JPH0841595A - Iron-chromium-nickel alloy steel having superior corrosion resistance in chloride-containing molten salt - Google Patents
Iron-chromium-nickel alloy steel having superior corrosion resistance in chloride-containing molten saltInfo
- Publication number
- JPH0841595A JPH0841595A JP17426794A JP17426794A JPH0841595A JP H0841595 A JPH0841595 A JP H0841595A JP 17426794 A JP17426794 A JP 17426794A JP 17426794 A JP17426794 A JP 17426794A JP H0841595 A JPH0841595 A JP H0841595A
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- Prior art keywords
- corrosion resistance
- molten salt
- alloy steel
- chloride
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、３００℃以上の高温
の塩化物を含む溶融塩に接する機器、構造物用材料とし
て使用される、耐腐食性に優れたＦｅ−Ｃｒ−Ｎｉ系合
金鋼に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a Fe-Cr-Ni alloy steel having excellent corrosion resistance, which is used as a material for equipment and structures in contact with molten salt containing chloride at a high temperature of 300 ° C or higher. It is about.
【０００２】[0002]
【従来の技術】ゴミ焼却炉の余熱発電ボイラー等におい
て、スーパーヒータの蒸気温度が３００℃以上となる
と、塩化物の硫酸塩を主体とする溶融塩が付着し、激し
い腐食を生じることが知られている。このため、これら
の余熱発電ボイラー等においては、従来はスーパーヒー
タの蒸気温度が３００℃未満に収まるような運転を行っ
てきた。2. Description of the Related Art In a waste heat power generation boiler of a refuse incinerator, etc., when the steam temperature of a super heater exceeds 300 ° C., a molten salt composed mainly of sulfate of chloride adheres to cause severe corrosion. ing. Therefore, in these residual heat power generation boilers and the like, conventionally, operation has been performed such that the steam temperature of the super heater falls below 300 ° C.
【０００３】しかしながら、近年の地球環境を悪化させ
ないという課題と関連して、エネルギー効率を向上させ
るために、運転温度を高くする必要が生じてきた。この
要求を満たすためには、高温の塩化物を含む溶塩中で優
れた耐食性を有する合金鋼が必要となる。However, in connection with the recent problem of not deteriorating the global environment, it has become necessary to raise the operating temperature in order to improve energy efficiency. To meet this requirement, an alloy steel having excellent corrosion resistance in a molten salt containing high temperature chloride is required.
【０００４】３００℃以上の高温の塩化物を含む溶融塩
に接する機器、構造物用材料としては、従来、耐酸化性
に優れた合金鋼を適用しようとしてきた。例えば特開平
２−２１３４４９号公報に開示されたＡｌを高めた合
金、特開昭６２−２０８５６号公報に開示されたＳｉを
高めた合金、特開平４−２２１０３４号公報に開示され
たＣｏを高めた合金等が知られている。Conventionally, alloy steel having excellent oxidation resistance has been tried to be used as a material for equipment and structures which come into contact with molten salt containing chloride at a high temperature of 300 ° C. or higher. For example, the Al-enriched alloy disclosed in JP-A-2-213449, the Si-enriched alloy disclosed in JP-A-62-20856, and the Co disclosed in JP-A-4-221403 are enhanced. Alloys and the like are known.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、上述し
た従来の技術に示された合金は、Ａｌ、Ｓｉのように加
工性を阻害する成分を含有するため、加工費が高くなっ
たり、Ｃｏのように高価な金属を含有させるため、材料
費が高くなるという問題点がある。However, since the alloys shown in the above-mentioned prior arts contain components such as Al and Si that hinder the workability, the processing cost is high and the alloys such as Co are not used. Since expensive metal is contained in the material, there is a problem that the material cost becomes high.
【０００６】一方では、Ａｌ、Ｓｉ添加鋼のように耐酸
化性を向上させた合金は、ゴミ焼却炉の実際の使用条件
下では、必ずしも耐食性が十分ではないという問題点も
明らかになった。On the other hand, it has become clear that alloys having improved oxidation resistance, such as Al and Si-added steels, do not necessarily have sufficient corrosion resistance under actual conditions of use in a refuse incinerator.
【０００７】したがって、塩化物を含む溶融塩に晒され
る機器、構造物に使用される材料で価格が安く、かつ十
分に耐食性に優れているものは無いというのが現状であ
る。Therefore, at present, there is no material that is exposed to a molten salt containing chloride and is used for a structure, which is inexpensive and has excellent corrosion resistance.
