Shape memory and associated properties in Fe–Mn–Si-based ribbons produced by melt-spinning

Four Fe–Mn–Si alloys, Fe₆₂Mn₃₂Si₆, Fe₆₂Mn₂₀Si₅Cr₈Ni₅, Fe₆₂Mn₁₆Si₅Cr₁₂Ni₅ and Fe₆₅Mn₉Si₇Cr₁₀Ni₉, were obtained by the melt-spinning method. The samples were structurally, magnetic and shape memory effect (SME) investigated, both “as quenched” and thermally treated. The Mn-rich compositions show different phase, magnetic behavior and SME in comparison with Mn-poor compositions. The thermal treatments generate transformation between the two existing majority phases ( and γ), related magnetization and SME behavior. The features are derived from the corroboration of structural, magnetic interaction and magnitude of SME data.     

Coexisting antiferromagnetism and ferromagnetism in mechanically alloyed Fe-rich Fe–Ni alloys: implications regarding the Fe–Ni phase diagram below 400°C

Fe–Ni alloys below the Invar region with compositions Fe_100−xNi_x (x=21, 24, and 27 at%) were prepared by high-energy ball milling technique (mechanical alloying). The as-milled samples, characterized by X-ray diffraction and Mössbauer spectroscopy, contain a mixture of (BCC) and γ (FCC) phases, whereas the samples annealed at 650°C for 0.5 h show a single γ (FCC) phase displaying a single line Mössbauer spectrum at room temperature (RT). At low temperature, the Mössbauer spectra of annealed Fe₇₆Ni₂₄ and Fe₇₃Ni₂₇ alloys show the existence of a magnetically split pattern together with a broad singlet, which are ascribed to a high-moment ferromagnetic Ni-rich phase and a low-moment Fe-rich phase, respectively. The Fe-rich phase in annealed Fe₇₆Ni₂₄ alloy, which is paramagnetic at RT, undergoes antiferromagnetic ordering at 40 K, estimated from the dramatic line broadening of its spectrum, giving rise to a small hyperfine field (e.g. 2 T at 6 K). The coexistence of these phases is attributed to phase segregation occurring in these alloys as a result of enhanced atomic diffusion. The stability of these alloys towards martensitic (FCC→BCC) transformation at low temperatures is discussed in connection with the Fe–Ni phase diagram below 400°C.     

The influence of ingot annealing on the corrosion resistance of a PrFeCoBNbP alloy

The influence of the annealing time on the corrosion resistance of a Pr–Fe–Co–B–Nb alloy with the addition of 0.1 wt% P was investigated here using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The cast ingot alloys were annealed at 1100 °C for 10, 15 and 20 h. The specimens were immersed for 30 days in naturally aerated 0.02 M Na₂HPO₄ solution at room temperature, during which period the evolution of the electrochemical behavior was assessed using EIS. The results indicated that the corrosion resistance of the Pr₁₄Fe_balCo₁₆B₆Nb_0.1P_0.25 alloy was related to the annealing time and, hence, to its microstructure. Annealing at 1100 °C for 10 h was insufficient to eliminate the Fe- phase from the alloy microstructure, whereas annealing for 15 and 20 h removed an increasing amount of Fe- phase, thereby increasing the alloy's corrosion resistance.     

A TEM study of precipitation in Al–Mg–Si alloys

A set of extrusion samples of Al–Si–Mg alloys (0.5 wt%Mg and 0.3–0.8 wt%Si) were, respectively, T1- and T4-heat-treated. Differential scanning calorimetry (DSC) was used to heat the samples to particular temperatures to promote the formation of precipitates for study by transmission electron microscopy (TEM). It was found that, apart from β″, β′, and B′, there were many precipitates showing rectangular lattices when viewed along the long axes of the precipitates. It is considered that the residual stresses (or dislocations) in the extrusion after the T1-treatment facilitated the nucleation and growth of the precipitates during the heating in the DSC.     

