- Email: [email protected]
On magnetism in the quasicrystalline Ti45Zr38Ni17 alloy
Journal of Non-Crystalline Solids xxx (xxxx) xxx–xxx
Contents lists available at ScienceDirect
Journal of Non-Crystalline Solids journal homepage: www.elsevier.com/locate/jnoncrysol
On magnetism in the quasicrystalline Ti45Zr38Ni17 alloy J. Czuba,⁎, J. Przewoźnika, A. Żywczakb, A. Takasakic, A. Hoserd, Ł. Gondeka a
AGH University of Science and Technology, Faculty of Physics and Applied Computer Science, Mickiewicza 30, 30-059 Kraków, Poland AGH University of Science and Technology, Academic Centre for Materials and Nanotechnology, Mickiewicza 30, 30-059 Kraków, Poland Department of Engineering Science and Mechanics, Shibaura Institute of Technology, Toyosu, Kotoku, Tokyo 135-8548, Japan d Helmholtz Zentrum Berlin, Hahn-Meitner-Platz 1, 14109 Berlin, Germany b c
A R T I C L E I N F O
A B S T R A C T
Keywords: D. Magnetism A. Icosahedral quasicrystals D. Magnetic ordering D. Pauli paramagnet
Magnetism of 3D quasicrystals is extensively researched, mainly for rare-earth or iron-based alloys. In this contribution, magnetic properties of the icosahedral Ti45Zr38Ni17 quasicrystal are reported. Namely, the results of magnetometric and neutron diffraction studies in the broad temperature ranges of 1.5–300 K and 2–700 K respectively are discussed. The magnetometric studies reveal that the alloy exhibits an extremely weak ferromagnetic signal, however it is associated with the traces of nickel clusters at the grains boundaries. The neutron scattering studies, including diffraction in external magnetic field, indicate no possibility of long-rage magnetic ordering in the icosahedral Ti45Zr38Ni17 alloy. According to our studies, the investigated material exhibits Pauli-like paramagnetic behaviour.
1. Introduction Recently, the amorphous and quasicrystalline Ti-Zr-Ni alloys have raised an interest due to the wide range of their potential applications. Particularly, such systems can be exploited as electrodes in metalhydride batteries [1], shape memory alloys [2], high temperature protective coatings [3] and biomedical applications [4]. Apart from the above, the Ti-Zr-Ni alloys are considered as materials for hydrogen storage applications due to their hydrogen sorption properties [5–8]. Namely, the reported hydrogen concentrations exceed significantly 2 wt%. However, the basic properties of the Ti-Zr-Ni alloys, including the magnetic properties, have not been extensively researched yet. The electronic-related properties of the Ti-Zr-Ni quasicrystals are rarely investigated, while the reported findings are extremely interesting [9–16]. Particularly, for ribbons of the Ti53Zr27Ni20 and Ti45Zr38Ni17 compositions superconducting transitions were evidenced below 2 K [10]. Magnetic susceptibility of the Ti53Zr27Ni20 quasicrystal was reported to show a weak temperature dependence with an upturn at the lowest temperatures [9]. Similar findings were reported for the Ti55 − xZr33Ni12 + x (x = 7, 9) quasicrystals [16], for which ferromagnetic properties were suggested on the basis of the observed enhanced magnetisation at low temperatures. However, it must be emphasised that the relevant hysteresis loops were hardy detected [16]. For the hydrided Ti53Zr27Ni20 quasicrystal a decrease of the magnetisation as a result of the lattice expansion and the subsequent reduction of interactions between magnetic moments of Ni atoms was reported
⁎
[9]. Transport properties of the amorphous and quasicrystalline Ti-ZrNi ribbons were investigated by means of electrical conductivity, the Seebeck coefficient and thermal conductivity measurements [17]. The results showed negative temperature coefficients for all ribbons; however the dependence was rather weak with no anomalous behaviour in the entire temperature range. On the other hand, the Seebeck (S) coefficient showed some anomalous behaviour at about 20 K for the amorphous samples, while for the quasicrystalline alloys the S(T) dependence could be nicely described using the phonon-drag and electron-phonon enhancement models. Taking all of these into account, it must be concluded that the origin of magnetism in the Ti-Zr-Ni quasicrystals is unclear. Moreover, the essential question whether the icosahedral Ti-Zr-Ni quasicrystal can exhibit long-range magnetic ordering, at least at low temperatures, remains unanswered. For this reason, we address this issue carefully for the icosahedral Ti45Zr38Ni17 quasicrystal by means of magnetometric and neutron diffraction studies. 2. Experimental The amorphous Ti45Zr38Ni17 nano-powder was synthesised by mechanical alloying that was performed in the Frisch Pulverisette 7 planetary mill. A stoichiometric mixture of commercially available titanium (99.99%), zirconium (99.99%) and nickel (99,999%) powders was used as the starting material. The material was enclosed in a
Corresponding author. E-mail address: [email protected] (J. Czub).
