Effect of the sintering temperature on the properties of nanocrystalline Ca1−xSmxMnO3 (0 ≤ x ≤ 0.4) powders

Nanocrystalline Ca_1−xSm_xMnO₃ (0 ≤ x ≤ 0.4) manganites were prepared by a soft chemical method (Pechini method) followed by auto-combustion and sintering in air at 1073 or 1473 K. Single-phase powders with general composition Ca_1−xSm_xMnO₃ were obtained after 18 h annealing. The particle and grain sizes of the substituted Sm-manganites did not exhibit variation with samarium content, but increase with increasing the sintering temperature. All manganites show two active IR vibrational modes near 400 and 600 cm⁻¹ characteristic of the BO₆ octahedron vibrations.For the samples sintered at T_s = 1473 K, the partial substitution of calcium by samarium in the CaMnO₃ phase induces a marked decrease in the electrical resistivity, in the temperature range of 300-900 K, and at the same time a metal-to-insulator transition occurs; for T_s = 1073 K all the samples present semiconductor behaviour. With the increase of the annealing temperature the grain size increases and a metal-semiconductor transition appears. The results can be ascribed to the Mn⁴⁺/Mn³⁺ ratio and particle grain size. The effects of particle size on the electrical properties can be attributed to the domain status, changes in the Mn-O-Mn bond angle and Mn-O bond length.     

Investigation of the corrosion for Mg-xGd-3Y-0.4Zr (x = 6, 8, 10, 12 wt%) alloys in a peak-aged condition

The corrosion behaviour of Mg-6Gd-3Y-0.4Zr (GW63K), Mg-8Gd-3Y-0.4Zr (GW83K), Mg-10Gd-3Y-0.4Zr (GW103K) and Mg-12Gd-3Y-0.4Zr (GW123K) were investigated in peak-aged condition using immersion and salt spraying tests and electrochemical measurements in 5% NaCl solution. The corrosion resistances of Mg-xGd-3Y-0.4Zr alloys were found to decrease with the increase of Gd content from 6% to 10% and then increase from 10% to 12%. The corrosion products of Mg-xGd-3Y-0.4Zr alloys were discovered to be composed of voluminous tiny erect flakes by FE-SEM, and the compactness of the corrosion films decreases with the increase of Gd content. The results of AES revealed that the corrosion film is enriched with Gd and Y. The potentiodynamic polarization curves showed that the overpotentials of cathodic hydrogen evolution on GW63K and GW83K are much higher than on GW103K and GW123K. The results of EIS are in good agreement with the morphologies of the corrosion products and the corrosion rates of the corrosion tests.     

High-temperature corrosion behavior of sputtered K38 nanocrystalline coatings with and without yttrium addition in molten sulfate at 900 °C

The high temperature corrosion behavior of sputtered Ni-based superalloy K38 nanocrystalline coatings with and without yttrium addition in molten sulfate (75 wt.% Na₂SO₄ + 25 wt.% K₂SO₄) was investigated at 900 °C in air. The results indicated that nanocrystallization significantly increased the corrosion resistance through the rapid formation of a protective oxide scale. The addition of yttrium in the nanocrystalline coating furthermore improved the corrosion resistance of the coating.     

Influence of grain size on the oxidation behavior of NbCr2 alloys at 950-1200 °C

The oxidation behavior of mechanically alloyed microcrystalline NbCr₂ intermetallics was investigated at 950-1200 °C in air by SEM in comparison with coarse-grain cast alloys. Results indicate that the mechanically alloyed alloys possess a better oxidation resistance and are less permeable to nitrogen than the cast alloys. At 1200 °C, the mechanically alloyed NbCr₂ alloys show a better resistance to scale spallation than the cast materials. The differences observed above are attributed to the finer grains increasing the relaxation of the oxide scale stress and improving the adhesion of the oxide layer on the matrix.     