【０００８】この発明は、従来技術の上述のような問題
点を解消するためになされたものであり、価格が安く、
かつ塩化物を含む溶融塩中において優れた耐食性を有す
るＦｅ−Ｃｒ−Ｎｉ系合金鋼を提供することを目的とし
ている。The present invention has been made to solve the above-mentioned problems of the prior art, and is inexpensive and
Moreover, it aims at providing the Fe-Cr-Ni system alloy steel which has the outstanding corrosion resistance in the molten salt containing chloride.
【０００９】[0009]
【課題を解決するための手段】この発明に係る塩化物を
含む溶融塩中において優れた耐食性を有するＦｅ−Ｃｒ
−Ｎｉ系合金鋼は、重量％で、Ｃ：０.０４％以下、Ｓ
ｉ：０．５％以下、Ｍｎ：１．５％以下、Ｃｒ：１８％
を越え３０％未満、Ｎｉ：１０％を越え３５％未満、Ｃ
ａ＋Ｍｇ：０.０００５〜０.００５％を含有し、Ｃｒの
含有量とＦｅの含有量との比Ｃｒ／Ｆｅが０．３３を超
え０．７未満、Ｎｉの含有量とＦｅの含有量との比Ｎｉ
／Ｆｅが０．３３を超え１．０未満であるものである。Fe-Cr having excellent corrosion resistance in a molten salt containing chloride according to the present invention.
-Ni alloy steel, by weight%, C: 0.04% or less, S
i: 0.5% or less, Mn: 1.5% or less, Cr: 18%
Over 30%, Ni: over 10% and under 35%, C
a + Mg: 0.0005 to 0.005%, the ratio of the content of Cr to the content of Fe Cr / Fe is more than 0.33 and less than 0.7, the content of Ni and the content of Fe. Ratio Ni
/ Fe is more than 0.33 and less than 1.0.
【００１０】[0010]
【作用】本発明では、Ｃｒ、Ｎｉの作用を再検討すると
ともに、従来ほとんど検討されていないＦｅの作用を詳
細に調査した。その結果、合金の加工性を劣化させる添
加元素や高価な添加元素を使用しない、低コストで耐食
性に優れた材料を見いだしたものである。以下に各成分
の含有する範囲を限定した理由を説明する。In the present invention, the actions of Cr and Ni were reexamined, and the action of Fe, which had not been studied so far, was investigated in detail. As a result, they have found a material that does not use an additive element or an expensive additive element that deteriorates the workability of the alloy and has a low cost and excellent corrosion resistance. The reason for limiting the range of each component will be described below.
【００１１】Ｃ：材料の強度を上げるために必要である
が、０．０４％を越えて多量に含有させると溶接後の耐
食性を劣化させるので、０．０４％以下とした。C: It is necessary to increase the strength of the material, but if it is contained in a large amount exceeding 0.04%, the corrosion resistance after welding deteriorates, so it was made 0.04% or less.
【００１２】Ｓｉ：脱酸剤として使用されるが、０．５
％を越えると耐食性を劣化させるため０．５％以下とし
た。Si: used as a deoxidizer, but 0.5
%, The corrosion resistance deteriorates, so the content was made 0.5% or less.
【００１３】Ｍｎ：オーステナイト相を安定化させると
ともに、Ｓの悪影響を軽減する元素であるが、耐食性に
は影響がない。しかし、１．５％をこえて多量に含有量
させると脆化の原因になるため１．５％以下とした。Mn: An element that stabilizes the austenite phase and reduces the adverse effect of S, but does not affect the corrosion resistance. However, if it is contained in a large amount exceeding 1.5%, it causes embrittlement, so the content was made 1.5% or less.
【００１４】Ｃａ＋Ｍｇ：合金鋼の熱間加工性を改善す
るとともに、Ｏ、Ｓを固定し、耐食性を向上させるが、
０．０００５％以下では効果がなく、０．００５％以上
では介在物が増加し有害である。したがって、Ｃａ＋Ｍ
ｇは０．０００５％を超え０．００５％未満とした。Ca + Mg: Improves hot workability of alloy steel and fixes O and S to improve corrosion resistance.
If it is less than 0.0005%, there is no effect, and if it is more than 0.005%, inclusions increase and it is harmful. Therefore, Ca + M
g was set to more than 0.0005% and less than 0.005%.
【００１５】Ｃｒ：塩化物を含む高温溶融塩中での耐食
性を向上させる元素であるが、含有量が１８％以下では
効果がない。また、３０％以上添加しても効果が飽和
し、また熱間加工性を阻害するようになる。したがっ
て、Ｃｒは１８％を超え３０％未満とした。Cr: An element that improves the corrosion resistance in a high temperature molten salt containing chloride, but is ineffective if the content is 18% or less. Further, even if added in an amount of 30% or more, the effect is saturated and the hot workability is impaired. Therefore, Cr is set to more than 18% and less than 30%.
