JPS59157285A - Pretreatment of martensitic stainless steel - Google Patents

Pretreatment of martensitic stainless steel

Info

Publication number
JPS59157285A
JPS59157285A JP2933183A JP2933183A JPS59157285A JP S59157285 A JPS59157285 A JP S59157285A JP 2933183 A JP2933183 A JP 2933183A JP 2933183 A JP2933183 A JP 2933183A JP S59157285 A JPS59157285 A JP S59157285A
Authority
JP
Japan
Prior art keywords
purity water
high purity
corrosion
stainless steel
water
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.)
Pending
Application number
JP2933183A
Other languages
Japanese (ja)
Inventor
Toshinori Ozaki
敏範 尾崎
Hiroshi Sakata
坂田　寛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hitachi Ltd
Original Assignee
Hitachi Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hitachi Ltd filed Critical Hitachi Ltd
Priority to JP2933183A priority Critical patent/JPS59157285A/en
Publication of JPS59157285A publication Critical patent/JPS59157285A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/18—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/18—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors
    • C23F11/185—Refractory metal-containing compounds

Abstract

PURPOSE:To prevent the progression of corrosion in high purity water of a high temp. by holding a martensitic stainlss steel for a specified time in the high purity water of a specific temp. contg. dissolved oxygen to generate a stable surface film on the member surface. CONSTITUTION:A martensitic stainless steel to be used in high purity water kept at a high temp. of >=60 deg.C is held for a specified time in high purity water of 200-350 deg.C incorporated therein with dissolved oxygen before or during use and is thus pretreated, by which the surface film stable in high temp. water is formed on the member surface. The progressing speed of corrosion is thus thoroughly decreased and the formation of rust in high temp. water and pitting or the environmental brittle cracking initiated from the pitting are prevented. The soln. prepd. by incorporating 0.1-8ppm dissolved oxygen or any one of 0.1-30ppm H2O2, 1-300ppm Cr2O3 or 10-300ppm MoO3<-2> ion in the high purity water is usable as the treating soln. in the above-mentioned method.

Description

【発明の詳細な説明】 〔発明の利用分野〕 本発明は高温高純度水中で用いるマルテンサイト系ステ
ンレス鋼の錆付もしくは環境脆化割れ防止のための前処
理法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to a pretreatment method for preventing rusting or environmental embrittlement cracking of martensitic stainless steel used in high-temperature, high-purity water.

〔従来技術〕[Prior art]

従来、前処理は行なわれておらず、このため８０Ｃ〜２
００ｔｌｌ’の温度域では激しい錆発生あるいは孔食発
生があり、部材間の錆付、あるいは孔食を起点とした環
境脆化割れが生ずることが多い欠点がある。Conventionally, no pretreatment has been performed, and therefore 80C~2
In the temperature range of 00tll', severe rust or pitting corrosion occurs, and there is a drawback that environmental embrittlement cracks often occur due to rusting between members or pitting corrosion.

〔発明の目的〕[Purpose of the invention]

本発明の目的は高温水中で安定な表面皮膜を与えること
で、腐食の進行速度を十分低下させ、高温水中における
錆付あるいは環境脆化割れを防止できるマルテンサイト
系ステンレス鋼の前処理法全提祇することにある。The purpose of the present invention is to provide a complete pretreatment method for martensitic stainless steel that can sufficiently reduce the rate of corrosion and prevent rusting or environmental embrittlement cracking in high-temperature water by providing a stable surface film in high-temperature water. It's about serving.

