EP0303957A1 - Korrosionsbeständige Legierung und korrosionsbeständige Gegenstände - Google Patents

Korrosionsbeständige Legierung und korrosionsbeständige Gegenstände Download PDF

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Publication number
EP0303957A1
EP0303957A1 EP88112984A EP88112984A EP0303957A1 EP 0303957 A1 EP0303957 A1 EP 0303957A1 EP 88112984 A EP88112984 A EP 88112984A EP 88112984 A EP88112984 A EP 88112984A EP 0303957 A1 EP0303957 A1 EP 0303957A1
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EP
European Patent Office
Prior art keywords
alloy
rem
dipping
corrosion resisting
alloy according
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
EP88112984A
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English (en)
French (fr)
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EP0303957B1 (de
Inventor
Yoshio Takizawa
Masatoshi Noguchi
Ichiro Sekine
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.)
Mitsubishi Materials Corp
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Mitsubishi Metal Corp
Mitsubishi Materials Corp
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Publication of EP0303957A1 publication Critical patent/EP0303957A1/de
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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
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/052—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 40%

Definitions

  • the present invention relates to a Ni-Cr alloy member having excellent corrosion resistance and excellent bending workability.
  • the alloy member is suitable for constituting a dipping equipment represented by a dipping bath, a dipping jig such as a bucket, an agitating instrument or the like within the dipping bath, and a pipe, a valve, a pump component or the like.
  • the alloy according to the invention is not limited merely to the dipping equipment, but reveals remarkable advantages in application also to, for example, an electrode of an electrolytic polishing apparatus or other electrodes exposed to corrosion atmosphere.
  • the inventors also recognize that the alloy according to the invention is not limited to the above applications, but is epoch-making new one having both corrosion resistance and workability.
  • Corrosion resisting alloys are known, for example, from U.S. Patent No. 2,777,766 (Hastelloy G), U.S. Patent No. 3,203,792 (Hastelloy C-276), U.S. Patent No. 3,160,500 (Inconel 625), U.S. Patent No. 3,573,901 (Inconel 690) and the like.
  • any of these alloys are not sufficient in corrosion resistance.
  • the inventors of this application have developed an alloy improved in corrosion resistance, as disclosed in Japanese Patent Application Laid-Open No. 58-17247.
  • the alloy developed by the inventors cannot be said to be superior in plastic workability, and is limited in application to cast material. Further, G.B.
  • Patent No. 1,281,597 has proposed a technique of improvement in mechanical strength of a corrosion resisting alloy formed of a Ni-base alloy high in Cr, exposed to high temperature.
  • the present invention can be said to be a further improvement in a mechanical characteristic of the alloy disclosed in the G.B. patent.
  • a conventional corrosion resisting alloy which is insufficient in corrosion resistance, but is excellent in plastic workability, in particular, in bending workability, has been used for a member for which bending working is required at manufacturing of the member, such as, for example, a dipping equipment represented by a dipping bath, a dipping jig such as a bucket, an agitating instrument or the like within the dipping equipment, and a pipe, a valve, a pump component or the like, as well as an electrode of, for example, an electrolytic polishing apparatus exposed to corrosion atmosphere.
  • the inventors of this application have perceived the fact that when the content of the Cr is brought to 38 to 50 wt%, a Ni-Cr alloy fundamentally maintains a predetermined corrosion resistance while damages such as cracking or the like at working or processing are difficult to occur and, in addition thereto, when a solid soluble range of one or both of Mo and W is 0.1 to 2 wt%, corrosion resistance and plastic workability remarkably coexist within the range.
  • Cu together with Cr, Mo and W, has a function of improving corrosion resistance of the alloy.
  • the content of Cu exceeding 2% does not reveal a further improvement in effect. Accordingly, the content of Cu is determined to 2% or less.
  • an amount of Cr to 43 to 47 wt% causes a precipitation amount of the alpha phase of the Cr solid solution to be restrained to a value equal to or less than 10% in area ratio, making it possible to secure the corrosion resistance and the plastic workability at a high level.
