EP0314805A1 - Hochkorrosionsbeständige amorphe legierung - Google Patents

Hochkorrosionsbeständige amorphe legierung Download PDF

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Publication number
EP0314805A1
EP0314805A1 EP88903960A EP88903960A EP0314805A1 EP 0314805 A1 EP0314805 A1 EP 0314805A1 EP 88903960 A EP88903960 A EP 88903960A EP 88903960 A EP88903960 A EP 88903960A EP 0314805 A1 EP0314805 A1 EP 0314805A1
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EP
European Patent Office
Prior art keywords
atomic
alloy
amount
amorphous
corrosion resistance
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP88903960A
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English (en)
French (fr)
Other versions
EP0314805B1 (de
EP0314805A4 (en
Inventor
Akira Hikawaryo Mitsuhashi
Katsuhiko Asami
Asahi Kawashima
Yoshio Takizawa
Koji Hashimoto
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hashimoto Koji
Mitsubishi Materials Corp
Original Assignee
Hashimoto Koji
Mitsubishi Metal Corp
Mitsubishi Materials Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP62111466A external-priority patent/JPS63277735A/ja
Priority claimed from JP62111465A external-priority patent/JPS63277734A/ja
Priority claimed from JP62111467A external-priority patent/JPS63277736A/ja
Priority claimed from JP62113939A external-priority patent/JPS63277737A/ja
Priority claimed from JP62129286A external-priority patent/JPS63293135A/ja
Priority claimed from JP62134367A external-priority patent/JP2547020B2/ja
Priority claimed from JP62134368A external-priority patent/JP2569331B2/ja
Application filed by Hashimoto Koji, Mitsubishi Metal Corp, Mitsubishi Materials Corp filed Critical Hashimoto Koji
Publication of EP0314805A1 publication Critical patent/EP0314805A1/de
Publication of EP0314805A4 publication Critical patent/EP0314805A4/en
Publication of EP0314805B1 publication Critical patent/EP0314805B1/de
Application granted granted Critical
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/04—Amorphous alloys with nickel or cobalt as the major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/02—Alloys based on vanadium, niobium, or tantalum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent

Definitions

  • the present invention relates to an amorphous nickel alloy having a high corrosion resistance, which is suitable as a corrosion-resistant material in a severe corrosive environment such as high-temperature concentrated phosphoric acid.
  • the present inventors have previously found amorphous nickel alloys highly resistant to pit corrosion, interstitial corrosion and uniform corrosion, and applied for patent under Japanese Patent Provisional Application No. 53-57,120, Japanese Patent Provisional Application No. 61-210,143, Japanese Patent Provisional Application No. 62-33,735, and Japanese Patent Provisional Application No. 62-33,736.
  • An object of the present invention is therefore to provide an alloy capable of withstanding an environment which hardly passivates a metal, being non-oxidizing, and exhibits a very severe corrosivity such as high-temperature concentrated phosphoric acid.
  • An alloy is usually in the form of crystals in its solid state.
  • an amorphous structure similar to liquid is obtained, and the thus obtained alloy is called an amorphous alloy.
  • an amorphous alloy is a uniform single-phase alloy of a super-saturated solid-solution. It has a far higher strength as compared with conventional commercial metals, and shows various properties, depending upon the chemical composition, including an abnormally high corrosion resistance.
  • the present inventors carried out studies on utilization of properties of such amorphous alloys, and found as a result an amorphous nickel-base alloy having a high corrosion resistance not susceptible to pit corrosion, interstitial corrosion or uniform corrosion even in very corrosive aqueous solution such as aqueous solution containing a strong acid or high-concentration chlorine ions, and have applied for patent under Japanese Patent Provisional Application No. 53-57,120.
  • the present inventors found another amorphous alloy having a high corrosion resistance applicable in a severe corrosive environment such as that containing boiling concentrated nitric acid or additionally containing an oxidizer, and applied for patent under Japanese Patent Provisional Application No. 61-21, 043.
  • the present inventors carried out further studies while examining the various properties of amorphous alloys. As a result, they found availability of new amorphous nickel alloys provided with a high corrosion resistance through formation of a stable protecting film even in a severe corrosive acid poor in oxidizing ability such as high-temperature concentrated phosphoric acid, in addition to the alloys disclosed in the aforementioned Japanese Patent Provisional Applications Nos. 53-57,120, 61-210,143, 62-33,735, and 62-33,736, and applied for patent under Japanese Patent Application No. 61-225,435 and Japanese Patent Application No. 61-225,436.
  • the present inventors further continued their studies on corrosion resistance of amorphous alloys, and as a result, achieved the present invention by founding out availability of amorphous nickel alloys showing a high corrosion resistance even in high-temperature concentrated phosphoric acid through combination of various elements in addition to the alloys disclosed in the above-mentioned Japanese Patent Application No. 61-225,435 and Japanese Patent Application No. 61-225,436.
  • the present invention consists of Claims 1 to 7, the component elements and their contents of which are shown in Table 1.
  • the amorphous alloys available by various methods for preparing amorphous alloys through extra-rapid cooling and solidification of molten alloys of the above-mentioned chemical compositions or sputter deposition thereof are single-phase alloys in which the above elements are uniformly dissolved.
  • a very uniform protecting film which ensures a high corrosion resistance is therefore produced on any of the amorphous nickel alloys of the present invention.
  • a metal material easily melts in high-temperature concentrated phosphoric acid solution poor in oxidizing ability. In order to use a metal material in such an environment, therefore, it is necessary to impart the ability to produce a stable protecting film to the metal material. This is accomplished by preparing an alloy containing effective elements in required amounts. In the case of a crystalline metal, however, addition of diverse alloy elements in large quantities often results in a multiple-phase structure comprising different chemical properties, and a desired corrosion resistance cannot be achieved. Generation of chemical non-uniformity is detrimental to corrosion resistance.
  • the amorphous alloy of the present invention is a uniform solid-solution and uniformly contains effective elements in required amounts capable of forming a stable protecting film.
  • a uniform protecting film is produced and gives a sufficiently high corrosion resistance in such an amorphous nickel alloy,
  • the condition to be satisfied by a metal material to withstand high-temperature con- centrated phosphoric acid.poor in oxidizing power is to have a high ability to form a stable protecting film to be uniformly produced on the material in a non-oxidizing environment.
  • This is achieved by means of the chemical compositions of the alloys of the present invention, and- the fact that an alloy has an amorphous structure permits preparation of an alloy with a complicated chemical composition into a single-phase solid-solution and ensures formation of a uniform protecting film.
  • Ni is an element forming the basis of the alloys of the present invention, which forms an amorphous structure in the presence of at least one of Mo and Cr in a prescribed total amount with Ta, and forms an amorphous structure also in the presence of P. Ni assists the effects of Ta, Mo, Cr and W responsible for corrosion resistance.
  • T a, Mo, Cr and W are elements responsible for corrosion resistance through formation of a protecting film.
  • a metal-metal alloy thereof with Ni can form an amorphous structure.
  • the total content of at least one of Mo and Cr with Ta is therefore specified to be from 25 to 50 atomic % in Claims 1 to 5 of the present invention.
  • the total content of Cr with Ta in an alloy containing Ta in an amount of at least 25 atomic % should be under 30 atomic %.
  • P is an.effective element which assists formation of a protecting film of Ta, Mo, Cr or W.
  • the P content is set forth to be under 10 atomic % in Claims 4 and 5 of the present invention.
  • a high content of P produces an amorphous structure as a metal-semimetal alloy.
  • addition of excessive p rather hinders formation of an amorphous structure.
  • the P content is limited within the range of from 10 to 23 atomic % in Claims 6 and 7 of the present invention.
  • the alloy of Claim 6 of the present invention can have a sufficient corrosion resistance even in severely corrosive high-temperature concentrated phosphoric acid, if the total amount of at least one of Mo and W with Ta in an amount of at least 1 atomc % is at least 10 atomic %.
  • an amorphous metal-metal alloy can have a sufficient corrosion resistance in severely corrosive high-temperature concentrated phosphoric acid, if. the total amount of W in an amount of at least 3 atomic % and W is at least 10 atomic %, as in that claimed in Claim 7 of the present invention.
  • the total amount of at least one of Mo and W with Ta in an amount of 1 atomic % is therefore specified to be up to 30 atomic % in Claim 6 of the present invention, and the sum of Mo in an amount of at least 3 atomic % and W is set out to be up to 30 atomic % in Claim 7 of the present invention.
  • B and Si are elements effective for the formation of an amorphous structure in the presence of Ni and can replace P.
  • P in order not to reduce the effect of P of promoting formation of a protecting film, it is not desirable that P should be replaced by one or more of B and Si in a total amount of over 7 atomic %.
  • the amorphous nickel alloy of the present invention may contain Nb in an amount of up to 10 atomic %, and T i and Zr in an amount of up to 5 atomic % without impairing the object of the present invention.
  • any of the various popularly utilized methods for preparing an amorphous alloy may be applied, including that of extra-rapidly cooling and solidifying liquid alloy, those of forming an amorphous alloy through the gaseous phase, and that of destroying the long-period structure of solid through ion injection.
  • FIG. 1 An apparatus for preparing the amorphous alloy of the present invention is illustrated in Fig. 1.
  • Fig. 1 the portion enclosed by the dotted line is evacuated into vacuum, and then filled with inert gas.
  • 2 is a silica tube having a vertical nozzle 3 at the lower tip thereof, and the raw material 4 and the inert gas for preventing oxidation of the raw material 4 can be introduced through an inlet port 1 provided on the top of the silica tube 2.
  • a heating furnace 5 is installed around the silica tube 2 to heat the above-mentioned raw material 4.
  • a high-speed rotating roll 7 is placed vertically below the nozzle 3, and is rotated by means of a motor 6.
  • the raw material 4 having a prescribed chemical composition is charged in the silica tube 2, and first evacuating the apparatus to a vacuum of about 10-5 Torr, the tube is filled with inert gas.
  • the raw material 4 is heated and melted in the heating furnace 5, and the resulting molten metal is ejected by means of compressed inert gas onto the outer peripheral surface of the roll 7 rotating at such a high speed as from 1,000 to 10,000 rpm by the action of the motor 6.
  • Application of this method permits preparation of the amorphous alloy of the present invention as a long sheet having, for example, a'thickness of 0.1 mm, a width of 10 mm, and a length of several meters.
  • Fig. 1 is a schematic view illustrating an apparatus for the preparation of the amorphous alloy of the present invention.
  • 1 raw material inlet port
  • 2 silica tube
  • 3 nozzle section
  • 4 raw material
  • 5 heating furnace
  • 6 motor
  • 7 high-speed rotating roll.
  • Raw material metals were mixed so as to give the chemical compositions shown in Table 2, and raw material alloys were prepared in an argon arc melting furnace. These alloys were remelted in argon atmosphere, and extra-rapidly cooled and solidified by the application of the single roll method as shown in Fig. 1 into amorphous alloy sheets having a thickness of from 0.01 to 0 .05 mm, a width of from 1 to 3 mm and a length of from 3 to 20 m. Formation of an amorphous structure was confirmed by means of X-ray diffraction. The surfaces of these alloy specimens were ground in cyclohexane up to silicon carbide paper No. 1000.
  • alloy specimens of a prescribed length were cut, immersed in about 63% P 2 0 5 solution at 160°C and 72% P 2 0 5 solution at 200°C for a period of from 7 to 10 days, and the weight before and after immersion was measured by means of a micro-balance. The results obtained are shown in Table 3.
  • the corroding rate of the amorphous alloys of the present invention is very slight.
  • a protecting film of - hydrated oxide of concentrated Ta and Mo or hydrated oxyhydroxide was produced on the alloy, and this was found to be the cause of the high corrosion resistance of the alloy of the present invention.
  • the amorphous nickel alloy of the present invention is, as described above in detail,-highly corrosion-resistant in that it is not corroded through formation of a stable protecting film even in a severely corrosive environment poor in oxidizing ability such as high-temperature phosphoric acid.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Continuous Casting (AREA)
  • Fuel Cell (AREA)
  • Fuel-Injection Apparatus (AREA)
EP88903960A 1987-05-07 1988-05-07 Hochkorrosionsbeständige amorphe legierung Expired - Lifetime EP0314805B1 (de)

