JP2860260B2 - High corrosion resistance Ni-based alloy - Google Patents

High corrosion resistance Ni-based alloy

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Publication number
JP2860260B2
JP2860260B2 JP137995A JP137995A JP2860260B2 JP 2860260 B2 JP2860260 B2 JP 2860260B2 JP 137995 A JP137995 A JP 137995A JP 137995 A JP137995 A JP 137995A JP 2860260 B2 JP2860260 B2 JP 2860260B2
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JP
Japan
Prior art keywords
temperature
less
corrosion
corrosion resistance
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.)
Expired - Fee Related
Application number
JP137995A
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Japanese (ja)
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JPH08188841A (en
Inventor
修 松本
友博 土山
隆成 奥田
優行 藤原
武光 本庄
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Kobe Steel Ltd
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Kobe Steel Ltd
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Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【産業上の利用分野】本発明は、内燃機関部品である吸
排気弁棒等の高温腐食雰囲気で使用される高耐食性Ni
基合金に関するものである。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a highly corrosion-resistant Ni used in a high-temperature corrosive atmosphere such as an intake / exhaust valve rod as an internal combustion engine part.
It concerns the base alloy.

【0002】[0002]

【従来の技術】高温腐食雰囲気中に長時間曝される部
品、例えばディーゼルエンジンを構成する排気弁棒は、
耐熱耐摩耗性及び高温耐食性が要求されることから、従
来、耐熱鋼であるSUH31やSUH35が使用されて
きた。近年、ディーゼルエンジンの高出力化が進み、燃
焼ガス温度が高温になったため、従来の耐熱鋼製の排気
弁棒では、その触火面(燃焼室に面し、燃焼ガスと直接
接する面)の損傷が激しく、短時間で補修が必要とな
り、ディーゼルエンジンの稼働率が低下するという支障
があった。そのため、前記部品として、高温耐食性に優
れるNi基耐熱合金であるNimonic80Aの鍛造材や、特開
昭64-8699 に開示されているように、Ti:4%以下,
Al:4%以下,Nb:4%以下のいずれか1種又は2
種以上を含有した強析出硬化型Ni基耐熱合金が使用さ
れるようになった。
2. Description of the Related Art Parts exposed to a high-temperature corrosive atmosphere for a long time, for example, exhaust valve rods constituting a diesel engine,
Since heat resistance and wear resistance and high temperature corrosion resistance are required, conventionally, heat resistant steels SUH31 and SUH35 have been used. In recent years, as the output of diesel engines has increased and the combustion gas temperature has increased, the heat-resistant surface of the conventional exhaust valve stem made of heat-resistant steel (the surface facing the combustion chamber and directly in contact with the combustion gas) The damage was severe, repairs were required in a short time, and the operation rate of the diesel engine was reduced. Therefore, as the above-mentioned parts, a forged material of Nimonic80A, which is a Ni-base heat-resistant alloy excellent in high-temperature corrosion resistance, or a Ti: 4% or less, as disclosed in
Any one or more of Al: 4% or less, Nb: 4% or less
Strong precipitation hardening type Ni-base heat resistant alloys containing more than one kind have come to be used.

【0003】[0003]

【発明が解決しようとする課題】しかしながら、内燃機
関に使用される燃料は、エネルギー不足から低品位のも
のが使用されるようになったため、燃焼ガスに燃焼灰分
が多くなり、燃焼灰分が堆積する弁棒などの部品には、
バナジウムアタックが生じ易くなっている。更に、発電
用ディーゼルエンジンのように高出力で長時間連続運転
し、燃焼ガスが高温になと、燃料中の硫黄分により硫化
物が生成されるため、高温硫化腐食(サルファアタッ
ク)が生じる。
However, since the fuel used in the internal combustion engine is of low quality due to energy shortage, the combustion ash is increased in the combustion gas and the combustion ash is deposited. Parts such as valve stems
Vanadium attack is more likely to occur. Further, when the fuel cell is operated continuously for a long time at a high output like a diesel engine for power generation and the temperature of the combustion gas becomes high, sulfides are generated by sulfur content in the fuel, so that high-temperature sulfidation corrosion (sulfur attack) occurs.

