WO2004106575A1 - Composition d'alliage amorphe a base de cu - Google Patents

Composition d'alliage amorphe a base de cu Download PDF

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Publication number
WO2004106575A1
WO2004106575A1 PCT/KR2004/001281 KR2004001281W WO2004106575A1 WO 2004106575 A1 WO2004106575 A1 WO 2004106575A1 KR 2004001281 W KR2004001281 W KR 2004001281W WO 2004106575 A1 WO2004106575 A1 WO 2004106575A1
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WO
WIPO (PCT)
Prior art keywords
atomic
equal
amorphous alloy
alloy composition
composition
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Application number
PCT/KR2004/001281
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English (en)
Inventor
Seung-Yung Shin
Jong-Hyun Kim
Dong-Myoung Lee
Jung-Chan Bae
Hwi-Jun Kim
Jin-Kyu Lee
Jae-Young Ryu
Ha-Guk Jeong
Original Assignee
Korea Institute Of Industrial Technology
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Publication date
Priority claimed from KR10-2004-0019945A external-priority patent/KR100463578B1/ko
Application filed by Korea Institute Of Industrial Technology filed Critical Korea Institute Of Industrial Technology
Publication of WO2004106575A1 publication Critical patent/WO2004106575A1/fr

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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
    • C22C45/001—Amorphous alloys with Cu as the major constituent