Applications Claiming Priority (15)

Application Number Priority Date Filing Date Title
JP62111466A JPS63277735A (ja) 1987-05-07 1987-05-07 りん酸型燃料電池用セパレ−タ−
JP62111467A JPS63277736A (ja) 1987-05-07 1987-05-07 りん酸型燃料電池用セパレ−タ−
JP111465/87 1987-05-07
JP111466/87 1987-05-07
JP62111465A JPS63277734A (ja) 1987-05-07 1987-05-07 りん酸型燃料電池用セパレ−タ−
JP111467/87 1987-05-07
JP113939/87 1987-05-11
JP62113939A JPS63277737A (ja) 1987-05-11 1987-05-11 りん酸型燃料電池用セパレ−タ−
JP62129286A JPS63293135A (ja) 1987-05-26 1987-05-26 りん酸型燃料電池用セパレ−タ−
JP129286/87 1987-05-26
JP134368/87 1987-05-29
JP62134367A JP2547020B2 (ja) 1987-05-29 1987-05-29 高耐食アモルファスニッケル合金
JP62134368A JP2569331B2 (ja) 1987-05-29 1987-05-29 高温濃硫酸用高耐食アモルファスニッケル合金
JP134367/87 1987-05-29
PCT/JP1988/000449 WO1988008885A1 (en) 1987-05-07 1988-05-07 Highly corrosion-resistant amorphous alloy

Publications (3)

Publication Number Publication Date
EP0314805A1 true EP0314805A1 (de) 1989-05-10
EP0314805A4 EP0314805A4 (en) 1993-03-17
EP0314805B1 EP0314805B1 (de) 1995-03-01

