EP0026237A1 - Metal amorphe comprenant un element de la famille du fer et du zirconium et articles obtenus a partir de celui-ci - Google Patents

Metal amorphe comprenant un element de la famille du fer et du zirconium et articles obtenus a partir de celui-ci Download PDF

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Publication number
EP0026237A1
EP0026237A1 EP80900728A EP80900728A EP0026237A1 EP 0026237 A1 EP0026237 A1 EP 0026237A1 EP 80900728 A EP80900728 A EP 80900728A EP 80900728 A EP80900728 A EP 80900728A EP 0026237 A1 EP0026237 A1 EP 0026237A1
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Prior art keywords
alloys
atomic
amorphous
less
sum
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EP80900728A
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German (de)
English (en)
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EP0026237B1 (fr
EP0026237A4 (fr
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Tsuyoshi Masumoto
Kiyoyuki Esashi
Masateru Nose
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Shingijutsu Kaihatsu Jigyodan
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Shingijutsu Kaihatsu Jigyodan
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/008—Amorphous alloys with Fe, Co or Ni as the major constituent

Definitions

  • the present invention relates to amorphous alloys and articles made of said alloys and particularly to amorphous alloys containing iron group elements and zirconium and articles made of said alloys.
  • Solid metals or alloys generally possess crystalline structures but if a molten metal is quenched rapidly (the cooling rate is approximately 10 4- 10 6 °C/sec), a solid having a non-crystalline structure, which is similar to a liquid structure and has no periodic atomic arrangement, is obtained.
  • Such metals or alloys are referred to as amorphous metals or alloys.
  • metals of this type are alloys consisting of two or more elements and can be classified into two groups, generally referred to as metal-metalloid alloys and inter-metal (metal-metal) alloys.
  • Fi-Ni-P-B Japanese Patent Laid-Open Application No. 910/74
  • Fe-Co-Si-B Japanese Patent Laid-Open Application No. 73,920/76
  • amorphous metals of combination of iron group elements and metalloid for example, Fe-P-C or Fe-Ni-P-B have excellent properties in view of strength, hardness, magnetic properties and the like, however, the structure of these alloys is unstable, so that the properties are considerably varied during ageing and this is a great practical drawback.
  • metal-metal amorphous alloys it has been known that the content of elements having a small atomic radius is not large, so that the embrittlement at a lower temperature than the crystallization temperature scarcely occurs. Even at a higher temperature than the crystallization temperature, the extent of embrittlement of these amorphous alloyys is smaller than that of metal-metalloid amorphous alloys.
  • metal-metal amorphous alloys contain a large amount of IVB and VB Group elements (Ti, Zr, V, Nb, Ta), so that the cost of raw material is very high and the melting point of those alloys is high and the molten metal is easily oxidized, therefore the production of these amorphous alloys is very difficult, so there is a disadvantage with difficulties in production of ribbon, sheet and wire in good shapes, which can be utilized for practical usages in industries. Furthermore, a problem exists that the strong ferromagnetic property which is characteristic to iron group elements, is lost.
  • An object of the present invention is to provide metal-metal amorphous alloys in which the above described drawbacks and problems of already known metal-metalloid amorphous alloys or metal-metal amorphous alloys are obviated and improved.
  • the present invention can accomplish the above described object by providing amorphous alloys containing iron group elements and zirconium as described hereinafter
  • novel amorphous alloys which contain a small amount of 8 to 20 atomic% of Zr as an element which contributes to formation of amorphous alloys of iron group elements of Fe, Co and Ni, scarcely causes variation of properties during ageing or embrittlement, have excellent properties of strength, hardness, corrosion resistance and heat resistance and do not deteriorate magnetic properties which are characteristic to iron group elements, and accomplished the present invention.
  • a major part of amorphous alloys of the present invention have practically very useful characteristics that these alloys can maintain the ductility and toughness even at temperature close to the crystallization temperature as shown in Fig. 1 and that even at a higher temperature than the crystallization temperature, the extent of embrittlement is lower than that of amorphous alloys containing a large amount of metalloid.
  • the embrittlement of amorphous alloys has been estimated by the process wherein an amorphous alloy ribbon is put between two parallel plates and the distance L between the parallel plates is measured and a value L when the sample ribbon is fractured by bending, is determined and the fracture strain is defined by the following formula wherein t is the thickness of the ribbon.
  • the inventors have measured the fracture strain s f with respect to the samples maintained at each temperature for 100 minutes for comparison of the amorphous alloys of the present invention with the metal-metalloid amorphous alloys following to this method.
  • the amorphous alloys of the present invention are lower in the crystallization temperature Tx than (Co 94 Fe 6 ) 0.75 Si 15 B 10 alloy which is relatively strong against the embrittlement among the metal-metalloid amorphous alloys, the temperature at which the embrittlement starts, is 100°C higher and this shows that the embrittlement is hardly caused.