  • Cu, Zr, Nb, Ta and Hf have conventionally been added by 1 to 3% by volume as principal elements, for the purposes of improving corrosion resistance for Cu and workability for Zr, Nb, Ta and Hf.
  • C is brought to a value equal to or less than 0.01 wt% and N is brought to a value equal to or less than 0.01 wt%, whereby excellent corrosion resistance and plastic workability can be obtained without addition of the principal elements referred to above.
  • Ca has advantageous in deoxidation and desulfurization at dissolution and manufacturing of the alloy. However, if the content of Ca exceeds 0.01 wt%, the alloy is embrittled, so that damages tend to occur in the member after having been worked or processed.
  • the Ni-Cr alloy according to the invention contains, as unavoidable impurities, 0.3 wt% or less Fe, 0.3 wt% or less Mn, 0.3 wt% or less Ti, 0.3 wt% Al and 0.05 wt% or less Mg.
  • molten metals of the alloy having a required compositions were melted by using a high-frequency vacuum furnace, and cast in dies to form ingot of 60 mm in diameter and 200 mm in length. Subsequently, the ingots were melted again by using device for melting electroslag, and each ingot of 100 mm in diameter having compositions shown in Table 1 was prepared. Each ingot was held at the temperature from 1150 to 1250°C for 10 hours to be homogenized and then subjected to hot casting and hot rolling at a temperature suitable for starting the hot operations within the range of the above-identified temperature to form a hot rolling plate of 4 mm in thickness.
  • This plate was held at the temperature from 1100 to 1200°C for 30 minutes to be homogenized and then subjected to cool rolling to form cool rolling plate of 2 mm in thickness.
  • This plate was held at the latter condition to be homogenized, and thereby manufacturing alloy plates 1 to 55 of the present invention, and comparative alloy plates 56 to 67.
  • each of the comparative alloy plates 56 to 67 had a composition in which the content (represented by * in Table 1) of any of the components falls outside the range of the present invention.
  • each of the area ratios of the alpha phase of the Cr solid solution is restrained to a value equal to or less than 10% when the content of Cr of the alloy plate is at equal to or less than 47%.
  • the alloy plates 1 to 55 of the present invention and the comparative alloy plates 56 to 67 their extensions of a tensile test at a room temperature were measured to evaluate their formabilities, especially bending properties. Also, the plates were subjected to a bending test in accordance with JIS or Japanese Industrial Standard, bending them 180° to bring one inner face of each bending plate into contact with the other inner face and thereby detecting whether cracks appear or not on the bent portion of the plates. Then, the plates having no cracks after the bending test were subjected to an additional bending test, by which the plates were bent in the contrary direction to the former bending test to detect whether cracks appear or not on the bent portion.
  • the former bending test is prescribed as a test that the alloy plate 1 shown in Fig. 1 (a) is bent as shown in Fig. 1 (b) to detect whether cracks appear or not on the bent portion.
  • the latter bending test is prescribed as a severe or hard test that the alloy plate 1 bent by the former bending test is furthermore bent in a direction which is contrary to the bending direction of the former test to detect whether cracks appear or not on the bent portion.
  • the results are shown in Table 1.
  • the alloy plates were held to dip in a mixed acid such as an aqueous solution of 17% HNO3 containing 3% HF at 60°C for 24 hours, and were held to dip in a mixed acid having composition which is contrary to an aqua regia or an aqueous solution of 55% HNO3 containing 8% HCl at 60°C for 240 hours.
  • a mixed acid such as an aqueous solution of 17% HNO3 containing 3% HF at 60°C for 24 hours
  • a mixed acid having composition which is contrary to an aqua regia or an aqueous solution of 55% HNO3 containing 8% HCl at 60°C for 240 hours.
  • the contents of the corrosion were measured by performing the dippings, and the results are shown in Table 1.
  • a dipping jig shown in Fig. 2 was made of a rolled strip 5 of 3 mm in thick and a rod 6 of 5 mm in diameter made of the alloy of the present invention, which consists of 46 wt% Cr, 1 wt% Mo, 1 wt% Zr, 0.03 wt% C, 0.004 wt% N and the remainder Ni.
  • the thus made dipping jig serves as an exemplified member.