Formation of cementite in tempered Fe–Co–C alloys

In Fe–Co–C alloys, undesirable grain coarsening results from the specific austenite orientation variants that form after the γ→→γ transformations. Tempering of martensite before reheating prevents austenite returning to its original orientation and also limits grain coarsening. However, the reasons for this are unclear. It may be assumed that some differences between cementite formed in tempered and rapidly heated alloys may cause the variation in the final austenite structure. In the present work the orientation relationships between cementite and martensite in two tempered Fe–Co–C alloys have been studied using microbeam electron diffraction in a transmission electron microscope. In both alloys after short-term (rapid heating at 100°C s⁻¹ followed by quench) and long-term (1 and 3 h) tempering treatments the orientation relationships were shown to obey the Isaichev orientation relationships:

However, after rapid tempering, only one carbide variant was found in each crystal, while after long-term tempering, up to three variants were present. This might account for the observed crystallographic reversibility in rapidly heated alloys, contrary to the multiplication of γ variants formed from the long-term tempered martensite.     

Low-temperature specific heat of Ni–Mn–Ga ferromagnetic shape memory alloys

Results of the low-temperature specific heat measurements (2–80 K) for one austenitic and three martensitic Ni–Mn–Ga ferromagnetic alloys are presented. The alloy compositions are chosen to comprise a wide span of valence electron concentrations e/a=7.3–7.78. Debye temperature (261–345 K) is found to be an increasing function of e/a while the experimental values of the Sommerfeld coefficient (2.9–3.4 mJ/mol K²) appear to be increasing in the martensitic region only. Observation of those trends rekindles the discussion about the role of vibrational and electronic contributions to the lattice instability and transformation mechanism of studied alloys.     

The effects of a trace addition of silver upon elevated temperature ageing of an Al–Zn–Mg alloy

Microalloying additions of Ag (0.1 at.%) increase the hardening response of Al–Zn–Mg alloys to elevated temperature ageing in the range 100–200°C due to the formation of a high density of very fine η′ precipitate plates. The present study employed transmission electron microscopy (TEM) and three-dimension atom probe (3DAP) to study the early stages of ageing in the alloy Al–1.8Zn–3.4Mg–0.1Ag (at.%) in an attempt to identify the role of Ag in stimulating precipitation hardening. During isothermal ageing at 90°C, the hardening response is attributed to a high density of Zn–Mg–Ag rich solute clusters and GP zones. During ageing at 150°C, η′ precipitates nucleate at Zn–Mg–Ag rich solute clusters, the former growing as {111} platelets with an average composition of approximately 20 at.% Zn, 20 at.% Mg and 1.4 at.% Ag. The 3DAP data indicates that the co-segregation of Zn and Ag and subsequently Zn and Mg atoms precedes the formation of the Zn–Mg–Ag rich solute clusters. The GP zones and η′ precipitates were observed to possess a Zn:Mg ratio close to 1:1, whereas the equilibrium η precipitates possessed compositions consistent with MgZn₂. Furthermore, partitioning of Ag was observed inside all precipitate phases, viz. G.P. zones, η′ and η.     

Monte Carlo study of the magnetic properties of Fe0.9−qMn0.1Alq-disordered alloys

Within the framework of a random site-diluted Ising model with nearest-neighbor interactions, and using the Metropolis algorithm for equilibration and energy minimization, we have computed the ensemble and configurational averages for magnetization per site, magnetic susceptibility and specific heat of Fe_0.9−qMn_0.1Al_q-disordered alloys with 0.1q0.55. In the model, atoms have been randomly distributed on a body-centered cubic lattice in order to simulate the disorder and structure as that obtained in arc-melted Fe_0.9−qMn_0.1Al_q alloys treated at high temperatures during long periods of time and followed by fast quenching. Competitive interactions coming from Fe–Fe ferromagnetic bonds and Fe–Mn and Mn–Mn antiferromagnetic couplings, as well as the Al dilutor effect, have been taken into account in our study. Results allow us to conclude that, in agreement with previous Mössbauer data of the average hyperfine field, for which a comparison is also carried out, the Fe_0.9−qMn_0.1Al_q-disordered alloys are well characterized by a critical concentration at room temperature at around 40 at% Al, for which the system undergoes a transition from a ferromagnetic state to a paramagnetic one. The finite size scaling analysis to obtain the critical Al concentration in the thermodynamic limit, as well as the critical exponents, is also presented and discussed.     

