JP2020094235A - ANTICORROSIVE ALLOY OF HIGH Ni EXCELLENT IN INTERGRANULAR CORROSION RESISTANCE OR CORROSION RESISTANCE, AND EXCELLENT IN HOT WORKABILITY AND COLD WORKABILITY - Google Patents
ANTICORROSIVE ALLOY OF HIGH Ni EXCELLENT IN INTERGRANULAR CORROSION RESISTANCE OR CORROSION RESISTANCE, AND EXCELLENT IN HOT WORKABILITY AND COLD WORKABILITY Download PDFInfo
- Publication number
- JP2020094235A JP2020094235A JP2018231996A JP2018231996A JP2020094235A JP 2020094235 A JP2020094235 A JP 2020094235A JP 2018231996 A JP2018231996 A JP 2018231996A JP 2018231996 A JP2018231996 A JP 2018231996A JP 2020094235 A JP2020094235 A JP 2020094235A
- Authority
- JP
- Japan
- Prior art keywords
- alloy
- corrosion resistance
- grain size
- crystal grain
- workability
- 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
Links
- 238000005260 corrosion Methods 0.000 title claims abstract description 92
- 230000007797 corrosion Effects 0.000 title claims abstract description 92
- 239000000956 alloy Substances 0.000 claims abstract description 53
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 52
- 229910000990 Ni alloy Inorganic materials 0.000 claims abstract description 43
- 239000013078 crystal Substances 0.000 claims abstract description 41
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 238000005275 alloying Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 abstract 2
- 230000002093 peripheral effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 16
- 239000000463 material Substances 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 10
- 230000007423 decrease Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 230000004580 weight loss Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 229910001566 austenite Inorganic materials 0.000 description 6
- 238000005482 strain hardening Methods 0.000 description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 229910001651 emery Inorganic materials 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
Landscapes
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Testing Resistance To Weather, Investigating Materials By Mechanical Methods (AREA)
Abstract
Description
この出願は化学プラント用の部材、配管あるいは海水を用いた熱交換器などの各種の腐食しやすい環境下で使用する際に、優れた耐粒界腐食性および優れた耐孔食性を有し、かつ熱間加工性および冷間加工性に優れた高Ｎｉの耐食合金に関する。 This application has excellent intergranular corrosion resistance and excellent pitting corrosion resistance when used in various corrosive environments such as members for chemical plants, pipes or heat exchangers using seawater, The present invention also relates to a high Ni corrosion-resistant alloy having excellent hot workability and cold workability.
本願出願人は、これまでにも、耐食性に加え、熱間・冷間での加工性に特に着眼した加工性に優れる耐食合金に関する特許を既に取得している（例えば、特許文献１参照。）。しかし、この文献では、材料表面の結晶粒径が耐食性に与える影響については考慮されていなかった。 The applicant of the present application has already obtained a patent for a corrosion-resistant alloy excellent in workability particularly in view of hot and cold workability in addition to corrosion resistance (see, for example, Patent Document 1). . However, this document does not consider the influence of the crystal grain size of the material surface on the corrosion resistance.
さらに、管の軸方向および周方向の引張降伏強度や圧縮降伏強度の比などを調整することで、使用環境に応じて異なる応力分布が負荷されても、耐用可能なオーステナイト系合金管に関する特許が取得されている（例えば、特許文献２参照。）。ただし、この文献は、オーステナイト系合金管およびその製造方法に関するものもあり、材料表面の結晶粒径が耐食性に与える影響については考慮されておらず、記載も示唆もない。 Furthermore, by adjusting the ratio of the tensile yield strength and the compressive yield strength in the axial direction and the circumferential direction of the pipe, etc., even if different stress distributions are loaded depending on the operating environment, there is a patent on austenitic alloy pipe that can withstand. It has been acquired (for example, refer to Patent Document 2). However, this document also relates to an austenitic alloy tube and a method for producing the same, and does not consider, influence or influence the crystal grain size of the material surface on the corrosion resistance, and does not describe or suggest it.
また本願出願人は、耐粒界腐食性および耐孔食性に優れた高Ｎｉ合金に関して、特許文献３に記載の発明を提案している。この出願にかかる発明は、材料の成分調整と炭化物の粒界被覆率を制御・制限して耐粒界腐食性を改善させるものであって、結晶粒径による着眼とは異なっている。 Further, the applicant of the present application has proposed the invention described in Patent Document 3 with respect to a high Ni alloy excellent in intergranular corrosion resistance and pitting corrosion resistance. The invention according to this application is intended to improve the intergranular corrosion resistance by controlling the composition of the material and controlling the grain boundary coverage of carbides, which is different from the observation based on the crystal grain size.
化学プラントや熱交換器などのように高耐食性が求められる用途では、優れた耐粒界腐食性および耐孔食性が必要となる。もっとも、従来技術においては、耐粒界腐食性を向上させるメカニズムについては、十分に解明されておらず、全く記載されていない。出願人は、鋭意検討の結果、材料表面のみの結晶粒に着目し、表面のみの結晶粒を異常粒成長させることで、飛躍的に耐食性が向上することを見出したことから、本発明の着想を得た。 In applications requiring high corrosion resistance such as chemical plants and heat exchangers, excellent intergranular corrosion resistance and pitting corrosion resistance are required. However, in the prior art, the mechanism for improving the intergranular corrosion resistance has not been sufficiently clarified and has not been described at all. As a result of diligent study, the applicant has focused on crystal grains only on the surface of the material and found that the corrosion resistance is dramatically improved by abnormally growing crystal grains only on the surface. Got
発明が解決しようとする課題は、化学プラントや熱交換器などの高耐食性が求められる用途の機器の、合金表面の結晶粒径の限定という組織制御を用いた従来技術と異なるアプローチによって、耐粒界腐食性を飛躍的に向上させること、さらに使用環境を考慮して耐孔食性もあわせて向上させること、かつ熱間加工性および冷間加工性に優れた高Ｎｉ合金を提供することである。 The problem to be solved by the invention is to improve grain resistance by a different approach from the conventional technique using a structure control of limiting the grain size of the alloy surface of equipment for applications requiring high corrosion resistance such as chemical plants and heat exchangers. It is to provide a high Ni alloy that is excellent in hot workability and cold workability, by dramatically improving intercalation corrosion resistance, further improving pitting corrosion resistance in consideration of use environment. .