Study on edge cracking and texture evolution during 150 °C rolling of magnesium alloys: The effects of axial ratio and grain size

Pure Mg, AZ31 (Mg-3 wt%Al-1 wt%Zn) and experimental alloys, Mg-1 wt%Zn-1 wt%In, Mg-2 wt%Li-1 wt%Zn, Mg-2 wt%Li-1 wt%Zn-1 wt%In were rolled at 150 °C to 0.3 and 0.55 strain. The samples rolled to 0.3 strain were subsequently annealed for 10 min at 400 °C. The texture was evaluated in rolled and in rolled/annealed conditions. The axial ratio (c/a) of the alloys strongly influenced edge cracking during rolling (expressed as cracking index, I_C), which was explained via the influence of c/a on the twinning mode. The as-cast grain size did not correlate to I_C (edge cracking). Texture intensity was strongly influenced by the as-cast grain size (which was attributed to plastic compatibility at grain boundaries), showed weak correlation to the lattice parameter a, but did not depend on c/a. The Mg-2 wt%Li-1 wt%Zn alloy, with fine grain size and small c/a and a, exhibited the optimum combination of weak texture and crack-free rolling at 150 °C.     

Corrosion behavior of iron-based alloys in the LiBr + ethylene glycol + H2O mixture

The corrosion resistance of 1018 carbon steel, 304 and 316 type stainless steels in the LiBr (55 wt.%) + ethylene glycol + H₂O mixture at 25, 50 and 80 °C has been studied using electrochemical techniques which included potentiodynamic polarization curves, electrochemical noise and electrochemical impedance spectroscopy techniques. Results showed that, at all tested temperature, the three steels exhibited an active-passive behavior. Carbon steel showed the highest corrosion rate, since both the passive and corrosion current density values were between two and four orders of magnitude higher than those found for both stainless steels. Similarly, the most active pitting potential values was for 1018 carbon steel. For 1018 carbon steel, the corrosion process was under a mixed diffusion and charge transfer at 25 °C, whereas at 50 and 80 °C a pure diffusion controlled process could be observed. For 316 type stainless steel, at 25 and 50 °C a species adsorption controlled process was observed, whereas at 80 °C a diffusion controlled mechanism was present. Additionally, at 25 °C, the three steels were more susceptible to uniform type of corrosion, whereas at 50 and 80 °C they were very susceptible to localized type of corrosion.     

The oxidation of two ternary Fe-Cu-10 at.% Al alloys in 1 atm of pure O2 at 800-900 °C

The oxidation of two ternary Fe-Cu-Al alloys containing 10 at.% Al (Fe-65Cu-10Al and Fe-30Cu-10Al) has been studied at 800-900 °C under 1 atm O₂. Under all conditions both alloys show an initial faster stage during which Fe-65Cu-10Al corrodes more rapidly at 800 °C than at 900 °C, while Fe-30Cu-10Al follows nearly identical kinetics at both temperatures. As oxidation proceeds, a continuous alumina layer is eventually established on the surface of the two alloys, thus decreasing significantly their oxidation rates. Altogether, the Fe-rich alloy Fe-30Cu-10Al oxidizes slightly faster than the Cu-rich alloy Fe-65Cu-10Al at both temperatures. The possible reasons for the decrease in the critical Al content needed to form external alumina scales for the Cu-rich alloy in comparison with binary Cu-Al alloys are examined.     

Perpendicular magnetic anisotropy in 70 nm CoFe2O4 thin films fabricated on SiO2/Si(1 0 0) by the sol-gel method

Cobalt ferrite CoFe₂O₄ films were fabricated on SiO₂/Si(1 0 0) by the sol-gel method. Films crystallized at/above 600 °C are stoichiometric as expected. With increase of the annealing temperature from 600 °C to 750 °C, the columnar grain size of CoFe₂O₄ film increases from 13 nm to 50 nm, resulting in surface roughness increasing from 0.46 nm to 2.55 nm. Magnetic hysteresis loops in both in-plane and out-of-plane directions, at different annealing temperatures, indicate that the films annealed at 750 °C exhibit obvious perpendicular magnetic anisotropy. Simultaneously, with the annealing temperature increasing from 600 °C to 750 °C, the out of plane coercivity increases from 1 kOe to 2.4 kOe and the corresponding saturation magnetization increases from 200 emu/cm³ to 283 emu/cm³. In addition, all crystallized films exhibit cluster-like structured magnetic domains.     