A comparative infrared study of H2O reactivity on Si(1 0 0)-(2 × 1), (2 × 1)-H, (1 × 1)-H and (3 × 1)-H surfaces

The water adsorption on the bare and H-terminated Si(1 0 0) surfaces has been studied by the BML-IRRAS technique. It is found that H-terminated surfaces are much less reactive compared to the bare silicon surfaces. The (1 × 1)-H and (3 × 1)-H surfaces show similar and less reactivity pattern compared to the (2 × 1)-H surface. At higher exposures, the water reaction with coupled monohydride species provides an effective channel for oxygen insertion into the back bonds of dihydride species. It is not attributed to the H–Si–Si–H + H₂O → H–S–Si–OH + H₂, which could give rise to the characteristic Si–H and Si–OH modes, respectively at 2081 and 921 cm⁻¹. A more suitable reaction mechanism involving a metastable species, H–Si–Si–H + H₂O → H₂Si  HO–Si–H (metastable) explains well the bending modes of oxygen inserted silicon dihydride species which are observed relatively strongly in the reaction of water with H-terminated Si(1 0 0) surfaces.     

Synthesis, characterization and magnetic properties of Fe–Al nanopins

We report the synthesis of Fe–Al nanopins using arc discharge. The morphology and chemical composition of the Fe–Al nanopins were studied by means of X-ray diffraction, X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDX), and high-resolution transmission electron microscopy (HRTEM). The nanopins are composed of a spherical base of about 20–100 nm and a needle-like tip of about several hundred nanometers. EDX and HRTEM studies indicate that the spherical base is mainly composed of -Fe and FeAl core coated with a thin Al₂O₃ layer, while the needle-like part contains only Al and O and corresponds to Al₂O₃. The formation mechanism of the nanopins is suggestive of a vapor–liquid–solid (VLS) growth process. The as-prepared Fe–Al nanopins show ferromagnetic properties. The temperature dependence of the magnetization at high temperatures indicates the existence of some phase transformations.     

Laser surface alloying of pure titanium with TiN–B–Si–Ni mixed powders

Laser alloying was carried out on the surface of pure titanium substrate with TiN–B–Si–Ni mixed powders. The result of X-ray diffraction (XRD) analysis shows that the alloyed layer consists of many kinds of intermetallic compounds. The test results show that the alloyed layers have high microhardness (1500–1600 HV_0.1), low friction coefficient (about 0.4), and are more resistant to oxidation than untreated substrate.     

Effect of Ti and C additions on structural and magnetic properties of (Pr,Nd)–Fe–B nanocrystalline magnetic materials

Effects of titanium carbide (TiC) addition on structural and magnetic properties of isotropic (Pr,Nd)–Fe-B nanocrystalline magnetic materials have been investigated. In this work, we investigate the effect of TiC addition on a (Pr,Nd)-poor and B-rich composition, as well as on a B-poor and (Nd,Pr)-rich composition. Rapidly solidified (Pr,Nd)–Fe–B alloys were prepared by melt-spinning. The compositions studied were (Pr_1−xNd_x)₄Fe₇₈B₁₈ (x=0, 0.5, and 1) with addition of 3 at% TiC. Unlike the (Pr_xNd_1−x)_9.5Fe_84.5B₆ materials that present excellent values for coercive field and energy product, the (Pr,Nd)-poor and B-rich composition alloys with TiC addition present lower values. Rietveld analysis of X-ray data and Mössbauer spectroscopy revealed that samples are predominantly composed of Fe₃B and -Fe. For the RE-rich compositions (Pr_xNd_1−x)_9.5Fe_84.5B₆ (x=0.1, 0.25, 0.5, 0.75, and 1) with the addition of 3 at% TiC, the highest coercive field and energy product (8.4 kOe and 14.4 MGOe, respectively) were obtained for the composition Pr_9.5Fe_84.5B₆.     