Definitions

  • the present invention relates to a copper (Cu) -based amorphous alloy composition; and, more particularly, to an amorphous alloy composition including four elements of copper (Cu) used as a main component, zirconium (Zr) , titanium (Ti) and nickel (Ni) .
  • the present invention relates to a Cu- based amorphous alloy composition that can be formed in a bulk shape if cooled up to a temperature less than a glass transition temperature at a cooling rate equal to or less than 10 3 °C/s from a liquid phase because of having an excellent glass forming ability and having a supercooled liquid region in a temperature equal to or grater than 31 "C
  • a fast cooling rate ranging from 10 4 °C/s to 10 6 °C/s is required.
  • a rapid quenching technique is used for forming the amorphous phase, and a fabricated sample has a form of a thin film or fine powder.
  • a practical applicability of an amorphous alloy fabricated by the rapid quenching method has been limited because a form and a size of the amorphous alloy are small.
  • the glass forming ability is excellent, it is "possible to fabricate a bulk amorphous phase through a conventional casting method. Also, it is very important in an industrial perspective that the amorphous alloy has a wide supercooled liquid region. It is because components having a certain shape can be fabricated by an enabled forming process of the bulk amorphous alloy in the supercooled liquid region with use of viscous flow.
  • the supercooled liquid region may still be small and the glass forming ability may be relatively low. Therefore, a development of an alloy having with an excellent glass forming ability is still required.
  • an object of the present invention to provide a copper (Cu) -based amorphous alloy capable of solving problems arising when a conventional Cu-based amorphous alloy is employed.
  • a Cu-based amorphous alloy has a high degree of strength, thereby having high industrial and economical advantages. Therefore, if the Cu-based bulk amorphous alloy can be fabricated, it can be used as a structuring material in a very useful manner. According to an article by X.H. Lin and W. L. Johnson, entitled “Formation of Ti-Zr-Cu-Ni Bulk Metallic Glasses", Journal of Applied Physi cs, Volume 78, Issue 11, pp. 6514-6519, Dec.
  • a bulk amorphous alloy having a maximum thickness of 4 mm is obtained with use of a copper mold casting method and the bulk amorphous alloy has a supercooled liquid region in a temperature of approximately 45 ° C.
  • a new Cu-based bulk amorphous alloy can be fabricated from various alloys through an appropriate alloy-design, and a development on the Cu-based amorphous alloy having an excellent glass forming ability and a wide supercooled liquid region is still required for a practical use.
  • an object of the present invention to provide a Cu-based amorphous alloy having an excellent glass forming ability compared with a conventional alloy and a wide supercooled liquid region and being made of common metal elements, to thereby- have a good industrial and economical applicability and an enhanced practical usage.
  • a Cu-based bulk amorphous alloy composition having chemical formula:
  • a' expressing atomic % of Cu equals to or grater than 44 atomic percent (%%) and is equal to or less than 60 atomic %;
  • ⁇ b' expressing atomic % of Ni is equal to or greater than 1 atomic % and equal to or less than 20 atomic %;
  • 'c' is equal to or greater than 36 atomic % and equal to or less than 44 atomic %;
  • ⁇ x' is equal to or greater than 0.34 and equal to or less than 0.47.
  • ⁇ amorphous' does not mean that the alloy comprises 100 % of an amorphous phase.
  • the term ⁇ amorphous' is used for the composition having typically amorphous properties,, e.g., a halo-type X-ray diffraction pattern, obtained when the alloy mainly comprises the amorphpus phase. Accordingly, a part of the amorphous phase can be existed as a crystalline phase therein. However, a portion of the crystalline phase does not exceed that of the amorphous phase; thus, the amorphous property is not lost due to the high portion of the crystalline phase.
  • the amorphous alloy can have an excellent glass forming ability due to a multi atomic composition including more than three atomic composition, a high difference in atomic diameters greater than 10 %,. and a combination of atoms having a negative heat of mixing.
  • Ni is added to a main composition including copper, zirconium and titanium, thereby satisfying the aforementioned condition to make a multi atomic composition as a quaternary composition.
  • each element has a high atomic radius ratio.
  • Copper (Cu) has the atomic radius of 1.27 A
  • zirconium (Zr) has the atomic radius of 1.61 A
  • titanium (Ti) has the atomic radius of 1.45 A
  • nickel (Ni) has the atomic radius of 1.24 A.
  • the high negative heat of mixing is existed between each main element.
  • the heat of mixing between Cu and Zr is -23 kJ/mol
  • the heat of mixing between Cu and Ti is -17 kJ/mol
  • the heat of mixing between Ni and Zr is -49 kJ/mol
  • the heat of mixing between Ni and Ti is -35 kJ/mol .
  • the bulk amorphous composition can be obtained by an arc melting method in an atmosphere of argon gas.
  • the molten alloy is filled into a copper mold through the use of a suction casting method to thereby obtain a bulk amorphous phase with a certain shape.
  • it is possible to fabricate the bulk amorphous composition by employing another method.
  • the alloy composition is first melted by a high frequency induction heating in an atmosphere of vacuum or argon gas. Then, the molten alloy composition is filled into a water-cooled copper mold to thereby form the alloy composition with a certain shape of a bulk phase. This method is called injection casting method.
