JPH049428A - Manufacture of low cr stainless steel having ti oxide film - Google Patents
Manufacture of low cr stainless steel having ti oxide filmInfo
- Publication number
- JPH049428A JPH049428A JP11302390A JP11302390A JPH049428A JP H049428 A JPH049428 A JP H049428A JP 11302390 A JP11302390 A JP 11302390A JP 11302390 A JP11302390 A JP 11302390A JP H049428 A JPH049428 A JP H049428A
- Authority
- JP
- Japan
- Prior art keywords
- stainless steel
- atmosphere
- oxide film
- low
- heating
- 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
- 239000010935 stainless steel Substances 0.000 title claims abstract description 18
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- 238000005260 corrosion Methods 0.000 claims abstract description 24
- 230000007797 corrosion Effects 0.000 claims abstract description 24
- 239000011261 inert gas Substances 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 5
- 239000010959 steel Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 229910045601 alloy Inorganic materials 0.000 abstract description 5
- 239000000956 alloy Substances 0.000 abstract description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 4
- 235000002639 sodium chloride Nutrition 0.000 abstract description 4
- 239000011780 sodium chloride Substances 0.000 abstract description 4
- 238000010828 elution Methods 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 229910019589 Cr—Fe Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract 1
- 239000000463 material Substances 0.000 description 19
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- 101500021165 Aplysia californica Myomodulin-A Proteins 0.000 description 1
- 241000269821 Scombridae Species 0.000 description 1
- 229910009973 Ti2O3 Inorganic materials 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 235000020640 mackerel Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000008447 perception Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- GQUJEMVIKWQAEH-UHFFFAOYSA-N titanium(III) oxide Chemical compound O=[Ti]O[Ti]=O GQUJEMVIKWQAEH-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Landscapes
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Heat Treatment Of Steel (AREA)
- Physical Vapour Deposition (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、海塩粒子を含有する大気中や高温高圧水環境
下等で使用される耐食性に優れた低Ｃｒステンレス鋼の
製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing a low Cr stainless steel having excellent corrosion resistance and used in an atmosphere containing sea salt particles, a high temperature, high pressure water environment, etc.
（従来の技術）
低Ｃｒステンレス鋼を海塩粒子が飛来する海岸近くに立
地したプラントの構造材や建材などに使用する場合、赤
錆の発生が著しく、そのため、鋼表面に防錆油を塗布し
たり、塩化ビニルやエポキシ樹脂のような有機物をコー
ティングして使用している。しかし、防錆油の塗布は、
特に鋼を屋外で使用する場召定朋的に行わなげればなら
ず、また、存機コーティングにおいてもコーテイング材
が劣化するので補修が必要である。(Prior technology) When low Cr stainless steel is used for structural and building materials of plants located near the coast where sea salt particles fly, red rust occurs significantly, so rust preventive oil is applied to the steel surface. or coated with organic materials such as vinyl chloride or epoxy resin. However, the application of anti-rust oil
Particularly when steel is used outdoors, it must be carefully inspected, and even in existing coatings, the coating material deteriorates and must be repaired.
一方、低Ｃｒステンレス鋼を高温高圧水を扱う原子力用
伝熱管や腐食性の強い流体に曝される化学工業用材料な
どに使用する場合には、前記のような防錆油の塗布やコ
ーティングができず、全面腐食が大きい。これは、防錆
油を塗布しても、例えば原子力用伝熱管にあっては使用
する超純水が汚染され、化学工業用材料にあっては取り
扱う溶液が汚染されるのに加えて腐食性の強い流体によ
ってすぐに除去されてしまい、また、有機物をコーティ
ングしても、耐熱性に問題があるので高温に曝されると
すぐにその効果がなくなるからである。On the other hand, when low Cr stainless steel is used in nuclear power heat exchanger tubes that handle high-temperature, high-pressure water, or chemical industry materials that are exposed to highly corrosive fluids, it is necessary to apply anti-rust oil or coating as described above. It is not possible to do so, and the entire surface is corroded. This means that even if anti-rust oil is applied, for example, the ultrapure water used in nuclear power heat exchanger tubes will be contaminated, and in the case of materials for the chemical industry, the solutions handled will be contaminated and corrosive. This is because they are quickly removed by strong fluids, and even if organic substances are coated, they have problems with heat resistance, so they quickly lose their effectiveness when exposed to high temperatures.