Thermodynamic modeling of Fe–Ni pentlandite

Gibbs energy modeling of iron–nickel pentlandite has been performed using experimental data of ternary phase equilibria. A three-sublattice approach in the framework of the Compound Energy Formalism is developed to refine a two-sublattice model of pentlandite recently applied within a complete assessment of the Fe–Ni–S system. Experimental data about the iron site fraction on the octahedral sublattice at 523.15 K for the composition Fe₅Ni₄S₈ as well as the enthalpy of formation at 298.15 K for the composition Fe_4.5Ni_4.5S₈ are predicted satisfactorily by the novel model. New possibilities to interpret experimental phase equilibrium data on complex phase relations with pentlandite are discussed together on the basis of the recent extension of a second high-temperature heazlewoodite phase to a ternary solution phase.     

Si–SiO2 interface formation in low-dose low-energy separation by implanted oxygen materials

The evolution of the Si–SiO₂ interface morphology of low-dose low-energy separation by implanted oxygen materials was investigated by transmission electron microscopy and atomic force microscopy. The Si–SiO₂ interface morphology and the RMS roughness are strongly affected by the implantation conditions and the annealing process. Three main types of the domains including round, square, and pyramid shapes with the step-terrace structure were observed on the buried SiO₂ surface. Round domains are observed in the early stage of the annealing process, while the square and pyramid domains are observed after the high temperature annealing. The mean RMS roughness decreases with increasing time and annealing temperature, while in the 1350 °C 4-h annealed samples, the mean RMS roughness decreases with either increasing the implantation dose or decreasing implantation energy. The scaling analysis shows that the Si–SiO₂ interfaces were found to be self-affine on the short length scales with a roughness exponent above 0.50. Qualitative mechanisms of Si–SiO₂ surface flattening are presented in terms of the variations of morphological features with the processing conditions.     

An evaluation of surface properties and frictional forces generated from Al–Mo–Ni coating on piston ring

Surface properties of the Al–Mo–Ni coating plasma sprayed on the piston ring material and the frictional forces obtained by testing carried out under different loads, temperatures and frictional conditions were evaluated.

Al–Mo–Ni composite material was deposited on the AISI 440C test steel using plasma spraying method. The coated and uncoated samples were tested by being exposed to frictional testing under dry and lubricated conditions. Test temperatures of 25, 100, 200, and 300 °C and loads of 83, 100, 200, and 300 N were applied during the tests in order to obtain the frictional response of the coating under conditions similar to real piston ring/cylinder friction conditions. Gray cast iron was used as a counterface material. All the tests were carried out with a constant sliding speed of 1 m/s.

The properties of the coating were determined by using EDX and SEM analyses. Hardness distribution on the cross-section of the coating was also determined. In addition, the variations of the surface roughness after testing with test temperatures and loads under dry and lubricated conditions were recorded versus sliding distance.

It was determined that the surface roughness increased with increasing loads. It increased with temperature up to 200 °C and then decreased at 300 °C under dry test conditions.

Under lubricated conditions, the roughness decreased under the loads of 100 N and then increased. The roughness decreased at 200 °C but below and above this point it increased with the test temperature.

Frictional forces observed under dry and lubricated test conditions increased with load at running-in period of the sliding. The steady-state period was then established with the sliding distance as a normal situation. However, the frictional forces were generally lower at a higher test temperature than those at a lower test temperature. Surprisingly, the test temperature of 200 °C was a critical point for frictional forces and surface roughness.     

Role of surface reactions in the transpassive dissolution of ferrous alloys in concentrated H3PO4

The transpassive dissolution of a range of ferrous alloys (Fe–12% Cr, Fe–12% Cr–5% Mo, Fe–25% Cr, Fe–25% Cr–10% Mo) in concentrated H₃PO₄ was studied within the frames of an investigation of electropolishing mechanisms. Measurements by the contact electric resistance (CER) technique have demonstrated that in the transpassive region, the resistance of the anodic film first decreases with increasing potential due to enhanced conductivity of that film and then increases at higher potentials, indicating transpassive film growth. The release of soluble Cr(VI) as detected by rotating ring–disc measurements is the higher, the higher the Cr content in the alloy, and further increases upon addition of 10% Mo to the Fe–Cr alloys. Impedance spectra in the transpassive region have been found to include contributions both from the anodic film and a multistep transpassive dissolution reaction at the film/solution interface. The results were interpreted using a generalised model of transpassive dissolution. The kinetic parameters of the process were determined and the influence of alloy composition on their values is discussed in relation to the processes of anodic surface treatment.     