【0004】このような高温腐食雰囲気になると、バナ
ジウムアタックとサルファアタックが相まって、腐食挙
動が複雑になり、硫化作用に弱いNiを主成分とする前
記Nimonic80Aの鍛造材により形成された排気弁棒では、
十分な高温耐食性(耐バナジウムアタック性、耐サルフ
ァアタック性)が得られず、触火面での損耗量が多いと
いう問題がある。
[0004] In such a high-temperature corrosive atmosphere, vanadium attack and sulfur attack combine to complicate the corrosion behavior, and the exhaust valve stem made of a forged Nimonic80A material mainly composed of Ni, which is weak in sulfidation, is used. ,
There is a problem that sufficient high-temperature corrosion resistance (vanadium attack resistance, sulfa attack resistance) cannot be obtained, and a large amount of wear occurs on the ignition surface.

【0005】本発明はかかる問題に鑑みなされたもの
で、高温耐食性に優れた高耐食性Ni基合金を提供する
ことを目的とする。
The present invention has been made in view of such a problem, and an object of the present invention is to provide a highly corrosion-resistant Ni-based alloy having excellent high-temperature corrosion resistance.

【0006】[0006]

【課題を解決するための手段】本発明の高耐食性Ni基
合金は、化学組成が重量%で、C: 0.05%以下、S
i: 0.5 %以下、Mn: 0.7%以下、Ni:
40.0〜60.0%、Cr: 23.0〜35.0%、Al: 0.1〜
2.0%、Ti: 1.0〜 2.0%、Nb: 2.0〜 6.0
%、B:0.0005〜0.02%、Zr: 0.001〜0.05%、残部
Fe及び不可避的不純物からなる。また、Coを15重
量%以下添加することができる。
The high corrosion-resistant Ni-based alloy of the present invention has a chemical composition in weight%, C: 0.05% or less, and S
i: 0.5% or less, Mn: 0.7% or less, Ni:
40.0-60.0%, Cr: 23.0-35.0%, Al: 0.1-
2.0%, Ti: 1.0 to 2.0%, Nb: 2.0 to 6.0
%, B: 0.0005 to 0.02%, Zr: 0.001 to 0.05%, the balance being Fe and unavoidable impurities. In addition, Co can be added in an amount of 15% by weight or less.

【0007】[0007]

【作用】本発明に含有されるCrは、バナジウムアタッ
クに対し有効であり、耐酸化性を向上させる。しかも、
高温に暴露され高温腐食が始まっても、Cr2O3 酸化膜の
生成速度が速く、腐食の進行を遅延させるため、サルフ
ァアタックには有効である。従って、Crの添加によ
り、良好な高温耐食性を有するNi基合金の耐サルファ
アタック性が更に改善される。
The Cr contained in the present invention is effective against vanadium attack and improves oxidation resistance. Moreover,
Even if exposure to high temperature causes high-temperature corrosion, the formation rate of Cr 2 O 3 oxide film is high and the progress of corrosion is delayed, so it is effective for sulfur attack. Therefore, the addition of Cr further improves the sulfur attack resistance of a Ni-based alloy having good high-temperature corrosion resistance.

【0008】Coは、Niと同様、オーステナイト相を
安定にする作用があるため、素地の高温強度が高められ
る。しかも、Niとは異なり、特にサルファアタックに
強いため、Coを添加すると、基地の高温強度を保持し
つつ、高温耐食性が著しく向上する。
[0008] Co, like Ni, has the effect of stabilizing the austenite phase, so that the high-temperature strength of the substrate is increased. Moreover, unlike Ni, it is particularly resistant to sulfur attack, so that the addition of Co significantly improves the high-temperature corrosion resistance while maintaining the high-temperature strength of the matrix.

【0009】[0009]

【実施例】本発明に係る高耐食性Ni基合金の実施例に
ついて説明する。本発明の基本組成は、重量%で、C:
0.05%以下、Si: 0.5 %以下、Mn:
0.7%以下、Ni: 40.0〜60.0%、Cr: 23.0〜35.
0%、Al: 0.1〜 2.0%、Ti: 1.0〜 2.0%、
Nb: 2.0〜 6.0%、B:0.0005〜0.02%、Zr:
0.001〜0.05%、であり、残部はFe及び不可避的不純
物からなる。また、Coを15重量%以下添加すること
ができる。
EXAMPLES Examples of the high corrosion-resistant Ni-based alloy according to the present invention will be described. The basic composition of the present invention is, by weight%, C:
0.05% or less, Si: 0.5% or less, Mn:
0.7% or less, Ni: 40.0 to 60.0%, Cr: 23.0 to 35.
0%, Al: 0.1 to 2.0%, Ti: 1.0 to 2.0%,
Nb: 2.0 to 6.0%, B: 0.0005 to 0.02%, Zr:
0.001 to 0.05%, with the balance being Fe and unavoidable impurities. In addition, Co can be added in an amount of 15% by weight or less.

