JPH0680191B2 - Method for improving rust resistance of brightly annealed ferrite stainless steel - Google Patents
Method for improving rust resistance of brightly annealed ferrite stainless steelInfo
- Publication number
- JPH0680191B2 JPH0680191B2 JP61303231A JP30323186A JPH0680191B2 JP H0680191 B2 JPH0680191 B2 JP H0680191B2 JP 61303231 A JP61303231 A JP 61303231A JP 30323186 A JP30323186 A JP 30323186A JP H0680191 B2 JPH0680191 B2 JP H0680191B2
- Authority
- JP
- Japan
- Prior art keywords
- stainless steel
- rust resistance
- oxide
- bright
- improving
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229910001220 stainless steel Inorganic materials 0.000 title claims description 23
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 title claims description 21
- 238000000034 method Methods 0.000 title claims description 16
- 239000010935 stainless steel Substances 0.000 title description 10
- 229910000859 α-Fe Inorganic materials 0.000 title description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000000463 material Substances 0.000 claims description 23
- 238000011282 treatment Methods 0.000 claims description 16
- 238000000137 annealing Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 101150065537 SUS4 gene Proteins 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
Landscapes
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- ing And Chemical Polishing (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Description
【発明の詳細な説明】 本発明は、自動車、家庭電化製品、厨房設備、建築材等
の各種内外装材に用いられるフェライト系ステンレス鋼
光輝焼鈍材の耐銹性を改善する方法に関する。The present invention relates to a method for improving the rust resistance of ferritic stainless steel bright annealed materials used for various interior and exterior materials such as automobiles, home appliances, kitchen equipment, and building materials.
〈先行技術とその問題点〉 フェライト系ステンレス鋼による光輝焼鈍（以下「BA」
と略称する）材は、黒光りのする美麗な表面光沢を有す
るため、自動車、家庭電化製品、建築材等の各種内外装
材として用いられているが、海岸地帯での外装や、塩分
を含む食品を入れるショーケース等Cl-イオンの存在す
る環境で使用された場合、発銹し易いという問題が生じ
ている。特にBA材は、通常の不動態被膜に保護されたス
テンレス鋼材と異なり、光輝焼鈍時の極く薄い酸化被膜
に覆われているため耐銹性が劣化し易い傾向にあった。<Prior art and its problems> Bright annealing with ferritic stainless steel (hereinafter "BA")
Is used as various interior and exterior materials for automobiles, home appliances, building materials, etc. because it has a beautiful surface luster that shines black. When used in an environment where Cl - ions are present, such as in a showcase, there is a problem that rusting is easy. In particular, the BA material, unlike a stainless steel material protected by a normal passivation film, was covered with an extremely thin oxide film at the time of bright annealing, so that the rust resistance was likely to deteriorate.
そこで、近年、フェライト系ステンレス鋼BA材の耐銹性
を改善する方法が種々検討されている。Therefore, in recent years, various methods for improving the rust resistance of the ferritic stainless steel BA material have been investigated.
従来、光輝焼鈍ステンレス鋼の耐銹性改善方法に関する
技術としては、特開昭59-23882号公報、特開昭54-14214
0号公報、特開昭54-142142号公報等に開示されている
が、これらはいずれも光輝焼鈍後のステンレス鋼を電解
処理することにより行われるものである。Conventionally, as a technique relating to the method of improving the rust resistance of bright annealed stainless steel, JP-A-59-23882 and JP-A-54-14214 are known.
No. 0, JP-A-54-142142, etc., all of which are carried out by electrolytically treating the stainless steel after bright annealing.
このような電解処理を行う場合、製造ライン中に新たな
電解処理設備の設置が必要となり、コストアップを招
く。また、電解処理によって、光輝焼鈍による酸化被膜
のみならずステンレス素地も溶解され、その結果表面光
沢を損うという欠点もある。When such electrolytic treatment is performed, it is necessary to install new electrolytic treatment equipment in the production line, which causes an increase in cost. Further, the electrolytic treatment has a drawback that not only the oxide film formed by bright annealing but also the stainless steel substrate is dissolved, and as a result, the surface gloss is impaired.