  • Such properties are very advantageous, because the amorphous alloys of the present invention are not embrittled even by the inevitable raised temperature in the heat treatment or production step, when the alloys are used for tools, such as blades, saws, etc., for hard wires, such as tire cords, wire ropes, etc., and for composite materials with vinyl, rubber, etc.
  • the amorphous alloys are obtained by rapidly quenching molten alloys and a variety of quenching processes have been proposed.
  • the process wherein a molten metal is continuously ejected on an outer circumferential surface of a disc (Fig. 2(a)) rotating at a high speed or between two rolls (Fig. 2(b)) reversely rotating with each other at a high speed to rapidly cool the molten metal on the surface of the rotary disc or both rolls at a cooling rate of about 10 5 to 10 6 °C/see and to solidify the molten metal has been publicly known.
  • the amorphous alloys of the present invention can be similarly obtained by rapidly quenching the molten metal and by the above described various processes wire- shaped or sheet-shaped amorphous alloys of the present invention can be produced. Furthermore, amorphous alloy powders from about several pm to 10 pm can be produced by blowing the molten metal to a cooling copper plate using a high pressure gas (nitrogen, argon gas and the like) to rapidly cool the molten metal in fine powder form, for example, by an atomizing process. Accordingly, powders, wires or plates composed of amorphous alloys of iron group elements of the present invention, which contain zirconium, can be produced in commercial scale.
  • a high pressure gas nitrogen, argon gas and the like
  • the object of the present invention can be accomplished.
  • Hf is generally contained in an amount of 1 to 3% in raw ore of Zr to be used as one component of the alloys of the present invention and Hf is very similar to Zr in the physical and chemical properties, so that it is very difficult to separate both the components and refine Zr by usual refining process.
  • Hf is very similar to Zr in the physical and chemical properties, so that it is very difficult to separate both the components and refine Zr by usual refining process.
  • the object of the present invention can be attained.
  • composition of the first and second aspects of the present invention is shown in the following Table 1 and the reason for limiting the component composition is explained hereinafter.
  • Zr has the effect to act as an amorphous forming element for iron group elements but in the alloys of the first aspect of the present invention wherein only iron group elements and Zr are combined, at least 8 atomic% of Zr is necessary for amorphous formation and when Zr is less than 8 atomic%, even if the molten metal is rapidly quenched and solidified, for example in the composition of Co 95 Zr 5 or Fe 94 Zr 6 , a complete crystalline state is formed and in the composition of Co 93 Zr 7 , the ratio of the amorphous structure is about 50% in the whole structure.
  • the melting point is higher than 2,000°C and the production becomes difficult, so that the amount of Zr added must be from 8 to 20 atomic%.
  • Cr and Mo have the effect for improving the corrosion resistance and increase the strength, but when at least one element of Cr, Mo and W is added in the total amount of more than 40 atomic%, the embrittlement occurs and the production of alloys becomes difficult, so that the upper limit is 40 atomic%.
  • the amorphous formation of iron group elements can be attained.
  • the amount of Zr is less than 5 atomic% or more than 20 atomic%, the amorphous formation cannot be attained, so that Zr must be 5 to 20 atomic%.
  • the sum of the above described VIB Group elements and Zr is less than 8 atomic%, the amorphous formation is difficult, so that said sum must be not less than 8 atomic%.
  • Cr has particularly a large effect for improving the magnetic property but in any case of Cr, Mo and W, when the amount of these elements exceeds 20 atomic%, the strong ferromagnetic property is substantially lost or the magnetic induction is considerably reduced, so that for improvement of the magnetic properties, not more than 20 atomic% is preferable.
  • Ti, V, Nb, Ta, Cu and Mn are added in order to make the production of the alloys more easy, increase the strength and improve the thermal stability and the magnetic properties for magnetic materials.
  • V has the noticeably effect for raising the crystallization temperature and making the production of the alloys easy
  • Ti, Nb and Ta have the noticeable effect for raising the crystallization temperature and improving the thermal stability
  • Cu and Mn have the effect for making the production of the alloys easy
  • Cu is effective for improving the corrosion resistance.
  • the addition of more than 35 atomic% of any of these elements makes the production of the alloys difficult, so that the upper limit must be 35 atomic%.
  • Concerning each element of V, Nb and Ta belonging to VB Group the addition of more than 20 atomic% increases the embrittlement of the amorphous alloys, so that said amount is preferred to be not more than 20 atomic%.
  • Zr can form amorphous alloys of iron group elements by the synergistic effect with the above described elements, even if the amount of Zr is less than 8 atomic% of the lower limit of Zr in the alloys of the first aspect of the present invention. However, if said amount is less than 5 atomic% or more than 20 atomic%, the amorphous formation is infeasible, so that the amount of Zr must be 5 to 20 atomic%. Furthermore, when the sum of Zr and at least one of V, Nb, Ta, Cu, Mn, and Ti is less than 8 atomic%, the amorphous formation becomes difficult, so that said sum must be not less than 8 atomic%.