そのため、より耐食性に優れた高級な材料に変更しなけ
ればならない場合も生ずる。Therefore, there may be cases where it is necessary to change to a higher grade material with better corrosion resistance.
（発明が解決しようとする課Ｂ）
本発明は、上記のように赤錆の発生を防錆油の塗布や表
面コーティングで防止したり、全面腐食の増大を避ける
ため高級な材料に変更したすせず、材料表面の性質を変
えることにより優れた耐食性を有する低Ｃｒステンレス
鋼を製造する方法を提供することを目的とする。(Problem B to be Solved by the Invention) As mentioned above, the present invention prevents the occurrence of red rust by applying rust preventive oil or surface coating, and changes to high-grade materials to avoid increase in general corrosion. First, it is an object of the present invention to provide a method for manufacturing low Cr stainless steel having excellent corrosion resistance by changing the properties of the material surface.
（課題を解決するための手段）
本発明者は、上記の目的を達成するため検討を重ねた結
果、Ｔｉを含有するＣｒ −Ｆｅ合金を高真空下あるい
は高濃度の不活性ガス雰囲気下で適当な温度で適当な時
間加熱すると合金表面にＴｆが濃化し、Ｔ１の酸化物皮
膜が形成され、この皮膜が錆が発生しやすい大気中にお
いて優れた防錆効果を有することを見出した。また、こ
の皮膜は高温水中においても保護皮膜として働き、金属
の溶出を抑制する作用を有することを確認した。(Means for Solving the Problems) As a result of repeated studies to achieve the above object, the inventors of the present invention have discovered that a Ti-containing Cr-Fe alloy is suitable for use under high vacuum or in a highly concentrated inert gas atmosphere. It was discovered that when heated at a certain temperature for an appropriate period of time, Tf becomes concentrated on the alloy surface and a T1 oxide film is formed, and this film has an excellent rust-preventing effect in the atmosphere where rust is likely to occur. It was also confirmed that this film acts as a protective film even in high-temperature water and has the effect of suppressing metal elution.
本発明はこの知覚に基づいてなされたもので、その要旨
は［重量％で、０．２〜１．０％の１１と、１１〜１８
％のＣｒを含有する鋼を、真空度が１０−’Ｔｏｒｒ以
上１０− ’Ｔｏｒｒ未満あるいは不活性ガス濃度が９
９．９〜９９．９９９％である低酸素ポテンシャル雰囲
気下で６００〜１０５０°Ｃで１分〜１０時間加熱して
、その表面にＴｉ＃化物皮膜を形成させることを特徴と
する耐食性に優れた低Ｃ「ステンレス鋼の製造方法Ｊに
ある（以下、金属元素の「％」は重量％を意味する）。The present invention was made based on this perception, and its gist is [0.2-1.0% 11 and 11-18% by weight]
% of Cr at a vacuum degree of 10-' Torr or more and less than 10-' Torr or an inert gas concentration of 9
Excellent corrosion resistance characterized by forming a Ti# compound film on the surface by heating at 600 to 1050°C for 1 minute to 10 hours in a low oxygen potential atmosphere of 9.9 to 99.999%. Low C "stainless steel manufacturing method J" (hereinafter "%" of metal elements means weight %).