Magnetostriction of Fe–Sn polycrystalline alloys

In the present work we study the magnetostriction of Fe₉₁Sn₉ and Fe₈₀Sn₂₀ polycrystalline samples produced by arc melting and heat treated at temperatures of 1153 K for 6 h and 1023 K for 24 h, looking for high values of magnetostriction as in Fe–Ga alloys. Magnetostriction, as well as saturation magnetization measurements, was carried out at temperatures close to 203 K in the magnetic field interval 0 to 1.5 T. Results of magnetostriction on sample Fe₉₁Sn₉, which has almost pure -phase, show magnitude and behavior similar to pure Fe. The two additional Fe₈₀Sn₂₀ samples have a combination of -phase plus either Fe₅Sn₃ or Fe₃Sn₂ and show a peculiar behavior of the magnetostriction. For μ₀H<0.3 T the magnetostriction grows from zero to saturation of the -phase. Following, for μ₀H>0.3 T, the magnetostriction starts again to grow linearly with the field, but saturation was not observed up to 5 T. This behavior was attributed to the presence of Fe₅Sn₃ or Fe₃Sn₂ phases in these samples that are also ferromagnetic as the -phase is.     

Hysteretic behavior of Fe0.9−qMn0.1Alq-disordered alloys: a Monte Carlo study

In this work we have simulated the Fe_0.9−qMn_0.1Al_q alloy series with Al contents ranging from 10 up to 50 at%, and for several system sizes. In the simulation, the atoms are randomly distributed on a body-centered cubic according to the atomic disorder achieved through quenching techniques for the experimental samples. In computing the thermodynamic quantities such as the magnetization per site as a function of an external applied magnetic field, we have employed a Monte Carlo algorithm based on a Metropolis dynamics implemented with a random site-diluted Ising model. In this model, we have taken into account nearest-neighbor interactions for which both the ferromagnetic (Fe–Fe) and antiferromagnetic (Fe–Mn, Mn–Mn) interactions are present. From the simulation of the hysteresis loops at room temperature, the remanence and the coercive force as a function of the Al concentration have been obtained. Finally, a comparison with the previous experimental data on coercivity obtained by means of vibrating sample magnetometry is also carried out and discussed.     

Magnetic properties of ball-milled Fe–Mn alloys

BCC, FCC and HCP phases in Fe–13.7 wt% Mn alloys were studied by Mössbauer spectroscopy and X-ray diffraction, after ball milling. The relative amounts of the HCP and FCC phases increase with milling times up to 9 h and decline afterwards. Preliminary AC susceptibility measurements show that the blocking temperatures change for different milling times.     

Covalent binding of cyclohexene, 1,3-cyclohexadiene and 1,4-cyclohexadiene on Si(1 1 1)-7 × 7

The adsorption reactions and binding configurations of cyclohexene, 1,3-cyclohexadiene and 1,4-cyclohexadiene on Si(1 1 1)-7 × 7 were studied using high-resolution electron energy loss spectroscopy (HREELS), ultraviolet photoelectron spectroscopy (UPS), X-ray photoelectron spectroscopy (XPS) and DFT calculation. The covalent attachments of these unsaturated hydrocarbons to Si(1 1 1)-7 × 7 through the formation of Si–C linkages are clearly demonstrated by the observation of the Si–C stretching mode at 450–500 cm⁻¹ in their HREELS spectra. For chemisorbed cyclohexene, the involvement of π_C=C in binding is further supported by the absence of C=C stretching modes and the disappearance of the π_C=C photoemission. The chemisorption of both 1,3-cyclohexadiene and 1,4-cyclohexadiene leads to the formation of cyclohexene-like intermediates through di-σ bonding. The existence of one π_C=C bond in their chemisorbed states is confirmed by the observation of the C=C and (sp²)C---H stretching modes and the UPS and XPS results. DFT calculations show that [4 + 2]-like cycloaddition is thermodynamically preferred for 1,3-cyclohexadiene on Si(1 1 1)-7 × 7, but a [2 + 2]-like reaction mechanism is proposed for the covalent attachment of cyclohexene and 1,4-cyclohexadiene.