〔発明の概要〕[Summary of the invention]

本発明はマルテンサイト系ステンレス鋼の高温高純度水
中における腐食挙動が液温により複雑に変化することを
見いだした点を発明の基本としている。すなわち、高温
水中における腐食速度および腐食形態は液浸漬直後は別
とし、長時間浸漬後は次のようになる。液温２００Ｃ以
下では腐食速度大、孔食発生、液＄２００Ｃ以上では腐
食速度小、全面腐食（均一腐食）。また、一度、２００
Ｃ以上の液中に一定時間保持すると、次に２００゜Ｃ以
下の液中に浸漬しても表面皮膜は安定で孔食を生じない
。したがって、この性質を積極的に利用したものが本発
明である。The present invention is based on the discovery that the corrosion behavior of martensitic stainless steel in high-temperature, high-purity water changes in a complex manner depending on the liquid temperature. That is, the corrosion rate and corrosion form in high-temperature water are different immediately after immersion in the liquid, and after long-term immersion, the corrosion rate and corrosion form are as follows. When the liquid temperature is below 200C, the corrosion rate is high and pitting corrosion occurs, and when the liquid temperature is above 200C, the corrosion rate is low and the entire surface is corroded (uniform corrosion). Also, once, 200
When kept in a liquid with a temperature of C or higher for a certain period of time, the surface film remains stable and does not cause pitting corrosion even if it is subsequently immersed in a liquid with a temperature of 200°C or lower. Therefore, the present invention actively utilizes this property.

〔発明の実施例〕[Embodiments of the invention]

以下本発明の実施例について説明する。 Examples of the present invention will be described below.

〈実施？ｌ１１〉 Ａｌ５１４１４　　マルテンサイト糸ステンレス鋼を９
７０ＣＸ１ｈｒ−＋油冷、６００ＣＸ５ｈｒ＋空冷の熱
処理を与えた後、３０Ｘ６０Ｘ２ｔの試料を切出した。<implementation? l11〉 Al51414 martensitic thread stainless steel 9
After heat treatment of 70CX1hr-+oil cooling and 600CX5hr+air cooling, a 30X60X2t sample was cut out.

この試料表面をエメリー紙≠６００で研摩後、３００ｍ
ｔの小型オートクレーブを用いて表に示す条件で前処理
を与えた。その後、これらの試料を水洗、乾燥後、表に
示す条件で腐食試験した。そして、試料表面に発生した
孔食の発生密度およびその深さを測定した。その結果を
表の左方に示す。表より以下のことが明らかである。After polishing the sample surface with emery paper≠600,
Pretreatment was performed using a small-sized autoclave of 100 ml under the conditions shown in the table. Thereafter, these samples were washed with water, dried, and then subjected to a corrosion test under the conditions shown in the table. Then, the density and depth of pitting corrosion generated on the sample surface were measured. The results are shown on the left side of the table. The following is clear from the table.

イ）ＡＸ　　２より前処理なし試料には激しい孔食が生
ずること、 口）ＡＸ　　１より大気中で表面皮膜（酸化物）をつけ
ても防食効果はなく、逆に深い孔食が生ず。b) Severe pitting corrosion occurs in samples without pretreatment from AX 2. Mouth) Even if a surface film (oxide) is applied in the atmosphere from AX 1, there is no corrosion prevention effect, and on the contrary, deep pitting occurs.

ること、 ハ）屋Ａ−１〜Ａ−６より２５０〜３５０Ｃの前処理は
耐孔食性改善に有効であること、二）ＡＡ、−４および
Ｂ−１〜Ｂ−３よりＤｏが多いとき耐孔食性が改善され
、ＤＯ＝０．１〜７．２ｐｐｍ　が有効であること、 ホ）ＡＡ−４およびｃ−ｉ〜Ｃ−３より前処理時間が長
いとき耐孔食性は改善され、保持時間は１００ｈｒ以上
が望ましいこと、 ））ＡＤ　　１−Ｄ　　４よシＨｚＯ２濃度は０．１〜
３０　ｐｐｍで耐孔食性が改善されること、チ）　Ａ　
Ｅ　　１〜Ｅ　、　４よりＣｒ２Ｏ３は、１〜３００ｐ
ｐｍで耐孔食性が改善されること、 す）　Ａ　Ｆ−１〜Ｆ　−４よｐ　Ｍ　ｏ　０３−２　
は１０〜３００ｐｐｍで耐孔食性が改善されること、 が明らかである。c) Pretreatment at 250 to 350C is effective in improving pitting corrosion resistance from A-1 to A-6, and b) When Do is higher than AA, -4 and B-1 to B-3. Pitting corrosion resistance is improved and DO = 0.1 to 7.2 ppm is effective; e) Pitting corrosion resistance is improved when the pretreatment time is longer than that of AA-4 and c-i to C-3, and retention It is desirable that the time is 100 hr or more, )) AD 1-D 4, HzO2 concentration is 0.1~
Pitting corrosion resistance is improved at 30 ppm, h) A
From E 1 to E, 4, Cr2O3 is 1 to 300p
Pitting corrosion resistance is improved by pm) A F-1 to F-4 p Mo 03-2
It is clear that the pitting corrosion resistance is improved at 10 to 300 ppm.