本発明の対象となる低Ｃｒステンレス鋼とは、上記の成
分範囲のＴｉとＣｒを含有するステンレス鋼で、その代
表的なものを例示すれば、５ＩＩＳ ４０５．５ＵＳ４
１０Ｔｉ、 ＳＵＳ ＸＭ８、ＳＯＳ ４３０などであ
る。Ｎｉ基合金は錆びにくく、また、高温水中で耐食性
が良好であるため敢えて本発明方法を適用する必要はな
い。The low Cr stainless steel that is the object of the present invention is a stainless steel containing Ti and Cr in the above-mentioned range, and a typical example thereof is 5IIS 405.5US4.
10Ti, SUS XM8, SOS 430, etc. Since Ni-based alloys are resistant to rust and have good corrosion resistance in high-temperature water, there is no need to apply the method of the present invention.
本発明の対象となる低Ｃｒステンレス鋼の形状は、管、
棒、板などいずれでもよい。The shape of the low Cr stainless steel that is the object of the present invention is a pipe,
It can be a stick, a board, etc.
前記の低酸素ポテンシャル雰囲気とは、後述するように
、真空度が１０−’Ｔｏｒｒ以上１０−’Ｔｏｒｒ未満
の高真空あるいは純度が９９．９〜９９．９９９％の不
活性ガス１００％、換言すれば、不活性ガス濃度が９９
．９〜９９．９９９％である雰囲気である。As described later, the above-mentioned low oxygen potential atmosphere means a high vacuum with a degree of vacuum of 10-'Torr or more and less than 10-'Torr, or a 100% inert gas with a purity of 99.9-99.999%, in other words. If the inert gas concentration is 99
．． The atmosphere is 9 to 99.999%.
（作用）
以下に、本発明方法において規定した諸条件について述
べる。(Operation) The various conditions specified in the method of the present invention will be described below.
まず、本発明の対象となる低Ｃｒステンレス鋼において
Ｃｒ含有量を１１〜１８％とした理由は、厳しい環境下
で使用される化学工業プラント用材料や原子力用伝熱管
材料は耐食性が大きいことが必要であり、耐食性を支配
する元素であるＣｒの含有量が１１％未満では要求され
る耐食性能が得られず、方、１８％を超えると使用が長
期間にわたった場合脆化（４７５℃ＩＩｋ化）しやすく
なるためである。First of all, the reason why the Cr content is set at 11 to 18% in the low Cr stainless steel that is the subject of the present invention is that materials for chemical industrial plants and heat exchanger tube materials for nuclear power use, which are used in harsh environments, have high corrosion resistance. If the content of Cr, which is an element that is necessary and controls corrosion resistance, is less than 11%, the required corrosion resistance cannot be obtained, while if it exceeds 18%, it will become brittle (at 475°C) if used for a long time. This is because it becomes easier to convert into IIk).
Ｔｉは低Ｃｒステンレス鋼の表面にＴｉ酸化物（ＴｉＯ
□、Ｔｉｔ’ｓ）の皮膜を形成させるために必須の元素
である。しかし、Ｔｉ含有蓋が０．２％未満では通常の
熱処理時間内で耐食性を確保するために必要な少なくと
も５００人（０，０５μｍ）の厚さを有するＴｉ酸化物
皮膜を得ることができず、一方、１．０％を趙えて多量
に含有させてもその効果は飽和してしまうと共に、Ｆｅ
ＴｉやＦｅｚＴｉなどの金属間化合物が多量に生成し、
靭性を低下させる。従って、Ｔｉ含有量は０．２〜１．
０％とした。Ti is formed by forming Ti oxide (TiO) on the surface of low Cr stainless steel.
□, Tit's) is an essential element for forming a film. However, if the Ti content is less than 0.2%, it is impossible to obtain a Ti oxide film with a thickness of at least 500 mm (0.05 μm) necessary to ensure corrosion resistance within the normal heat treatment time. On the other hand, even if a large amount of 1.0% is contained, the effect is saturated and Fe
A large amount of intermetallic compounds such as Ti and FezTi are generated,
Decrease toughness. Therefore, the Ti content is between 0.2 and 1.