〈発明の目的〉 本発明の目的は、上述した従来技術の欠点を解消し、ス
テンレス鋼BA材に電解処理を施こすことなくその耐銹性
を改善することができるフェライト系ステンレス鋼光輝
焼鈍材の耐銹性改善方法を提供することにある。<Object of the Invention> The object of the present invention is to eliminate the drawbacks of the prior art described above, and to improve the rust resistance of stainless steel BA material without subjecting it to electrolytic treatment, a ferritic stainless steel bright annealed material. It is to provide a method of improving rust resistance.
〈発明の構成〉 このような目的を達成するために、本発明者らはBA材の
酸化被膜について詳細に調査研究した結果、耐銹性を劣
化させる原因は、BA被膜の最表面に存在するMn酸化物層
にあり、このMn酸化物層を除去または薄くすることによ
り著しく耐銹性が向上することを見い出した。<Structure of the Invention> In order to achieve such an object, the present inventors have conducted a detailed investigation and research on the oxide film of the BA material, and as a result, the cause of deteriorating the rust resistance exists on the outermost surface of the BA film. It was found in the Mn oxide layer that the rust resistance was remarkably improved by removing or thinning the Mn oxide layer.
そこで、本発明者らは更に研究を進め、BA被膜中に存在
するSi酸化物（SiO2であると考えられる）がアルカリに
溶解し易いことを利用し、Si酸化物と共にMn酸化物も同
時に溶解除去するアルカリ浸漬法を開発し、本発明に至
った。Therefore, the present inventors have conducted further research, utilizing the fact that the Si oxide (which is considered to be SiO 2 ) existing in the BA film is easily dissolved in alkali, and at the same time, the Si oxide and the Mn oxide are simultaneously dissolved. The present invention has been accomplished by developing an alkali dipping method for dissolving and removing.
即ち、本発明は、フェライト系ステンレス鋼光輝焼鈍材
を製造するに際し、光輝焼鈍処理後に、光輝焼鈍材を１
〜20wt％のNaOHを含有し、室温〜100℃の水溶液に１分
以上浸漬することを特徴とするフェライト系ステンレス
鋼光輝焼鈍材の耐銹性改善方法を提供するものである。That is, according to the present invention, in producing a bright annealed material of ferritic stainless steel, after the bright annealing treatment,
A method for improving rust resistance of a bright annealed material of a ferritic stainless steel, which comprises immersing in an aqueous solution at room temperature to 100 ° C. for 1 minute or more, containing ˜20 wt% of NaOH.
なお、前述した従来技術である各種電解処理を施す方法
でもMn酸化物層を除去することができるが、この場合に
はステンレス素地まで溶解されてしまうために表面光沢
が劣化する。これに対し、本発明法ではMn酸化物とBA被
膜のみを溶解し、ステンレス素地は溶解されないため、
表面光沢の劣化がほとんどない。Although the Mn oxide layer can be removed by the above-described method of performing various electrolytic treatments, which is the conventional technique, in this case, the surface luster is deteriorated because the stainless steel body is also dissolved. On the other hand, in the method of the present invention, only the Mn oxide and the BA coating are dissolved, and the stainless steel base is not dissolved,
Almost no deterioration of surface gloss.
以下、本発明のフェライト系ステレンス鋼光輝焼鈍材の
耐銹性改善方法について詳細に説明する。Hereinafter, the method for improving the rust resistance of the bright annealed ferrite-based stainless steel of the present invention will be described in detail.
本発明は、BA処理後のフェライト系ステンレス鋼を、強
アルカリのNaOH溶液に浸漬することにより、Si酸化物と
共に耐銹性に悪影響を及ぼすMn酸化物を溶解除去するも
のである。In the present invention, the ferritic stainless steel after BA treatment is immersed in a strong alkaline NaOH solution to dissolve and remove Si oxide and Mn oxide that adversely affects rust resistance.