【0010】以下に、上記組成の限定理由について記述
する。 C:0.05%以下 Cは、高硬度の炭化物を形成し耐摩耗性の向上に寄与す
る。しかし、0.05%を越えて添加すると、炭化物が
増加し、延性が著しく低下するため、0.05%以下と
する。 Si: O.5%以下 Siは、鋳造性を良くすると供に、硬度の向上に寄与す
る。0.5%を越えて添加すると、ラーベス相等の脆化
相を析出し、熱間加工時に割れを生じたり、延性を低下
させるため、0.5%以下とする。 Mn: 0.7%以下 Mnは、Sと結合してMnSを生成し、Sによる脆化を
防ぐ元素である。0.7%を越えて添加されると、材料
の耐食性を劣化させるため、0.7%以下が好ましい。 Ni:40.0〜60.0% Niは、オーステナイト相の安定化に必要であり、ま
た、析出強化相γ’,γ”を形成させるために必要であ
る。40%未満では十分な析出強化ができず、60%を
越えると、サルファアタックに対する耐食性が十分得ら
れない。 Cr:23.0〜35.0% Crは、耐食性を向上させる元素として不可欠であり、
バナジウムアタック及びサルファアタックの両方に対し
て効果がある。23.0%未満であると、その効果が十
分得られず、高温耐食性が改善されない。一方、35.
0%を越えると、強度が低下すると供に、脆性が劣化す
る。 Al: 0.1〜 2.0% Alは、Ti,Nbと同様に析出強化元素であり、高温
強度の向上に寄与する。0.1%未満であると、析出強
化の効果が得られず、2.0%を越えると、脆性の低下
を招くため好ましくない。 Ti: 1.0〜 2.0% Tiは、Al,Nbと同様に析出強化元素であり、高温
強度の向上に寄与する。1.0%未満であると、析出強
化の効果が少なく、2.0%を越えると、脆性の劣化を
来すため好ましくない。 Nb: 2.0〜 6.0% Nbは、Al,Tiと同様に析出強化元素であり、高温
強度の向上に寄与する。2.0%未満であると、析出強
化の効果が期待できない。一方、6.0%を越えると、
脆性の劣化を来し好ましくない。 B:0.0005〜0.02% Bは、高温におけるクリープ強度を向上させる。0.0
005%未満であると、その効果がなく、高温強度が改
善されない。一方、0.02%を越えてBが含有される
と、溶接性が劣化する。 Zr: 0.001〜0.05% Zrは、耐酸化性を向上させる元素であり、バナジウム
アタックに対して有効である。0.001%未満である
と、その効果がなく、0.05%を越えると、溶接性が
劣化する。 Co:15.0%以下 Coは、Niの置換元素として添加でき、素地の固溶強
化に寄与する。しかし、15.0%を越えてCoが添加
されると、逆に固溶強化の効果が少なくなり、しかも、
高価になるため、15.0%以下とする。
The reasons for limiting the composition will be described below. C: 0.05% or less C forms carbide of high hardness and contributes to improvement of wear resistance. However, if added in excess of 0.05%, the amount of carbides increases, and the ductility is significantly reduced. Si: O.5% or less Si contributes to improvement of hardness as well as improvement of castability. If it is added in excess of 0.5%, an embrittlement phase such as a Laves phase is precipitated, cracking occurs during hot working or ductility is reduced, so the content is made 0.5% or less. Mn: 0.7% or less Mn is an element that combines with S to generate MnS and prevents embrittlement due to S. If added in excess of 0.7%, the corrosion resistance of the material is degraded, so it is preferably 0.7% or less. Ni: 40.0 to 60.0% Ni is necessary for stabilizing the austenite phase and for forming the precipitation strengthening phase γ ′, γ ″. If it is less than 40%, sufficient precipitation strengthening cannot be performed. If it exceeds 60%, sufficient corrosion resistance to sulfur attack cannot be obtained Cr: 23.0-35.0% Cr is indispensable as an element for improving corrosion resistance,
Effective against both vanadium and sulphur attacks. If it is less than 23.0%, the effect cannot be sufficiently obtained, and the high-temperature corrosion resistance is not improved. On the other hand, 35.
If it exceeds 0%, the strength is reduced and the brittleness is deteriorated. Al: 0.1 to 2.0% Al is a precipitation strengthening element like Ti and Nb, and contributes to improvement in high-temperature strength. If it is less than 0.1%, the effect of strengthening the precipitation cannot be obtained, and if it exceeds 2.0%, the brittleness is undesirably reduced. Ti: 1.0 to 2.0% Ti is a precipitation strengthening element like Al and Nb, and contributes to improvement in high-temperature strength. If it is less than 1.0%, the effect of precipitation strengthening is small, and if it exceeds 2.0%, brittleness is deteriorated, which is not preferable. Nb: 2.0 to 6.0% Nb is a precipitation strengthening element like Al and Ti, and contributes to improvement in high-temperature strength. If it is less than 2.0%, the effect of precipitation strengthening cannot be expected. On the other hand, if it exceeds 6.0%,
It is not preferable because brittleness is deteriorated. B: 0.0005 to 0.02% B improves the creep strength at high temperatures. 0.0
If it is less than 005%, the effect is not obtained and the high-temperature strength is not improved. On the other hand, when B exceeds 0.02%, the weldability deteriorates. Zr: 0.001 to 0.05% Zr is an element that improves oxidation resistance and is effective against vanadium attack. If it is less than 0.001%, there is no effect, and if it exceeds 0.05%, the weldability deteriorates. Co: 15.0% or less Co can be added as a substitution element for Ni and contributes to solid solution strengthening of the substrate. However, when Co is added in excess of 15.0%, the effect of solid solution strengthening is reduced, and
Since it is expensive, the content is set to 15.0% or less.