http://dx.doi.org/10.1016/j.jnoncrysol.2017.05.007 Received 7 February 2017; Received in revised form 8 May 2017; Accepted 10 May 2017 0022-3093/ © 2017 Elsevier B.V. All rights reserved.
Please cite this article as: Czub, J., Journal of Non-Crystalline Solids (2017), http://dx.doi.org/10.1016/j.jnoncrysol.2017.05.007
Journal of Non-Crystalline Solids xxx (xxxx) xxx–xxx
J. Czub et al.
Fig. 1. TEM image of the Ti45Zr38Ni17 quasicrystalline powder with the SAED pattern of nickel precipitations (the contribution from the quasicrystalline phase was extracted).
Fig. 2. Temperature dependence of the magnetic susceptibility for the quasicrystalline Ti45Zr38Ni17. Error bars are smaller than the data points.
platform. The measurements (magnetic susceptibility and isothermal magnetisation) were performed in the very broad temperature range starting from 2 K up to 700 K. The isothermal magnetisation studies were conducted in external magnetic fields up to 9 T. In order to ensure a good quality of isothermal magnetisation curves, the instrument was calibrated to eliminate spurious magnetic fields. Additionally, the internal calibration procedures excluded systematic errors originating from sample displacement. The standard samples were used to calibrate the temperature reading in the experimental range. The neutron diffraction measurements were performed at the E6 focusing powder diffractometer (BENSC-Berlin) using an incident neutron wavelength of 2.45 Å. The sample stage was equipped with the vertical cryo-magnet VM3 (AS Scientific) that enables measurement in the range of 1.5–300 K and in magnetic field up to 5 T. The sample powder weighting about 5 g was placed in a vanadium container. A small quantity of deuterided alcohol was poured inside the container in order to achieve mechanical stability of the powder during applying of magnetic field at low temperatures. The systematic errors related to the geometry of the diffractometer were calibrated using measurements of the Y2O3 standard. Also the efficiencies of the detectors banks were
stainless steel vial (45 ml), together with stainless steel balls (14 mm in diameter). The ball to powder weight ratio was equal to 8:1. Then the vial was evacuated by a scroll pump and then refilled with argon gas (99.999%). This procedure was repeated several times in order to remove spurious gases from the vial. The final argon pressure was maintained at 0.1 MPa. To avoid a temperature increase during MA, the alloying periods of 0.5 h were alternated with the rest periods of the 0.5 h. After 20 h of milling the vial was opened under argon atmosphere and the powder was mixed. Then alloying was continued for the next 20 h. The obtained powder was subsequently annealed under argon atmosphere for 12 h at 480 °C. That temperature was chosen according to the data presented in Fig. 2 in ref. [18]. The transmission electron microscopy (TEM) and X-ray diffraction (XRD) methods were used for a quality assessment of the obtained quasicrystal. The resulting quasicrystalline powder with the grains mean diameter of 250 nm was found to be homogeneous with extremely small traces of pure Ni at the boundaries of some grains as presented in Fig. 1. The magnetic measurements were carried out using the vibrating sample magnetometer (VSM) option of the Quantum Design PPMS-9 T 2
Journal of Non-Crystalline Solids xxx (xxxx) xxx–xxx
J. Czub et al.
Fig. 3. Thermal evolution of the isothermal magnetisation curves for the quasicrystalline Ti45Zr38Ni17. Error bars are smaller than the data points.
no change in the reflections intensities ratios is noticed with temperature raising from 1.5 K to 300 K. Therefore, it can be concluded that the icosahedral Ti45Zr38Ni17 quasicrystal does not exhibit the long-range magnetic order. Moreover, nickel atoms do not carry magnetic moment what allow us to classify the Ti45Zr38Ni17 quasicrystal as a Pauli paramagnet.
calibrated by measuring the patterns of a water-filled vanadium container.