対象材は、フェライト系のステレンス鋼（鋼板、条鋼、
鋼管等）である。フェライト系以外のステレンス鋼材に
対しては、BA被膜中にMn酸化物があまり生成しないた
め、それほど有効とはならない。The target material is ferritic stainless steel (steel plate, bar steel,
Steel pipe). For stainless steel materials other than ferritic steel, it is not so effective because Mn oxide is not formed much in the BA film.
光輝焼鈍処理としては、例えばフェライト系ステレンス
鋼の冷延板をアンモニア分解ガスまたはN2＋H2混合ガス
の雰囲気中で800〜1000℃程度で0.5〜３分間光輝焼鈍す
る。ただし、BA処理の条件は、これらに限定されるもの
ではない。As the bright annealing treatment, for example, a cold rolled sheet of ferritic stainless steel is bright annealed at about 800 to 1000 ° C. for 0.5 to 3 minutes in an atmosphere of ammonia decomposition gas or N 2 + H 2 mixed gas. However, the BA processing conditions are not limited to these.
BA処理後のアルカリ浸漬に用いる溶液は１〜20wt％のNa
OH水溶液である。溶液濃度を１〜20wt％の範囲に限定す
る理由は、1wt％未満ではアルカリ性が不足し、Mn酸化
物を十分に除去することができず、また20wt％を超えて
もMn酸化物を除去する能力が飽和し、耐銹性向上の効果
に伸びがないからである。The solution used for alkali immersion after BA treatment is 1-20 wt% Na
It is an aqueous OH solution. The reason for limiting the solution concentration to the range of 1 to 20 wt% is that the alkalinity is insufficient when it is less than 1 wt% and the Mn oxide cannot be sufficiently removed, and when it exceeds 20 wt%, the Mn oxide is removed. This is because the ability is saturated and the effect of improving rust resistance does not extend.
前記NaOH水溶液の液温は、室温（20℃前後）〜100℃の
範囲、好ましくは60〜80℃の範囲とする。その理由は、
液温が室温未満であると反応に時間がかかるため不経済
であり、また液温が100℃を超えても反応速度が速まら
ず、時間短縮にならないからである。The solution temperature of the NaOH aqueous solution is in the range of room temperature (around 20 ° C.) to 100 ° C., preferably 60 to 80 ° C. The reason is,
This is because if the liquid temperature is lower than room temperature, the reaction takes time, which is uneconomical, and even if the liquid temperature exceeds 100 ° C., the reaction speed does not increase and the time is not shortened.
BA材の前記NaOH水溶液への浸漬時間は、１分以上であ
る。その理由は、浸漬時間が１分未満であると、前記濃
度のNaOH水溶液ではMn酸化物を十分に除去することがで
きないからである。The immersion time of the BA material in the NaOH aqueous solution is 1 minute or more. The reason is that if the immersion time is less than 1 minute, the Mn oxide cannot be sufficiently removed with the aqueous NaOH solution having the above concentration.
〈実施例〉 代表的フェライト系ステンレス鋼であるSUS430を1.0mm
厚まで冷間圧延し、露点−48℃のアンモニア分解ガス中
にて830℃、１分間の光輝焼鈍を行い、次いでスキンパ
ス圧延を行った（上記工程はすべて商用生産の設備を用
いて行われた）。<Example> 1.0 mm of typical ferritic stainless steel SUS430
Cold rolled to a thickness, brightly annealed at 830 ° C. for 1 minute in an ammonia decomposition gas with a dew point of −48 ° C., and then skin pass rolled (all of the above steps were performed using commercial production equipment). ).