【００１６】Ｎｉ：耐食性を向上させるとともに、オー
ステナイト相を安定させるための元素であるが、１０％
以下では耐食性に対する効果がないばかりか、オーステ
ナイト相が不安定となる。３５％以上添加すると耐食性
がむしろ劣化する。したがって、Ｎｉは１０％を超え３
５％未満とした。Ni: an element for improving the corrosion resistance and stabilizing the austenite phase, but 10%
Below, not only is there no effect on corrosion resistance, but the austenite phase becomes unstable. If it is added in an amount of 35% or more, the corrosion resistance deteriorates. Therefore, Ni exceeds 10% and 3
It was less than 5%.
【００１７】Ｆｅ：ＦｅはＣｒ、Ｎｉとともに塩化物を
含む高温溶融塩中で酸化物を形成するため、耐食性に強
く影響する元素である。発明者等は、Ｆｅの適正な含有
量は、合金鋼のＣｒ、Ｎｉ量によって決まり、Ｃｒの含
有量とＦｅの含有量との比Ｃｒ／ＦｅおよびＮｉの含有
量とＦｅの含有量との比Ｎｉ／Ｆｅが、ある特定の範囲
内にあるときに、耐食性が最大となることを見いだした
のである。これは、上記したような環境下においては、
酸化物の安定性ではなくて、酸化物の溶融塩中への溶解
速度が腐食を支配しているので、ＦｅとＣｒおよびＦｅ
とＮｉの含有量比がある特定の範囲にある場合に腐食速
度が最小となるためである。以上のことからＣｒ／Ｆｅ
は０．３３を超え０．７未満、Ｎｉ／Ｆｅは０．３３を
超え１．０未満としたのである。Fe: Fe is an element that strongly affects the corrosion resistance because it forms an oxide in a high temperature molten salt containing chloride together with Cr and Ni. The inventors have found that the proper content of Fe depends on the Cr and Ni contents of the alloy steel, and the ratio of the Cr content and the Fe content is Cr / Fe and the Ni content and the Fe content. It has been found that the corrosion resistance is maximized when the ratio Ni / Fe is within a specific range. In the environment described above, this is
Corrosion is governed by the rate of dissolution of the oxide in the molten salt, not the stability of the oxide.
This is because the corrosion rate becomes the minimum when the content ratio of Ni to Ni is in a certain range. From the above, Cr / Fe
Is more than 0.33 and less than 0.7, and Ni / Fe is more than 0.33 and less than 1.0.
【００１８】炭化物形成元素であるＴｉ，Ｎｂ，Ｖを添
加しても、腐食速度には影響を与えない。また少量のＭ
ｏ，Ｃｕ，Ｎを含有する場合も同様に優れた耐食性が得
られる。なお、Ｐ、Ｓはいずれも耐食性、加工性を阻害
する元素であり、実用的に可能な範囲で少なくする。一
応の目安としてはＳは０．０１％以下、Ｐは０．０３％
以下である。The addition of the carbide forming elements Ti, Nb, V does not affect the corrosion rate. Also a small amount of M
Similarly, excellent corrosion resistance can be obtained when the alloy contains O, Cu, and N. Both P and S are elements that impair corrosion resistance and workability, and are reduced in a practically possible range. As a rough guide, S is 0.01% or less, P is 0.03%
It is the following.
【００１９】[0019]
【実施例】表１に示す成分組成からなる本発明合金鋼お
よび比較材を、各１０ｋｇ溶製し、熱間圧延機で１５ｍ
ｍ厚さの熱延板に圧延した後、溶体化処理を施した。こ
のようにして得られた材料から、機械加工により幅１５
ｍｍ×長さ２０ｍｍ×厚さ５ｍｍの腐食試験片を製作し
た。各試験片は研磨紙の８００番まで研磨後、脱脂を施
した。EXAMPLES 10 kg of each of the alloy steels of the present invention having the compositional composition shown in Table 1 and a comparative material were melted, and then 15 m in a hot rolling mill.
After being rolled into a hot-rolled sheet having a thickness of m, solution treatment was performed. From the material thus obtained, a width of 15
A corrosion test piece of mm × length 20 mm × thickness 5 mm was produced. Each test piece was degreased after polishing up to 800 of polishing paper.