3. Results and discussion The results of the VSM measurements performed in the wide temperature range are presented in Fig. 2. As apparent from the figure, the signal is extremely weak, however several interesting features can be observed. Firstly, the magnetic susceptibility χ(T) exhibits a prominent increase below 20 K, what is in consistency with the other reports concerning similar quasicrystals [9,16]. Secondly, the χ(T) is almost temperature-independent in the broad temperature range from 50 to 400 K. Lastly, a systematic decrease of χ(T) is evidenced above 400 K with a pronounced drop at about 650 K, above which temperature a further decrease is exhibited. The shape of the χ(T) curve above 400 K is typical for nano-crystalline nickel with relatively small clusters sizes [19]. The precise isothermal magnetisation studies in external magnetic fields up to 9 T presented in Fig. 3 shows that between 50 and 600 K an extremely weak ferromagnetic signal accompanied by tiny hysteresis loops can be observed. Apparently, this signal can be associated with nickel nano-clusters, not the quasicrystalline phase as it diminishes above 650 K. It is worth-noting that at 300 K the magnetic moment yields only 0.8 · 10− 4 μB/Ni at 9 T. A comparison between this value and the expected ~0.6 μB/Ni can be a good quantitative detection method of nickel nano-clusters precipitations in the quasicrystalline alloy. Finally, we address an issue of enhanced χ(T) at low temperatures. To clarify its origin, the high-statistics neutron diffraction patterns in the 1.5–300 K temperature range were collected. The data measured at temperature of 1.5 K at external magnetic field of 5 T compared to zero field are presented in Fig. 4. In the 1.5 K–300 K temperature range no changes in the diffraction patterns can be seen after applying magnetic field. On the other hand,
4. Concluding remarks The presented research addresses the very important problem of tracing magnetic impurities that are unavoidable in either MA or spinmelting techniques. Those impurities are undetectable by XRD and hardly detectable by TEM as their share in the alloy is extremely small. In our case, it is much less than 0.04 wt%, but as the ferromagnetic signal of Ni clusters the VSM technique is sensitive even for such small quantities of magnetic impurities. Moreover, due to the Curie temperatures (usually much above the room temperature) of the possible impurities (Fe, Co, Ni etc.), the high-temperature measurements give a first-hand evidence of their presence in quasicrystalline alloys. Usually, magnetometric properties of quasicrystals are measured below room temperature; hence the true origin of the observed ferromagnetic signal may be overlooked. For the discussed case, the icosahedral Ti45Zr38Ni17 alloy does not exhibit intrinsic magnetic properties in the entire stability range. Moreover, the results of the studies in external magnetic field exclude long-range magnetic ordering as well as the possibility of the magnetostriction effects in magnetic field up to 5 T, what is an important information considering possible applications of this alloy. Acknowledgements This research project was supported by the Polish-Norwegian Research Programme operated by the National Centre for Research and Development through the project ‘Nanomaterials for hydrogen storage’ number 210733, the European Commission under the 7th 3
Journal of Non-Crystalline Solids xxx (xxxx) xxx–xxx
J. Czub et al.
Fig. 4. The neutron diffraction patterns for the quasicrystalline Ti45Zr38Ni17 measured at 1.5 K at zero field and external magnetic field of 5 T, respectively. Traces of the Laves C14 phase are marked with asterisks. Error bars are smaller than the line widths.
Framework Programme through the ‘Research Infrastructure’ action of the ‘Capacities’ Programme, NMI3-II Grant number 283883.