ここで、耐食性が改善された試料は例外なく薄く、ち密
な黒色皮膜がついたものであシ、Ｘ線回析の結果、Ｆｅ
３Ｏ４を主体とした皮、摸であることが確認された。Here, all the samples with improved corrosion resistance had a thin, dense black film, and as a result of X-ray diffraction, Fe
It was confirmed that the skin was made mainly of 3O4.

〈実施例２〉 実施例１で示した材料を用いＭＩＯのボルトおよびナツ
トを作った。この部品を表のＡＡ　　４の前処理を与え
た後、相互に組合せ表に示す腐食試験を行なった。その
後、ボルト、ナツトのゆるめ力をトルクレンチを用い測
定した。その結果、本ボルト、ナツトは５本の平均値が
ｚｓＫ９・ｍであった。<Example 2> MIO bolts and nuts were made using the materials shown in Example 1. The parts were subjected to the AA 4 pretreatment shown in the table and then subjected to the corrosion tests shown in the combination table. Thereafter, the loosening force of the bolts and nuts was measured using a torque wrench. As a result, the average value of the five bolts and nuts was zsK9·m.

一方、前記、前処理を行なわ７ず腐食試験を行なったボ
ルト、ナツトでは５本の平均迫が３５．５匈・ｍであっ
た。On the other hand, for the bolts and nuts that were subjected to the corrosion test without being pretreated, the average strength of the five bolts was 35.5 cm.

また、腐食試験後のボルトの上下に治具を溶接し、小野
式回転曲げ疲労試験片を作成した。そして、真応力４０
ＫＩｉ−ｆ／ｒｒａｎ２で疲労試験を行なった。その結
果、破断繰返し数、Ｎは前処理を与えた試料が５本とも
Ｎ）１０７サイクルであるのに対し、前処理なしの試料
では、５本の平均値がＮ＝１．８Ｘ１０６サイクルであ
った。In addition, jigs were welded to the top and bottom of the bolts after the corrosion test to create Ono-type rotary bending fatigue test pieces. And true stress 40
A fatigue test was conducted using KIi-f/rran2. As a result, the number of rupture cycles, N, was 107 cycles for all five samples with pretreatment, whereas the average value for the five samples without pretreatment was N=1.8×106 cycles. Ta.

以上よシ、本発明前処理材は錆付防止に有効であると同
時に環境脆化割れ性にも有効と判断される。Based on the above, it is judged that the pretreated material of the present invention is effective in preventing rusting and is also effective in reducing environmental embrittlement cracking.

〔発明の効果〕〔Effect of the invention〕

以上説明したように本発明によれば次の効果が得られる
。As explained above, according to the present invention, the following effects can be obtained.

（イ）新しい機能 使用環境中で一定時間保持するのみで耐孔食性を改善す
ることが可能である。したがって、部材表面に異質な物
質が付着していないので、２使用環境を汚染することが
ない。(a) New function It is possible to improve pitting corrosion resistance simply by holding the product in a usage environment for a certain period of time. Therefore, since no foreign substances adhere to the surface of the member, the environment in which it is used will not be contaminated.

