EP 0132907 B1 Europaisches Patentamt 0132907 B1 European Patent Office @ Publication number: » » ® Office européen des brevets EUROPEAN PATENT SPECIFICATION @® Date of publication of patent specification: 02.11.88 @ Int.ci.t: C22 C 1/00 34301693.2 @® Application numbe @® dsto of fling: 13.03.84 @ Method of producing amorphous metallic material. @ Proprietor: OSAKA UNIVERSITY 1-1 Yamadaoka ‘Suita City Osaka-Fu (JP) @ Priority: 16.07.85 4 128709/83 @ Date of publication of application: : 13.02, Bulletin 65/07 Suita City Osake-Fu (JP) Inventor: Fujita, Hiroshi atedal, §-Chome Ibaraki City Osaks-Fu (JP) @ Poblication of the grant of the patent: 02.11.88 Bulletin 88/44 @ Designated contracting tates: BEDEFRGS NL Representative: Rooney, Paul Blase et al D.Young & Co, 10 Staple inn London WC1V 7RD (68) @ References cited: CHEMICAL ABSTRACTS, vol. 100, no. 26, 11th June 1924, page 270, no. 196258r, Columbus, ‘Ohio, US; H. FUJITA et al.:"A crystalline- ‘amorphous transition in nickel-titanium alloys induced by high-energy electron LAWRENCE BERKELEY LAB,,REP.r LBL 1983, LBL 16031 CHEMICAL ABSTRACTS, vol. 99, no. 14, rd October 1983, page 237, no. 109217, Columbus, Ohio, US; G. VAN TENDELOO et al "Ordering in alloys under electron irradiation” & PROC. INT. CONF. SOLID-SOLID PHASE. ‘TRANSFORM. 1981 (Pub. 1982), 305-8 Roferences cited: CHEMICAL ABSTRACTS, vol. 99, no. 10, 5th ‘September 1983, page 494, no. 78788e, Columbus, Ohio, US; V.V. CHEKIN et ai "Structure of intermetallics and phase transformations in zirconium-based alloys during annealing and irradiation by a pulsed electron beam’ ‘Note: Within nine months from the publication of tie mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall bo files in a written reasoned statement. It shall not be deamed to have been filed until the opposition fee has been paid. (Art. 9911) European patent convention). Courier Prass, Leamington Spe, England.0 132 907 @ Rotoronces cited: CHEMICAL ABSTRACTS, vol. 99, no. 6, 8th August 1983, page 224, no. 42116r, Columbus, ‘Ohio, US; H.C. LIU etal: "radiation induced ‘order-disorder in nickel-aluminum (NigAl) and NiAW & ACTA METALL 1983, 31(6), 863-72 CHEMICAL ABSTRACTS, vol. 98, no. 4, 26th January 1983, page 239, no. 20751x, Columbus, Ohio, US; H.C. LIU et a.: "Defect aggregation and disordering in nickel-aluminum (NI3Al and NiAl) by electron irradiation” & PHASE STAB. IRRADIAT., PROC. SYMP. 1980 (Pub. 1981), 343-55, (CHEMICAL ABSTRACTS, vol. 95, no. 12, 3rd ‘September 1981, page 225, no. 101522p, Columbus, Ohio, US; Li. IVANOV et: "Formation of the MgBAIB phase in an unsaturated aluminum-magnesium solid solution in electron irradiation” & DOKL, AKAD. NAUK SSSR 1981, 257(5), 1175-8 Japanese Journal Applied Physics, vol.21, no. 8, 1982, pp. L494-L496 Japanese Journal of Applied Physics, vol. 22, no. 2, 1983, pp. L94-L9610 20 35 4s 0 132 907 Description ‘This invention relates to a method of producing amorphous non-crystalline metallic material by converting at least the surface of an intermetallic compound to obtain an amorphous phese therein. ‘Amorphous metallic materials such as amorphous metals have recently attracted interest as new materials with many uses over a broad industrial field because of their excellent physical and chemical properties. it has been proposed to produce these amorphous metals by rapidly cooling a molten metal and by ‘vapor deposition but the former has been the most popular method. In this proposed method, a metal is heated and melted and the molten metal is sprayed onto a quickly rotating copper plate through anozzie to ‘quench the molten metal, whereby the desired amorphous metal is obtained. In this proposed method, itis fssential to obtain @ high quenching rate, so that the form of the product produced by this method is limited to 2 ribbon or to a foll. Additionally with this proposed method it is impossible to obtain @ thick product and impossible to make only a surface thereof amorphous. Furthermore, itis difficult with the proposed method to control the quenching rate and therefore, its impossible to control the rate of change to the amorphous state or degree of non-crystallinity of the product. These drawbacks are inevitably ‘caused and the commercially applicable range of the resulting product is narrow and limited. in the other or Tater proposed method, a metal is vaporized, condensed