The nature of the third-element effect in the oxidation of Fe-xCr-3 at.% Al alloys in 1 atm O2 at 1000 °C

The oxidation of an Fe-Al alloy containing 3 at.% Al and of four ternary Fe-Cr-Al alloys with the same Al content plus 2, 3, 5 or 10 at.% Cr has been studied in 1 atm O₂ at 1000 °C. Both Fe-3Al and Fe-2Cr-3Al formed external iron-rich scales associated with an internal oxidation of Al or of Cr+Al. The addition of 3 at.% Cr to Fe-3Al was able to stop the internal oxidation of Al only on a fraction of the alloy surface covered by scales containing mixtures of the oxides of the three alloy components, but not beneath the iron-rich oxide nodules which covered the remaining alloy surface. Fe-5Cr-3Al formed very irregular external scales where areas covered by a thin protective oxide layer alternated with others covered by thick scales containing mixtures of the oxides of the three alloy components, undergrown by a thin layer rich in Cr and Al, while internal oxidation was completely absent. Conversely, Fe-10Cr-3Al formed very thin, slowly-growing external Al₂O₃scales, providing an example of third-element effect (TEE). However, the TEE due to the Cr addition to Fe-3Al was not directly associated with a prevention of the internal oxidation of Al, but rather with the inhibition of the growth of external scales containing iron oxides. This behavior has been interpreted on the basis of a qualitative oxidation map for ternary Fe-Cr-Al alloys taking into account the existence of a complete solid solubility between Cr₂O₃ and Al₂O₃.     

The oxidation of three Ni-6Si-xAl alloys in 1 atm O2 at 1000 °C

The oxidation of three ternary Ni-6Si-xAl alloys containing 6, 10 and 15 at.% Al and of the corresponding binary Ni-Al alloys has been studied at 1000 °C under 1 atm O₂ to examine the effect of different Al additions on the behavior of ternary Ni-Al-Si alloys containing 6 at.% Si. Of the three binary Ni-Al alloys only Ni-15Al was able to form external alumina scales. Conversely, all the three ternary alloys formed an innermost layer of alumina directly in contact with the alloy following very similar and approximately parabolic kinetics after a short faster initial stage due to transient formation of NiO. Thus, the presence of silicon is very effective to reduce the critical Al content needed to form exclusive alumina scales with respect to binary Ni-Al alloys. The third-element effect due to silicon is interpreted on the basis of an extension of Wagner’s criterion for the transition from the internal to the external oxidation of the most reactive component in binary alloys.     

Internal friction, dilatometric and calorimetric study of anelasticity in Fe-13 at.% Ga and Fe-8 at.% Al-3 at.% Ga alloys

This paper investigates the structural transitions associated with different cooling rates from a high temperature disordered state and the effect of substitution of Ga atoms by Al atoms in Fe-Ga binary alloys on the ordering processes. Two iron-based low carbon (about 0.04 at.% C) alloys Fe-13 at.% Ga and Fe-8 at.% Al-3 at.% Ga are studied. Internal friction, dilatometric and calorimetric tests are carried out to check ordering in these alloys and contribution of structural defects to relaxation spectrum. Several thermally activated internal friction peaks have been observed and their activation parameters evaluated by means of temperature and frequency dependent internal friction tests using forced vibration. For most of these peaks physical mechanisms are proposed. Apart from these thermally activated relaxation peaks, a structural, frequency independent relaxation takes place at 250-300 °C. Dilatometric and DSC curves show the appearance of a contraction effect in the same temperature range. This effect was studied in alloys cooled down with different cooling rates. We believe that the frequency independent internal friction peak (denoted as the P3 peak in this paper) and peaks at dilatometric and DSC curves are controlled by the same structural mechanism and therefore the activation energy for this anelastic mechanism is derived from DSC data.     