It was set to 0%.
Ｔｉ酸化物皮膜の適正な厚さは０，０５μｍ＝ｌμ−で
、１μ鋼を超えると皮膜自身の成長に伴う内部応力の増
加によりひび割れや剥離が生しやすくなる。The proper thickness of the Ti oxide film is 0.05 μm=lμ−, and if it exceeds 1 μm, cracks and peeling tend to occur due to the increase in internal stress accompanying the growth of the film itself.
加熱時の雰囲気を前述の真空度が１０− ’丁ｏｒｒ以
上あるいは不活性ガス濃度が９９，９％以上の低酸素ポ
テンシャル雰囲気とするのは、低Ｃｒステンレス鋼の表
面にＣｒ ’Ｐ Ｆ ｅ （７）ｆａ化物ではなく、Ｔ
ｉの酸化物を生成させるためである。酸素ポテンシャル
がこれより高い雰囲気中では、表面にＣｒやＦｅの酸化
物［（Ｆｅ、 Ｃｒ）ｓ０４や（Ｆｅ、 Ｃｒ）ｚｏｚ
］が形成され、トｅが外部環境と直接接触する状態とな
るため、ＴＦａｏｏｌｌを主成分とする錆が発生し、ま
た、高温水中での溶出も大きい。しかし、真空度が１０
− ’Ｔｏｒｒ以上の高真空、あるいは濃度が９９．９
９９％を超える不活性ガス雰囲気中では、Ｔｉ酸化物皮
膜を形成させるのに必要な酸素量が不足するので、真空
中で加熱する場合は真空度を１０−’Ｔｏｒｒ以上１０
−’Ｔｏｒｒ未満、不活性ガス雰囲気中で加熱する場合
はガスの濃度を９９゜９〜９９．９９９％とする。The reason why the atmosphere during heating is a low oxygen potential atmosphere with a degree of vacuum of 10-' orr or more or an inert gas concentration of 99.9% or more is because Cr'P Fe ( 7) T instead of fa compound
This is to generate the oxide of i. In an atmosphere where the oxygen potential is higher than this, oxides of Cr and Fe [(Fe, Cr)s04 and (Fe, Cr)zoz] are formed on the surface.
] is formed, and TFaooll comes into direct contact with the external environment, so rust containing TFaooll as a main component occurs, and elution in high-temperature water is also large. However, the degree of vacuum is 10
- High vacuum of Torr or higher or concentration of 99.9
In an inert gas atmosphere of more than 99%, the amount of oxygen necessary to form a Ti oxide film is insufficient, so when heating in vacuum, the degree of vacuum should be 10-' Torr or more.
-' Torr, when heating in an inert gas atmosphere, the gas concentration is 99°9 to 99.999%.
前述の低酸素ポテンシャル雰囲気下での加熱温度は、６
００℃未満では金属材料中のＴｉの表面への拡散速度が
極めて遅いため長時間加熱することが必要で、実用的で
はなく、一方、加熱温度が１０５０°Ｃを超えると材料
自身の結晶粒が粗大化して靭性の低下を招くと共に、冷
却過程で鋭敏化しやすくなる。従って、加熱温度は６０
０〜１０５０℃とする。The heating temperature in the aforementioned low oxygen potential atmosphere was 6.
If the heating temperature is lower than 1050°C, the diffusion rate of Ti in the metal material to the surface is extremely slow, making it necessary to heat it for a long time, which is not practical. On the other hand, if the heating temperature exceeds 1050°C, the crystal grains of the material itself will They become coarse, leading to a decrease in toughness, and tend to become more sensitive during the cooling process. Therefore, the heating temperature is 60
The temperature shall be 0 to 1050°C.