Family

ID=27565786

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88903960A Expired - Lifetime EP0314805B1 (de) 1987-05-07 1988-05-07 Hochkorrosionsbeständige amorphe legierung

Country Status (5)

Country Link
EP (1) EP0314805B1 (de)
KR (1) KR940004900B1 (de)
DE (1) DE3853190T2 (de)
FI (1) FI98074C (de)
WO (1) WO1988008885A1 (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0537710A1 (de) * 1991-10-16 1993-04-21 Koji Hashimoto Hochkorrosionsbeständige amorphe Legierungen
WO2001031085A2 (en) * 1999-10-26 2001-05-03 Stuart Energy Systems Corporation Amorphous metal/metallic glass electrodes for electrochemical processes
US6303015B1 (en) 1994-06-17 2001-10-16 Steven J. Thorpe Amorphous metallic glass electrodes for electrochemical processes

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100682730B1 (ko) * 1999-12-29 2007-02-15 주식회사 포스코 하역기용 와이어 이탈방지장치

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4133681A (en) * 1978-01-03 1979-01-09 Allied Chemical Corporation Nickel-refractory metal-boron glassy alloys
US4410490A (en) * 1982-07-12 1983-10-18 Marko Materials, Inc. Nickel and cobalt alloys which contain tungsten aand carbon and have been processed by rapid solidification process and method
US4496635A (en) * 1980-04-09 1985-01-29 The United States Of America As Represented By The United States Department Of Energy Amorphous metal alloy and composite
DE3608656A1 (de) * 1985-03-14 1986-09-25 Koji Izumi Miyagi Hashimoto Korrosionsbestaendige amorphe legierung
DE3616008A1 (de) * 1985-08-06 1987-02-19 Koji Izumi Miyagi Hashimoto Hochkorrosionsbestaendige, amorphe legierung
EP0224724A1 (de) * 1985-11-05 1987-06-10 The Perkin-Elmer Corporation Amorphe Legierung

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6043896B2 (ja) * 1978-04-28 1985-10-01 新日本製鐵株式会社 太陽熱の直接吸収材及びその製造方法
JPS5950031B2 (ja) * 1978-04-28 1984-12-06 新日本製鐵株式会社 太陽放射エネルギ−の吸収特性にすぐれた材料およびその製造方法
JPS55125248A (en) * 1979-03-23 1980-09-26 Toshiba Corp Pointer material
US5598976A (en) * 1992-12-04 1997-02-04 Goldstar Co., Ltd. Spray arm pulsation device of a dish washer

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4133681A (en) * 1978-01-03 1979-01-09 Allied Chemical Corporation Nickel-refractory metal-boron glassy alloys
US4496635A (en) * 1980-04-09 1985-01-29 The United States Of America As Represented By The United States Department Of Energy Amorphous metal alloy and composite
US4410490A (en) * 1982-07-12 1983-10-18 Marko Materials, Inc. Nickel and cobalt alloys which contain tungsten aand carbon and have been processed by rapid solidification process and method
DE3608656A1 (de) * 1985-03-14 1986-09-25 Koji Izumi Miyagi Hashimoto Korrosionsbestaendige amorphe legierung
DE3616008A1 (de) * 1985-08-06 1987-02-19 Koji Izumi Miyagi Hashimoto Hochkorrosionsbestaendige, amorphe legierung
EP0224724A1 (de) * 1985-11-05 1987-06-10 The Perkin-Elmer Corporation Amorphe Legierung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO8808885A1 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0537710A1 (de) * 1991-10-16 1993-04-21 Koji Hashimoto Hochkorrosionsbeständige amorphe Legierungen
US6303015B1 (en) 1994-06-17 2001-10-16 Steven J. Thorpe Amorphous metallic glass electrodes for electrochemical processes
WO2001031085A2 (en) * 1999-10-26 2001-05-03 Stuart Energy Systems Corporation Amorphous metal/metallic glass electrodes for electrochemical processes
WO2001031085A3 (en) * 1999-10-26 2001-09-20 Stuart Energy Sys Corp Amorphous metal/metallic glass electrodes for electrochemical processes

Also Published As

Publication number Publication date
WO1988008885A1 (en) 1988-11-17
FI890031A0 (fi) 1989-01-04
FI98074C (fi) 1997-04-10
FI98074B (fi) 1996-12-31
KR890701786A (ko) 1989-12-21
FI890031A (fi) 1989-01-04
DE3853190D1 (de) 1995-04-06
EP0314805B1 (de) 1995-03-01
DE3853190T2 (de) 1995-08-24
KR940004900B1 (ko) 1994-06-04
EP0314805A4 (en) 1993-03-17

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