上記の課題を解決するための手段では、第１の手段は、質量％で、Ｃ：０．００１〜０．０５０％、Ｓｉ：０．０１〜１．５０％、Ｍｎ：０．０１〜１．５０％、Ｓ：≦０．０５０％、Ｎｉ：３０．０〜５０．０％、Ｃｒ：１８．５〜２５．０％、Ｍｏ：２．００〜５．００％、Ｃｕ：１．００〜５．００％、Ａｌ：０．０１〜０．５０％、Ｔｉ：０．５〜２．０％、Ｎ：０．０００１〜０．０５００％、Ｆｅ：≧２０．０％の合金元素、および不可避不純物からなり、
以下の式（１）に示す、耐孔食性指数のＰＲＥ値＝［％Ｃｒ］＋３．３［％Ｍｏ］＋１６［％Ｎ］：≧３１．５・・・式（１）であるＮｉ合金であって、
該Ｎｉ合金からなる合金棒または合金管の外表面の結晶粒径（ＯＧ）と中周部の結晶粒径（ＭＧ）の比であるＯＧ／ＭＧ：≧１．５であること
を特徴とする耐粒界腐食性および耐孔食性に優れ、かつ熱間加工性および冷間加工性に優れた高Ｎｉ合金である。
なお、上記式（１）における［％元素］には各元素の質量％における値を代入する。また、上記における外表面の結晶粒径（ＯＧ）とは外表面から深さ１００μｍまでの結晶粒径のことであり、上記における中周部の結晶粒径（ＭＧ）とは、合金棒であればＤ／４の位置を中心に、もしくは合金管であれば外表面からの深さが合金管肉厚の半分となる位置を中心に、それぞれ±５００μｍの範囲の結晶粒径である。
ただし、Ｄは合金棒の直径である。
In the means for solving the above-mentioned problems, the first means is, in mass %, C: 0.001 to 0.050%, Si: 0.01 to 1.50%, Mn: 0.01 to 1 .50%, S: ≤0.050%, Ni: 30.0 to 50.0%, Cr: 18.5 to 25.0%, Mo: 2.00 to 5.00%, Cu: 1.00. To 5.00%, Al: 0.01 to 0.50%, Ti: 0.5 to 2.0%, N: 0.0001 to 0.0500%, Fe: ≧20.0% alloying element, And inevitable impurities,
PRE value of pitting corrosion resistance index=[%Cr]+3.3[%Mo]+16[%N] shown in the following formula (1):≧31.5... There
OG/MG, which is the ratio of the crystal grain size (OG) of the outer surface of the alloy rod or alloy tube made of the Ni alloy to the crystal grain size (MG) of the middle portion, is ≧1.5. It is a high Ni alloy that has excellent intergranular corrosion resistance and pitting corrosion resistance, as well as hot workability and cold workability.
In addition, the value in mass% of each element is substituted for [% element] in the above formula (1). Further, the crystal grain size (OG) of the outer surface in the above is a crystal grain size from the outer surface to a depth of 100 μm, and the crystal grain size (MG) of the middle portion in the above is an alloy rod. For example, the crystal grain size is in the range of ±500 μm around the position of D/4 or around the position where the depth from the outer surface of the alloy pipe is half the thickness of the alloy pipe.
However, D is the diameter of the alloy rod.
第２の手段は、第１の手段の合金元素に加えて、
熱間加工性を改善するべく、さらに質量％で、Ｂ：０．０００１〜０．０２５０％、Ｃａ：０．０００１〜０．０２５０％、Ｍｇ：０．０００１〜０．０２５０％の合金元素のうち少なくとも１種以上を含有し、および不可避不純物からなり、
以下の式（１）に示す、耐孔食性指数のＰＲＥ値＝［％Ｃｒ］＋３．３［％Ｍｏ］＋１６［％Ｎ］：≧３１．５・・・式（１）であるＮｉ合金であって、
該Ｎｉ合金からなる合金棒または合金管の外表面の結晶粒径（ＯＧ）と中周部の結晶粒径（ＭＧ）の比であるＯＧ／ＭＧ：≧１．５であること
を特徴とする耐粒界腐食性および耐孔食性に優れ、かつ熱間加工性および冷間加工性に優れた高Ｎｉ合金である。
なお、上記式（１）における［％元素］には各元素の質量％における値を代入する。また、上記における外表面の結晶粒径（ＯＧ）とは外表面から深さ１００μｍまでの結晶粒径のことであり、上記における中周部の結晶粒径（ＭＧ）とは、合金棒であればＤ／４の位置を中心に、もしくは合金管であれば外表面からの深さが合金管肉厚の半分となる位置を中心に、それぞれ±５００μｍの範囲の結晶粒径である。
ただし、Ｄは合金棒の直径である。
The second means is, in addition to the alloy element of the first means,
In order to improve hot workability, B: 0.0001 to 0.0250%, Ca: 0.0001 to 0.0250%, Mg: 0.0001 to 0.0250% of alloying elements in mass% are further included. Containing at least one of these and consisting of unavoidable impurities,
PRE value of pitting corrosion resistance index=[%Cr]+3.3[%Mo]+16[%N] shown in the following formula (1):≧31.5... There
OG/MG, which is the ratio of the crystal grain size (OG) of the outer surface of the alloy rod or alloy tube made of the Ni alloy to the crystal grain size (MG) of the middle portion, is ≧1.5. It is a high Ni alloy that has excellent intergranular corrosion resistance and pitting corrosion resistance, as well as hot workability and cold workability.
In addition, the value in mass% of each element is substituted for [% element] in the above formula (1). Further, the crystal grain size (OG) of the outer surface in the above is a crystal grain size from the outer surface to a depth of 100 μm, and the crystal grain size (MG) of the middle portion in the above is an alloy rod. For example, the crystal grain size is in the range of ±500 μm around the position of D/4 or around the position where the depth from the outer surface of the alloy pipe is half the thickness of the alloy pipe.
However, D is the diameter of the alloy rod.
本願発明によると、上記構成の高Ｎｉ合金とすることによって、化学プラント用の部材や、配管あるいは海水を用いた熱交換器などの用途に使用される、耐粒界腐食性や耐孔食性に優れることに加えて、熱間加工性および冷間加工性に優れた高Ｎｉの耐食合金を得ることができる。 According to the invention of the present application, by using the high Ni alloy having the above-mentioned configuration, it is possible to obtain intergranular corrosion resistance and pitting corrosion resistance, which are used for applications such as members for chemical plants, pipes or heat exchangers using seawater. In addition to being excellent, it is possible to obtain a high Ni corrosion-resistant alloy having excellent hot workability and cold workability.
