EP0475101B1 - Hochfeste Legierungen auf Aluminiumbasis - Google Patents

Hochfeste Legierungen auf Aluminiumbasis Download PDF

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Publication number
EP0475101B1
EP0475101B1 EP19910113667 EP91113667A EP0475101B1 EP 0475101 B1 EP0475101 B1 EP 0475101B1 EP 19910113667 EP19910113667 EP 19910113667 EP 91113667 A EP91113667 A EP 91113667A EP 0475101 B1 EP0475101 B1 EP 0475101B1
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EP
European Patent Office
Prior art keywords
aluminum
matrix
intermetallic compounds
alloys
group
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EP19910113667
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English (en)
French (fr)
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EP0475101A1 (de
Inventor
Junichi Nagahora
Takeshi Terabayashi
Makoto Kawanishi
Katsuyuki Taketani
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YKK Corp
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YKK Corp
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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
    • C22C45/08—Amorphous alloys with aluminium as the major constituent

Definitions

  • the present invention relates to aluminum-based alloys having a high strength together with a high hardness, high wear resistance, high heat resistance and superior toughness.
  • Aluminum-based alloys having a high strength and a high heat resistance have heretofore been produced by a liquid quenching method.
  • Japanese Patent Application Laid-Open No. 1-275732 & EP-A-0339676 discloses aluminum-based alloys produced by the liquid quenching method and the aluminum-based alloys have an amorphous or fine crystalline structure and are superior alloys characterized by having an advantageous combination of properties of high strength, high heat resistance and high corrosion resistance.
  • the aluminum-based alloys disclosed in the above Japanese Patent Application Laid-Open No. 1-275732 are superior alloys having a high strength, high heat resistance and high corrosion resistance and also exhibit a high degree of processability as high strength materials. However, the aluminum-based alloys should still be improved in their toughness for applications as materials where a high toughness is required.
  • the present invention provides a high strength aluminum-based alloy having a composition consisting of the general formula (I) Al a M b Ln c or the general formula (II) Al a M b X d Ln c , wherein: M is at least one metal element selected from the group consisting of Co, Ni, and Cu; X is at least one metal element selected from the group consisting of V, Mn, Fe, Mo, Ti and Zr; Ln is at least one element selected from the group consisting of Y, rare earth elements and Mm (misch metal), which is a composite of rare earth elements; and a, b, c and d are, in atomic percentage, 75 ⁇ a ⁇ 97, 0.5 ⁇ b ⁇ 15, 0.5 ⁇ c ⁇ 10 and 0.5 ⁇ d ⁇ 3.5, the alloy being composed of an aluminum matrix or an aluminum supersaturated solid solution matrix having an average crystal grain size of from 0.1 to 80 »m and containing therein a uniform dispersion of meta
  • FIG. 1 shows a schematic illustration of a single-roller melt spinning apparatus employed to prepare a thin ribbon by rapidly quenching and solidifying alloys of the present invention.
  • FIG. 2 is a graph showing the test results of alloys of the present invention.
  • the aluminum-based alloys of the present invention can be obtained by rapidly solidifying a melt of the alloy having the composition as specified above by employing liquid quenching techniques.
  • the liquid quenching techniques are methods for rapidly cooling a molten alloy and, particularly, single-roller melt-spinning, twin-roller melt-spinning and in-rotating-water melt-spinning are effective. In these techniques, a cooling rate of about 104 to 106 K/sec can be obtained.
  • the molten alloy is ejected from the bore of a nozzle onto a roll of, for example, copper or steel, with a diameter of about 30 - 300 mm, which is rotating at a constant rate within the range of about 300 - 10000 rpm.
  • a roll of, for example, copper or steel with a diameter of about 30 - 300 mm, which is rotating at a constant rate within the range of about 300 - 10000 rpm.
  • a jet of the molten alloy is directed, under application of a back pressure of argon gas, through a nozzle into a liquid refrigerant layer having a depth of about 1 to 10 cm and which is held by centrifugal force in a drum rotating at a rate of about 50 to 500 rpm.
  • the angle between the molten alloy ejecting from the nozzle and the liquid refrigerant surface is preferably in the range of about 60° to 90° and the relative velocity ratio of the ejected molten alloy to the liquid refrigerant surface is preferably in the range of about 0.7 to 0.9.