（ロ）性能、効率の向上 機器の信頼性向上が期待される。また、錆付防止につい
ては、分解点検が容易となる。また、組立後の機器をま
るごと処理することが出来、組立作業の効率向上にも有
効である。(b) Improved performance and efficiency It is expected that the reliability of equipment will be improved. In addition, as for rust prevention, disassembly and inspection becomes easier. Furthermore, it is possible to process the entire device after assembly, which is effective in improving the efficiency of assembly work.

Claims (1)

【特許請求の範囲】[Claims] １．６０Ｃ以上の高温高純度水中で使用するマルテンサ
イト系ステンレス鋼の前処理法において、使用前又は使
用途中溶存酸素を含有させた２００〜３５０Ｃの高純度
水中に一定時間保持し、部材表面に安定な表面皮膜を生
成させることを特徴とする、マルテンサイト系ステンレ
ス鋼の前処理法。 ２、　前項における処理質として高純度水中に溶存酸素
：　０．１〜８　ｐｐｍ　　６ル１．−、ばＨ２Ｏ２：
　０．１〜３０　ｐＩ）ｍ　、　Ｃｒ２Ｏ３：　１〜３
００　ｐｐｍ　ｈるいはＭ　Ｏ０３−２イオ７：１０〜
３００ｐｐｍ　のいずれかを含有させたことを特徴とす
るマルテンサイト系ステンレス鋼の前処理法。In the pretreatment method for martensitic stainless steel used in high-temperature, high-purity water of 1.60 C or higher, the material is kept in high-purity water of 200 to 350 C containing dissolved oxygen for a certain period of time before or during use, and the surface of the material is A pretreatment method for martensitic stainless steel that produces a stable surface film. 2. Oxygen dissolved in high-purity water as the treatment quality in the previous section: 0.1-8 ppm 1. -, H2O2:
0.1-30 pI)m, Cr2O3: 1-3
00 ppm hruiha M O03-2io7:10~
A pretreatment method for martensitic stainless steel characterized by containing 300 ppm of either.
JP2933183A 1983-02-25 1983-02-25 Pretreatment of martensitic stainless steel Pending JPS59157285A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2933183A JPS59157285A (en) 1983-02-25 1983-02-25 Pretreatment of martensitic stainless steel

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2933183A JPS59157285A (en) 1983-02-25 1983-02-25 Pretreatment of martensitic stainless steel

Publications (1)

Publication Number Publication Date
JPS59157285A true JPS59157285A (en) 1984-09-06

Family

ID=12273240

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2933183A Pending JPS59157285A (en) 1983-02-25 1983-02-25 Pretreatment of martensitic stainless steel

Country Status (1)

Country Link
JP (1) JPS59157285A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998024948A1 (en) * 1996-12-06 1998-06-11 Siemens Aktiengesellschaft Surface processing of steel or nickel alloy and processed steel or nickel alloy
WO1999027161A1 (en) * 1997-11-21 1999-06-03 Zakrytoe Aktionernoe Obschestvo 'firma Novye Sistemnye Tekhnologii' Method of metallic and metalliferous surface protection
WO2003033766A3 (en) * 2001-10-16 2003-10-30 Unilever Plc Corrosion protection process
CN109338345A (en) * 2018-11-30 2019-02-15 中国科学院金属研究所 A kind of environment-friendly type surface passivation treatment method of medical high-nitrogen nickel-free stainless steel

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998024948A1 (en) * 1996-12-06 1998-06-11 Siemens Aktiengesellschaft Surface processing of steel or nickel alloy and processed steel or nickel alloy
WO1999027161A1 (en) * 1997-11-21 1999-06-03 Zakrytoe Aktionernoe Obschestvo 'firma Novye Sistemnye Tekhnologii' Method of metallic and metalliferous surface protection
WO2003033766A3 (en) * 2001-10-16 2003-10-30 Unilever Plc Corrosion protection process
CN109338345A (en) * 2018-11-30 2019-02-15 中国科学院金属研究所 A kind of environment-friendly type surface passivation treatment method of medical high-nitrogen nickel-free stainless steel

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