加熱時間については、材料の寸法を考慮して、例えば１
分〜ＩＯＱ間の間で適宜定めればよいが、１分未満では
耐食性を確保するために必要とされる５００人（０，０
５μ−）以上の厚さを有するＴｉ酸化皮膜が得られず、
一方、１０時間以上加熱すると皮膜が厚くなりすぎ、ひ
び割れや剥離を生しやすくなる。Regarding the heating time, take into consideration the dimensions of the material, for example 1
It may be set as appropriate between minutes and IOQ, but if it is less than 1 minute, 500 people (0,0
A Ti oxide film having a thickness of 5μ-) or more cannot be obtained,
On the other hand, if the film is heated for more than 10 hours, the film becomes too thick and tends to crack or peel.
従って、加熱時間は１分〜１０時間とする。Therefore, the heating time is 1 minute to 10 hours.
（実施例）
第１表に示すＡ、８２種の供試材（低Ｃｒステンレス鋼
）を真空溶解法により溶製し、鍛造後熱間圧延を行って
厚さ７ｍｍの板材とし、さらに冷間圧延により厚さ３１
の板材を作製した。供試材Ａは本発明で定めた範囲の組
成を有する低Ｃｒステンレス鋼、供試材ＢはＴ１の含有
量が本発明の範囲を外れる低Ｃｒステンレス鋼である。(Example) A, 82 types of test materials (low Cr stainless steel) shown in Table 1 were melted by vacuum melting, forged and then hot rolled into a 7 mm thick plate material, and then cold rolled. Thickness 31 by rolling
A plate material was prepared. Test material A is a low Cr stainless steel having a composition within the range defined by the present invention, and test material B is a low Cr stainless steel having a T1 content outside the range defined by the present invention.
次いで、これらの板材の表面をエメリー紙で８００番ま
で研摩し、第２表に示す条件（加熱温度、加熱時間、加
熱雰囲気）で再結晶焼鈍をかねた熱処理を施した後、生
成した酸化物皮膜の厚さの測定、錆発生試験および高温
水中での腐食試験を行った。Next, the surfaces of these plates were polished with emery paper to No. 800, and heat treatment was performed under the conditions (heating temperature, heating time, heating atmosphere) shown in Table 2, which also served as recrystallization annealing. Measurement of film thickness, rust occurrence test, and corrosion test in high temperature water were conducted.
皮膜厚さは、Ｉ ＭＭ Ａ（Ｉｏｎ Ｍｉｃｒｏ Ｍａ
ｓｓ Ａｎａｌｙｓｅｒ）を使用して供試材の表面から
板厚方向にイオンスパッタリング分析を行って求めた。The film thickness is I MM A (Ion Micro Ma
It was determined by performing ion sputtering analysis from the surface of the sample material in the thickness direction using a ss analyzer).
なお、生成相の同定はうマン分光分析により行った。In addition, the identification of the formed phase was performed by Fellman spectroscopy.
錆発生試験においては、３％ＮａＣ４１！水溶液をしみ
込ませたガーゼの上に前記の板材から切り出した厚さ３
１１Ｉｍ、幅２０１Ｉ１１、長さ４０軒の板状の試験片
を載せ、室温で３ケ月間放置した後、目視で赤錆発生の
有無を判定した。In the rust generation test, 3% NaC41! Thickness 3 cut out from the board material above on gauze impregnated with aqueous solution
A plate-shaped test piece measuring 11 Im, width 201 I11, and length 40 was placed on the test piece, and after being left at room temperature for 3 months, the presence or absence of red rust was visually determined.
高温水中での腐食試験においては、厚さ３＃Ｉ１１、輻
１０ｍｍ、長さ４０ｍｍの板状の試験片を２８０°Ｃの
高温純水中に１０００時間浸漬した後の腐食減量を測定
した。In the corrosion test in high-temperature water, a plate-shaped test piece with a thickness of 3#I11, a radius of 10 mm, and a length of 40 mm was immersed in high-temperature pure water at 280° C. for 1000 hours, and then the corrosion loss was measured.
調査結果を第２表に示す。The survey results are shown in Table 2.