  • the alloy of the present invention can also be obtained in the form of a thin film by a sputtering process. Further, rapidly solidified powder of the alloy composition of the present invention can be obtained by various atomizing processes (for example, high pressure gas atomizing) or spray process.
  • the grain sizes of individual crystals can be measured from the contrast resulting from the difference in crystal orientation of the respective crystals which contrast is observed in a bright-field of about 1000 to 100,000 magnifications.
  • the individual crystals can not be distinctly observed in the bright-field, they can be examined through observation in a dark-field of a certain electron diffraction spot.
  • the average particle size of intermetallic compounds can be examined in the same way. The presence of intermetallic compounds can be confirmed through an ordinary electron diffraction. The intermetallic compounds can be easily distinguished from an aluminum matrix in the electron diffraction image.
  • the alloys of the present invention can be obtained by the above-mentioned single-roller melt-spinning process, twin-roller melt spinning process, in-rotating-water melt spinning process, sputtering process, various atomizing processes, spraying process, mechanical alloying process, mechanical grinding process, etc. It is possible to control the average sizes of crystal grains and intermetallic compound particles of the resultant alloys by appropriately varying the processing conditions according to the need.
  • alloys having an amorphous structure can be obtained but the amorphous structure decomposes into a crystalline structure when being heated to a certain temperature or higher.
  • the alloys of the present invention can also be obtained by the thermal decomposition of the amorphous structure and, in this decomposition process, the average grain size can be controlled within the range of the present invention by properly adjusting the heating conditions.
  • a, b, c and d are limited to the atomic percentages ranging from 75 to 97%, 0.5 to 15%, 0.5 to 10% and 0.5 to 3.5%, respectively.
  • the reason for these limitations is that when a, b, c and d are outside the specified ranges, the resultant alloys become brittle and toughness and high strength can not be achieved. Consequently, alloys having properties contemplated by the present invention can not be obtained by industrial rapid quenching processes employing a liquid quenching or the like.
  • the M element is at least one metal element selected from the group consisting of Co, Ni and Cu.
  • the M element has a relatively poor diffusion tendency in an aluminum matrix, it forms various stable or metastable fine intermetallic compounds in coexistence with the Ln element.
  • the resultant intermetallic compounds are finely dispersed throughout the aluminum matrix, thereby effectively preventing an extraordinary grain coarsening as well as strengthening the matrix. Consequently, the M element considerably improves the hardness and strength of the alloys and stabilizes fine crystalline phases both at room temperature and at an elevated temperature, thereby providing an improved heat resistance.
  • the X element is at least one metal element selected from the group consisting of V, Mn, Fe, Zr, Ti and Mo. Although the X element exhibits a relatively low diffusion tendency in an aluminum matrix, it has an effect in retaining the room temperature hardness and strength up to elevated temperatures. Further, addition of the X element in amounts of 0.5 to 3.5 atomic percent is advantageous, especially when processed materials are produced by a hot plastic forming, because the X element addition provides ductility.
  • the Ln element is at least one element selected from the group consisting of Y, rare earth elements and Mm (misch metal).
  • the Ln element also has a low diffusion ability in an aluminum matrix but, when it is contained in coexistence with the foregoing M element, it forms stable intermetallic compounds and makes a great contribution to stabilization of the fine crystalline structure.
  • an amorphous phase or an average crystal grain size of less than 0.1 »m can also be obtained.
  • the ductility i.e., toughness
  • the strength is high.
  • an average crystal grain size of 0.1 »m or greater is essential.
  • an average crystal grain size exceeding 80 »m may be obtained by employing an excessively reduced cooling-rate or an excessively increased processing temperature for the thermal decomposition, but, in such conditions, the strength will be drastically reduced. Therefore, the object of the present invention can not be achieved.
  • the particle size of intermetallic compounds is limited to the range of 10 to 500 nm because when the size is outside the specified range, the intermetallic compounds do not act as a matrix strengthening component.
  • an excessively increased cooling rate or an inadequate processing temperature for the thermal decomposition results in intermetallic compounds having a particle size of less than 10 nm.