【００２０】[0020]
【表１】 [Table 1]
【００２１】腐食試験は、都市ごみ焼却炉の加熱器管上
に堆積したダストを採取し、このダストを塗布した腐食
試験片を、実験室の加熱炉で加熱するという方法で実施
した。上述した腐食試験を詳述すると、重量比でダスト
９および腐食を加速するための塩化亜鉛１の混合塩を調
整し、腐食試験片の全表面に５０ｍｇ／ｃｍ2 の割合で
均一に塗布し乾燥した後、アルミナボートの上に試験片
を置き、４５０℃の炉温で２０時間加熱した。The corrosion test was carried out by collecting the dust accumulated on the heater tube of the municipal solid waste incinerator and heating the corrosion test piece coated with the dust in the heating furnace of the laboratory. The corrosion test described above will be described in detail. A mixed salt of dust 9 and zinc chloride 1 for accelerating the corrosion was prepared in a weight ratio, uniformly coated on the entire surface of the corrosion test piece at a rate of 50 mg / cm 2 , and dried. After that, the test piece was placed on an alumina boat and heated at a furnace temperature of 450 ° C. for 20 hours.
【００２２】加熱中炉内雰囲気ガスとして、３０％Ｈ2
Ｏ、０．１％ＨＣｌ、０．０３％ＮＯ2 、０．０３％Ｓ
Ｏ2 および残部が空気からなる混合ガスを、継続して炉
内に供給した。雰囲気の圧力は常圧であり、混合ガスの
供給割合は１リットル／分とした。As the atmosphere gas in the furnace during heating, 30% H 2
O, 0.1% HCl, 0.03% NO 2 , 0.03% S
A mixed gas consisting of O 2 and the balance air was continuously supplied into the furnace. The pressure of the atmosphere was normal pressure, and the supply rate of the mixed gas was 1 liter / min.
【００２３】各試験片の腐食による減量は、加熱後試験
片の表面に生成された腐食スケールを、薬品を用いて除
去した後、試験片の重量を測定し、あらかじめ測定して
おいた加熱前の試験片の重量から加熱後の試験片の重量
を差し引いて算出した。さらに、算出した腐食減量を基
に腐食速度（ｍｍ／年）を求めた。The weight loss of each test piece due to corrosion is determined by removing the corrosion scale produced on the surface of the test piece after heating with a chemical and then measuring the weight of the test piece before heating. It was calculated by subtracting the weight of the test piece after heating from the weight of the test piece of. Further, the corrosion rate (mm / year) was calculated based on the calculated corrosion weight loss.
【００２４】腐食試験の結果を表１に示す。表１から明
らかなように、本発明合金鋼の腐食速度はいずれも３ｍ
ｍ／年以下であるのに対して、比較材の腐食速度は４ｍ
ｍ／年を超えるものがほとんどであり、本発明合金鋼が
ごみ焼却炉のような、塩化物を多量に含む高温溶融塩中
でも十分に使用に耐えることが分かる。The results of the corrosion test are shown in Table 1. As is clear from Table 1, the corrosion rates of the alloy steels of the present invention are all 3 m
m / year or less, whereas the corrosion rate of the comparative material is 4 m
Most of them exceed m / year, and it can be seen that the alloy steel of the present invention can be sufficiently used even in a high temperature molten salt containing a large amount of chloride such as in a refuse incinerator.
【００２５】図１は、Ｃｒ−Ｎｉ−Ｆｅ系３元状態図上
に各合金鋼の腐食量を表したものである。図中に線で囲
んだ部分が本発明合金鋼のＣｒ、Ｎｉの限定範囲および
ＦｅとＣｒ、ＦｅとＮｉの量比を満足する範囲である
が、この範囲の腐食速度が、範囲外の合金鋼の腐食速度
と比較して小さいことが分かる。FIG. 1 shows the amount of corrosion of each alloy steel on the Cr-Ni-Fe ternary phase diagram. The portion surrounded by a line in the figure is a range satisfying the limited ranges of Cr and Ni of the alloy steel of the present invention and the quantitative ratio of Fe and Cr, and Fe and Ni, but the corrosion rate in this range is out of the range. It can be seen that it is small compared to the corrosion rate of steel.
【００２６】[0026]
【発明の効果】本発明により、塩化物を含む高温溶融塩
中で使用する機器、構造物の素材として、価格が安く、
かつ十分に耐食性に優れているＦｅ−Ｃｒ−Ｎｉ系合金
鋼を提供することができる。EFFECTS OF THE INVENTION According to the present invention, the price is low as a material for equipment and structures used in high temperature molten salt containing chloride,
Further, it is possible to provide an Fe-Cr-Ni-based alloy steel having sufficiently excellent corrosion resistance.