本発明の実施するための形態の記載に先立ち、本願発明の第１の手段および第２の手段における高Ｎｉ合金の各化学成分、耐孔食性指数の式（１）および表面結晶粒径（ＯＧ）対中周部の結晶粒径（ＭＧ）の比の限定理由について、以下に記載する。なお、化学成分における％はいずれも質量％である。 Prior to the description of the embodiment for carrying out the present invention, each chemical component of the high Ni alloy in the first means and the second means of the present invention, the formula (1) of the pitting corrosion resistance index and the surface crystal grain size (OG ) The reason for limiting the ratio of the crystal grain size (MG) to the middle part is described below. All the percentages in the chemical composition are% by mass.
Ｃ：０．００１〜０．０５０％
Ｃは、高Ｎｉ合金の強度を高める効果を有し、熱間加工性および冷間加工性、耐粒界腐食性指数、および耐孔食性指数に影響を及ぼす元素である。Ｃが０．００１％未満であると、高Ｎｉ合金の強度不足となる。一方、Ｃが０．０５０％を超えると、高Ｎｉ合金の耐食性が低下し、熱間加工性および冷間加工性が低下する。そこで、Ｃは０．００１〜０．０５０％とする。
C: 0.001 to 0.050%
C is an element that has the effect of increasing the strength of the high Ni alloy and affects the hot workability and cold workability, the intergranular corrosion resistance index, and the pitting corrosion resistance index. When C is less than 0.001%, the strength of the high Ni alloy becomes insufficient. On the other hand, when C exceeds 0.050%, the corrosion resistance of the high Ni alloy decreases, and the hot workability and cold workability decrease. Therefore, C is set to 0.001 to 0.050%.
Ｓｉ：０．０１〜１．５０％
Ｓｉは、合金製造時の脱酸剤として作用し、またＮｉ合金の熱間加工性および冷間加工性に影響を及ぼす元素である。Ｓｉが０．０１％未満であると脱酸剤として不足する。一方、Ｓｉが１．５０％を超えると高Ｎｉ合金の熱間加工性および冷間加工性が低下する。そこで、Ｓｉは０．０１〜１．５０％とする。
Si: 0.01 to 1.50%
Si is an element that acts as a deoxidizing agent during alloy production and also affects the hot workability and cold workability of the Ni alloy. If Si is less than 0.01%, it will be insufficient as a deoxidizing agent. On the other hand, when Si exceeds 1.50%, the hot workability and cold workability of the high Ni alloy deteriorate. Therefore, Si is set to 0.01 to 1.50%.
Ｍｎ：０．０１〜１．５０％
Ｍｎは、熱間加工性に影響を与える元素であり、さらにオーステナイト相に影響を与える元素である。Ｍｎが０．０１％未満であると、高Ｎｉ合金の熱間加工性が低下するとともに、オーステナイト相が不安定となる。一方、Ｍｎが１．５０％を超えると熱間加工性が飽和する。そこで、Ｍｎは０．０１〜１．５０％とする。
Mn: 0.01 to 1.50%
Mn is an element that affects the hot workability and further an element that affects the austenite phase. If Mn is less than 0.01%, the hot workability of the high Ni alloy deteriorates and the austenite phase becomes unstable. On the other hand, when Mn exceeds 1.50%, the hot workability is saturated. Therefore, Mn is set to 0.01 to 1.50%.
Ｓ：≦０．０５０％
Ｓは、低融点硫化物を形成して熱間加工性に影響を与える元素である。Ｓが０．０５０％より多いと高Ｎｉ合金の熱間加工性が低下する。そこで、Ｓは０．０５０％以下とする。
S: ≤0.050%
S is an element that forms a low melting point sulfide and affects the hot workability. When S is more than 0.050%, the hot workability of the high Ni alloy deteriorates. Therefore, S is set to 0.050% or less.
Ｎｉ：３０．０〜５０．０％
Ｎｉは、高Ｎｉ合金の化学成分の残部として不可避不純物とともに、本願の高Ｎｉ合金中でもっとも多く含有されるベース元素であり、かつ高Ｎｉの表面にＮｉ硫化物皮膜を生成し、その結果、この合金の耐硫化物腐食割れ性を高める元素である。Ｎｉが３０．０％未満であると高Ｎｉ合金のオーステナイト系ベース元素となり得ない。Ｎｉが５０．０％を超えるとＮｉの耐硫化物腐食割れ性の効果は飽和する。そこで、Ｎｉは３０．０〜５０．０％とする。
Ni: 30.0-50.0%
Ni is a base element that is contained most in the high Ni alloy of the present application together with inevitable impurities as the balance of the chemical components of the high Ni alloy, and forms a Ni sulfide film on the surface of high Ni, and as a result, It is an element that enhances the sulfide corrosion cracking resistance of this alloy. When Ni is less than 30.0%, it cannot serve as an austenitic base element for high Ni alloys. If the Ni content exceeds 50.0%, the effect of Ni on the sulfide corrosion cracking resistance is saturated. Therefore, Ni is set to 30.0 to 50.0%.
Ｃｒ：１８．５〜２５．０％
Ｃｒは、耐粒界腐食性指数および耐孔食性に影響を及ぼす元素であり、また、熱間加工性および冷間加工性に影響を及ぼす元素である。Ｃｒが１８．５％未満であると耐粒界腐食性指数が低下し、かつ耐孔食性指数が低下する。一方、Ｃｒが２５．０％より多く含有されると熱間加工性および冷間加工性が低下する。そこで、Ｃｒは１８．５〜２５．０％とする。
Cr: 18.5 to 25.0%
Cr is an element that affects the intergranular corrosion resistance index and pitting corrosion resistance, and is an element that affects hot workability and cold workability. If Cr is less than 18.5%, the intergranular corrosion resistance index decreases and the pitting corrosion resistance index decreases. On the other hand, when Cr is contained in an amount of more than 25.0%, hot workability and cold workability are deteriorated. Therefore, Cr is set to 18.5 to 25.0%.