  • At least one element of Be, B, Al and Si belonging to IIA, IIIA or IVA Group aids the amorphous formation and not only makes the production of the alloys easy but also improves the magnetic properties and the corrosion resistance.
  • the magnetic induction is not only lowered but also the thermal stability which is one great characteristic of the amorphous alloys of the present invention is deteriorated, so that the amount of less than 13 atomic%, preferably less than 10 atomic% is preferred.
  • Zr can form the amorphous alloys of iron group elements by the synergistic effect with Be, B, AQ or Si, even if the amount is less than 8 atomic% of the lower limit of Zr in the alloys of the first aspect of the present invention.
  • the amount is less than 3 atomic% or more than 20 atomic%, the amorphous formation is infeasible, so that Zr must be 3 to 20 atomic%.
  • the sum of Zr and at least one of Be, B, A-e and Si is less than 8 atomic%, the amorphous formation becomes difficult, so that the sum must be not less than 8 atomic%.
  • At least one element of C, N, P, Ge, In, Sn, As and Sb belonging to IIIA, IVA or VA Group aids the formation of the amorphous alloys and makes the production of the amorphous alloy easy and particularly P improves the corrosion resistance in coexistence of Cr but when the amount exceeds 10 atomic%, the alloys are embrittled, so that said amount must be not more than 10 atomic%.
  • Zr can form the amorphous alloys of iron group elements by the synergistic effect with C, N, P, Ge, In, Sn, As or Sb, even when the amount of Zr is less than 8 atomic% of the lower limit of Zr in the alloys of the first aspect of the present invention.
  • Zr can form the amorphous alloys of iron group elements by the synergistic effect with the third elements mentioned in the above described groups (A)-(E), even if the amount is less than 8 atomic% of the lower limit of Zr in the first aspect of the present invention.
  • the amount is less than 5 atomic% or more than 20 atomic%, the amorphous formation is impossible, so that Zr must be 5 to 20 atomic%.
  • the sum of the above described elements and Zr is less than 8 atomic%, the amorphous formation becomes difficult, so that the above described sum must be not less than 8 atomic%.
  • amorphous alloy ribbons having a width of 2 mm and a thickness of 25 pm according to the present invention were produced.
  • Table 2 shows the component composition of the alloys of the present invention and the crystallization temperature and hardness of these alloys.
  • the alloys of the present invention have the crystallization temperature higher than about 410°C and particularly said temperature of the alloys consisting of multi-elements reaches about 600°C and the Vickers hardness is more than 500 and the alloys are very hard.
  • the magnetic induction is high as 7,000 to 15,800 and the coercive force is relatively low, and the alloys show the soft magnetic property.
  • the amorphous alloy having the composition of Fe 45 Co 36 Cr 9 Zr 10 in Table 3 was heated at 465°C for 10 minutes to remove the strain, and then heated at 100°C for 1,000 minutes.
  • the coercive force was 0.03 Oe and no variation was found. This shows that the alloy of the present invention is more magnetically stable than a prior metal-metalloid amorphous alloy, for example, Fe 5 Co 70 Si 15 B 10 .
  • the alloy Fe 5 Co 70 Si 15 B 10 was heated at 100°C for 1,000 minutes, the coercive force varied from 0.01 Oe to 0.06 Oe.
  • Ribbon-formed samples of the alloys of the present invention were immersed in aqueous solutions of 1N-H 2 SO 4 , 1N-HCl and 1N-NaCl at 30°C for one week to carry out a corrosion test.
  • the obtained results are shown in the following Table 4 together with the results of stainless steels.
  • the amorphous alloys containing Cr or Mo have particularly excellent corrosion resistance but in other alloys, the corrosion resistance is equal to or higher than that of stainless steels. That is, the amorphous alloys consisting of iron group elements and Zr , for example, Fe 54 Co 36 Zr 10 are inferior to 13% Cr steel in the corrosion resistance against H 2 SO 4 and HCl but possess 40 times higher corrosion resistance against NaCl than 13% Cr steel. Furthermore, when Cr and Mo are added, such alloys have more excellent properties than 304 steel and 316 L steel.
  • the alloys of the present invention are completely novel amorphous alloys, the composition range of which has been generally considered not to form amorphous alloys, and which are completely different from the previously known metal-metalloid amorphous alloys and also metal-metal amorphous alloys.
  • the alloys wherein Fe and/or Co is rich are high in the magnetic induction and relatively low in the coercive force and are very excellent in the thermal stability, so that these alloys also have the characteristics that the magnetic and mechanical properties are thermally stable.
  • the crystallizing temperature is raised, the thermal stability is improved and the corrosion resistance can be noticeably improved.
  • the amorphous alloys of the present invention can greatly improve the thermal stability, which has not been satisfied in the well known metal-metalloid amorphous alloys and have the high strength and toughness which are the unique properties of amorphous alloys. Accordingly, these alloys can be used for various applications which utilize effectively these properties, for example, materials having a high strength, such as composite materials, spring materials, and a part of the alloys can be used for materials having a high magnetic permeability and materials having a high corrosion resistance.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Soft Magnetic Materials (AREA)
  • Arc Welding Control (AREA)