【0011】次に、本発明の高耐食性Ni基合金の具体
的実施例について述べる。 (1) まず、20kg鋳塊を真空溶解炉を用いて、No.
1〜6の合金を溶製した。No.1〜5の合金は本発明
に係る合金であり、No.6は従来例に係る合金であ
り、今回はNimonic80Aを使用した。各合金の化学成分
は、下記表1に示す通りである。
Next, specific examples of the high corrosion resistant Ni-based alloy of the present invention will be described. (1) First, a 20 kg ingot was placed in a No.
Alloys Nos. 1 to 6 were melted. No. The alloys Nos. 1 to 5 are the alloys according to the present invention. Reference numeral 6 denotes an alloy according to a conventional example, and this time Nimonic80A was used. The chemical components of each alloy are as shown in Table 1 below.

【0012】[0012]

【表1】 [Table 1]

【0013】(2) 続いて、各合金を、均質処理(115
0℃×12Hr)した後、ハンマにより30×20mm
の角材になるまで鍛造した。鍛造温度範囲は、1100
〜900℃であった。 (3) さらに、No.1〜5の鍛造材に、720℃×16
Hr/FC+620℃×16Hr/ACの時効処理を施
し、実施例に係る合金材を得た。一方、No.6の鍛造
材に、750℃×16Hr/ACの時効処理を行い、従
来例に係る合金材を得た。
(2) Subsequently, each alloy is homogenized (115
0 ° C × 12Hr), then 30 × 20mm by hammer
It was forged until it became square wood. Forging temperature range is 1100
900900 ° C. (3) Furthermore, No. 720 ° C × 16 for 1-5 forgings
An aging treatment of Hr / FC + 620 ° C. × 16 Hr / AC was performed to obtain an alloy material according to the example. On the other hand, No. The forged material of No. 6 was subjected to an aging treatment at 750 ° C. × 16 Hr / AC to obtain an alloy material according to the conventional example.

