EP0329192A2 - Nickel-Chrom-Legierung - Google Patents

Nickel-Chrom-Legierung Download PDF

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Publication number
EP0329192A2
EP0329192A2 EP89103551A EP89103551A EP0329192A2 EP 0329192 A2 EP0329192 A2 EP 0329192A2 EP 89103551 A EP89103551 A EP 89103551A EP 89103551 A EP89103551 A EP 89103551A EP 0329192 A2 EP0329192 A2 EP 0329192A2
Authority
EP
European Patent Office
Prior art keywords
alloy
resistance
less
stress corrosion
present
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
EP89103551A
Other languages
English (en)
French (fr)
Other versions
EP0329192B1 (de
EP0329192A3 (en
Inventor
Toshio Takasago Technical Institute Yonezawa
Nobuya Takasago Technical Institute Sasaguri
Kichiro Takasago Technical Institute Onimura
Hiroshi Takasago Technical Institute Susukida
Katsuji Takasago Technical Institute Kawaguchi
Takaya Kobe Shipyard & Engine Works Kusakabe
Hiroo Nagano
Takao Minami
Kazuo Yamanaka
Yasutaka Okada
Mamoru Inoue
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 Heavy Industries Ltd
Nippon Steel Corp
Original Assignee
Mitsubishi Heavy Industries Ltd
Sumitomo Metal Industries Ltd
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 JP57197362A external-priority patent/JPS5985850A/ja
Priority claimed from JP10409583A external-priority patent/JPS59232246A/ja
Priority claimed from JP10409483A external-priority patent/JPS59229457A/ja
Priority claimed from JP58156427A external-priority patent/JPS6050134A/ja
Application filed by Mitsubishi Heavy Industries Ltd, Sumitomo Metal Industries Ltd filed Critical Mitsubishi Heavy Industries Ltd
Priority to EP19890103551 priority Critical patent/EP0329192B1/de
Publication of EP0329192A2 publication Critical patent/EP0329192A2/de
Publication of EP0329192A3 publication Critical patent/EP0329192A3/en
Application granted granted Critical
Publication of EP0329192B1 publication Critical patent/EP0329192B1/de
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
    • C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
    • 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
    • C22C19/053—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 30% but less than 40%
    • 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
    • C22C19/055—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon

Definitions

  • the present invention relates to a non-deposition hardening type nickel based alloy which will be subjected to a high-temperature and high-pressure water or vapor and which has a remarkably improved crystal boundary etching resistance, mechanical properties and pitting corrosion resistance, in addition to the maintenance of a stress corrosion cracking resistance, and further has a bettered stress corrosion resistance in an aqueous NaOH solution.
  • the present invention relates to a nickel-chromium alloy excellent in a stress corrosion cracking resistance, more specifically, to a nickel-chromium alloy in which the stress corrosion cracking resistance is noticeably improved by depositing an insolubilized carbide in grains thereof and by strengthening a coating on the surface thereof.
  • the present invention also relates to an alloy for a heat transfer pipe, particularly to an alloy for a heat transfer pipe on the secondary side of a nuclear reactor.
  • nickel based alloys such as INCOROI 800 (trade name), and INCONEL 600 (trade name) and INCONEL 690 (trade name) set forth in Table 1 below.
  • these alloys have further been treated by heating them at a rather lower temperature than a level (hereinafter referred to as T°C) at which a carbide is thoroughly solubilized, alternatively by further addi­tionally specifically heating and retaining them at a temperature of 650 to 750°C, in order to improve the crystal boundary etching resistance and stress corrosion cracking resistance.
  • T°C a level at which a carbide is thoroughly solubilized
  • the nickel based alloys which have undergone such a conventional thermal treatment are still poor in the pitting corrosion resistance and stress corrosion cracking resistance.
  • an object of the present invention is to provide a method for a thermal treatment of a nickel based alloy without such drawbacks above, i.e. a method for thermal treat­ment of a nickel based alloy by which its mechanical properties, pitting corrosion resistance, stress corrosion cracking resistance and crystal boundary etching resistance can be improved.
  • an object of the present invention is to provide an alloy which can overcome such a drawback inherent in the 30% Cr-60% Ni system alloy and which is excellent in a corrosion resistance, especially the stress corrosion cracking resistance so that it may be used for the tubes, the containers and their fittings in the nuclear reactors, the chemical plants and the like in the form of thick-walled plates, round rods or pipes.
  • the gist of the present invention is directed to a nickel-chromium alloy excellent in a stress corrosion cracking resistance which is obtained by carrying out an annealing treatment under required conditions, said alloy having the following composition: in terms of % by weight, 0.04% or less of C; 1.0% or less of Mn; 0.02% or less of S; 25 to 35% of Cr; 0.05 to 1.0% of Ti; 1.0% or less of Si; 0.030% or less of P; 40 to 70% of Ni; 0.1 to 0.5 % of Al; 0.5 to 5.0% in all of one or more of Mo, W and V; and the residue comprising substantially Fe.
  • the above-mentioned required conditions mean anneal­ing conditions within a range (Y) surrounded by points A, B, C, D and E in Figure 1 attached hereto.
  • the stress corrosion cracking resistance of the Ni-Cr alloy which is heretofore insuf­ficient, can be remarkably improved.
  • Such an unexpected effect would be considered to be due to a synergistic effect of (i) the requirement that the C content is limited to 0.04% or less and a final annealing is carried out at a relatively low temperature in compliance with the C content, and (ii) the requirement that at least one of Mo, W and V is added as an element for reinforcing the coating.
  • This element is effective to improve a corrosion resistance, particularly it serves to improve an acid resistance and the SCC resistance in a high-temperature water including Cl ⁇ ions.
  • the content of Ni is required to be 40% or more, and its upper limit is set to 70%, taking addition proportions of alloy elements of Cr, Mo, W, V and the like into consideration.
  • the element Cr is essential for the improvement in the corrosion resistance, but its amount less than 25% is insufficient to enhance the SCC resistance. On the contrary, when it is more than 35%, a hot workability will remarkably deteriorate. Therefore, the content of Cr is limited to the range of 25 to 35% in the present invention.
  • the element P is present in the alloy as an impurity. If its content is above 0.030%, it will exert a harmful influence upon the acid resistance and the hot workability.
  • the element S is also one of the impurities. If being present in an amount more than 0.02%, it will be deleterious to the acid resistance and hot workability, as in the case of P.
  • This element Ti is added as a stabilizing agent. That is to say, even if the contents of P and S are controlled below the above-mentioned levels, a remarkable effect cannot be obtained. Therefore, in the present invention, Ti is added in an amount of 0.05% or more to assure the desired hot workability. On the contrary, when the content of Ti is more than 1.0%, its effect will reach a ceiling level. Therefore, the upper limit of this element is to be set to 1.0%.
  • these elements are effective to heighten the pitting corrosion resistance especially in a high-temperature water including Cl ⁇ ions.
  • the content of at least one of these elements is less than 0.5% in all, the passive coating on the surface will not be heightened and a pitting corrosion will occur, thereby deteriorating the stress corrosion cracking resistance.
  • the content of at least one of them is more than 5.0% in all, the effect of the improvement in the pitting corrosion resistance will reach a ceiling level, and the hot workability will noticeably be deteriorated.
  • the amount of one or more of Mo, W and V to be added is limited to the range of 0.5 to 5.0% in all.
  • Nb is greater in the effect of a carbon fixation than Ti.
  • the content of Nb is set to the range of 0.2 to 5.0%. In this range, the ratio of Nb/C will become 10 to 125. In the case of its amount being 0.2% or less, the effect of fixing carbon is small and a sensitization will thus occur, thereby generating the SCC (stress corrosion cracking).
  • the content of Nb is more than 5%, the effect (carbon fixation) will reach a ceiling level, and additionally the hot workability will noticeably be deteriorated. Therefore, its upper limit is set to 5.0%.
  • lines BC and CD represent recrystallization lines of the alloy according to the present invention. If the annealing treatment is carried out at a temperature below the levels of the lines BC and CD, no recrystallization will occur, so that the strength of the annealed alloy will be high and its corrosion resistance will be bad. Therefore, the annealing treatment is required to be carried out at a temperature above the levels of the lines BC and CD in accordance with a C content in the alloy.
  • a line AE in the same drawing means an upper limit of temperatures at which the carbon in the alloy is not thoroughly solubilized. Accordingly, so long as the annealing treatment is carried out at a temperature below this upper limit, a carbide will be present in the grains.
  • the annealing opera­tion is done at a temperature above a level of the line AE, all the carbide will be deposited on crystal boundaries in the case that a sensitization treatment is accomplished at at a temperature of 600°C for a period of 3 hours. This will lead to the deterioration in the crystal boundary etching resistance. Therefore, the final annealing is required to be carried out at a temperature below the level of the line AE.
  • Alloys (Alloy Nos. of the present invention 1 to 29, conventional alloys Nos. 30 to 37 and comparative alloys Nos. 38 to 41) of compositions comprising chemical com­ponents exhibited in Table 1 below were dissolvingly formed in a l7-kg vacuum furnace and subjected to a forging, hot rolling and thermal treatment under usual conditions, and they were then cold rolled as much as 30%, followed by annealing at a variety of temperatures. Further, a thermal treatment, i.e.
  • the specimens for the stress corrosion cracking tests were, after polished, caused to overlap each other every 2 specimens and each pair of them was bent into a U-shape to prepare double U-bent speciments.
  • the thus prepared specimens were immersed in a solution including 1000 ppm of Cl ⁇ (as NaCl) at 325°C for 1500 hours by the use of an autoclave (a high-temperature and high-pressure container). After the completion of the tests, cracks on inside surfaces of the specimens were measured for their depth by a microscope.
  • the specimens for the crystal boundary etching tests were immersed in a boiling solution including 60% of HNO3 and 0.1% of HF for 4 hours, and a weight loss caused by the corrosion was measured.
  • the annealing temperature is high and when 3 hours' heating at 600°C (the sensitization treatment) and an air cooling operation are carried out, the carbide of Cr will all deposit on the crystal boundaries and Cr-free layers will be formed in the vicinity of the crystal boundaries, so that corrosion will occur. Therefore, it is necessary to lower the annealing temperature.
  • the graphs in Figure 3 show the crystal boundary etching resistances of the alloys comprising the composi­tions regarding the present invention and conventional allohs.
  • the alloys in both the groups which had the composition of 0.02 to 0.03% of C and 0.6% of Mo were heated at 900°C for 30 minutes to accomplish the annealing treatment. After water cooling, they were heated at 600°C for 3 hours to accomplish the sensitization treatment, followed by air cooling.
  • white and black circles represent the alloys including more than 30% of Cr and those including 25 to 30% of Cr, respectively.
  • the alloys including an Ni amount below 40% are all great in a corrosion rate; the alloys including an Ni amount of 40% or more have an improved crystal boundary etching resistance. Therefore, the Ni content of 40% or more is necessary.
  • the total amount of one or more of the added Mo, V and W is required to be 0.5% or more.
  • the graphs in Figure 5 show influences of an Ni content (%) and Cr content (%) upon the SCC resistance.
  • Used alloy specimens were prepared through the annealing treatment of 30 minutes' heating at 900°C, water cooling, sensitization treatment of 3 hours' heating at 600°C, and air cooling.
  • white and black circles represent the alloys without stress corrosion cracks and those with some cracks of 20 ⁇ is or more.
  • the Ni content is required to be 40% or more.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)
  • Heat Treatment Of Nonferrous Metals Or Alloys (AREA)
EP19890103551 1982-11-10 1983-11-09 Nickel-Chrom-Legierung Expired - Lifetime EP0329192B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP19890103551 EP0329192B1 (de) 1982-11-10 1983-11-09 Nickel-Chrom-Legierung