Antiferromagnetic ordering below 1.7 K in PrIr2Ge2

We present our investigations on magnetic and transport properties of polycrystalline PrIr₂Ge₂ which forms in CaBe₂Ge₂-type primitive tetragonal structure (space group P4/nmm). The ac magnetic susceptibility data exhibit two well pronounced peaks at 2.08 K and 0.76 K due to the onset of magnetic order. The specific heat also exhibits a sharp λ-type anomaly at 1.7 K confirming the onset of bulk antiferromagnetic order. The temperature dependence of magnetic part of entropy suggests a quasi-triplet ground state in this compound. The onset of magnetic order is also confirmed by the electrical resistivity data.     

Corrosion behaviour of magnesium/aluminium alloys in 3.5 wt.% NaCl

Corrosion behaviour of commercial magnesium/aluminium alloys (AZ31, AZ80 and AZ91D) was investigated by electrochemical and gravimetric tests in 3.5 wt.% NaCl at 25 °C. Corrosion products were analysed by scanning electron microscopy, energy dispersive X-ray analysis and low-angle X-ray diffraction. Corrosion damage was mainly caused by formation of a Mg(OH)₂ corrosion layer. AZ80 and AZ91D alloys revealed the highest corrosion resistance. The relatively fine β-phase (Mg₁₇Al₁₂) network and the aluminium enrichment produced on the corroded surface were the key factors limiting progression of the corrosion attack. Preferential attack was located at the matrix/β-phase and matrix/MnAl intermetallic compounds interfaces.     

Near room temperature magnetic entropy changes in as-cast Gd100−xMnx (x = 0, 5, 10, 15, and 20 at.%) alloys

A series of Gd_100−xMn_x (x = 0, 5, 10, 15, and 20 at.%) alloys were prepared by arc-melting. The Curie temperature (T_C) associated with the ferromagnetic-paramagnetic transitions, derived from M-T curves, show decrease in T_C for as-cast alloys (∼279 K) as compared to as-cast Gd (∼292 K). No appreciable decrease in the |ΔS_M|_max values ∼4.6 J/kg K (0-2 T) and ∼8.6 J/kg K (0-5 T) were observed upon alloying Gd with Mn up to x ≤ 15 at.%. Refrigerant capacity (q) showed negligible variation ∼195 J/kg (0-2 T) and ∼450 J/kg (0-5 T) with increasing Mn (up to x ≤ 15 at.%) content. Similar values of |ΔS_M|_max and q coupled with ∼13 K decrease in T_C for as-cast Gd_100−xMn_x (0 ≤ x ≤ 15) alloys as compared to Gd, suggests expansion of working temperature region of Gd upon alloying with Mn up to 15 at.%. Low cost, adjustable T_C, favorable magnetocaloric properties make Gd_100−xMn_x alloys potential candidates as second-order transition based magnetic refrigerants for near room temperature air-conditioning and magnetic refrigeration.     

Mössbauer studies of phase separation in nanocrystalline Fe0.55−xCr0.45Snx alloys prepared by mechanical alloying

Mössbauer spectrometry (⁵⁷Fe and ¹¹⁹Sn) was used to investigate phase separation in coarse-grained Fe_0.55Cr_0.45 and in mechanically-alloyed nanocrystalline Fe_0.55Cr_0.45, Fe_0.52Cr_0.45Sn_0.03 and Fe_0.49Cr_0.45Sn_0.06 alloys during isothermal annealing at 748 K. Phase separation occurs faster in nanocrystalline Fe–Cr than in cold-rolled coarse-grained alloys. The effect of the interconnected microstructure on room-temperature hyperfine magnetic field distributions of alloys aged for hundreds of hours is qualitatively discussed. Tin hinders grain growth of nanocrystalline alloys.     

