cu²⁺ ions in sodium fluoride-sodium borate (NFNB) glasses were present in octahedral sites with tetragonal distortion. The number of spins (N) participating in resonance was calculated as a function of temperature for NFNB glass sample containing 1 mol% of Cu²⁺ ions and the activation energy was calculated. From the EPR data, the paramagnetic susceptibility () was calculated at various temperatures and the Curie constant was calculated from the 1/ – T graph. The optical absorption spectra of these samples show a broad absorption band centered at 13280 cm^–1 which is assigned to the ² B _1g ² B _2g transition of Cu²⁺ ions in distorted octahedral sites. The optical band gap energy (E _opt) and Urbach energy (E) are calculated from their ultraviolet edges. It is observed that as the copper ion concentration increases, E _opt decreases while E increases. This has been explained as due to the creation of additional localized states by CuO, which overlap and extend in the mobility gap of the matrix. By correlating the EPR and optical data, the molecular orbital coefficients have been evaluated.     

Chemical and structural properties of the system Fe2O3-Cr2O3

Chemical and structural properties of the mixed metal oxides (1–x)Fe₂O₃+xCr₂O₃ were studied by different techniques. X-ray powder diffraction showed the existence of solid solutions, (Fe_1–x Cr _x )₂O₃, over the whole concentration region, 0x1. The gradual replacement of Fe³⁺ with Cr³⁺ ions in samples prepared at 900°C caused changes in unit-cell parameters; most of these changes took place in the region fromx0.3–0.9. The samples having the fraction of Cr₂O₃ in the region from 0.7–0.8, contained two closely related phases, with slightly different compositions. After an additional heat treatment at 1100°C, these samples contained only one phase.⁵⁷Fe Mössbauer spectroscopy showed a gradual decrease of hyperfine magnetic field with increasing Cr₂O₃ content. The sample having the fraction of Cr₂O₃ of 0.7, and prepared at 900°C, exhibited two separated sextets at room temperature, in comparison with other compositions showing one sextet. It was shown that Fourier transform infrared (FT-IR) spectroscopy is a powerful method for the investigation of structural changes in these solid solutions. The increase in the Cr₂O₃ content resulted in shifts of the corresponding infrared bands. In addition, a gradual transition of the spectrum typical for -Fe₂O₃ to the spectrum typical for Cr₂O₃ was shown. The transition effects observed in the FT-IR spectra were correlated with the X-ray powder diffraction and⁵⁷Fe Mössbauer spectroscopic results.     

The observation of stress effects during the high temperature oxidation of iron

Electron microscopy has been used to characterize the stress effects which occur during the oxidation of iron in the temperature range 400–700° C. Spalling and de-cohesion of the outer hematite (-Fe₂O₃) layer is often observed, and analysis of the resulting scrolled oxide indicates a strong compressive stress gradient. In contrast, tensile cracks are frequently seen in the magnetite (Fe₃O₄) layer, while the underlying wustite (Fe_1–xO) and the iron substrate are apparently able to accommodate the stresses to some extent by plastic deformation. The Pilling-Bedworth model can adequately be applied at the -Fe₂O₃-Fe₃O₄ interface since anion diffusion occurs in the hematite. However, since cation diffusion is dominant in the other oxides, it is suggested that the anion volume ratio can be applied to the Fe₃O₄-Fe_1–xO interface where the anion sublattice remains unchanged, in order to predict the stress state.     

The effect of a Cr2O3-addition on the phase transformation and catalytic properties of γ-Al2O3 in treatment of lean-burn exhausts

The solid-state thermal behaviour of -Al₂O₃ doped with 10 mol% Cr (oxide) was studied with respect to phase-transition behaviour and the co-ordination of the dopant Cr cations. A series of transformations: -Al₂O₃ -Al₂O₃ -Al₂O₃ -Al₂O₃ was observed for Cr₂O₃-doped alumina samples between 500 °C and 1100 °C. Rapid grain growth occurred at temperatures close to 1100 °C. The electron spin resonance (ESR) spectra for the sample heat-treated at 500 °C corresponded to the resonance of -Cr³⁺ in an amorphous Cr oxide impregnated onto the - and -alumina support. The change of ESR spectrum indicated the existence of Cr³⁺, suggesting the formation of a solid solution with the same structures as -Al₂O₃ and/or -Al₂O₃ at 800–1000 °C. The evaluation of catalytic activities for model exhaust was performed under lean-burn (an excess of oxygen) condition of air/fuel ratio A/F = 18 and space velocity SV = 100 000 h^–1 . The modified Al₂O₃ catalyst heat-treated at 1000 °C in air showed removal conversion of 100% for hydrocarbon (C₃H₆), 92% for CO and 5% for NO at 550 °C. Present results suggest that Cr-modification to Al₂O₃ leads to catalytic improvement with good thermal durability.     

Scaling and intergranular oxidation of an Fe/48 wt% Ni alloy in carbon dioxide at 700 to 1000°C

The oxidation of Nilo 48 has been studied using thermogravimetric, metallographic, and electron probe microanalysis techniques at 700 to 1000° C. After a short period of ill-defined oxidation, the parabolic law was obeyed throughout the exposure period, which varied from 1050 h at 713° C to 50 h at 1000° C. The activation energy for the oxidation reaction was 48±6 kcal/mole. Examination of the external scale indicated that this was single phase and, at 1000° C, its composition corresponded to Ni_xFe^3–xO₄, wherex 0.4. There were also intergranular oxidation and nickel enrichment of the alloy underlying the external scale. After oxidation for only 10 min at 1000° C, the nickel-enriched alloy zone contained 65 wt % Ni. The manganese concentration in the scale was similar to that in the alloy. The results are discussed and compared with those of other workers and it is concluded that the rate-controlling process is the diffusion of iron through the Ni_xFe_3–xO₄ lattice.