  • the atomic percentages of the alloy composition out of a total composition should fall within the following ranges: Cu is equal to or greater than 44 atomic % and equal to or less than 60 atomic %, and a compound of Zr and Ti is equal to or greater than 36 atomic % and equal to or less than 44 atomic %. Meanwhile, it is preferable to add Ni to the above ternary composition within a range between 1 atomic % and 20 atomic %.
  • Ni is not added, a sufficient glass forming ability is hardly expected and if the atomic % of Ni exceeds 20 atomic %, the glass forming ability rather shows a tendency to be reduced. Furthermore, x representing an atomic fraction of Zr and Ti falls within a range equal to or greater than 0.34 and equal to or less than 0.47, and in this case, it is confirmed that the alloy composition has the excellent glass forming ability.
  • the amorphous alloy in accordance with the present invention can be fabricated through a rapid quenching method, a mold casting method, a high pressure casting method, and an atomizing method.
  • the amorphous alloy in accordance with the present invention has an excellent high-temperature workability, thereby being able to be fabricated through working processes such as a forging process, a rolling process and an extruding process.
  • a liquid phase is solidified into an amorphous phase under a cooling rate equal to or much less than 10 3 °C/s.
  • the Cu-based bulk amorphous alloy composition has a glass transition temperature (Tg) ranging from 428 °C to 481 'C and a crystallization temperature (Tx) ranging from 475 °C to 522 °C.
  • Tg glass transition temperature
  • Tx crystallization temperature
  • ⁇ T which is an important factor indicating the glass forming ability obtained by subtracting Tg from Tx, ranges from 31 "C to 68 °C.
  • the Cu-based amorphous composition has the supercooled liquid region wider than -that of a conventional quaternary composition of the Cu-based amorphous alloy and the excellent glass forming ability.
  • the present invention makes it possible to fabricate the bulk amorphous phase having a maximum diameter of 6 mm through the use of the suction casting method.
  • a quasi-ternary composition diagram of Fig. 1 illustrates a range of Cu-based alloy composition with a diameter grater than 1 mm among the Cu-based bulk amorphous alloy compositions.
  • the composition of copper, nickel, and a compound of zirconium and titanium is indicated on the quasi-ternary composition diagram of Fig. 1, and Co and Ni have a ratio of 0.53 to 0.66 and Zr and Ti have a ratio of 0.34 to 0.47, respectively, as mentioned in the above chemical formula.
  • the bulk amorphous phase equal to or greater than 1 mm is formed at a cooling rate equal to or greater than 10 3 °C/s, and the region is the supercooled liquid region where temperature is equal to or greater than 31 °C.
  • the composition region denoted with (A) it is possible to form the amorphous phase with a diameter equal to or greater than 4 mm.
  • a' is equal to or greater than 48 atomic % and equal to or less than 55 atomic %
  • b' is equal , to or greater than 6 atomic % and equal to or less than 10 atomic %
  • c' is equal to or greater than 39 atomic % and equal to or less than 43 atomic %
  • x' is equal to or greater than 0.39 and equal to or less than
  • x a' is equal to or greater than 50 atomic % and equal to or less than 54 atomic %
  • c' is equal to or greater than 40 atomic % and equal to or less than 43 atomic %
  • ⁇ x' is equal to or greater than 0.39 and equal to or less than 0.46.
  • a compressive fracture strength of the bulk amorphous phase is from 1.9 GPa to 2.2 GPa, thereby showing an ' excellent mechanical property.
  • the Cu-based bulk amorphous alloy composition of the present invention has a wider supercooled liquid region ( ⁇ T) than the conventional quaternary composition of the bulk amorphous alloy and an enhanced glass forming ability.
  • a method for fabricating the bulk amorphous phase can use the rapid quenching method such as a melt spinning process and an atomizing process.
  • the Cu-based bulk amorphous alloy composition according to the present invention can be easily processed at a high temperature since the Cu-based bulk amorphous alloy composition has a wide supercooled liquid region. Therefore, the bulk amorphous alloy can be fabricated through processes such as a rolling process, a drawing process, a forging process and a molten metal forging process.
  • the crystalline phase can be contained in the Cu-based bulk amorphous alloy composition in a certain ratio.
  • Studies by the inventors of the present invention release that, in case of the crystalline phase, synthesized in a nano unit ranging from 1 to 10 according to the present invention, is uniformly dispersed in the Cu-based bulk amorphous alloy composition, the amorphous property is generally maintained.
  • the Cu-based bulk amorphous alloy composition containing the crystalline phase in a certain ratio has improved properties in terms of mechanical strength and so on compared with a composition containing the amorphous phase of 100 %.
  • a ratio of the uniformly dispersed crystalline phase should not exceed 10 weight % from a total weight of the Cu-based amorphous alloy composition.
  • a ratio of the uniformly dispersed crystalline phase should not exceed 10 weight % from a total weight of the Cu-based amorphous alloy composition.
  • an increase in the aforementioned crystalline phase may degrade strength and toughness.
  • Fig. 1 is a quasi-ternary composition diagram of Cu- Ni-(Zr + Ti) illustrating a region confirming a formation of a bulk amorphous phase with a thickness equal to or greater than 1 mm in accordance with the present invention.
  • Fig. 2 is an X-ray diffraction pattern of Cu 5 Ni 6 Zr2 2 Ti ⁇ 8 fabricated with use of a casting method in accordance with a preferred example of the present invention;
  • Fig. 3 is a micrograph of high resolution transmission electron microscope of Cu 54 Ni 6 Zr22Tii8 fabricated with use of a casting method in accordance with the preferred example of the present invention.
  • Fig. 4 is a graph showing a compressive strength of Cu 54 Ni 6 r22Tii8 fabricated with use of a casting method in accordance with the preferred example of the present invention.
  • Examples 1-23 alloy compositions fabricated by a suction casting method • First, each alloy composition given in table 1 is melted with use of an arc melting method and then, is fabricated in a rod shape with a diameter equal to or greater than 1 mm and with a length ranging from 10 mm to 50 mm through a suction casting method. It is confirmed that these samples have an amorphous property by showing a diffraction peak of a halo type from an X-ray diffraction analysis.
  • Fig. 2 illustrates a diffraction pattern of Cu 5 4Ni 6 Zr22Tii8, i.e., the sample number 5 of Table 1, obtained by employing a casting method.
  • Table 1 shows a glass transition temperature (Tg) , a crystallization temperature (Tx) and an amount of exothermic enthalpy generated during the crystallization measured through a differential scanning calorimeter (DSC) .
  • Table 1 also shows a supercooled liquid region, i.e., ⁇ T, determined by the glass transition temperature (Tg) and the crystallization temperature (Tx) .
  • the supercooled liquid region ( ⁇ T) is obtained by subtracting Tg from Tx.
  • the alloy composition having the supercooled liquid region with a temperature of 60 °C among the compositions suggested by the present invention in respect of forming and fabricating a component for maintaining a bulk amorphous structure.
  • Examples 24 ⁇ 47 alloy compositions fabricated by a melt spinning method
  • Each alloy composition listed in table 3 is fabricated in a button shape through an arc melting method and then, is melted in a vacuum high frequency induction furnace with use of a quartz tube. Afterwards, the molten alloy compositions are sprayed to a copper wheel roll at a speed of approximately 3000 rpm through a nozzle with a diameter of approximately 1 mm, thereby fabricating a ribbon with a thickness of approximately 60 ⁇ m. It is confirmed from an X-ray diffraction analysis that the samples fabricated through the melt spinning method has the amorphous property as a diffraction peak of the halo type is exhibited.
  • Table 3 shows a glass transition temperature (Tg) , a crystallization temperature (Tx) , and an amount of exothermic enthalpy ( ⁇ H) generated during crystallization obtained by employing a differential scanning calorimeter (DSC) .
  • Table 3 also shows a supercooled liquid region determined the glass transition temperature (Tg) and the crystallization temperature (Tx) .
  • the examples 5 and 30 are fabricated through the suction casting method and the melt spinning method, respectively, and these two examples provided identical
  • the example 30 according to the melt spinning method is set to be the amorphous phase of 100 % and based on the example 30 as a comparative reference, the exothermic enthalpy of the example 5 according to the casting method is compared. As a result of this comparison, the example 5 has the exothermic enthalpy of approximately 90 %; thus, it is possible to infer that the crystalline phase of approximately 10 weight % is contained in the alloy composition of the example 5.
  • Fig. 2 and 3 show an X-ray diffraction pattern and a micrograph of high resolution transmission electron microscopy (HRTEM) of Cu 54 Ni 6 Zr 22 Ti ⁇ 8 of the preferred example 5 fabricated with use of the casting method, respectively.
  • HRTEM transmission electron microscopy
  • the alloy composition fabricated in accordance with the present invention generally shows the amorphous property.
  • this X-ray diffraction pattern does not become a strong evidence to conclude that the alloy composition fabricated according to the present invention is an amorphous structure comprising the amorphous phase of 100 %.
  • the alloy composition generally shows the amorphous phase.
  • Fig. 4 is a graph showing a result a compression test on the alloy composition, Cu 54 Ni6Zr 22 Ti 18 in accordance with the example 5.
  • the compression is carried out under a uniaxial compression strain rate of 1 x 10 ⁇ 4 /s.
  • the compression test exhibits that a total strain, a plastic elongation and a, fracture strength are 5.3 %, 3.5 % and 2.2 GPa, respectively.
  • the Cu-based amorphous alloy composition containing • the crystalline phase has a higher mechanical strength and a better plastic elongation than the composition comprising the amorphous phase of 100 %. Therefore, the Cu-based amorphous alloy composition containing the crystalline phase can have much broader fields of applicability and extended industrial value.
  • a Cu-based amorphous alloy composition makes it possible to fabricate a bulk amorphous phase with a size equal to or greater than 1 mm as a quaternary composition and to perform a forming process at a high temperature more easily than a conventional amorphous alloy composition since a supercooled liquid region reaches a maximum temperature of 68 °C.
  • a Cu-based amorphous alloy composition makes it possible to fabricate a bulk amorphous phase with a size equal to or greater than 1 mm as a quaternary composition and to perform a forming process at a high temperature more easily than a conventional amorphous alloy composition since a supercooled liquid region reaches a maximum temperature of 68 °C.
  • the bulk amorphous alloy can have wide applicability in various products requiring high strength and high toughness.