Abstract

Un alliage amorphe de type metal-metal possede une composition fondamentale representee par XaZc (dans laquelle X represente un, deux atomes ou plus de Fe, Co et Ni, a represente 80-92 atomes%, Z represente Zr et c represente 8-20 atomes%, la somme de a et c etant 100 atomes%) et contenant du Zr en tant que metal pour rendre l'alliage amorphe, et des articles prepares a partir de cet alliage. En comparaison avec les alliages amorphes du type metal-semimetal, cet alliage subit moins de changements avec le temps et moins de fragilisation, a cause des proprietes essentiellement metal-metal de cet alliage et de plus presente une excellente resistance, durete resistance a la corrosion, resistance a la chaleur, etc., tout en retenant les proprietes magnetiques du fer.
EP19800900728 1979-04-11 1980-10-23 Metal amorphe comprenant un element de la famille du fer et du zirconium et articles obtenus a partir de celui-ci Expired EP0026237B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP4384879A JPS55147481A (en) 1979-04-11 1979-04-11 Protector for arc welding
JP43838/79 1979-04-11

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EP0026237A1 true EP0026237A1 (fr) 1981-04-08
EP0026237A4 EP0026237A4 (fr) 1982-05-26
EP0026237B1 EP0026237B1 (fr) 1986-07-16

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EP19800900728 Expired EP0026237B1 (fr) 1979-04-11 1980-10-23 Metal amorphe comprenant un element de la famille du fer et du zirconium et articles obtenus a partir de celui-ci

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011001784A1 (de) * 2011-04-04 2012-10-04 Vacuumschmelze Gmbh & Co. Kg Verfahren zur Herstellung einer Feder für ein mechanisches Uhrwerk und Feder für ein mechanisches Uhrwerk
DE102011001783A1 (de) * 2011-04-04 2012-10-04 Vacuumschmelze Gmbh & Co. Kg Feder für ein mechanisches Uhrwerk, mechanisches Uhrwerk, Uhr mit einem mechanischen Uhrwerk und Verfahren zur Herstellung einer Feder

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8075712B2 (en) 2005-11-14 2011-12-13 Lawrence Livermore National Security, Llc Amorphous metal formulations and structured coatings for corrosion and wear resistance

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1202412B (it) * 1976-07-27 1989-02-09 Allied Chem Leghe metalliche amorfe contenenti zirconio

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011001784A1 (de) * 2011-04-04 2012-10-04 Vacuumschmelze Gmbh & Co. Kg Verfahren zur Herstellung einer Feder für ein mechanisches Uhrwerk und Feder für ein mechanisches Uhrwerk
DE102011001783A1 (de) * 2011-04-04 2012-10-04 Vacuumschmelze Gmbh & Co. Kg Feder für ein mechanisches Uhrwerk, mechanisches Uhrwerk, Uhr mit einem mechanischen Uhrwerk und Verfahren zur Herstellung einer Feder
DE102011001784B4 (de) * 2011-04-04 2018-03-22 Vacuumschmelze Gmbh & Co. Kg Verfahren zur Herstellung einer Feder für ein mechanisches Uhrwerk und Feder für ein mechanisches Uhrwerk
DE102011001783B4 (de) 2011-04-04 2022-11-24 Vacuumschmelze Gmbh & Co. Kg Feder für ein mechanisches Uhrwerk, mechanisches Uhrwerk, Uhr mit einem mechanischen Uhrwerk und Verfahren zur Herstellung einer Feder

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EP0026237B1 (fr) 1986-07-16
JPS55147481A (en) 1980-11-17
EP0026237A4 (fr) 1982-05-26

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