High temperature scaling of Ni-xSi-10 at.% Al alloys in 1 atm of pure O2

The oxidation of Ni-xSi-10Al alloys (with x = 0, 2, 4 and 6 at.%), has been studied at 900 and 1000 °C in 1 atm of pure O₂ to examine the effect of different silicon additions on the behavior of ternary Ni-Si-10Al alloys. The kinetic curves of Ni-10Al are approximately parabolic at both 900 and 1000 °C. Conversely, the kinetics of the ternary alloys at both temperatures correspond generally to a rate decrease faster than predicted by the parabolic rate law, except for the oxidation of Ni-6Si-10Al at 1000 °C, which exhibits a single nearly-parabolic stage. Oxidation of the binary alloy formed at both temperatures an internal oxidation zone beneath a layer of NiO. Oxidation of Ni-2Si-10Al at both temperatures and of the other two alloys at 900 °C formed initially a zone of internal oxidation of Al + Si. However, a layer of alumina forming at the front of internal oxidation after some time blocked the internal oxidation and produced a gradual conversion of the metal matrix of this region into NiO, with a simultaneous decrease of the oxidation rate. Conversely, the oxidation of Ni-4Si-10Al and Ni-6Si-10Al at 1000 °C did not produce an internal oxidation, but formed an alumina layer directly on the alloy surface after an initial stage when also Ni was oxidized. Therefore, silicon exerts the third-element effect by reducing the critical Al content needed for the transition from its internal to its external oxidation with respect to the corresponding Ni-Al alloy. This result is interpreted by means of an extension to ternary alloys of Wagner’s criterion for the same transition in binary alloys based on the attainment of a critical volume fraction of internal oxide.     

Effects of boron concentration on the corrosion resistance of Fe-B alloys immersed in 460 °C molten zinc bath

In order to investigate the effects of boron concentration on the corrosion resistance of Fe-B alloys in molten zinc, Fe-B alloys, with the boron concentrations of 1.5 wt.%, 3.5 wt.% and 6.0 wt.% respectively, were dipped into a pure molten zinc bath at 460 °C and kept in different time intervals. The results show that, in comparison with 1Cr18Ni9Ti stainless steel, Fe-B alloy with 3.5 wt.%B exhibits excellent corrosion resistance, due to the dense continuous network or parallel Fe₂B phase which hinders the Fe/Zn interface reaction in Fe-B alloys. The energy dispersive spectrum (EDS) results indicate that the coarse and compact δ phase with the length about 40 μm generates near the matrix of Fe-B alloy and massive ζ phase occurs close to the liquid zinc. The corrosion process includes Fe/Zn reaction and the isolation and fracture of Fe₂B. The failure of boride is mainly caused by the microcrack.     

Blue and green emissions with high color purity from nanocrystalline Ca2Gd8Si6O26:Ln (Ln = Tm or Er) phosphors

Blue and green light emissive nanocrystalline Ca₂Gd₈Si₆O₂₆ (CGS):Tm³⁺ and CGS:Er³⁺ phosphors with high color purity were prepared by solvothermal reaction method. The structural and morphological properties of these phosphors were evaluated by the powder X-ray diffraction (XRD) and scanning electron microscopy, respectively. From the XRD results, Tm³⁺:CGS and Er³⁺:CGS phosphors had the characteristic peaks of oxyapatite in the hexagonal lattice structure. The visible luminescence properties of phosphors were obtained by ultraviolet (UV) or near-UV light and low voltage electron beam (0.5-5 kV) excitation. The photoluminescence and cathodoluminescence properties were investigated by changing the variation of Tm³⁺ or Er³⁺ concentrations and the acceleration voltage, respectively. The CGS:Tm³⁺ phosphors exhibited the blue emission due to ¹D₂→³F₄ transition, while the CGS:Er³⁺ phosphors showed the green emission due to ⁴S_3/2→⁴I_15/2 transition. The color purity and chromaticity coordinates of the fabricated phosphors are comparable to or better than those of standard phosphors for lighting or imaging devices.