  • Such fine intermetallic compounds have no effect in strengthening the aluminum matrix.
  • the intermetallic compounds excessively dissolve in the matrix as a solid solution, a problem of brittleness may arise.
  • the cooling rate is excessively reduced or the processing temperature of the thermal decomposition is too high, the resultant intermetallic compounds have an average particle size exceeding 500 nm and produce no strengthening effect. That is, the dispersed particles become too large and it does not exhibit any strengthening effect.
  • greatly improved Young's modulus, high-temperature strength and fatigue strength can be obtained.
  • the average crystal grain size and the intermetallic compound particle size are controlled to small sizes.
  • the crystal grain size and the intermetallic compound particle size are controlled to large sizes. In such a manner, the properties can be controlled according to the purposes.
  • the alloys of the present invention can be obtained in the form of ribbons, thin strips or powders and can be readily processed into bulk materials using hot plastic forming processes, such as extrusion, press forming or forging, within the temperature range of one-fifth (1/5) to one half (1/2) the melting point of the alloys. Also, bulk materials can also be readily obtained from the alloys having an amorphous structure or a supersaturated solid solution structure by appropriately controlling the powder consolidation conditions.
  • the alloys of the present invention exhibit superior properties as extremely tough and strong alloys and, thus, are especially useful as highly reliable structural materials.
  • Molten alloy 3, having a predetermined composition was prepared using a high-frequency melting furnace and charged into a quartz tube 1 having a small opening 5 (diameter: 0.5 mm) at the tip thereof, as shown in FIG. 1. After being heated to melt the alloy 3, the quartz tube 1 was disposed right above a copper roll 2. Then, the molten alloy 3 contained in the quartz tube 1 was ejected from the small opening 5 of the quartz tube 1 under the application of an argon gas pressure of 0.7 kg/cm2 and brought into contact with the surface of the copper roll 2 rapidly rotating at a rate of 1,000 rpm. The molten alloy 3 was rapidly quenched and solidified into an alloy thin ribbon 4.
  • alloy powders having an average particle size of not greater than 45 »m and consisting of an amorphous phase, were prepared by an atomizing process with a high-pressure gas (Ar) and consolidated into bulk materials by a powder extrusion process described below.
  • Ar high-pressure gas
  • the powders were compacted at 230 °C in a vacuum to provide green compacts, 24 mm in diameter and 30 mm long, having relative densities of 75 to 85% and formed into billets for extrusion.
  • the billets were extruded at 450 °C to produce extruded bars, about 6 mm in diameter, with an extrusion ratio of 15 and machined into test pieces for a tensile test. (measuring part: 3 mm in diameter and parallel parts: 15 mm).
  • the test results are shown in Table 2.
  • test pieces were cut from the respective extruded bars for observation by TEM and average crystal grain size measurements were conducted. It was found that all of the test pieces had an average crystal grain size within the range of 5 to 60 »m and had a structure composed of a crystalline matrix containing uniformly dispersed intermetallic compounds of 20 to 50 nm.
  • Table 2 Composition (at.
  • test pieces had high strength and ductility and were superior as structural materials.
  • a further billet of Al87Ni6Mm7 for extrusion was prepared in the same manner as described above and extruded at various temperatures to produce extruded bars.
  • the changes in the tensile strength, hardness and tensile elongation were examined with respect to the changes in the average crystal grain size. The results are shown in FIG. 2.
  • the average crystal grain size was at least 0.1 »m
  • the tensile elongation was at least 0.5%.
  • an average grain size of not more than 80 »m provided a high hardness of 200 (DPN), which was more than 2 times the hardness (Hv: 50 to 100 DPN) of a commercial aluminum-based alloy, coupled with a high strength level of at least 650 (MPa).
  • a strength of at least 800 (MPa), a hardness of at least 230 (DPN) and an elongation of at least 1.2 (%) are the most desirable conditions for structural materials and it will be noted that these conditions can be satisfied within an average crystal grain size range of 22 to 60 »m.
  • the alloys of the present invention have a high degree of hardness, strength, wear resistance and heat resistance together with a superior toughness and are useful as highly reliable materials in structural components, etc.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Continuous Casting (AREA)