Ｍｏ：２．００〜５．００％
Ｍｏは、耐孔食性に影響を与える元素であり、また、熱間加工性および冷間加工性に影響する元素である。Ｍｏが２．００％未満では耐食性が低下する。一方、Ｍｏが５．００％を超えると、熱間加工性および冷間加工性が低下し、かつコストアップとなる。そこで、Ｍｏは２．００〜５．００％とする。
Mo: 2.00-5.00%
Mo is an element that affects pitting corrosion resistance, and also an element that affects hot workability and cold workability. If Mo is less than 2.00%, the corrosion resistance decreases. On the other hand, when Mo exceeds 5.00%, hot workability and cold workability are deteriorated and the cost is increased. Therefore, Mo is set to 2.00 to 5.00%.
Ｃｕ：１．００〜５．００％
Ｃｕは、耐食性に影響を与える元素であり、さらにオーステナイト相に影響する元素である。さらに、Ｃｕは熱間加工性にも影響する元素である。Ｃｕが１．００％未満では耐食性が低下し、かつオーステナイト相が不安定となる。一方、Ｃｕが５．００％を超えると熱間加工性が低下しコストアップとなる。そこで、Ｃｕは１．００〜５．００％とする。
Cu: 1.00 to 5.00%
Cu is an element that affects the corrosion resistance and also an element that affects the austenite phase. Further, Cu is an element that also affects hot workability. If Cu is less than 1.00%, the corrosion resistance decreases and the austenite phase becomes unstable. On the other hand, if the Cu content exceeds 5.00%, the hot workability is lowered and the cost is increased. Therefore, Cu is 1.00 to 5.00%.
Ａｌ：０．０１〜０．５０％
Ａｌは、製錬時の脱酸材として作用し、高Ｎｉ合金の強度および靭性に有効な元素である。Ａｌが０．０１％より少ないと脱酸材として不足し、かつ高Ｎｉ合金の強度および靭性が不足する。一方、Ａｌが０．５０％より多いと、耐食性が低下し、かつ熱間加工性および冷間加工性が低下する。そこで、Ａｌは０．０１〜０．５０％とする。
Al: 0.01 to 0.50%
Al acts as a deoxidizing material during smelting and is an element effective for the strength and toughness of the high Ni alloy. When Al is less than 0.01%, it is insufficient as a deoxidizing material, and the strength and toughness of the high Ni alloy are insufficient. On the other hand, when Al is more than 0.50%, the corrosion resistance decreases, and the hot workability and cold workability decrease. Therefore, Al is set to 0.01 to 0.50%.
Ｔｉ：０．５〜２．０％
Ｔｉは、耐粒界腐食性指数に影響を及ぼす元素であり、さらに熱間加工性および冷間加工性に影響する元素である。Ｔｉが０．５％より少ないと耐粒界腐食性指数が低下する。一方、Ｔｉが２．０％を超えると、熱間加工性および冷間加工性が低下し、かつ耐食性が低下する。そこで、Ｔｉは０．５〜２．０％とする。
Ti: 0.5-2.0%
Ti is an element that affects the intergranular corrosion resistance index, and also an element that affects hot workability and cold workability. If Ti is less than 0.5%, the intergranular corrosion resistance index decreases. On the other hand, when Ti exceeds 2.0%, hot workability and cold workability are deteriorated, and corrosion resistance is deteriorated. Therefore, Ti is set to 0.5 to 2.0%.
Ｎ：０．０００１〜０．０５００％
Ｎは、オーステナイト相を安定化する元素である。Ｎが０．０００１％より少ないとオーステナイト相が不安定となる。一方、Ｎが０．０５００％より多いと窒化物の生成により、耐食性と冷間加工性が低下する。そこで、Ｎは０．０００１〜０．０５００％とする。
N: 0.0001 to 0.0500%
N is an element that stabilizes the austenite phase. If N is less than 0.0001%, the austenite phase becomes unstable. On the other hand, when N is more than 0.0500%, the corrosion resistance and cold workability are deteriorated due to the formation of nitrides. Therefore, N is set to 0.0001 to 0.0500%.
Ｆｅ：≧２０．０％
Ｆｅは、熱間加工および冷間加工の際の変形抵抗に影響する元素である。Ｆｅが２０.０％未満であると熱間加工性および冷間加工性が低下する。そこで、Ｆｅは２０．０％以上とする。
Fe: ≧20.0%
Fe is an element that affects the deformation resistance during hot working and cold working. When Fe is less than 20.0%, hot workability and cold workability are deteriorated. Therefore, Fe is set to 20.0% or more.
耐孔食性指数のＰＲＥ＝［％Ｃｒ］＋３．３［％Ｍｏ］＋１６［％Ｎ］・・・式（１）：≧３１．５
耐孔食性指数のＰＲＥ＝［％Ｃｒ］＋３．３［％Ｍｏ］＋１６［％Ｎ］・・・式（１）は、３１．５未満だと、高Ｎｉ合金材の表面層に孔食が発生する。そこで、耐孔食性とするためには、耐孔食性指数のＰＲＥ＝［％Ｃｒ］＋３．３［％Ｍｏ］＋１６［％Ｎ］である式（１）の値は３１．５以上とする。
PRE of pitting corrosion resistance index=[%Cr]+3.3[%Mo]+16[%N]... Formula (1): ≧31.5
PRE of pitting corrosion resistance index=[%Cr]+3.3[%Mo]+16[%N]... If the expression (1) is less than 31.5, pitting corrosion will occur in the surface layer of the high Ni alloy material. appear. Therefore, in order to obtain the pitting corrosion resistance, the value of the equation (1) of PRE=[%Cr]+3.3[%Mo]+16[%N] of the pitting corrosion resistance index is set to 31.5 or more.
高Ｎｉ合金からなる合金管における外表面の結晶粒径（ＯＧ）と中周部の結晶粒径（ＭＧ）との比：≧１．５
ＯＧ／ＭＧの比の値は、高Ｎｉ合金からなる合金管の粒界腐食の進行度合いに影響する値である。高Ｎｉ合金からなる合金管における外表面の結晶粒径（ＯＧ）と中周部の結晶粒径（ＭＧ）との比が１．５より小さいと粒界腐食が進行する。そこで、高Ｎｉ合金からなる合金管における外表面の結晶粒径（ＯＧ）と中周部の結晶粒径（ＭＧ）との比は１．５以上とする。
Ratio of the crystal grain size (OG) of the outer surface and the crystal grain size (MG) of the middle part in the alloy tube made of a high Ni alloy: ≧1.5
The value of the ratio OG/MG is a value that influences the degree of progress of intergranular corrosion of an alloy tube made of a high Ni alloy. If the ratio of the crystal grain size (OG) of the outer surface and the crystal grain size (MG) of the middle portion of the alloy tube made of a high Ni alloy is smaller than 1.5, intergranular corrosion proceeds. Therefore, the ratio of the crystal grain size (OG) of the outer surface and the crystal grain size (MG) of the middle portion of the alloy tube made of a high Ni alloy is set to 1.5 or more.