Abstract

L'invention concerne une composition d'alliage amorphe à base de Cu ; plus précisément, une composition d'alliage amorphe à base de Cu quaternaire comportant quatre atomes principaux, soit des atomes principaux de Cu, Zr et Ti et un atome supplémentaire de Ni. La composition de Cu est comprise entre environ 44 % atomique et environ 60 % atomique ; celle de Ni entre environ 1 % atomique et environ 20 % atomique ; et celle d'un composé de Zr et Ti est comprise entre environ 36 % atomique et environ 44 % atomique. Cette composition d'alliage amorphe en masse possède une excellente capacité de formage de verre, la fabrication s'effectuant selon un procédé de coulée et un diamètre égal ou supérieur à 1 mm. De plus, ladite composition présente une vaste région liquide en surfusion à une température comprise entre 31 °C et 68 °C. Il est donc possible de réaliser un procédé de formage à haute température avec utilisation d'un écoulement visqueux et d'employer la composition d'alliage amorphe à base de Cu comme matériau de structuration à résistance élevée.
PCT/KR2004/001281 2003-05-30 2004-05-29 Composition d'alliage amorphe a base de cu WO2004106575A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
KR10-2003-0034922 2003-05-30
KR20030034922 2003-05-30
KR20030084943 2003-11-27
KR10-2003-0084943 2003-11-27
KR10-2004-0019945A KR100463578B1 (ko) 2003-05-30 2004-03-24 Ｃｕ기 비정질 합금조성물
KR10-2004-0019945 2004-03-24

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105448514A (zh) * 2016-01-04 2016-03-30 宁波大学 一种制备钕铁硼精密永磁体的方法
CN106975747A (zh) * 2017-04-10 2017-07-25 大连交通大学 非晶合金成分的高通量筛选方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06264200A (ja) * 1993-03-12 1994-09-20 Takeshi Masumoto Ｔｉ系非晶質合金
JPH0754086A (ja) * 1993-08-12 1995-02-28 Takeshi Masumoto Ｔｉ−Ｃｕ系非晶質合金
JPH08253847A (ja) * 1995-03-16 1996-10-01 Takeshi Masumoto Ｔｉ−Ｚｒ系非晶質金属フィラメント
WO2002053791A1 (fr) * 2000-12-27 2002-07-11 Japan Science And Technology Corporation Alliage amorphe à base de cuivre

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06264200A (ja) * 1993-03-12 1994-09-20 Takeshi Masumoto Ｔｉ系非晶質合金
JPH0754086A (ja) * 1993-08-12 1995-02-28 Takeshi Masumoto Ｔｉ−Ｃｕ系非晶質合金
JPH08253847A (ja) * 1995-03-16 1996-10-01 Takeshi Masumoto Ｔｉ−Ｚｒ系非晶質金属フィラメント
WO2002053791A1 (fr) * 2000-12-27 2002-07-11 Japan Science And Technology Corporation Alliage amorphe à base de cuivre

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105448514A (zh) * 2016-01-04 2016-03-30 宁波大学 一种制备钕铁硼精密永磁体的方法
CN106975747A (zh) * 2017-04-10 2017-07-25 大连交通大学 非晶合金成分的高通量筛选方法

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