このようにして製造されたSUS430BA材のBA被膜の構造を
グロー放電分光法により分析した。その結果を第１図の
グラフに示す。同図に示すように、BA被膜の最表面には
耐銹性を劣化させる原因となるMn酸化物層が存在するこ
とがわかる。The structure of the BA coating film of the SUS430BA material thus manufactured was analyzed by glow discharge spectroscopy. The results are shown in the graph of FIG. As shown in the figure, it can be seen that there is an Mn oxide layer that causes deterioration of rust resistance on the outermost surface of the BA coating.
次に、このSUS430BA材を表１に示す種々の条件のNaOH水
溶液に浸漬し、水洗して試料Ａ〜Ｎを得た。Next, this SUS430BA material was immersed in a NaOH aqueous solution under various conditions shown in Table 1 and washed with water to obtain samples A to N.
また、NaOH水溶液に浸漬していないSUS430BA材（前記と
同様の方法により製造）の試料ＯおよびSUS430BA材（前
記と同様の方法により製造）に電解処理（60℃、10％HN
O3、15C/dm2）を施した試料Ｐを作製した。In addition, sample O of SUS430BA material (manufactured by the same method as above) not immersed in the NaOH aqueous solution and electrolytic treatment (60 ° C, 10% HN) at SUS430BA material (manufactured by the same method as above)
A sample P having O 3 , 15 C / dm 2 ) was prepared.
かくして得られた各試料Ａ〜Ｐについて耐銹性評価試験
および表面の白色度の測定を行った。その結果を表１に
示す。For each of the samples A to P thus obtained, the rust resistance evaluation test and the whiteness of the surface were measured. The results are shown in Table 1.
なお、耐銹性評価試験としてはJIS Z 2371に規定される
塩水噴霧試験に基づき、50℃にて16時間塩水噴霧した
後、噴霧を休止した状態で８時間保持した。これを１サ
イクルとし、３サイクル試験した後の試験片の単位面積
当りの発銹個数により耐銹性を評価した。As the rust resistance evaluation test, based on the salt spray test defined in JIS Z 2371, after spraying salt water for 16 hours at 50 ° C., the spray was held for 8 hours in a suspended state. This was defined as one cycle, and the rust resistance was evaluated by the number of rusting per unit area of the test piece after three cycles of testing.
また、白色度は、デジタル測色色差計ND-101DC型（日本
電色工業（株））によって測定した。この白色度の数値
が大きいほど表面光沢が劣ることを示す。The whiteness was measured with a digital colorimetric color difference meter ND-101DC type (Nippon Denshoku Industries Co., Ltd.). The larger the whiteness value, the poorer the surface gloss.
下記表１の結果からわかるように、本発明法により得ら
れた試料Ａ〜Ｉは、それ以外の使用Ｊ〜Ｐに比べ、白色
度の増加を伴うことなく、即ち表面光沢を損うことな
く、耐銹性が著しく向上している。As can be seen from the results shown in Table 1 below, Samples A to I obtained by the method of the present invention did not cause an increase in whiteness, that is, did not impair the surface gloss, as compared with the other uses J to P. , The rust resistance is remarkably improved.
次に、本発明法によるNaOH水溶液浸漬処理後のBA被膜の
構造を調べるために、表１中の試料ＦについてそのBA被
膜の構造をグロー放電分光法により分析した。その結果
を第２図のグラフに示す。同図に示すように、BA被膜中
のSi酸化物が溶解され減少していると同時に、Mn酸化物
層も除去され、薄くなっていることがわかる。Next, in order to investigate the structure of the BA film after the immersion treatment with the aqueous NaOH solution according to the method of the present invention, the structure of the BA film of Sample F in Table 1 was analyzed by glow discharge spectroscopy. The results are shown in the graph of FIG. As shown in the figure, it can be seen that the Si oxide in the BA coating is dissolved and reduced, and at the same time, the Mn oxide layer is also removed and thinned.