Ｂ：０．０００１〜０．０２５０％、Ｃａ：０．０００１〜０．０２５０％、Ｍｇ：０．０００１〜０．０２５０％の合金元素のうち少なくとも１種以上を含有すること
これらの元素は本発明における選択的・付加的成分であって、いずれの元素も材料の熱間加工性に影響を及ぼす元素である。Ｂは粒界偏析し易く、ＳやＰ等の有害元素の粒界偏析を妨げ、ＣａおよびＭｇはＳと結合して粒内に固定することでＳの粒界偏析を妨げるため、添加によって熱間加工性が改善する元素である。いずれも０．０００１％未満ではその効果が十分には得られないが、０．０２５０％を超えると過剰であり、材料自体の融点を下げる、あるいは低融点化合物の形成を促して熱間加工性に悪影響を及ぼす。そこで、付加する場合は、いずれの元素も０．０００１〜０．０２５０％とする。
B: 0.0001 to 0.0250%, Ca: 0.0001 to 0.0250%, Mg: 0.0001 to 0.0250% At least one or more of the alloying elements are contained. Any of the elements that are selective and additional components in the invention are elements that affect the hot workability of the material. B tends to segregate at the grain boundaries and prevents grain boundary segregation of harmful elements such as S and P. Ca and Mg bind to S and fix in the grains to prevent segregation of S at the grain boundaries. It is an element that improves inter-workability. If the content is less than 0.0001%, the effect is not sufficiently obtained, but if it exceeds 0.0250%, the effect is excessive and the melting point of the material itself is lowered, or the formation of a low-melting compound is promoted, and hot workability is increased. Adversely affect. Therefore, when adding, all the elements are made 0.0001 to 0.0250%.
次いで、本願発明の実施をするための形態について、以下に実施例を通じて記載することとする。 Next, modes for carrying out the present invention will be described below through examples.
表１に示す化学成分からなる発明例のＮｏ．１〜２５の高Ｎｉ合金および比較例のＮｏ．２６〜３９の高Ｎｉ合金の、各Ｎｏ．のそれぞれの化学成分からなる１００ｋｇの高Ｎｉ合金をＶＩＭにて溶解し、それらをインゴットに鋳造した。次いで、それらのインゴットを熱間での鍛造および圧延である熱間加工および機械加工を行ない、さらに冷間での圧延である冷間加工を行なって、外径２５ｍｍ、内径２０ｍｍのそれぞれの高Ｎｉの合金管を製造した。 No. 1 of the invention examples having the chemical components shown in Table 1. Nos. 1 to 25 of high Ni alloy and Comparative Example No. No. 26 to 39 high Ni alloys. 100 kg of high Ni alloys consisting of the respective chemical components were melted by VIM and cast into ingots. Then, these ingots are subjected to hot forging and rolling, which is hot working and machining, and cold working, which is cold rolling, to obtain high Ni of 25 mm outside diameter and 20 mm inside diameter. Alloy pipes were manufactured.
上記で得られたこれらの高Ｎｉの合金管を評価対象材とした。続いて、これらの評価対象材の合金管は、冷間加工にて形成した加工組織を解消するために、９００〜１０００℃で５〜３０分程度の溶体化処理を施した。その後、これらの合金管の熱処理曲りを矯正機で矯正し、最後に仕上げの安定化処理を９００〜１０００℃で５〜１２０分間実施して評価用の試験片とした。 These high Ni alloy tubes obtained above were used as materials to be evaluated. Subsequently, the alloy tubes of these evaluation target materials were subjected to solution treatment at 900 to 1000° C. for about 5 to 30 minutes in order to eliminate the processed structure formed by cold working. Then, the heat treatment bending of these alloy tubes was corrected by a straightening machine, and finally, stabilization treatment for finishing was carried out at 900 to 1000° C. for 5 to 120 minutes to obtain test pieces for evaluation.
その後、試験片のＬ面（すなわち長手方向の断面であるＬ断面）のミクロ組織観察を行い、外表面から深さ１００μｍまでの範囲における結晶粒径（ＯＧ）と、合金管の平均的な結晶粒径を有する部位である合金管中周部（合金管外表面からの深さが合金管肉厚の半分となる位置を中心に、±５００μｍの範囲内）の結晶粒径（ＭＧ）の両方を切断法にて測定した。これらの測定結果を、表１および表２に示した。 After that, microstructure observation of the L surface of the test piece (that is, the L section which is the cross section in the longitudinal direction) is performed, and the crystal grain size (OG) in the range from the outer surface to the depth of 100 μm and the average crystal of the alloy tube Both of the crystal grain size (MG) in the middle part of the alloy pipe (within a range of ±500 μm around the position where the depth from the outer surface of the alloy pipe is half the thickness of the alloy pipe) which is the part having the grain size Was measured by the cutting method. The results of these measurements are shown in Tables 1 and 2.
以上の測定結果から得られた、表１における、式（１）の欄には、耐孔食性指数のＰＲＥ値＝［％Ｃｒ］＋３．３［％Ｍｏ］＋１６［％Ｎ］が３１．５以上となる本願の発明の値を満足するもので、その値 を表記した。さらに表１における、ＯＧ／ＭＧの欄には、ＯＧ／ＭＧの比の値が１．５以上となる本願の発明の値を満足するもので、その値を表記した。ただし、表１の比較例においてＯＧ／ＭＧの比の値が１．５未満のものは、その実測値に下線を付して表記した。 The PRE value of the pitting corrosion resistance index=[%Cr]+3.3[%Mo]+16[%N] is 31.5 in the column of formula (1) in Table 1 obtained from the above measurement results. The above values of the invention of the present application are satisfied, and the values are shown. Further, in Table 1, the column of OG/MG satisfies the value of the invention of the present application in which the value of the ratio of OG/MG is 1.5 or more, and the value is shown. However, in the comparative examples of Table 1, those in which the ratio of OG/MG is less than 1.5 are shown by underlining the measured values.