and grown on a base plate to obtain amorphous metal. In this method, only a thinner product than in the former method can be produced and the cost is very high, Electron-irradition induced amorphization of NiTi-alloys is known from Vol. 21, No. 8, 1982, pp. L4g4—L486 and Vol. 22, No. 2, 1983, pp. L94—L96 of Japanese Journal of Applied Physics. ‘According to the present invention there is provided a method for converting at least the surface of an intermetallic compound in the form of FeTi, ZraAl, CuZr, CusTie, CosTi, CusaZt7, 2raNi, NByNig, MoNi, MnzTI, CuTI, VaSi or iron zirconium to obtain an amorphous phase therein, characterised by the steps of: {a) irradiating said intermetallic compound with an electron beam having a flux density within @ rango of from 85 x 10" to 1.3 x 10% e/m®.see, to introduce a lattice defect into said intermetallic compound; {(b) heating said intermetallic compound to a temperature within the range of from 160 to 290°K; and {c) maintaining said electron beam irradiation for a time in the range of from 60 to 1020 seconds to obtain en amorphous phase in at least the surface of said intermetallic compound. “The method of the invention may thus at least minimise the foregoing drawbacks associated with the prior art methods, may enable amorphous metallic materials having a desired shepe and size to be produced cheaply, and may ensure rapid transformation of a metallic material into amorphous metallic ‘material. “The term “damage” used herein means that the arrangonient of atoms forming a crystal is disturbed, ‘The method of the present invention can be used to produce a pipe, rod: plate- or complicated shape ‘amorphous metellic material or metal product or an amorphous metallic material or metal coated metal ‘The term “amorphous metallic material” used herein means not only amorphous metal and ‘amorphous intermetallics but also an amorphous metal or intermetallic coated metal or intermetallic. “The amorphous metallic materials produced by the method of the present invention can be used for a shape memory alloy and in this case, the shape memory alloy can safely be used by a memory erasing method. For a better understanding of the present invention, reference will now be made by way of example to the accompanying drawing, in which: Figure 1 is a schematic perspective view showing a step for irradiating a metal with an electron beam ‘according to the method of the present invention. ‘in Figure 1, metallic material such as a metal 1 of @ given shape or form is irradiated with a high speed ‘electron beam 2 having an energy sufficient to damage the metal, that is having a flux density in the range Of from 8.5 x 10® to 1.3 x 10" elm?.see. The irradiation is performed by keaping the electron beam flux at a Value greeter than a critical value determined by the metal and controlling the irradiating temperature determined by the metal and the electron beam flux. By irradiation under such conditions, lattice defects introduced into the metal by damage caused by the irradiation gradually are accumulated in the metal end the concentration is increased with Irradiation time. When this concentration reaches © given value determined by the metal, the irradiated metal is transformed into amorphous (non-crystalline) metal ‘In the method of the present invention, the introduction of the lattice defect is performed by using an electron beam having a far higher penetrability than other particle rays, 80 that when the material or metal being irradiated is a plate or a wire having a thickness of less than several um, the whole of the metallic material or metal ofthe plate or wire is transformed into amorphous metal. Alternatively, when the metallic ‘material such as metal being irradiated has @ greater thickness than the above decribed value, at least @ surface layer region having 2 thickness of several um in the base material or metel has an amorphous pphase formed therein. Examples of irradiating conditions necessary for the formation of amorphous ‘metallic material or metal are shown in the following Table 1.0 132 907 TABLE 1 MATERIAL] ELECTRON | ELECTRON IRRADIATING | IRRADIA- ENERGY | BEAMFLUX TEMPERATURE| TING TIME (in Mev) | (in e/m?.sec) (nek) (in seconds) FegTi 2 1.3 x 1024 290 100 Zr2Al 2 1.3 x 1028 160 300 cuzr 2 13 x 1024 250 6 cutis | 2 1.0 x 1024 230 120 Cogti 2 dad x 1024 160 180 Curozr? | 2 1.2 x 1024 160 60 2r2Ni 2 1.0 x 1024 170 120 NorNig | 2 9.5 x 1023 160 120 ‘MoNi 2 1.2 x 1024 160 1,020 MngTi 2 1.2.x 1024 170 300 cui 2 1.2 x 1024 160 010 bs 3 “5 50 5s 6 © 132 907 ‘As shown in Table 1, the intermetallic compounds can be converted into amorphous metal by iradiation with an electron beam having @ flux density in the range of from 9.5 x 10% to 1.3 x 10% @/iné.sec, for an irradiation time in the range of from 60 to 1020 seconds, and at an irradiation temperature in the range of from 160 to 290°K. (Other metals or intermetallics sultable for utilisation in the method of the invention to form amorphous ‘metal include V,Si and iron-zirzonium compound. “The merits of the method of the present invention are as follows. (1) No quenching step as in the prior artis neaded, so that even if an irradiated article is of a large size, the lattice defect is introduced by the irradiation of the electron beam and the region where the lattice defect is accumulated of concentrated can be formed into an amorphous phase. Therefore, its possible to ‘coat the inner wall and outer wall of metal pipes having various diameters, with an amorphous metal having excellent mechanical strength and corrosion resistance. {2} A quenching step, which is difficult to control, is not performed, and therefore the formed ‘amorphous metal is even and the rate of transformation to the amorphous state ean be continuously controlled by varying the irradiated dosage. (8) By utlizing the property that the olectron beam can be easily curved by an electro-magnetic field the shape of the irradiated region, that is the region capable of being transformed into amorphous metal, may optionally be controlled. Namely, an amorphous region having a desired size and shape, either large in area or very smail having a diameter of 1 um or less, may be formed in a given metal base with 9 good connection to the metal of the base. ‘A method for converting at least the surface of an intermetallic compound in the form of FesTi, ZraAl, Cuz, CusTis, COT, CureZty, ZrNi, NbyNig, MONi, MngTi, CuTi, VsSi or iron-zirconium to obtain an ‘amorphous phase therein, characterised by the steps of: (a) irradiating said intermetallic compound (1) with an electron beam (2) having a flux density within a range of from 9.5 x 10% to 1.3 x 10 elm®sec, to introduce a lattice defect into said intermetallic compound { {(b) heating said intermetallic compound (1) to a temperature within the range of from 160 to 290K; and {6} maintaining said electron beam irradiation for a time in the range of from 60 to 1020 seconds to obtain an amorphous phase in at least the surface of said intermetallic compound (1). Patentanspruch Verfahren zur Umwendlung wenigstens der Oberflache einer intermetallischen Verbindung in der Form von Fes, ZreAl, Cuzr, CusTla, COzTI, CugZry, ZrzNi, Nb;Nigy MON, MnTi, CuTi, V3SI oder von Eisen- Zirconium, um eine amorphe Phase darin zu erhaiten, gekennzeichnet durch die Stufen, bei denen man (a) die intermetalische Verbindung (1) mit einem Elektronenstrahl (2) mit einer FluSdichte im Bereich von 9,5 x 10 bis 1,3 x 10% e/m®.sec bestrahit, um eine Gittorstérung in die intermetalische Verbindung (1) einzufahren, {(6) die intermetallische Verbindung (1) auf eine Temperatur im Bereich von 160 bis 290°K erhitat und {c} die Elektronenstrahibestrahlung wahrend einer Zeit im Bereich von 60 bis 1020 sec aufrechterhait, tum eine amorphe Phase in wenigstens der Oberflache der intermetallischen Verbindung (1) zu erhalten. Revendication Procédé pour convertir au moins la surface d'un composé intermétallique, se présentant sous la forme FegTi, Zr9Al, CUZt, CusTi, CO;T, CuyeZty, ZraNi, ND;Nig, MONi, MnzTi, CuTi, VaSi ou fer-zirconium, pour obtenir une phase emorphe a l'intérleur de co composé, caractérisé en ce qu'il comprend les étapes consistant: {a} & exposer ledit composé intermétallique (1) & un faisceau électronique (2) ayant une densité de fluence comprise entre 9,5.10% et 1,3.10* elm?.s, pour introduire dans ledit composé intermétallique (1) un défaut du réseau cristallin; (b} & chauffer ledit composé intermétallique (1) & une température comprise entre 160 et 290°; et (c)& maintenir adite exposition au falsceau électronique pendant un temps compris entre 60 et 1020 secondes, pour abtenir une phase amorphe dans au moins la surface dudit composé intermétellique (1).