【0014】本熱処理条件は機械的特性を得るための条
件であり、耐食性には直接大きな影響を及ぼさない。熱
処理この他に溶体化処理を行い、その後、時効処理を行
う方法でも、同等の機械的特性が得られる。溶体化処理
の条件は980−1100℃×1時間以上保持後油また
は水冷を行う。時効処理条件は1)700−750℃で
8Hr以上保持する1段時効および2)700−750
℃で8Hr以上保持した後、続けて600−650℃で
8Hr以上保持する2段時効の方法があり、いずれも実
施例と同等の特性を得ることが可能であるが、時効温度
を高めること、2段時効処理を行うことで高強度が得ら
れる。 (4) 実施例及び従来例に係る合金材に対して、室温にお
ける引張特性及び表面硬度の測定を行った。実施例とし
ては、No.2とNo.5を使用した。その測定結果
は、下記表2の通りである。
The heat treatment conditions are conditions for obtaining mechanical properties, and do not directly affect the corrosion resistance. In addition to the heat treatment, a method of performing a solution treatment and then performing an aging treatment can obtain the same mechanical properties. The condition of the solution treatment is to carry out oil or water cooling after holding at 980-1100 ° C. × 1 hour or more. The aging treatment conditions are 1) one-stage aging in which the temperature is maintained at 700-750 ° C. for 8 hours or more, and 2) 700-750.
There is a two-stage aging method in which the aging temperature is maintained at 600 ° C. for 8 hours or more, and subsequently, the temperature is maintained at 600 to 650 ° C. for 8 hours or more. High strength can be obtained by performing the two-stage aging treatment. (4) Tensile properties and surface hardness at room temperature of the alloy materials according to the examples and the conventional examples were measured. As an example, as shown in FIG. 2 and No. 5 was used. The measurement results are as shown in Table 2 below.

【0015】[0015]

【表2】 [Table 2]

【0016】(5) 次に、実施例及び従来例に係る合金材
全てに対して、高温硫化腐食試験及びバナジウムアタッ
ク試験を行い、耐腐食性を評価した。試験片としては、
各合金材を25×15×5mmに機械加工した後、エメ
リー紙で鏡面研磨したのものを使用した。 (6) 高温硫化腐食試験では、食合成灰として Na2SO4(90
%)+NaCl(10%)を用い、800℃×20Hr恒温保持した
後、試験片に付着した腐食生成物を除去し、腐食減量を
測定した。測定結果は、図1に示す通りである。 (7) バナジウムアタック試験では、食合成灰として V2O
5(85%)+Na2SO4(15%)を用い、前記高温硫化腐食試験と同
様に測定した。測定結果は、図2に示す通りである。 (8) 機械的性質を示した表2より、実施例は従来例と同
等以上の強度、耐摩耗性を持ってることが明らかになっ
た。また、図1より、実施例はいずれも、従来例に比較
して格段に優れた耐高温硫化腐食特性を示していること
が分かる。そして、図2より、耐バナジウムアタック特
性については、実施例は従来例とほぼ同等であることが
確認された。従って、本発明に係る化学成分を有する合
金は、従来のNimonic80A以上の機械的性質を有しつつ、
高温硫化腐食(サルファアタック)及びバナジウムアタ
ックに対して優れた耐食性を示している。
(5) Next, a high-temperature sulfidation corrosion test and a vanadium attack test were performed on all the alloy materials according to the examples and the conventional examples, and the corrosion resistance was evaluated. As a test piece,
Each alloy material was machined to 25 × 15 × 5 mm and then mirror-polished with emery paper. (6) In the high-temperature sulfide corrosion test, Na 2 SO 4 (90
%) + NaCl (10%), and kept at a constant temperature of 800 ° C. for 20 hours. Then, corrosion products attached to the test piece were removed, and the corrosion loss was measured. The measurement results are as shown in FIG. (7) In the vanadium attack test, V 2 O
Using 5 (85%) + Na 2 SO 4 (15%), the measurement was performed in the same manner as in the high-temperature sulfidation corrosion test. The measurement results are as shown in FIG. (8) From Table 2 showing the mechanical properties, it was clarified that the examples had the same strength or wear resistance as the conventional examples. Further, from FIG. 1, it can be seen that all of the examples show much higher resistance to high-temperature sulfide corrosion than the conventional example. From FIG. 2, it was confirmed that the vanadium attack resistance of the example was almost the same as that of the conventional example. Therefore, the alloy having the chemical composition according to the present invention has mechanical properties higher than that of the conventional Nimonic80A,
It shows excellent corrosion resistance to high-temperature sulfidation corrosion (sulfur attack) and vanadium attack.