ｋｌ、３．５．７．９．１１は本発明で定めた範囲の組
成を有する低Ｃ「ステンレス鋼（供試材Ａ）を用い、適
正な条件で加熱処理を行った本発明例で、鋼表面ニＴｉ
ｅ１１化物（Ｔｉ２Ｏ３） ｈ’ ラ成ル０．０５〜１
．Ｏｕ ｔａの適正な厚さの耐食性に優れた皮膜が形成
されており、鯖の発生がなく、また、高温水中での耐食
性（耐全面腐食性）も良好であった。kl, 3.5.7.9.11 is an example of the present invention in which low-C stainless steel (sample material A) having a composition within the range specified by the present invention was heat-treated under appropriate conditions. Steel surface Ni
e11 compound (Ti2O3) h' Rasel 0.05-1
．． A film with an appropriate thickness and excellent corrosion resistance was formed, and there was no occurrence of mackerel, and the corrosion resistance in high-temperature water (general corrosion resistance) was also good.
これに対して、Ｔｉ含含量量本発明で定めた範囲の組成
から外れる０、２％に満たない供試材Ｂを用いた比較例
（Ｎａ２．４．６．８、］０．１２）では、加熱温度、
加熱雰囲気などの条件が本発明の範囲内にあっても赤錆
が発生し、高温水中での耐食性も供試材Ａを用いた場合
に比較してやや劣っている。On the other hand, in a comparative example (Na2.4.6.8, ]0.12) using sample B with a Ti content of less than 0.2%, which is outside the composition range defined by the present invention, ,Heating temperature,
Even if the conditions such as the heating atmosphere are within the range of the present invention, red rust occurs, and the corrosion resistance in high-temperature water is also slightly inferior to that when sample material A is used.
また、生成した酸化物はＦｅＣｒｚＯａやＦｅｚＣｒＱ
、主体のスピネル型酸化物であった。In addition, the generated oxides are FeCrzOa and FezCrQ.
, was mainly a spinel type oxide.
一方、供試材Ａでも、加熱時間が短い比較例（Ｎｏ、１
７．１９．２１．２３）、あるいは加熱温度が本発明の
範囲を外れる６００°Ｃ未満の比較例（Ｎｏ、２５）で
は、生成する酸化物皮膜が極めて薄く、錆が発生し、高
温水中での耐食性も劣っている。On the other hand, even with sample material A, the comparative example (No. 1
7.19.21.23) or a comparative example (No. 25) in which the heating temperature was less than 600°C outside the range of the present invention, the oxide film formed was extremely thin, rust occurred, and it It also has poor corrosion resistance.
また、加熱温度が本発明の範囲内であっても、加熱時の
雰囲気が１０−’ＴｏｒｒＯ高真空の比較例（Ｎ。Moreover, even if the heating temperature is within the range of the present invention, the atmosphere during heating is a comparative example (N.
１４）、および９９．９９９％以上の高濃度のアルゴン
ガス（Ａｒ）雰囲気の比較例（Ｎα１６）では、酸化物
皮膜が極めて薄く、上記と同様の結果になった。また逆
に、加熱時雰囲気の真空度が１０−’Ｔｏｒｒ以下であ
る１０−’Ｔｏｒｒの比較例（Ｎａ１３）、あるいは、
濃度が９９．９％未満である９９％のアルゴンガス雰囲
気の比較例（Ｎ１１１５）では、材料表面にスピネル型
のＦｅＣｒｚＯ＋主体の酸化物が生成しており、赤錆が
発生し、高温水中での耐食性も劣っている。14) and a comparative example (Nα16) in a high concentration argon gas (Ar) atmosphere of 99.999% or more, the oxide film was extremely thin and the same results as above were obtained. Conversely, a comparative example (Na13) of 10-'Torr in which the degree of vacuum of the atmosphere during heating is 10-'Torr or less, or
In a comparative example (N1115) in a 99% argon gas atmosphere where the concentration is less than 99.9%, spinel-type FeCrzO+-based oxides are formed on the material surface, causing red rust and poor corrosion resistance in high-temperature water. is also inferior.