[10] V. Azhazha, A. Grib, G. Khadzhay, S. Malikhin, B. Merisov, A. Pugachov, Phys. Lett. A 303 (2002) 87. [11] P. Weinberger, L. Szunyogh, C. Blaas, C. Sommers, P. Entel, Phys. Rev. B 63 (2001) 094417. [12] M.D. Nunez-Regueiro, E. Chappel, G. Chouteau, C. Delmas, Eur. Phys. J. B. 16 (2000) 37. [13] K.F. Kelton, Mater. Sci. Eng. A 375–377 (2004) 31. [14] J.P. Davis, E.H. Majzoub, J.M. Simmons, K.F. Kelton, Mater. Sci. Eng. 294–296 (2000) 104. [15] R.G. Hennig, A.E. Carlsson, K.F. Kelton, C.L. Henley, Phys. Rev. B 71 (2005) 144103. [16] Y. Lee, H. Shin, J.-Y. Kim, S.-W. Sohn, D.-H. Kim, IEEE Trans. Magn. 45 (2009) 2594. [17] Y.K. Kuo, N. Kaurav, W.K. Syu, K.M. Sivakumar, U.T. Shan, S.T. Lin, Q. Wang, C. Dong, J. Appl. Phys. 104 (2008) 06705. [18] D. Rusinek, J. Czub, J. Niewolski, Ł. Gondek, M. Gajewska, A. Takasaki, A. Hoser, A. Żywczak, J. Alloys Compd. 646 (2015) 90. [19] I.M.L. Billas, A. Châtelain, W.A. de Heer, Science 16 (1994) 1682.
References [1] B. Guiose, F. Cuevas, B. Décamps, E. Leroy, A. Percheron-Guégan, Electrochim. Acta 54 (2009) 2781. [2] S. Inoue, N. Sawada, T. Namazu, Vacuum 83 (2009) 664. [3] Y. Guan, J.-G. Liu, C.-W. Yan, Int. J. Electrochem. Sci. 6 (2011) 4853. [4] H. Lefaix, F. Prima, S. Zanna, P. Vermaut, P. Dubot, P. Marcus, D. Janickovic, P. Svec, Mater. Trans. 48 (2007) 278. [5] Yu.V. Zhernovenkova, L.A. Andreev, S.D. Kaloshkin, T.A. Sviridova, V.V. Tcherdyntsev, I.A. Tomilin, J. Alloys and Compd. 434-435 (2007) 747. [6] A. Takasaki, K.F. Kelton, J. Alloys Compd. 347 (2002) 295. [7] R.R. Shahi, T.P. Yadav, M.A. Shaz, O.N. Srivastava, S. van Smaalen, Int. J. Hydrog. Energy 36 (2011) 592. [8] A. Kocjan, P.J. McGuiness, S. Kobe, Int. J. Hydrog. Energy 35 (2010) 259. [9] H.S. Shin, S. Lee, Y. Jo, J. Kim, J. Korean Phys. Soc. 61 (2012) 1541.
4
Contents lists available at ScienceDirect
Journal of Non-Crystalline Solids journal homepage: www.elsevier.com/locate/jnoncrysol
On magnetism in the quasicrystalline Ti45Zr38Ni17 alloy J. Czuba,⁎, J. Przewoźnika, A. Żywczakb, A. Takasakic, A. Hoserd, Ł. Gondeka a
AGH University of Science and Technology, Faculty of Physics and Applied Computer Science, Mickiewicza 30, 30-059 Kraków, Poland AGH University of Science and Technology, Academic Centre for Materials and Nanotechnology, Mickiewicza 30, 30-059 Kraków, Poland Department of Engineering Science and Mechanics, Shibaura Institute of Technology, Toyosu, Kotoku, Tokyo 135-8548, Japan d Helmholtz Zentrum Berlin, Hahn-Meitner-Platz 1, 14109 Berlin, Germany b c
A R T I C L E I N F O
A B S T R A C T
Keywords: D. Magnetism A. Icosahedral quasicrystals D. Magnetic ordering D. Pauli paramagnet
Magnetism of 3D quasicrystals is extensively researched, mainly for rare-earth or iron-based alloys. In this contribution, magnetic properties of the icosahedral Ti45Zr38Ni17 quasicrystal are reported. Namely, the results of magnetometric and neutron diffraction studies in the broad temperature ranges of 1.5–300 K and 2–700 K respectively are discussed. The magnetometric studies reveal that the alloy exhibits an extremely weak ferromagnetic signal, however it is associated with the traces of nickel clusters at the grains boundaries. The neutron scattering studies, including diffraction in external magnetic field, indicate no possibility of long-rage magnetic ordering in the icosahedral Ti45Zr38Ni17 alloy. According to our studies, the investigated material exhibits Pauli-like paramagnetic behaviour.