【図１】合金鋼の腐食量を表したＣｒ−Ｎｉ−Ｆｅ系３
元状態図である。FIG. 1 Cr—Ni—Fe system 3 showing the amount of corrosion of alloy steel
It is an original state diagram.
Claims (1)
０．５％以下、Ｍｎ：１．５％以下、Ｃｒ：１８％を越
え３０％未満、Ｎｉ：１０％を越え３５％未満、Ｃａ＋
Ｍｇ：０.０００５〜０.００５％を含有し、Ｃｒの含有
量とＦｅの含有量との比Ｃｒ／Ｆｅが０．３３を超え
０．７未満、Ｎｉの含有量とＦｅの含有量との比Ｎｉ／
Ｆｅが０．３３を超え１．０未満であることを特徴とす
る塩化物を含む溶融塩中において優れた耐食性を有する
Ｆｅ−Ｃｒ−Ｎｉ系合金鋼。1. By weight%, C: 0.04% or less, Si:
0.5% or less, Mn: 1.5% or less, Cr: more than 18% and less than 30%, Ni: more than 10% and less than 35%, Ca +
Mg: 0.0005 to 0.005%, Cr / Fe ratio Cr / Fe is more than 0.33 and less than 0.7, Ni content and Fe content Ratio Ni /
Fe is more than 0.33 and less than 1.0, and Fe-Cr-Ni based alloy steel having excellent corrosion resistance in a molten salt containing chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17426794A JPH0841595A (en) | 1994-07-26 | 1994-07-26 | Iron-chromium-nickel alloy steel having superior corrosion resistance in chloride-containing molten salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17426794A JPH0841595A (en) | 1994-07-26 | 1994-07-26 | Iron-chromium-nickel alloy steel having superior corrosion resistance in chloride-containing molten salt |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0841595A true JPH0841595A (en) | 1996-02-13 |
Family
ID=15975666
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17426794A Withdrawn JPH0841595A (en) | 1994-07-26 | 1994-07-26 | Iron-chromium-nickel alloy steel having superior corrosion resistance in chloride-containing molten salt |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0841595A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100334253B1 (en) * | 1999-11-22 | 2002-05-02 | 장인순 | Alloy steel having corrosion resistance in molten salt |
| WO2019138987A1 (en) | 2018-01-10 | 2019-07-18 | 日本製鉄株式会社 | Austenitic heat-resistant alloy, method for producing same, and austenitic heat-resistant alloy material |
| WO2019138986A1 (en) | 2018-01-10 | 2019-07-18 | 日本製鉄株式会社 | Austenitic heat-resistant alloy and method for producing same |
-
1994
- 1994-07-26 JP JP17426794A patent/JPH0841595A/en not_active Withdrawn
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100334253B1 (en) * | 1999-11-22 | 2002-05-02 | 장인순 | Alloy steel having corrosion resistance in molten salt |
| WO2019138987A1 (en) | 2018-01-10 | 2019-07-18 | 日本製鉄株式会社 | Austenitic heat-resistant alloy, method for producing same, and austenitic heat-resistant alloy material |
| WO2019138986A1 (en) | 2018-01-10 | 2019-07-18 | 日本製鉄株式会社 | Austenitic heat-resistant alloy and method for producing same |
| CN111601913A (en) * | 2018-01-10 | 2020-08-28 | 日本制铁株式会社 | Austenitic heat-resistant alloy and method for producing same |
| KR20200103822A (en) | 2018-01-10 | 2020-09-02 | 닛폰세이테츠 가부시키가이샤 | Austenitic heat-resistant alloy and its manufacturing method |
| KR20200105703A (en) | 2018-01-10 | 2020-09-08 | 닛폰세이테츠 가부시키가이샤 | Austenitic heat-resistant alloy and its manufacturing method, and austenitic heat-resistant alloy material |
| US11248297B2 (en) | 2018-01-10 | 2022-02-15 | Nippon Steel Corporation | Austenitic heat resistant alloy and method for producing same, and austenitic heat-resistant alloy material |
| CN111601913B (en) * | 2018-01-10 | 2022-03-04 | 日本制铁株式会社 | Austenitic heat-resistant alloy and method for producing same |
| US11268195B2 (en) | 2018-01-10 | 2022-03-08 | Nippon Steel Corporation | Austenitic heat resistant alloy and method for producing the same |
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| A300 | Withdrawal of application because of no request for examination |
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