加熱温度が本発明の範囲内で、加熱雰囲気が適正であっ
ても、加熱時間が１０時間を超える比較例（Ｎα１８．
２０．２２．２４）では、酸化物皮膜が厚く成長し、外
尭的には錆の発生は認められなかったが、高温水中で皮
膜が剥離したため、
高温水中での腐
素置は大きかった。Even if the heating temperature is within the range of the present invention and the heating atmosphere is appropriate, the heating time exceeds 10 hours (Nα18.
In 20.22.24), the oxide film grew thick and no rust was observed on the outside, but the film peeled off in high-temperature water, so there was a large amount of corrosion in the high-temperature water.
（以下、
余白〕
（発明の効果）
本発明方法により製造される低Ｃｒステンレス鋼は、耐
食性に優れたＴｉ酸化物皮膜を有しており、防錆油の塗
布やを機動質などのコーティングを行わずに海塩粒子を
含む大気中で使用することができる。また、高温高圧水
環境下でも優れた耐食性を有し、原子力用伝熱管、化学
工業用材料などとして使用可能である。(Hereinafter, the margins) (Effects of the invention) The low Cr stainless steel produced by the method of the present invention has a Ti oxide film with excellent corrosion resistance, and it is easy to apply anti-rust oil or coat with a mobile material. It can be used in an atmosphere containing sea salt particles without any heat treatment.It also has excellent corrosion resistance even in high-temperature, high-pressure water environments, and can be used as heat exchanger tubes for nuclear power, materials for the chemical industry, etc.
Claims (1)
Ｃｒを含有する鋼を、真空度が１０＾−＾４Ｔｏｒｒ以
上１０＾−＾７Ｔｏｒｒ未満あるいは不活性ガス濃度が
９９．９〜９９．９９９％である低酸素ポテンシャル雰
囲気下で６００〜１０５０℃で１分〜１０時間加熱して
、その表面にＴｉ酸化物皮膜を形成させることを特徴と
する耐食性に優れた低Ｃｒステンレス鋼の製造方法。Steel containing 0.2 to 1.0% Ti and 11 to 18% Cr by weight is heated at a vacuum level of 10^-^4 Torr or more and less than 10^-^7 Torr or an inert gas concentration of 99 Low Cr with excellent corrosion resistance characterized by forming a Ti oxide film on the surface by heating at 600 to 1050°C for 1 minute to 10 hours in a low oxygen potential atmosphere of .9 to 99.999%. Method of manufacturing stainless steel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11302390A JPH0676614B2 (en) | 1990-04-26 | 1990-04-26 | Method for producing low Cr stainless steel having Ti oxide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11302390A JPH0676614B2 (en) | 1990-04-26 | 1990-04-26 | Method for producing low Cr stainless steel having Ti oxide film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH049428A true JPH049428A (en) | 1992-01-14 |
| JPH0676614B2 JPH0676614B2 (en) | 1994-09-28 |
Family
ID=14601506
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11302390A Expired - Fee Related JPH0676614B2 (en) | 1990-04-26 | 1990-04-26 | Method for producing low Cr stainless steel having Ti oxide film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0676614B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113699480A (en) * | 2021-08-23 | 2021-11-26 | 华能国际电力股份有限公司 | Method and device for simultaneously improving corrosion resistance of inner wall and outer wall of power station boiler tube |
-
1990
- 1990-04-26 JP JP11302390A patent/JPH0676614B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113699480A (en) * | 2021-08-23 | 2021-11-26 | 华能国际电力股份有限公司 | Method and device for simultaneously improving corrosion resistance of inner wall and outer wall of power station boiler tube |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0676614B2 (en) | 1994-09-28 |
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