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Evolution of microstructure and magnetic properties in Co–Pt alloys bracketing the eutectoid composition

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... The resulting button consisted of a metastable, polycrystalline, A1 (FCC) solid solution of Co and Pt with 20-40 µm grain size, as discussed previously. 13,14 To promote the phase transformation A1 → L1 0 + L1, encapsulated samples were slow-cooled through the eutectoid isotherm (nominally 736 • C) 12 at various rates and then held isothermally for several days prior to quenching. The two samples of interest here were cooled from 750 • C to 600 • C at a rate of 40 • C/day or 80 • C/day and then isothermally annealed at 600 • C for 1 week or 4 days, respectively. ...
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The Co-Pt nanochessboard is a quasi-periodic, nanocomposite tiling of L10 and L12 magnetic phases that offers a novel structure for the investigation of exchange coupling, relevant to permanent magnet applications. Periodicity of the tiling is controlled by the rate of cooling through the eutectoid isotherm, resulting in control over the L10-L12 exchange coupling. First order reversal curve analysis reveals a transition from partial coupling to nearly complete exchange-coupling in a Co40.2Pt59.8 nanochessboard structured alloy as the periodicity is reduced below the critical correlation length. Micromagnetic simulations give insights into how exchange coupling manifests in the tiling, and its impact on microscopic magnetization reversal mechanisms.
... In situations where a change in lattice symmetry accompanies ordering, it can be possible to measure both the true order parameter and the volume fraction of the ordered phase. 34 For all films analyzed here, integrated intensity from the 1 = 2 (111) reflection was taken as the superlattice intensity. For the fundamental reflection, both (111) and (333) integrated peak intensities were used to calculate the order parameter independently and averaged to reduce the peak fitting errors. ...
Article
Chemical ordering in semiconductor alloys could modify thermal and electronic transport, with potential benefits to thermoelectric properties. Here, metastable ordering that occurs during heteroepitaxial growth of Si1-xGex thin film alloys on Si(001) and Ge(001) substrates is investigated. A parametric study was performed to study how strain, surface roughness, and growth parameters affect the order parameter during the alloy growth. The order parameter for the alloy films was carefully quantified using x-ray diffraction, taking into account an often-overlooked issue associated with the presence of multiple spatial variants associated with ordering along equivalent (111) directions. Optimal ordering was observed in the films having the smoothest surfaces. Extended strain relaxation is suggested to reduce the apparent order through creation of anti-phase boundaries. Ordering surprisingly persists even when the film surface extensively roughens to form {105} facets. Growth on deliberately miscut Si(001) surfaces does not affect the volume-averaged order parameter but does impact the relative volume fractions of the equivalent ordered variants in a manner consistent with geometrically necessary changes in step populations. These results provide somewhat self-contradictory implications for the role of step edges in controlling the ordering process, indicating that our understanding is still incomplete.
... This is consistent with the TEM, which shows that lateral length scales of the hard and soft tiles in the chessboard are in the range 25–40 nm. For the L1 0 phase at this Pt concentration, we have estimated in previous work that the uniaxial anisotropy constant is K 1 = 1 × 10 7 erg/cm 3 and the exchange coupling coefficient is A = 2.5 × 10 −6 erg/cm [Ghatwai 2015] . The hard wall thickness is δ ≈ π √ A/K = 16 nm. ...
... Eutectoid triple points are expected to exist that connect the high-temperature A1 face-centered cubic (fcc) phase to a two-phase coexistence region between the L1 0 tetragonal and Pd/Pt-rich cubic L1 2 phases of these systems, although there is limited experimental verification of the eutectoid temperature, composition or the expanse of the two-phase region for any of these materials [12][13][14][15], and those studies that do exist are sometimes conflicted [16][17][18][19]. The work presented in this paper began as an attempt to explore the complicated phase behavior of this unexplored region of the Fe-Pd binary diagram near the expected Fe 38.5 Pd 61.5 eutectoid composition [20]. ...
Article
The existence of an L10–L12 hybrid ordered phase for face-centered cubic (fcc) crystal symmetry was first theorized by William Shockley in 1938, but has not been verifiably observed to date. Ordered magnetic thin films of Fe38.5Pd61.5, the expected L10–L12 eutectoid composition, grown epitaxially on MgO(0 0 1) substrates by pulsed laser deposition, are shown to exhibit the first empirical confirmation of L1′ type ordering. A formal treatment of L1′ ordering requiring the definition of two independent ordering parameters is discussed in conjunction with the crystallographic and magnetic characterization of the Fe38.5Pd61.5 thin films. Two theories regarding origination of the unique metastable ordering behavior induced by the non-equilibrium strain conditions are proposed.
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In this paper, we report Lorentz Transmission Electron Microscopy (LTEM) observations of magnetic domain structures in a near-eutectoid Co40Pt60 alloy. The crystallographic microstructure is characterized using conventional bright field/dark field TEM imaging. The magnetic induction orientation inside magnetic domains is extracted from Fresnel through-focus images by reconstructing the phase of electron wave using the transport-of-intensity equation. The alloy shows a nano-chessboard pattern composed of the L10 tetragonal and L12 cubic phases. The magnetization distribution in four neighboring L10 tiles in the nano-chessboard structure is found to follow a vortex/anti-vortex configuration to reduce the magnetostatic and magneto-crystalline anisotropy energies. An unconventional domain wall referred to as an inter phase magnetic domain wall (IPMDW) is observed at the inter-phase boundaries of L10 and L12 phases. Magnetic domain walls in other microstructures (tweed microstructure, macro-twinned structure, coarsened L10 plates) are also documented.
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In the present work, a series of Ta/Ru/Co-23 at%Pt thin films with varied Ru underlayer thicknesses were fabricated by magnetron sputtering. All of the films show c-axis preferred orientation perpendicular to the film surface. The drop of c/a ratio and lattice expansion of Co–Pt layer with the increase in Ru underlayer thickness was revealed by X-ray diffraction (XRD). The coercivity of the Ta/Ru/Co–Pt thin films increases drastically with Ru underlayer thickness increasing, due to the enhancement of effective magneto-crystalline anisotropy constant and exchange decoupling of magnetic nano-grains. The enhancement of effective magneto-crystalline anisotropy constant is ascribed to the lattice deformation of Co–Pt layer by mismatching the Ru layer and Co–Pt surface. Moreover, the exchange decoupling of magnetic nano-grains is attributed to the further isolation of magnetic nano-grains.
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The evolution of the structural and magnetic properties in epitaxial film systems Co/Pt(111) of equiatomic composition during vacuum annealing has been presented. Annealing to the temperature of 400°C does not lead to the variation of the structural and magnetic properties of the films, which indicates the absence of considerable mixing of the Co/Pt interface. With the increase in the annealing temperature from 400 to 750°C, nanoclusters containing the main magnetically hard L10CoPt(111) phase epitaxially intergrown with the CoPt3 phase are formed. High rotatable magnetic anisotropy has been found in the prepared films. In magnetic fields above the coercive force (H > H C = 8 kOe), the easy anisotropy axis with the angle of lag taken into account can be oriented in any spatial direction. Possible mechanisms of the formation of the rotatable magnetic anisotropy have been discussed. It has been assumed that the high rotatable magnetic anisotropy makes the main contribution to the magnetic perpendicular anisotropy in Cox Pt1–x films.
Article
Anti-phase boundaries (APBs) in an ordered CoPt alloy are planar defects which disturb the ordered structure in their vicinity and decrease the magnetic properties. However, it has not yet been clarified to what extend the APBs disturb the ordering. In this study, high-resolution HAADF-STEM images are statistically analysed based on the image intensities estimated by the statistical parameter estimation theory. In the procedure, averaging intensities, fitting the intensity profiles to specific functions, and assessment based on a statistical test are performed. As a result, the APBs in the stable CoPt are found to be characterized by two atomic planes, and a contrast transition range as well as the centre of an inclined APB is determined. These results show that the APBs are quite sharp and therefore may have no notable effect on the net magnetic properties due to their small volume fraction.
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The frequencies of the normal modes of vibration of CoPt3 and FePd single crystals have been measured using inelastic neutron scattering. The measurements were performed in the L12 ordered phase (at 300 and 930 K) for CoPt3 and in the L10 ordered phase (at 300 and 860 K) for FePd. Dispersion curves were also measured in the fcc disordered states, at 1060 and 1020 K for CoPt3 and FePd, respectively. The activation enthalpy of atomic migration has been evaluated from the phonon density of states by applying Schober’s model [H. R. Schober et al., J. Phys.: Condens. Matter 4, 9321 (1992)] and its extension to the L12 ordered structure. The phonon properties of FePd3 reported in the literature have been analyzed similarly and are compared with the results for CoPt3 and FePd. The contribution of the long-range order to the migration enthalpy estimated in the present analyses agrees well in magnitude with the previous evaluation by Monte Carlo simulation for alloys of the fcc, L12, and L10 structures.
Article
The frequencies of the normal modes of vibration of CoPt3 and FePd single crystals have been measured using inelastic neutron scattering. The measurements were performed in the L12 ordered phase (at 300 and 930 K) for CoPt3 and in the L10 ordered phase (at 300 and 860 K) for FePd. Dispersion curves were also measured in the fcc disordered states, at 1060 and 1020 K for CoPt3 and FePd, respectively. The activation enthalpy of atomic migration has been evaluated from the phonon density of states by applying Schober's model [H. R. Schober et al., J. Phys.: Condens. Matter 4, 9321 (1992)] and its extension to the L12 ordered structure. The phonon properties of FePd3 reported in the literature have been analyzed similarly and are compared with the results for CoPt 3 and FePd. The contribution of the long-range order to the migration enthalpy estimated in the present analyses agrees well in magnitude with the previous evaluation by Monte Carlo simulation for alloys of the fcc, L12, and L10 structures.
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Epitaxial films of Fe38.5Pd61.5 at the L10-L12 eutectoid composition have been grown on MgO (001) oriented substrates by pulsed laser deposition. The effect of deposition temperature on the magnetic, microstructural, and crystallographic natures of these films are discussed. The films in this study exhibit atomic ordering with increasing deposition temperature, transitioning from the disordered face centered cubic (FCC) phase to an L12 ordered phase, which is tetragonally distorted due to epitaxial strain. This distortion leads to a perturbation in the Fe occupancy of the Pd superlattice sites at nonstoichiometric compositions. Additionally, Fe38.5Pd61.5 films grown at 550 °C have been found in an unique two-phase microstructure of prismatic, Fe60Pd40 disordered FCC secondary phases with 10–100 nm facets oriented along the 〈110〉 substrate directions, embedded within a nearly stoichiometric ordered L12-Fe27Pd73 matrix. These secondary phase precipitates exhibit single domain magnetic axis rotation, while the ordered L12 matrix has a magnetic easy axis aligned in-plane.
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Magnetization processes in particulate L10 FePt nanostructures are investigated by model calculations and numerical simulations. The systems considered include anisotropic nanograins embedded in non-magnetic matrix; randomly oriented nanoclusters embedded in a C matrix, and nanocomposites of FePt particles in a semi-hard matrix. The reversal mechanisms depend on both intra- and intergranular features. Quasi-coherent rotation dominates the reversal in weakly-coupled granular magnets, but interface imperfections yield a disproportionately strong coercivity reduction. Strong intergranular exchange leads to a transition to a discrete pinning regime, which is accompanied by a coercivity maximum.
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Magnetic properties of the pseudo-binary Co1-xMxPt3 (M = Mn, Fe) compounds have been investigated. Under adequate preparation conditions, these compounds display the L12 structure. For M = Mn the magnetic phase diagram presents a continuous ferromagnetic region from CoPt3 to MnPt3 with a re-entrant spin glass (RSG) phase emerging at low T and H between x = 0.2 and 0.6. For M = Fe, a spin glass (SG) phase separates the ferromagnetic region on the Co-rich side, from the antiferromagnetic region on the Fe-rich side. The results are qualitatively discussed in terms of the three dominant competing magnetic interactions JCoCo, JCoM, JMM.
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Conventional and high resolution electron microscopy have been used to investigate the L12-L10, two-phase mixtures in the Co-Pt system. The domain of coexistence of the phases L12 (Copt3) and L10 (Copt) has been determined. Three different processes of formation of the two phase mixture from the high temperature disordered state (A1) have been studied as a function of the aging temperature: (1) A1 → L10 → L10 + L12, (2) A1 → L12 → L1 0 + L12, (3) A1 → L10 + L12. In the final state, the microstructures present the same main topologies. Processes (1) and (2) involve two steps, the first one consists in ordering one of the single phases. The second step is shown to involve an interfacial wetting of the domains walls of the ordered structure formed during the first step. When the phases L10 and L12 simultaneously appear within the disordered matrix (process (3)), an archetypal microstructure is formed: it consists of a regular tiling of domains according to a precise and fascinating topology driven by long range strain interactions.
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An electron microscopy study shows that order in the equiatomic Pt-Co alloy proceeds by means of nucleation and growth of ordered particles which are coherent with the matrix. Isochronous thermal treatments lead to a three dimensioned array of domains in which one of the three possible ordering directions is favoured; there is no microtwinning. On the contrary, a treatment at a temperature just below the critical tempertaure leads to a microtwinned structure. The residual contrast of the antiphase boundaries is analysed and it is shown that the boundary is constituted by a narrow zone in which the atoms are closer than in the ordered state.ZusammenfassungEine elektronenmikroskopische Untersuchung der Ordnungsvorgänge in einer Pt-Co-Legierung mit gleichen Anteilen Pt und Co zeigt, daβ sich die Ordnung durch Keimbildung und Wachstum geordneter, in der Matrix kohärenter Teilchen einstellt. Isochrone thermische Behandlungen führen zu dreidimensionalen Anordnungen von Domänen, in denen jeweils eine der drei möglichen Ordnungsrichtungen begünstigt ist; die Entstehung von Mikrozwillingen wurde nicht beobachtet. Im Gegensatz dazu führt eine Wärmebehandlung dicht unterhalb der kritischen Temperatur zu einer Struktur, die Mikrozwillinge enthält. Der Kontrast von Antiphasengrenzen wird analysiert und es wird gezeigt, daβ die Antiphasengrenze aus einer schmalen Zone besteht, in der die Atome dichter gepackt sind als im geordneten Zustand.
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Alloys near the composition PtCo can be quenched to retain a disordered fcc phase. Aging at a suitable temperature produces an ordered tetragonal phase of type AuCuI. The C axis is an easy axis of magnetization with an anisotropy constant of ~ 107 erg cm-3. Aging produces a magnetically hard alloy. In the early stages of aging ordered regions of diameter 50-100A˚ were found with their C axes oriented at random parallel to one or other of the three original disordered cubic 'a' axes. In the optimum high coercivity state particles of like C axis (diameter ~200A˚) group together on {110} planes; the c axis being at 45° to the {110} plane. In the overaged state like particles merge to form lamellae of one particular C axis the other orientations being consumed. Approaches to a better understanding of the hardening process are discussed.
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L10-type Co100−xPtx single crystals were prepared by atomic ordering under compressive stress and the magnetic properties were investigated. The second order magnetocrystalline anisotropy constant K1 at 298K exhibits a maximum value of 4.1×107ergcm−3 at x=50. On the other hand, the fourth order magnetocrystalline anisotropy constant K2 becomes minimum at the same composition. The large uniaxial magnetocrystalline anisotropy constant KU with a low saturation magnetization MS in L10-type Co100−xPtx would bring about the thermal stability of the single magnetic domain state, as well as the sharp coherent magnetization reversal.
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The theory of fine‐particle magnets is based on the theorem that the state of lowest free energy of a ferromagnetic particle is one of uniform magnetization for particles of less than a certain critical size and one of nonuniform magnetization for larger particles. The theorem is inferred from several approximate calculations and has not been proved rigorously. Rigorous statements can be made if one is content to replace equalities by inequalities and exact values of critical radii by upper and lower bounds. For a sphere of radius a with uniaxial anisotropy, it can be shown that the lowest‐free‐energy state is one of uniform magnetization if a ac1 (for low anisotropy) or ac2 (for high anisotropy), where ac0, ac1 (>ac0), and ac2(>ac0) are determined by the exchange and anisotropy constants and the spontaneous magnetization. These bounds locate the critical radius to within about 12% at low anisotropy but only to within an order of magnitude or more at high.
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We have studied the effect of the atomic disorder–order transformation on remanence enhancement and coercivity in CoPt ingots by isothermal annealing at various temperatures well below the transformation point. The relative amount of the low-temperature hard-magnetic face-centered-tetragonal (fct) phase precipitated in the high-temperature magnetically soft face-centered-cubic (fcc) phase was determined by means of x-ray diffraction. As a function of annealing temperature, the mean grain size and the relative amount of the fct phase increase at the cost of the fcc phase. These changes were followed by means of magnetic measurements. We observed a continuous increase in coercivity with increasing annealing temperature, eventually reaching a maximum. The Kneller–Hawig model was used to explain the occurrence of remanence enhancement and the continuously changing degree of exchange coupling between the magnetically soft and hard phases. © 2002 American Institute of Physics.
Article
Transmission electron microscopy techniques are used to characterize the development of the polytwinned microstructures during Al → Ll0 ordering in FePd and FePt alloys. Also, Lorentz microscopy methods are used to image the magnetic domain structures which are associated with these magnetically modulated twin assemblies. A modified APB pinning model including thermally activated wall motion is formulated to account for the levels of coercivity and the temperature dependence of the coercivity in polytwinned ferromagnets.Mittels Transmissionselektronenmikroskopie wird die Entwicklung der vielfachverzwillingten Mikrostruktur während der Al → Ll0-Umordnung in FePd- und FePt-Legierungen charakterisiert. Lorentz-Mikroskopie wird benutzt, um die magnetische Bereichstruktur, die mit diesen magnetisch modulierten Zwillingsanordungen verknüpft ist, abzubilden. Ein modifiziertes APB-Pinning-Modell, das thermisch aktivierte Wandbewegung einschließt, wird formuliert, um Größe und Temperaturabhängigkeit der Koerzivität in vielfachverzwillingten Ferromagneten zu berücksichtigen.
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The effect of nanoscale exchange coupling has been investigated in the CoPt alloy system. The experimental results of XRD and TEM indicate that in the early stage of the disorder–order transformation, the ordered fct regions with a mean size smaller than 8 nm are uniformly distributed and randomly oriented along the a-, b- and c-axes of the cubic structure of the original disordered fcc matrix phase. Both phases are completely coherent. The degree of atomic order in the ordered regions continuously increases, but this process is different for the various ordered regions. Also the degree of atomic order of the matrix phase increases, albeit at a low rate. There is a broad continuous distribution of the degree of order in the initial stage of the ordering transformation. An ordered region with higher degree of order has a higher magnetocrystalline anisotropy. The effect of nanocomposite exchange coupling between the regions with different degree of order is very clear. A remanence ratio of 0.78 is obtained after annealing the sample at 675 °C for 20 min. When the annealing time is longer than 60 min at 675 °C, the growth of ordered regions leads to a situation in which the disordered regions are swallowed up and the ordered regions meet each other to form antiphase boundaries. Cross-intersected polytwin bands of several hundreds nm length and a few nm width are formed along the {111} and {211} planes to relax the strain energy. It is suggested that the mechanism of magnetization reversal changes from coherent rotation to magnetic-domain wall movement. Since the widths of the polytwin bands are still within the length of exchange coupling, the strong remanence enhancement is preserved.
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Highly coercive granular SmCo/CuTi films were produced by thermal processing of sputtered SmCo5/(CuTi) multilayers and investigated experimentally and theoretically. Electron microscopy shows that the processed films consist of spherical grains that have diameters of 5-10 nm and are embedded in a matrix. Both the grains and the matrix phase exhibit the CaCu5 structure, but the matrix is probably Cu-rich. The films have high coercivities of up to 50.4 kOe at 300 K. Analytical calculations and micromagnetic simulations yield a transition from a nucleation-type weak-interaction regime to a discrete-pinning-type strong-interaction regime. The transition occurs at packing fractions similar to those encountered in the investigated films and is accompanied by a coercivity maximum.
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The tetragonal L10 family of ferromagnets including the Co-Pt, Fe-Pt, Fe-Pd and Mn-Al alloy systems exhibits high, uniaxial magnetocrystalline anisotropies with first anisotropy constants K1 ~ 107–108 ergs/cm3. The domain parameters of these materials are similar to the rare earth permanent magnets and the defect structure is dominated by planar faults such as APB's, stacking faults, and twins. In this study the micromagnetic analysis of Kronmüller has been applied to elucidate the mechanism of coercivity controlling the hysteresis of the polytwinned L10 FePd equiatomic alloy and the results are consistent with pinning control involving atomically thick, planar defects. Also, Lorentz microscopy has been used to observe the interaction of magnetic domain walls with the planar faults characteristic of these materials. Finally, a thermomechanical treatment involving concomitant ordering and recrystallization is shown to eliminate the well-known polytwinned structures which generally evolve during the formation of the L10 phase leading to enhanced coercivities. The fundamental structure-property relationships involved are discussed.
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ZnO nanoparticles (ZnO-NPs) were prepared by a sol-gel combustion method from a zinc acetate precursor and acetic acid. The ZnO-NPs were synthesized at calcination temperatures of 650 degrees C and 750 degrees C for 1 h. The synthesized ZnO-NPs were characterized by X-ray diffraction analysis (XRD) and TEM. The XRD results revealed that the sample product was crystalline with a hexagonal wurtzite phase. High-magnification transmission electron microscopy (TEM) showed single-crystal ZnO-NPs with nearly spherical shapes. The crystalline development in the ZnO-NPs was investigated by X-ray peak broadening. The Williamson-Hall (W-H) analysis and size-strain plot method were used to study the individual contributions of crystallite sizes and lattice strain on the peak broadening of the ZnO-NPs. The physical parameters such as strain, stress and energy density values were calculated more precisely for all the reflection peaks of XRD corresponding to the wurtzite hexagonal phase of ZnO lying in the range of 20 degrees-100 degrees from the modified form of the W-H plot assuming a uniform deformation model (UDM), uniform stress deformation model (USDM), uniform deformation energy density model (UDEDM) and by the size-strain plot method (SSP). The results obtained showed that the mean particle size of the ZnO-NPs estimated from the TEM, W-H analysis and the SSP method were highly intercorrelated. (C) 2010 Elsevier Masson SAS. All rights reserved.
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