Claims (2)

  1. Hochfeste Legierung auf Aluminiumbasis, die eine Zusammensetzung hat, welche aus der allgemeinen Formel (I) besteht



            AlaMbLnc,



    worin:
       M wenigstens ein metallisches Element, ausgewählt aus der aus Co, Ni und Cu bestehenden Gruppe, ist;
       Ln wenigstens ein Element, ausgewählt aus der aus Y, Seltenerdelementen und Mm (Mischmetall), was ein Verbund aus Seltenerdelementen ist, bestehenden Gruppe, ist; und
       a, b und c in Atomprozentsätzen sind:
    75 ≦ a ≦97 , 0,5 ≦ b ≦ 15 , 0,5 ≦ c ≦ 10,
    wobei die Legierung besteht aus einer Aluminiummatrix oder einer an Aluminium übersättigten festen Lösungsmatrix, die eine durchschnittliche Kristallkorngröße von 0,1 bis 80 »m hat und die hierin eine gleichförmige Dispersion von Teilchen einer metastabilen oder stabilen Phase enthält, zusammengesetzt aus intermetallischen Verbindungen, welche zwischen dem Wirtselement (Matrixelement) und den obengenannten Legierungselementen und oder zwischen den Legierungselementen gebildet sind, wobei die intermetallischen Verbindungen eine Durchschnittsteilchengröße von 10 bis 500 nm besitzen.
  2. Hochfeste Legierung auf Aluminiumbasis, die eine Zusammensetzung hat, welche aus der allgemeinen Formel (II) besteht



            AlaMbXdLnc,



    worin:
       M wenigstens ein metallisches Element, ausgewählt aus der aus Co, Ni und Cu bestehenden Gruppe, ist;
       X wenigstens ein metallisches Element, ausgewählt aus der aus V, Mn, Fe, Mo, Ti und Zr bestehenden Gruppe, ist;
       Ln wenigstens ein Element, ausgewählt aus der aus Y, Seltenerdelementen und Mm (Mischmetall), was ein Verbund aus Seltenerdelementen ist, bestehenden Gruppe, ist; und
       a, b, c und d in Atomprozentsätzen sind:
    75 ≦ a ≦97 , 0,5 ≦ b ≦ 15 , 0,5 ≦ c ≦ 10 und 0,5 ≦ d ≦ 3,5,
    wobei die Legierung besteht aus einer Aluminiummatrix oder einer an Aluminium übersättigten festen Lösungsmatrix, die eine durchschnittliche Kristallkorngröße von 0,1 bis 00 »m hat und die hierin eine gleichförmige Dispersion von Teilchen einer metastabilen oder stabilen Phase enthält, zusammengesetzt aus intermetallischen Verbindungen, welche zwischen dem Wirtselement (Matrixelement) und den obengenannten Legierungselementen und oder zwischen den Legierungselementen gebildet sind, wobei die intermetallischen Verbindungen eine Durchschnittsteilchengröße von 10 bis 500 nm besitzen.
EP19910113667 1990-08-14 1991-08-14 Hochfeste Legierungen auf Aluminiumbasis Expired - Lifetime EP0475101B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP213755/90 1990-08-14
JP21375590 1990-08-14