【0017】[0017]

【発明の効果】以上説明した通り、本発明の高耐食性N
i基合金は、特定の化学組成を有しているため、優れた
高温耐食性、特にサルファアタックに対する耐食性を著
しく向上させることができる。しかも、Coを15重量
%添加させると、高強度及び高耐摩耗性を保持しつつ、
耐食性が改善された材料を得ることができる。
As described above, the high corrosion resistance N of the present invention is obtained.
Since the i-base alloy has a specific chemical composition, excellent high-temperature corrosion resistance, particularly corrosion resistance against sulfa attack can be significantly improved. Moreover, when Co is added at 15% by weight, while maintaining high strength and high wear resistance,
A material having improved corrosion resistance can be obtained.

【図面の簡単な説明】[Brief description of the drawings]

【図1】高温硫化腐食試験における腐食減量を示した図
である。
FIG. 1 is a diagram showing the corrosion weight loss in a high-temperature sulfidation corrosion test.

【図2】バナジウムアタック試験における腐食減量を示
した図である。
FIG. 2 is a diagram showing corrosion loss in a vanadium attack test.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 藤原 優行 兵庫県加古川市尾上町池田字池田開拓 2222−1 株式会社神戸製鋼所 加古川 研究地区内 (72)発明者 本庄 武光 兵庫県高砂市荒井町新浜2丁目3番1号 株式会社神戸製鋼所 高砂製作所内 (56)参考文献 特開 昭49−13018(JP,A) 特開 平3−120328(JP,A) 特開 平5−222475(JP,A) 特開 昭63−213631(JP,A) 特開 昭56−81661(JP,A) 特開 昭61−179834(JP,A) 特開 昭62−202041(JP,A) (58)調査した分野(Int.Cl.6,DB名) C22C 19/05──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yuki Fujiwara 2222-1 Ikeda Pioneer, Ikeda-cho, Onoe-cho, Kakogawa City, Hyogo Prefecture Within the Kakogawa Research Area, Kobe Steel Co., Ltd. 2-3-1, Kobe Steel Works, Ltd. Takasago Works (56) References JP-A-49-13018 (JP, A) JP-A-3-120328 (JP, A) JP-A 5-222475 (JP, A A) JP-A-63-213631 (JP, A) JP-A-56-81661 (JP, A) JP-A-61-179834 (JP, A) JP-A-62-202041 (JP, A) (58) Survey Field (Int.Cl. 6 , DB name) C22C 19/05

Claims (2)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】 化学組成が重量%で、 C: 0.05%以下、Si: 0.5 %以下、 Mn: 0.7%以下、Ni: 40.0〜60.0%、 Cr: 23.0〜35.0%、Al: 0.1〜 2.0%、 Ti: 1.0〜 2.0%、Nb: 2.0〜 6.0%、 B:0.0005〜0.02%、Zr: 0.001〜0.05%、 残部Fe及び不可避的不純物からなる高耐食性Ni基合
金。
1. Chemical composition in weight%, C: 0.05% or less, Si: 0.5% or less, Mn: 0.7% or less, Ni: 40.0 to 60.0%, Cr: 23.0 to 35.0%, Al: 0.1 to 2.0% , Ti: 1.0-2.0%, Nb: 2.0-6.0%, B: 0.0005-0.02%, Zr: 0.001-0.05%, High corrosion resistant Ni-based alloy consisting of balance Fe and unavoidable impurities.
【請求項2】 Coが15重量%以下添加されている請
求項1に記載の高耐食性Ni基合金。
2. The highly corrosion-resistant Ni-based alloy according to claim 1, wherein Co is added in an amount of 15% by weight or less.
JP137995A 1995-01-09 1995-01-09 High corrosion resistance Ni-based alloy Expired - Fee Related JP2860260B2 (en)

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JP2860260B2 true JP2860260B2 (en) 1999-02-24

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Publication number Priority date Publication date Assignee Title
JP4220186B2 (en) * 2002-06-20 2009-02-04 株式会社東芝 Valve device and manufacturing method thereof
JP3979281B2 (en) * 2002-12-04 2007-09-19 株式会社日立製作所 Manufacturing method of valve stem, valve stem manufactured by the manufacturing method, and steam valve using the same
US10041153B2 (en) * 2008-04-10 2018-08-07 Huntington Alloys Corporation Ultra supercritical boiler header alloy and method of preparation
DK177487B1 (en) * 2012-07-06 2013-07-15 Man Diesel & Turbo Deutschland An exhaust valve spindle for an exhaust valve in an internal combustion engine
CN113234963B (en) * 2021-05-19 2021-12-17 沈阳航空航天大学 Nickel-chromium-based superalloy for room temperature and low temperature environment and preparation method thereof

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