  • Two kinds of typical alloy compositions employed conventionally were set as follows, and were likewise formed respectively into dipping jigs. These two dipping jigs serve respectively as comparative members.
  • the members corresponding to their respective alloy compositions will be referred respectively to as "exemplified member", “comparative member A” and “comparative member B”.
  • Three buckets each as shown in Fig. 3, were made of respective rolled strips 11 of 3 mm in thick and respec­tive wire materials 12 of 2 mm in diameter formed of respec­tive three alloys the same in composition as the respective dipping jigs described above.
  • the three buckets were dip in the aqueous solution of 20% HNO3 + 3% HF (60°C) for ten days and, thereafter, reductions in weight of the respective buckets were measured.
  • the weight reduction amount of the comparative member A was 121 g/m2
  • the weight reduction amount of the comparative member B was 53 g/m2
  • the weight reduction amount of the instant exemplified member was 12 g/m2.
  • An exemplified member was formed into a pipe of 10 mm in diameter and 1 m in length, by an alloy composition consisting of 44 wt% Cr, 1.5 wt% Mo, 0.02 wt% C, 0.006 wt% N and the remainder Ni.
  • As comparative members two pipe members each the same in size as the exemplified member were made of respective comparative alloys A and B the same in composition as the dipping jig example. Subsequently, an aqueous solution of 50% P2O5 (80°C) was recirculated through each of the three members at flow velocity of 30 m/min for 2400 hours. Thereafter, corrosion rates of the respective pipe members were compared with each other in terms of a weight reduction amount.
  • the weight reduction amount of the comparative pipe A was 512 g/m2, and the weight reduction amount of the comparative pipe B was 174 g/m2, whereas the weight reduction amount of the pipe according to this exemplified member was 61 g/m2.
  • a dipping equipment member having its configuration shown in Fig. 4a or 4b was made of strip material 8 or 10 and pipe material 7 or 9 each having an alloy composition consisting of 44 wt% Cr, 1.2 wt% Mo, 0.5 wt% W, 0.007 wt% C, 0.006 wt% N and the remainder Ni.
  • Comparative members A and B were prepared each of which was the same in composition as the aforesaid dipping jig example and each of which was the same in size and configuration as the exemplified member.
  • a clad member was made, by a usual method, of an ordinary steel plate 2 or 4 and an alloy plate 1 or 3 having its alloy composition consisting of 44 wt% Cr, 0.8 wt% Mo, 0.005 wt% C, 0.004 wt% N and the remainder Ni. Subsequently, the clad member was formed into an electrode member for an electrolytic bath as shown in Fig. 5a or 5b.
  • clad members each made of conven­tional steel plate and stainless steel plate made of SUS304 in accordance with JIS were formed respectively into compara­tive electrode members each having the same size as the instant exemplified member.
  • the steel plate sections of the respective exemplified member and comparative member were properly sealed. Subsequently, these two members were used respectively as cathodes, and a stainless steel was employed as an anode. Electrolytic polishing was carried out by the use of an electrolytic solution of 30% HNO3 + 2% HCl (50°C) at current density of 20 A/m2. The cathodes were compared in consumptive amount with each other. As a result, the consumptive amount of the comparative electrode member was 1.3 mm after the use for 24 hours, whereas the consumptive amount of the electrode member according to the instant exemplified member was 0.1 mm after the use for 24 hours.
  • the alloy according to the invention is excellent as a member accompanied with plastic working such as rolling, wire stretching, drawing or the like.
  • the alloy according to the invention is effective in use for a dipping equipment represented by a dipping bath, a dipping jig such as a bucket, an agitating member or the like within the dipping bath, and a pipe, a valve, a pump component or the like, as well as an electrode member employed in corrosion atmosphere.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Prevention Of Electric Corrosion (AREA)
  • Heat Treatment Of Steel (AREA)
  • Heat Treatment Of Nonferrous Metals Or Alloys (AREA)
  • Conductive Materials (AREA)
EP19880112984 1987-08-11 1988-08-10 Korrosionsbeständige Legierung und korrosionsbeständige Gegenstände Expired EP0303957B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP200577/87 1987-08-11
JP20057787 1987-08-11
JP923388A JPH0694579B2 (ja) 1987-08-11 1988-01-19 曲げ加工性のすぐれた耐食性Ｎｉ−Ｃｒ合金
JP9233/88 1988-01-19

Publications (2)

Publication Number Publication Date
EP0303957A1 true EP0303957A1 (de) 1989-02-22
EP0303957B1 EP0303957B1 (de) 1992-03-25

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EP19880112984 Expired EP0303957B1 (de) 1987-08-11 1988-08-10 Korrosionsbeständige Legierung und korrosionsbeständige Gegenstände

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EP (1) EP0303957B1 (de)
JP (1) JPH0694579B2 (de)
DE (1) DE3869515D1 (de)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997018340A1 (fr) * 1995-11-14 1997-05-22 A.A.Bochvar's All-Russian Scientific Research Institute Of Inorganic Materials Alliage a base de nickel (variantes)
US7485199B2 (en) 2002-01-08 2009-02-03 Mitsubishi Materials Corporation Ni based alloy with excellent corrosion resistance to supercritical water environments containing inorganic acids
RU2515794C1 (ru) * 2013-01-15 2014-05-20 Открытое акционерное общество "Государственный научный центр Научно-исследовательский институт атомных реакторов" Сплав на основе никеля
CN112553517A (zh) * 2020-12-04 2021-03-26 湘潭大学 一种耐磨CrMoNiTaHfW高熵合金制备方法与工艺

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6057331B2 (ja) * 2013-01-29 2017-01-11 日立金属Ｍｍｃスーパーアロイ株式会社 硫化水素およびセレン化水素に対する耐侵食性に優れたＮｉ基合金およびそのＮｉ基合金からなる装置構成部材
JP6090911B2 (ja) * 2013-01-29 2017-03-08 日立金属Ｍｍｃスーパーアロイ株式会社 耐高温腐食に優れたＮｉ基合金防食板およびその防食板を接合したディーゼルエンジン用排気弁
JP6192760B1 (ja) * 2016-03-15 2017-09-06 日立金属Ｍｍｃスーパーアロイ株式会社 熱間鍛造性に優れた耐熱耐腐食性高Ｃｒ含有Ｎｉ基合金

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB451601A (en) * 1934-03-24 1936-08-07 Heraeus Vacuumschmelze Ag Improvements in and relating to the production of heat-resistant articles for use at high temperatures
GB459848A (en) * 1935-05-09 1937-01-11 William Thomas Griffiths Improvements in heat resistant alloys
US2809139A (en) * 1952-10-24 1957-10-08 Research Corp Method for heat treating chromium base alloy
GB1383995A (en) * 1972-01-17 1974-02-12 Int Nickel Ltd Heat treatment of nickel-chromium alloys
SU450844A1 (ru) * 1971-04-12 1974-11-25 Центральный Ордена Трудового Красного Знамени Научно-Исследовательский Институт Черной Металлургии Им. И.П.Бардина Сплав на основе никел
GB1470911A (en) * 1975-01-10 1977-04-21 Vni I Pi T Khim Kogo I Neftyan Alloy and weliing electrode formed therefrom
GB1532851A (en) * 1975-12-02 1978-11-22 Pompey Acieries Heat resisting nickel-chromium alloy having high resistance to oxidation carburization and creep at high temperatures

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB451601A (en) * 1934-03-24 1936-08-07 Heraeus Vacuumschmelze Ag Improvements in and relating to the production of heat-resistant articles for use at high temperatures
GB459848A (en) * 1935-05-09 1937-01-11 William Thomas Griffiths Improvements in heat resistant alloys
US2809139A (en) * 1952-10-24 1957-10-08 Research Corp Method for heat treating chromium base alloy
SU450844A1 (ru) * 1971-04-12 1974-11-25 Центральный Ордена Трудового Красного Знамени Научно-Исследовательский Институт Черной Металлургии Им. И.П.Бардина Сплав на основе никел
GB1383995A (en) * 1972-01-17 1974-02-12 Int Nickel Ltd Heat treatment of nickel-chromium alloys
GB1470911A (en) * 1975-01-10 1977-04-21 Vni I Pi T Khim Kogo I Neftyan Alloy and weliing electrode formed therefrom
GB1532851A (en) * 1975-12-02 1978-11-22 Pompey Acieries Heat resisting nickel-chromium alloy having high resistance to oxidation carburization and creep at high temperatures

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997018340A1 (fr) * 1995-11-14 1997-05-22 A.A.Bochvar's All-Russian Scientific Research Institute Of Inorganic Materials Alliage a base de nickel (variantes)
US7485199B2 (en) 2002-01-08 2009-02-03 Mitsubishi Materials Corporation Ni based alloy with excellent corrosion resistance to supercritical water environments containing inorganic acids
RU2515794C1 (ru) * 2013-01-15 2014-05-20 Открытое акционерное общество "Государственный научный центр Научно-исследовательский институт атомных реакторов" Сплав на основе никеля
CN112553517A (zh) * 2020-12-04 2021-03-26 湘潭大学 一种耐磨CrMoNiTaHfW高熵合金制备方法与工艺
CN112553517B (zh) * 2020-12-04 2022-06-21 湘潭大学 一种耐磨CrMoNiTaHfW高熵合金制备方法与工艺

Also Published As

Publication number Publication date
JPH0694579B2 (ja) 1994-11-24
JPH01132732A (ja) 1989-05-25
EP0303957B1 (de) 1992-03-25
DE3869515D1 (de) 1992-04-30

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