〈発明の効果〉 本発明のフェライト系ステンレス鋼光輝焼鈍材の耐銹性
改善方法によれば、光輝焼鈍処理後に、光輝焼鈍材を１
〜20wt％NaOHを含有し、室温〜100℃の水溶性液に１分
以上浸漬することにより、電解処理を行った場合に生じ
る表面光沢の劣化を伴うことなく、優れた耐銹性を得る
ことができる。 <Effects of the Invention> According to the method of improving rust resistance of the ferritic stainless steel bright annealed material of the present invention, the bright annealed material is treated with 1% after the bright annealing treatment.
~ 20wt% NaOH is contained, and by immersing in water-soluble liquid at room temperature ~ 100 ° C for 1 minute or more, excellent rust resistance can be obtained without deterioration of surface gloss caused by electrolytic treatment. You can
しかも、本発明は電解処理設備等の付設を必要としない
ため、コストの面で有利である。In addition, the present invention is advantageous in terms of cost because it does not require additional equipment such as electrolytic treatment equipment.
第１図は、実施例におけるSUS430BA材のBA被膜の構造を
示すグラフである。 第２図は、実施例におけるNaOH水溶液浸漬処理後のSUS4
30BA材（試料Ｆ）のBA被膜の構造を示すグラフである。FIG. 1 is a graph showing the structure of the BA coating of the SUS430BA material in the examples. FIG. 2 shows SUS4 after the immersion treatment in the NaOH aqueous solution in the example.
It is a graph which shows the structure of BA film of 30BA material (sample F).
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭60−5886（ＪＰ，Ａ) 特開 昭57−82421（ＪＰ，Ａ) 特開 昭63−7387（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-60-5886 (JP, A) JP-A-57-82421 (JP, A) JP-A-63-7387 (JP, A)
Claims (1)
造するに際し、 光輝焼鈍処理後に、光輝焼鈍材を１〜20wt％のNaOHを含
有し、室温〜100℃の水溶液に１分以上浸漬することを
特徴とするフェライト系ステンレス鋼光輝焼鈍材の耐銹
性改善方法。1. When producing a bright annealed material of ferritic stainless steel, after the bright annealing treatment, the bright annealed material contains 1 to 20 wt% of NaOH and is immersed in an aqueous solution at room temperature to 100 ° C. for 1 minute or more. A method for improving rust resistance of bright annealed ferritic stainless steel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61303231A JPH0680191B2 (en) | 1986-12-19 | 1986-12-19 | Method for improving rust resistance of brightly annealed ferrite stainless steel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61303231A JPH0680191B2 (en) | 1986-12-19 | 1986-12-19 | Method for improving rust resistance of brightly annealed ferrite stainless steel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63157886A JPS63157886A (en) | 1988-06-30 |
| JPH0680191B2 true JPH0680191B2 (en) | 1994-10-12 |
Family
ID=17918456
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61303231A Expired - Fee Related JPH0680191B2 (en) | 1986-12-19 | 1986-12-19 | Method for improving rust resistance of brightly annealed ferrite stainless steel |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0680191B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5499678B2 (en) * | 2009-12-15 | 2014-05-21 | 三菱瓦斯化学株式会社 | Surface treatment method for chromium molybdenum steel |
| KR102370505B1 (en) * | 2020-04-28 | 2022-03-04 | 주식회사 포스코 | Ferritic stainless steel with improved corrosion resistance and method for manufacturing the same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS531733A (en) * | 1976-06-28 | 1978-01-10 | San Toreedeingu Kk | Noise preventing apparatus for ignition energy augument apparatus |
| JPS5334167A (en) * | 1976-09-10 | 1978-03-30 | Ishikawatoki Tekkosho Kk | Apparatus for removing stuck material in roller crusher |
| JPS5782421A (en) * | 1980-11-10 | 1982-05-22 | Kawasaki Steel Corp | Bright annealing method of mo-containing middle cr concentration ferritic stainless steel |
| JPS637387A (en) * | 1986-06-25 | 1988-01-13 | Kawasaki Steel Corp | Manufacture of stainless steel having superior corrosion resistance at weld zone |
-
1986
- 1986-12-19 JP JP61303231A patent/JPH0680191B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63157886A (en) | 1988-06-30 |
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