Publications (2)

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EP0475101A1 EP0475101A1 (de) 1992-03-18
EP0475101B1 true EP0475101B1 (de) 1995-12-13

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Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3302031B2 (ja) * 1991-09-06 2002-07-15 健 増本 高靭性高強度非晶質合金材料の製造方法
DE69220164T2 (de) * 1991-09-26 1998-01-08 Tsuyoshi Masumoto Superplastisches Material aus Legierung auf Aluminiumbasis und Verfahren zur Herstellung
JP2790935B2 (ja) * 1991-09-27 1998-08-27 ワイケイケイ株式会社 アルミニウム基合金集成固化材並びにその製造方法
JPH05125499A (ja) * 1991-11-01 1993-05-21 Yoshida Kogyo Kk <Ykk> 高強度高靭性アルミニウム基合金
JPH05125473A (ja) * 1991-11-01 1993-05-21 Yoshida Kogyo Kk <Ykk> アルミニウム基合金集成固化材並びにその製造方法
JP2954775B2 (ja) * 1992-02-14 1999-09-27 ワイケイケイ株式会社 微細結晶組織からなる高強度急冷凝固合金
JP2945205B2 (ja) * 1992-03-18 1999-09-06 健 増本 非晶質合金材料とその製造方法
JP2911673B2 (ja) * 1992-03-18 1999-06-23 健 増本 高強度アルミニウム合金
EP0570910A1 (de) * 1992-05-19 1993-11-24 Honda Giken Kogyo Kabushiki Kaisha Hochfestes Konstruktionselement aus einer Aluminiumlegierung mit hoher Zähigkeit und Verfahren zu ihrer Herstellung
JPH05320803A (ja) * 1992-05-22 1993-12-07 Honda Motor Co Ltd 高強度Ａｌ合金
EP0584596A3 (en) * 1992-08-05 1994-08-10 Yamaha Corp High strength and anti-corrosive aluminum-based alloy
JP3142659B2 (ja) * 1992-09-11 2001-03-07 ワイケイケイ株式会社 高力、耐熱アルミニウム基合金
JPH07179974A (ja) * 1993-12-24 1995-07-18 Takeshi Masumoto アルミニウム合金およびその製造方法
JP2795611B2 (ja) * 1994-03-29 1998-09-10 健 増本 高強度アルミニウム基合金
JPH0835029A (ja) * 1994-07-19 1996-02-06 Toyota Motor Corp 高強度高延性鋳造アルミニウム合金およびその製造方法
JP4080013B2 (ja) * 1996-09-09 2008-04-23 住友電気工業株式会社 高強度高靱性アルミニウム合金およびその製造方法
DE102007056298A1 (de) * 2007-11-22 2009-05-28 Bayerische Motoren Werke Aktiengesellschaft Kolben
CN101942620B (zh) * 2010-09-29 2012-07-11 北京科技大学 一种高致密纳米晶铝合金及其制备方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4743317A (en) * 1983-10-03 1988-05-10 Allied Corporation Aluminum-transition metal alloys having high strength at elevated temperatures
DE3524276A1 (de) * 1984-07-27 1986-01-30 BBC Aktiengesellschaft Brown, Boveri & Cie., Baden, Aargau Aluminiumlegierung zur herstellung von ultra-feinkoernigem pulver mit verbesserten mechanischen und gefuegeeigenschaften
JPH0621326B2 (ja) * 1988-04-28 1994-03-23 健 増本 高力、耐熱性アルミニウム基合金

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DE69115394T2 (de) 1996-07-11
EP0475101A1 (de) 1992-03-18
DE69115394D1 (de) 1996-01-25

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