その他の測定における評価項目としては、表２に示す、熱間加工性、冷間加工性、耐孔食性（これはＡＳＴＭ Ｇ４８−Ａ法に準拠し、表２に孔食重量減（ｇ／ｃｍ2）で示す。）、および耐粒界腐食性（ＡＳＴＭ Ａ２６２−Ｃ法に準拠し、表２に粒界腐食度（ｍｍ／ｙｅａｒ）で示す。）である。 The evaluation items in the other measurements include hot workability, cold workability, and pitting corrosion resistance shown in Table 2 (this is based on the ASTM G48-A method, and Table 2 shows pitting corrosion weight loss (g/cm). 2 )) and intergranular corrosion resistance (in accordance with ASTM A262-C method, shown in Table 2 as intergranular corrosion degree (mm/year)).
これらの評価項目の評価方法については、以下に順次記載する。
熱間加工性は、評価対象となる合金管製造時の熱間加工において、キズや割れが発生する場合がある。そこで、熱間加工においてキズや割れの発生が無く、次工程の冷間加工に進めたものを、表２に○と表記した。一方、キズや割れが多発し、次の工程の冷間加工に進めなかったものを、表２に×と表記し下線を付した。さらに、この次工程に進めなかった例のそれ以降の工程の欄には−を表記した。
なお、表１の比較例においてＯＧ／ＭＧの欄に−と表記したものは、表２における熱間加工ができなかったことから、比を算定するに至らなかったものを意味する。
The evaluation methods for these evaluation items are described below in order.
The hot workability may cause scratches and cracks in the hot work during the production of the alloy pipe to be evaluated. Therefore, in the hot working, there are no scratches or cracks, and the cold working in the next step is indicated by "O" in Table 2. On the other hand, those in which scratches and cracks frequently occurred and which could not proceed to the cold working in the next step were marked with X in Table 2 and underlined. Furthermore, in the column of the subsequent steps of the example in which the next step was not proceeded, − was described.
In addition, in the comparative example of Table 1, what is written in the column of OG/MG as-means that the ratio could not be calculated because hot working in Table 2 could not be performed.
冷間加工性は、評価対象となる合金管製造時の冷間加工においても、キズや割れが発生する場合がある。そこで、冷間加工においてキズや割れの発生が無く、次工程に進めたものを、表２に○と表記した。一方、キズや割れが多発し、次の工程の耐孔食性の評価に進めなかったものを、表２に下線を付した×で表記した。さらに、この次工程に進めなかった場合は、それ以降の工程の欄には、測定結果がないので、−を表記した。 The cold workability may cause scratches and cracks even in the cold work at the time of manufacturing the alloy pipe to be evaluated. Therefore, in the cold working, there were no scratches and cracks, and those that proceeded to the next step were marked with ◯ in Table 2. On the other hand, those with many scratches and cracks that could not be evaluated for pitting corrosion resistance in the next step are shown in Table 2 with an underlined x. Furthermore, when the process could not be proceeded to the next step, there was no measurement result in the column of the subsequent steps, so − was described.
次工程での耐孔食性の評価は、ＡＳＴＭ Ｇ４８−Ａ法に準拠し、孔食重量減で表記するために、次の実験を行なった。供試材のＮｉ合金管の表面のスケール除去のために、このＮｉ合金管の全表面を湿式エメリーペーパーで研磨し、ＡＳＴＭ Ｇ４８−Ａ法に則って孔食試験を実施した。具体的には、Ｎｉ合金管から切り出した試験片の初期重量と表面積を測定した後、試験片を６％塩化第二鉄の２２℃の溶液中に７２時間浸漬させた後、洗浄して再度試験片の重量を測定した。試験片の得られた重量減から腐食度を、孔食重量減と称してｇ／ｃｍ2として算出した。孔食重量減が１．０ｇ／ｃｍ2以下の数値を、表２の孔食重量減の欄に表記し、それに続く評価の欄に○と表記した。一方、孔食重量減が１．０ｇ／ｃｍ2より大きな数値に下線を付し、表２の孔食重量減の欄に表記し、それに続く評価の欄に下線を付して×と表記した。さらに、この次工程に進めなかった場合、以降の工程の欄には−を表記した。 The evaluation of the pitting corrosion resistance in the next step was based on the ASTM G48-A method, and the following experiment was performed in order to express it by the weight loss of the pitting corrosion. In order to remove the scale on the surface of the Ni alloy tube as the test material, the entire surface of this Ni alloy tube was polished with wet emery paper, and a pitting corrosion test was carried out according to the ASTM G48-A method. Specifically, after measuring the initial weight and surface area of the test piece cut out from the Ni alloy tube, the test piece was immersed in a 6% ferric chloride solution at 22° C. for 72 hours, washed, and then again. The weight of the test piece was measured. From the obtained weight loss of the test piece, the corrosion degree was calculated as g/cm 2 , which is referred to as pitting weight loss. Numerical values of pitting corrosion weight loss of 1.0 g/cm 2 or less are shown in the column of pitting corrosion weight loss in Table 2, and are shown as ◯ in the subsequent evaluation column. On the other hand, numerical values with a pitting weight loss of more than 1.0 g/cm 2 are underlined, and are written in the column of pitting weight loss in Table 2, followed by underlining in the column of evaluation and are written as x. .. Furthermore, when the next step could not be proceeded to, − was written in the column of the subsequent steps.