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
JP57197362A JPS5985850A (ja) 1982-11-10 1982-11-10 Ｎｉ基合金の熱処理法
JP197362/82 1982-11-10
JP10409583A JPS59232246A (ja) 1983-06-13 1983-06-13 耐応力腐食割れ性に優れたＮｉ−Ｃｒ合金
JP104094/83 1983-06-13
JP104095/83 1983-06-13
JP10409483A JPS59229457A (ja) 1983-06-13 1983-06-13 耐応力腐食割れ性に優れたＮｉ基高Ｃｒ合金
JP58156427A JPS6050134A (ja) 1983-08-29 1983-08-29 伝熱管用合金およびその製造方法
JP156427/83 1983-08-29
EP19890103551 EP0329192B1 (de) 1982-11-10 1983-11-09 Nickel-Chrom-Legierung

Related Parent Applications (2)

Application Number Title Priority Date Filing Date
EP83730106.8 Division 1983-11-09
EP83730106A Division-Into EP0109350B1 (de) 1982-11-10 1983-11-09 Nickel-Chromlegierung

Publications (3)

Publication Number Publication Date
EP0329192A2 true EP0329192A2 (de) 1989-08-23
EP0329192A3 EP0329192A3 (en) 1989-10-18
EP0329192B1 EP0329192B1 (de) 1994-01-26

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP19890103551 Expired - Lifetime EP0329192B1 (de) 1982-11-10 1983-11-09 Nickel-Chrom-Legierung

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EP (1) EP0329192B1 (de)

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3573901A (en) * 1968-07-10 1971-04-06 Int Nickel Co Alloys resistant to stress-corrosion cracking in leaded high purity water

Also Published As

Publication number Publication date
EP0329192B1 (de) 1994-01-26
EP0329192A3 (en) 1989-10-18

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