1. Introduction Recently, the amorphous and quasicrystalline Ti-Zr-Ni alloys have raised an interest due to the wide range of their potential applications. Particularly, such systems can be exploited as electrodes in metalhydride batteries [1], shape memory alloys [2], high temperature protective coatings [3] and biomedical applications [4]. Apart from the above, the Ti-Zr-Ni alloys are considered as materials for hydrogen storage applications due to their hydrogen sorption properties [5–8]. Namely, the reported hydrogen concentrations exceed significantly 2 wt%. However, the basic properties of the Ti-Zr-Ni alloys, including the magnetic properties, have not been extensively researched yet. The electronic-related properties of the Ti-Zr-Ni quasicrystals are rarely investigated, while the reported findings are extremely interesting [9–16]. Particularly, for ribbons of the Ti53Zr27Ni20 and Ti45Zr38Ni17 compositions superconducting transitions were evidenced below 2 K [10]. Magnetic susceptibility of the Ti53Zr27Ni20 quasicrystal was reported to show a weak temperature dependence with an upturn at the lowest temperatures [9]. Similar findings were reported for the Ti55 − xZr33Ni12 + x (x = 7, 9) quasicrystals [16], for which ferromagnetic properties were suggested on the basis of the observed enhanced magnetisation at low temperatures. However, it must be emphasised that the relevant hysteresis loops were hardy detected [16]. For the hydrided Ti53Zr27Ni20 quasicrystal a decrease of the magnetisation as a result of the lattice expansion and the subsequent reduction of interactions between magnetic moments of Ni atoms was reported
⁎
[9]. Transport properties of the amorphous and quasicrystalline Ti-ZrNi ribbons were investigated by means of electrical conductivity, the Seebeck coefficient and thermal conductivity measurements [17]. The results showed negative temperature coefficients for all ribbons; however the dependence was rather weak with no anomalous behaviour in the entire temperature range. On the other hand, the Seebeck (S) coefficient showed some anomalous behaviour at about 20 K for the amorphous samples, while for the quasicrystalline alloys the S(T) dependence could be nicely described using the phonon-drag and electron-phonon enhancement models. Taking all of these into account, it must be concluded that the origin of magnetism in the Ti-Zr-Ni quasicrystals is unclear. Moreover, the essential question whether the icosahedral Ti-Zr-Ni quasicrystal can exhibit long-range magnetic ordering, at least at low temperatures, remains unanswered. For this reason, we address this issue carefully for the icosahedral Ti45Zr38Ni17 quasicrystal by means of magnetometric and neutron diffraction studies. 2. Experimental The amorphous Ti45Zr38Ni17 nano-powder was synthesised by mechanical alloying that was performed in the Frisch Pulverisette 7 planetary mill. A stoichiometric mixture of commercially available titanium (99.99%), zirconium (99.99%) and nickel (99,999%) powders was used as the starting material. The material was enclosed in a
Corresponding author. E-mail address: [email protected] (J. Czub).
http://dx.doi.org/10.1016/j.jnoncrysol.2017.05.007 Received 7 February 2017; Received in revised form 8 May 2017; Accepted 10 May 2017 0022-3093/ © 2017 Elsevier B.V. All rights reserved.
Please cite this article as: Czub, J., Journal of Non-Crystalline Solids (2017), http://dx.doi.org/10.1016/j.jnoncrysol.2017.05.007
Journal of Non-Crystalline Solids xxx (xxxx) xxx–xxx
J. Czub et al.
Fig. 1. TEM image of the Ti45Zr38Ni17 quasicrystalline powder with the SAED pattern of nickel precipitations (the contribution from the quasicrystalline phase was extracted).
Fig. 2. Temperature dependence of the magnetic susceptibility for the quasicrystalline Ti45Zr38Ni17. Error bars are smaller than the data points.
platform. The measurements (magnetic susceptibility and isothermal magnetisation) were performed in the very broad temperature range starting from 2 K up to 700 K. The isothermal magnetisation studies were conducted in external magnetic fields up to 9 T. In order to ensure a good quality of isothermal magnetisation curves, the instrument was calibrated to eliminate spurious magnetic fields. Additionally, the internal calibration procedures excluded systematic errors originating from sample displacement. The standard samples were used to calibrate the temperature reading in the experimental range. The neutron diffraction measurements were performed at the E6 focusing powder diffractometer (BENSC-Berlin) using an incident neutron wavelength of 2.45 Å. The sample stage was equipped with the vertical cryo-magnet VM3 (AS Scientific) that enables measurement in the range of 1.5–300 K and in magnetic field up to 5 T. The sample powder weighting about 5 g was placed in a vanadium container. A small quantity of deuterided alcohol was poured inside the container in order to achieve mechanical stability of the powder during applying of magnetic field at low temperatures. The systematic errors related to the geometry of the diffractometer were calibrated using measurements of the Y2O3 standard. Also the efficiencies of the detectors banks were
stainless steel vial (45 ml), together with stainless steel balls (14 mm in diameter). The ball to powder weight ratio was equal to 8:1. Then the vial was evacuated by a scroll pump and then refilled with argon gas (99.999%). This procedure was repeated several times in order to remove spurious gases from the vial. The final argon pressure was maintained at 0.1 MPa. To avoid a temperature increase during MA, the alloying periods of 0.5 h were alternated with the rest periods of the 0.5 h. After 20 h of milling the vial was opened under argon atmosphere and the powder was mixed. Then alloying was continued for the next 20 h. The obtained powder was subsequently annealed under argon atmosphere for 12 h at 480 °C. That temperature was chosen according to the data presented in Fig. 2 in ref. [18]. The transmission electron microscopy (TEM) and X-ray diffraction (XRD) methods were used for a quality assessment of the obtained quasicrystal. The resulting quasicrystalline powder with the grains mean diameter of 250 nm was found to be homogeneous with extremely small traces of pure Ni at the boundaries of some grains as presented in Fig. 1. The magnetic measurements were carried out using the vibrating sample magnetometer (VSM) option of the Quantum Design PPMS-9 T 2
Journal of Non-Crystalline Solids xxx (xxxx) xxx–xxx
J. Czub et al.
Fig. 3. Thermal evolution of the isothermal magnetisation curves for the quasicrystalline Ti45Zr38Ni17. Error bars are smaller than the data points.
no change in the reflections intensities ratios is noticed with temperature raising from 1.5 K to 300 K. Therefore, it can be concluded that the icosahedral Ti45Zr38Ni17 quasicrystal does not exhibit the long-range magnetic order. Moreover, nickel atoms do not carry magnetic moment what allow us to classify the Ti45Zr38Ni17 quasicrystal as a Pauli paramagnet.
calibrated by measuring the patterns of a water-filled vanadium container.
3. Results and discussion The results of the VSM measurements performed in the wide temperature range are presented in Fig. 2. As apparent from the figure, the signal is extremely weak, however several interesting features can be observed. Firstly, the magnetic susceptibility χ(T) exhibits a prominent increase below 20 K, what is in consistency with the other reports concerning similar quasicrystals [9,16]. Secondly, the χ(T) is almost temperature-independent in the broad temperature range from 50 to 400 K. Lastly, a systematic decrease of χ(T) is evidenced above 400 K with a pronounced drop at about 650 K, above which temperature a further decrease is exhibited. The shape of the χ(T) curve above 400 K is typical for nano-crystalline nickel with relatively small clusters sizes [19]. The precise isothermal magnetisation studies in external magnetic fields up to 9 T presented in Fig. 3 shows that between 50 and 600 K an extremely weak ferromagnetic signal accompanied by tiny hysteresis loops can be observed. Apparently, this signal can be associated with nickel nano-clusters, not the quasicrystalline phase as it diminishes above 650 K. It is worth-noting that at 300 K the magnetic moment yields only 0.8 · 10− 4 μB/Ni at 9 T. A comparison between this value and the expected ~0.6 μB/Ni can be a good quantitative detection method of nickel nano-clusters precipitations in the quasicrystalline alloy. Finally, we address an issue of enhanced χ(T) at low temperatures. To clarify its origin, the high-statistics neutron diffraction patterns in the 1.5–300 K temperature range were collected. The data measured at temperature of 1.5 K at external magnetic field of 5 T compared to zero field are presented in Fig. 4. In the 1.5 K–300 K temperature range no changes in the diffraction patterns can be seen after applying magnetic field. On the other hand,
4. Concluding remarks The presented research addresses the very important problem of tracing magnetic impurities that are unavoidable in either MA or spinmelting techniques. Those impurities are undetectable by XRD and hardly detectable by TEM as their share in the alloy is extremely small. In our case, it is much less than 0.04 wt%, but as the ferromagnetic signal of Ni clusters the VSM technique is sensitive even for such small quantities of magnetic impurities. Moreover, due to the Curie temperatures (usually much above the room temperature) of the possible impurities (Fe, Co, Ni etc.), the high-temperature measurements give a first-hand evidence of their presence in quasicrystalline alloys. Usually, magnetometric properties of quasicrystals are measured below room temperature; hence the true origin of the observed ferromagnetic signal may be overlooked. For the discussed case, the icosahedral Ti45Zr38Ni17 alloy does not exhibit intrinsic magnetic properties in the entire stability range. Moreover, the results of the studies in external magnetic field exclude long-range magnetic ordering as well as the possibility of the magnetostriction effects in magnetic field up to 5 T, what is an important information considering possible applications of this alloy. Acknowledgements This research project was supported by the Polish-Norwegian Research Programme operated by the National Centre for Research and Development through the project ‘Nanomaterials for hydrogen storage’ number 210733, the European Commission under the 7th 3
Journal of Non-Crystalline Solids xxx (xxxx) xxx–xxx
J. Czub et al.
Fig. 4. The neutron diffraction patterns for the quasicrystalline Ti45Zr38Ni17 measured at 1.5 K at zero field and external magnetic field of 5 T, respectively. Traces of the Laves C14 phase are marked with asterisks. Error bars are smaller than the line widths.
Framework Programme through the ‘Research Infrastructure’ action of the ‘Capacities’ Programme, NMI3-II Grant number 283883.
[10] V. Azhazha, A. Grib, G. Khadzhay, S. Malikhin, B. Merisov, A. Pugachov, Phys. Lett. A 303 (2002) 87. [11] P. Weinberger, L. Szunyogh, C. Blaas, C. Sommers, P. Entel, Phys. Rev. B 63 (2001) 094417. [12] M.D. Nunez-Regueiro, E. Chappel, G. Chouteau, C. Delmas, Eur. Phys. J. B. 16 (2000) 37. [13] K.F. Kelton, Mater. Sci. Eng. A 375–377 (2004) 31. [14] J.P. Davis, E.H. Majzoub, J.M. Simmons, K.F. Kelton, Mater. Sci. Eng. 294–296 (2000) 104. [15] R.G. Hennig, A.E. Carlsson, K.F. Kelton, C.L. Henley, Phys. Rev. B 71 (2005) 144103. [16] Y. Lee, H. Shin, J.-Y. Kim, S.-W. Sohn, D.-H. Kim, IEEE Trans. Magn. 45 (2009) 2594. [17] Y.K. Kuo, N. Kaurav, W.K. Syu, K.M. Sivakumar, U.T. Shan, S.T. Lin, Q. Wang, C. Dong, J. Appl. Phys. 104 (2008) 06705. [18] D. Rusinek, J. Czub, J. Niewolski, Ł. Gondek, M. Gajewska, A. Takasaki, A. Hoser, A. Żywczak, J. Alloys Compd. 646 (2015) 90. [19] I.M.L. Billas, A. Châtelain, W.A. de Heer, Science 16 (1994) 1682.
References [1] B. Guiose, F. Cuevas, B. Décamps, E. Leroy, A. Percheron-Guégan, Electrochim. Acta 54 (2009) 2781. [2] S. Inoue, N. Sawada, T. Namazu, Vacuum 83 (2009) 664. [3] Y. Guan, J.-G. Liu, C.-W. Yan, Int. J. Electrochem. Sci. 6 (2011) 4853. [4] H. Lefaix, F. Prima, S. Zanna, P. Vermaut, P. Dubot, P. Marcus, D. Janickovic, P. Svec, Mater. Trans. 48 (2007) 278. [5] Yu.V. Zhernovenkova, L.A. Andreev, S.D. Kaloshkin, T.A. Sviridova, V.V. Tcherdyntsev, I.A. Tomilin, J. Alloys and Compd. 434-435 (2007) 747. [6] A. Takasaki, K.F. Kelton, J. Alloys Compd. 347 (2002) 295. [7] R.R. Shahi, T.P. Yadav, M.A. Shaz, O.N. Srivastava, S. van Smaalen, Int. J. Hydrog. Energy 36 (2011) 592. [8] A. Kocjan, P.J. McGuiness, S. Kobe, Int. J. Hydrog. Energy 35 (2010) 259. [9] H.S. Shin, S. Lee, Y. Jo, J. Kim, J. Korean Phys. Soc. 61 (2012) 1541.
4