さらに、次工程の耐粒界腐食性は、ＡＳＴＭ Ａ２６２−Ｃ法に準拠し、粒界腐食度で表記するために、次の実験を行なった。供試材のＮｉ合金管に追加で、鋭敏化熱処理として６７５℃で６０分加熱保持して空冷した後、供試材のＮｉ合金管の表面のスケール除去のために、このＮｉ合金管の全表面を湿式エメリーペーパーで研磨し、ＡＳＴＭ Ａ２６２−Ｃ法に則って粒界腐食試験を実施した。具体的には、Ｎｉ合金管から切り出した試験片の初期重量と表面積を測定した後、試験片を６５％沸騰硝酸に４８時間浸漬させた後、洗浄して再度試験片の重量を測定した。試験片の表面積や合金の密度、そして得られた重量減から浸食度を、粒界腐食度と称してｍｍ／ｙｅａｒとして算出した。この操作を５回繰り返し、各回の浸食度である粒界腐食度および初期重量と最終重量から導き出されるトータルの試食度である粒界腐食度を算出した。
なお、この試験では、基本的に５回目の粒界腐食度が最も大きくなる傾向がある。そこで、５回目のみの粒界腐食度で比較、評価し、粒界腐食度が０．７５ｍｍ／ｙｅａｒ以下となるものを、表２の粒界腐食度の欄に表記し、それに続く評価の欄に○と表記した。一方、粒界腐食度が０．７５ｍｍ／ｙｅａｒより大きい数値に下線を付し、表２の粒界腐食度の欄に表記し、それに続く評価の欄に下線を付して×と表記した。
Further, the intergranular corrosion resistance in the next step was based on the ASTM A262-C method, and the following experiment was conducted in order to express it in terms of the intergranular corrosion degree. In addition to the Ni alloy pipe of the test material, after heating and holding at 675° C. for 60 minutes as a sensitizing heat treatment and air cooling, all of the Ni alloy pipe of the test material was removed in order to remove the scale of the surface of the Ni alloy pipe. The surface was ground with a wet emery paper, and an intergranular corrosion test was carried out according to the ASTM A262-C method. Specifically, after measuring the initial weight and surface area of the test piece cut out from the Ni alloy tube, the test piece was immersed in 65% boiling nitric acid for 48 hours, washed, and the weight of the test piece was measured again. From the surface area of the test piece, the density of the alloy, and the obtained weight loss, the erosion degree was calculated as mm/year, which is called the intergranular corrosion degree. This operation was repeated 5 times, and the intergranular corrosion degree, which is the erosion degree at each time, and the intergranular corrosion degree, which is the total corrosion degree derived from the initial weight and the final weight, were calculated.
In this test, basically, the intergranular corrosion degree at the fifth time tends to be the largest. Therefore, the intergranular corrosion degree of only the fifth time is compared and evaluated, and the intergranular corrosion degree of 0.75 mm/year or less is described in the intergranular corrosion degree column of Table 2 and the subsequent evaluation column. Is marked with a circle. On the other hand, the numerical value of the intergranular corrosion degree larger than 0.75 mm/year is underlined, and is written in the column of the intergranular corrosion degree in Table 2, and the column of the evaluation that follows is underlined and is written as x.
Claims (2)
以下の式（１）に示す、耐孔食性指数のＰＲＥ値＝［％Ｃｒ］＋３．３［％Ｍｏ］＋１６［％Ｎ］：≧３１．５・・・式（１）であるＮｉ合金であって、
該Ｎｉ合金からなる合金棒または合金管の外表面の結晶粒径（ＯＧ）と中周部の結晶粒径（ＭＧ）の比であるＯＧ／ＭＧ：≧１．５であること
を特徴とする耐粒界腐食性および耐孔食性に優れ、かつ熱間加工性および冷間加工性に優れた高Ｎｉ合金。
なお、上記式（１）における［％元素］には各元素の質量％における値を代入する。また、上記における外表面の結晶粒径（ＯＧ）とは外表面から深さ１００μｍまでの結晶粒径のことであり、上記における中周部の結晶粒径（ＭＧ）とは、合金棒であればＤ／４の位置を中心に、もしくは合金管であれば外表面からの深さが合金管肉厚の半分となる位置を中心に、それぞれ±５００μｍの範囲の結晶粒径である。
ただし、Ｄは合金棒の直径である。 In mass %, C: 0.001 to 0.050%, Si: 0.01 to 1.50%, Mn: 0.01 to 1.50%, S: ≦0.050%, Ni: 30.0. ~ 50.0%, Cr: 18.5 to 25.0%, Mo: 2.00 to 5.00%, Cu: 1.00 to 5.00%, Al: 0.01 to 0.50%, Ti: 0.5 to 2.0%, N: 0.0001 to 0.0500%, Fe: ≧20.0% of alloy elements and inevitable impurities,
PRE value of pitting corrosion resistance index=[%Cr]+3.3[%Mo]+16[%N] shown in the following formula (1):≧31.5... There
OG/MG, which is the ratio of the crystal grain size (OG) of the outer surface of the alloy rod or alloy tube made of the Ni alloy to the crystal grain size (MG) of the middle portion, is ≧1.5. High Ni alloy with excellent intergranular corrosion resistance and pitting corrosion resistance as well as hot workability and cold workability.
In addition, the value in mass% of each element is substituted for [% element] in the above formula (1). The above-mentioned crystal grain size (OG) of the outer surface means the crystal grain size from the outer surface to a depth of 100 μm, and the above-mentioned crystal grain size (MG) of the middle portion is an alloy rod. For example, the crystal grain size is in the range of ±500 μm around the position of D/4 or around the position where the depth from the outer surface of the alloy pipe is half the thickness of the alloy pipe.
However, D is the diameter of the alloy rod.
以下の式（１）に示す、耐孔食性指数のＰＲＥ値＝［％Ｃｒ］＋３．３［％Ｍｏ］＋１６［％Ｎ］：≧３１．５・・・式（１）であるＮｉ合金であって、
該Ｎｉ合金からなる合金棒または合金管の外表面の結晶粒径（ＯＧ）と中周部の結晶粒径（ＭＧ）の比であるＯＧ／ＭＧ：≧１．５であること
を特徴とする耐粒界腐食性および耐孔食性に優れ、かつ熱間加工性および冷間加工性に優れた高Ｎｉ合金。
なお、上記式（１）における［％元素］には各元素の質量％における値を代入する。また、上記における外表面の結晶粒径（ＯＧ）とは外表面から深さ１００μｍまでの結晶粒径のことであり、上記における中周部の結晶粒径（ＭＧ）とは、合金棒であればＤ／４の位置を中心に、もしくは合金管であれば外表面からの深さが合金管肉厚の半分となる位置を中心に、それぞれ±５００μｍの範囲の結晶粒径である。
ただし、Ｄは合金棒の直径である。 In addition to the alloy element according to claim 1, further, in mass%, B: 0.0001 to 0.0250%, Ca: 0.0001 to 0.0250%, and Mg: 0.0001 to 0.0250%. Contains at least one of alloying elements and consists of unavoidable impurities,
PRE value of pitting corrosion resistance index=[%Cr]+3.3[%Mo]+16[%N] shown in the following formula (1):≧31.5... There
OG/MG, which is the ratio of the crystal grain size (OG) of the outer surface of the alloy rod or alloy tube made of the Ni alloy to the crystal grain size (MG) of the middle portion, is ≧1.5. High Ni alloy with excellent intergranular corrosion resistance and pitting corrosion resistance as well as hot workability and cold workability.
In addition, the value in mass% of each element is substituted for [% element] in the above formula (1). Further, the crystal grain size (OG) of the outer surface in the above is a crystal grain size from the outer surface to a depth of 100 μm, and the crystal grain size (MG) of the middle portion in the above is an alloy rod. For example, the crystal grain size is in the range of ±500 μm around the position of D/4 or around the position where the depth from the outer surface of the alloy pipe is half the thickness of the alloy pipe.
However, D is the diameter of the alloy rod.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018231996A JP7332258B2 (en) | 2018-12-11 | 2018-12-11 | High-Ni corrosion-resistant alloy with excellent intergranular corrosion resistance and pitting corrosion resistance, as well as excellent hot workability and cold workability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018231996A JP7332258B2 (en) | 2018-12-11 | 2018-12-11 | High-Ni corrosion-resistant alloy with excellent intergranular corrosion resistance and pitting corrosion resistance, as well as excellent hot workability and cold workability |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2020094235A true JP2020094235A (en) | 2020-06-18 |
| JP7332258B2 JP7332258B2 (en) | 2023-08-23 |
Family
ID=71084632
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2018231996A Active JP7332258B2 (en) | 2018-12-11 | 2018-12-11 | High-Ni corrosion-resistant alloy with excellent intergranular corrosion resistance and pitting corrosion resistance, as well as excellent hot workability and cold workability |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP7332258B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7498416B1 (en) | 2023-03-28 | 2024-06-12 | 日本製鉄株式会社 | Cr-Ni alloy tube |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03297505A (en) * | 1990-04-13 | 1991-12-27 | Nippon Steel Corp | Drawing method for seamless steel pipe of austenitic high alloy superior in sour resistance |
| JPH04110419A (en) * | 1990-08-29 | 1992-04-10 | Sumitomo Metal Ind Ltd | Production of high ni stainless steel plate |
| JP2010159438A (en) * | 2009-01-06 | 2010-07-22 | Nippon Yakin Kogyo Co Ltd | High corrosion-resistant alloy excellent in grain-boundary corrosion resistance |
| WO2017168904A1 (en) * | 2016-03-31 | 2017-10-05 | 新日鐵住金株式会社 | Ni-Fe-Cr ALLOY |
| JP2018111846A (en) * | 2017-01-10 | 2018-07-19 | 山陽特殊製鋼株式会社 | HIGH Ni ALLOY EXCELLENT IN INTERGRANULAR CORROSION RESISTANCE AND CORROSION RESISTANCE |
-
2018
- 2018-12-11 JP JP2018231996A patent/JP7332258B2/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03297505A (en) * | 1990-04-13 | 1991-12-27 | Nippon Steel Corp | Drawing method for seamless steel pipe of austenitic high alloy superior in sour resistance |
| JPH04110419A (en) * | 1990-08-29 | 1992-04-10 | Sumitomo Metal Ind Ltd | Production of high ni stainless steel plate |
| JP2010159438A (en) * | 2009-01-06 | 2010-07-22 | Nippon Yakin Kogyo Co Ltd | High corrosion-resistant alloy excellent in grain-boundary corrosion resistance |
| WO2017168904A1 (en) * | 2016-03-31 | 2017-10-05 | 新日鐵住金株式会社 | Ni-Fe-Cr ALLOY |
| JP2018111846A (en) * | 2017-01-10 | 2018-07-19 | 山陽特殊製鋼株式会社 | HIGH Ni ALLOY EXCELLENT IN INTERGRANULAR CORROSION RESISTANCE AND CORROSION RESISTANCE |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7498416B1 (en) | 2023-03-28 | 2024-06-12 | 日本製鉄株式会社 | Cr-Ni alloy tube |
Also Published As
| Publication number | Publication date |
|---|---|
| JP7332258B2 (en) | 2023-08-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6766887B2 (en) | High-strength stainless seamless steel pipe for oil wells and its manufacturing method | |
| JP5211841B2 (en) | Manufacturing method of duplex stainless steel pipe | |
| CN109642282B (en) | Duplex stainless steel and method for producing same | |
| JP6369662B1 (en) | Duplex stainless steel and manufacturing method thereof | |
| KR102124914B1 (en) | Austenitic stainless steel | |
| JPWO2004001082A1 (en) | Stainless steel pipe for oil well and manufacturing method thereof | |
| JP6409827B2 (en) | Manufacturing method of seamless stainless steel pipe for oil well | |
| JP2010209402A (en) | High-strength stainless steel pipe having high toughness and excellent corrosion resistance for oil well | |
| JP6680142B2 (en) | High-strength seamless oil country tubular good and method for manufacturing the same | |
| JP5842769B2 (en) | Duplex stainless steel and manufacturing method thereof | |
| KR101539520B1 (en) | Duplex stainless steel sheet | |
| JP5217277B2 (en) | Manufacturing method of high alloy pipe | |
| JP6672620B2 (en) | Stainless steel for oil well and stainless steel tube for oil well | |
| KR20180125566A (en) | Ni-Fe-Cr alloy | |
| JP5640777B2 (en) | Cr-containing steel pipe for line pipes with excellent intergranular stress corrosion cracking resistance in weld heat affected zone | |
| JP5224780B2 (en) | High strength stainless steel pipe | |
| JP2019065343A (en) | Steel pipe for oil well and manufacturing method therefor | |
| JP7332258B2 (en) | High-Ni corrosion-resistant alloy with excellent intergranular corrosion resistance and pitting corrosion resistance, as well as excellent hot workability and cold workability | |
| JP7002197B2 (en) | High Ni alloy with excellent intergranular corrosion resistance and pitting corrosion resistance | |
| JP7046800B2 (en) | New austenitic stainless steel alloy | |
| JPWO2019098233A1 (en) | Duplex Stainless Steel and Duplex Stainless Steel Manufacturing Methods | |
| JP7415144B2 (en) | austenitic stainless steel | |
| JP7277731B2 (en) | Duplex stainless steel and method for producing duplex stainless steel | |
| JP7333327B2 (en) | new duplex stainless steel | |
| JP5365499B2 (en) | Duplex stainless steel and urea production plant for urea production plant |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20211101 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20221116 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20230110 |
|
| A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20230313 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20230511 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20230809 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20230809 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 7332258 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |