JPS624475B2 - - Google Patents
Info
- Publication number
- JPS624475B2 JPS624475B2 JP58012648A JP1264883A JPS624475B2 JP S624475 B2 JPS624475 B2 JP S624475B2 JP 58012648 A JP58012648 A JP 58012648A JP 1264883 A JP1264883 A JP 1264883A JP S624475 B2 JPS624475 B2 JP S624475B2
- Authority
- JP
- Japan
- Prior art keywords
- stainless steel
- annealing
- plating
- plate
- thin
- 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
Links
- 239000010935 stainless steel Substances 0.000 claims description 42
- 229910001220 stainless steel Inorganic materials 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 10
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000001953 recrystallisation Methods 0.000 claims description 5
- 238000005097 cold rolling Methods 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 238000000137 annealing Methods 0.000 description 39
- 230000007797 corrosion Effects 0.000 description 23
- 238000005260 corrosion Methods 0.000 description 23
- 238000007747 plating Methods 0.000 description 23
- 229910000831 Steel Inorganic materials 0.000 description 18
- 239000010959 steel Substances 0.000 description 18
- 229910052804 chromium Inorganic materials 0.000 description 13
- 238000009792 diffusion process Methods 0.000 description 7
- 229910000599 Cr alloy Inorganic materials 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000005554 pickling Methods 0.000 description 5
- 238000005254 chromizing Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 229910019589 Cr—Fe Inorganic materials 0.000 description 1
- 229910001361 White metal Inorganic materials 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010969 white metal Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Description
本発明はステンレス薄板の表面処理に関するも
のである。
従来のステンレス薄板の製造はFeにCr、Niあ
るいは少量のMo、Al、Ti等の添加元素を加えて
製鋼し、鋼片→熱間圧延→熱延板焼鈍酸洗→光輝
焼鈍、または酸化焼鈍→酸洗・調質圧延または研
磨して成品としている。
ところでステンレス鋼の主要成分であるCr
は、Feに較べ酸素との親和力がはるかに強いた
め酸化し易く、熱間圧延、酸化焼鈍の過程でFe
と共にスケールを形成し、数回の酸化―デスケー
ルをくりかえすうちに板厚の中心成分に較べ表面
層のCr成分はかなり少なくなつている。いわゆ
る脱Cr層を形成している。
本発明者らが代表的フエライトステンレスであ
るSUS430の薄板を調べたところ、第１図に示す
ように板厚中心のCr量は17.1％であつたのに対し
最表面のCr量は8.6％しかなかつた。ステンレス
薄板の特徴はその耐食性・耐錆性にあり、それは
鋼中のCr量に大きく影響するが、かんじんの最
表面でCr量が欠乏しているのは大きな問題であ
る。しかも耐食性・耐錆性に影響するのは実に最
表面の数十Åから数μｍの成分やCr2O3皮膜の緻
密さにある。
ステンレス薄板の製造工程で何回かのスケール
形成はさけられず、その限りにおいて表面の脱
Crはさけられない。そこで最終成品にCrをメツ
キすることにより表面の耐食性の向上が考えられ
るが、メツキだけではミクロ的にみると亀裂や点
欠陥があり必ずしも耐食性向上にはつながらな
い。
また、最近ステンレス薄板を屋根や外壁などい
わゆる外装材として使用される事が増えてきた。
この場合金属光沢として白く光るより塗装して使
用される場合が多い。ところでいかに高品質の塗
料を使用しようと有機物である以上老化を防ぐこ
とはできず、５年〜10年毎に塗り替えなければな
らない。せつかく高耐食性のステンレスを使用し
ても塗装を塗り替るのは無駄である。
また、従来のカラーステンレスは湿式化成処理
した後、封孔処理をおこなうが、メツキと同じで
完全に点欠陥を防ぐことはできなかつた。そこで
メンテナンスフリーの無機皮膜であれば永久的に
色調を保つことができる。いわゆるカラーステン
レスがこのような性質を有しているが、これまで
の湿式化成処理では処理時間が長いため帯状のス
テンレス薄板を連続的に化成処理するには無理で
あつたし、また設備をつくつても高価につくため
製造されなかつた。
本発明者らは種々の実験の結果、最終焼鈍の
前、すなわち冷延後のステンレス薄板にCrをメ
ツキして焼鈍―熱拡散することにより表面の脱
Cr層にCrを補い、むしろCrを富化することで高
耐食性の高品質ステンレス薄板にする方法を見い
出すとともに、上記焼鈍を酸化性雰囲気で行うこ
とにより、その雰囲気、焼鈍温度、焼鈍時間の調
節で黄金色から茶褐色、赤紫、青、青紫色、黒色
と選択することができ、これまでの湿式化成処理
よりはるかに安価にカラーステンレスを製造する
ことができることを見出したのである。
即ち、本発明の要旨とするところは次の通りで
ある。
(1) 冷延後のステンレス薄板にCrメツキをほど
こし、ついで酸化性雰囲気で再結晶温度以上
1000℃以下の温度範囲において焼鈍をおこなう
ことを特徴とするステンレス薄板の製造方法。
(2) 冷延後のステンレス薄板にCrを主成分とし
てこれにMo、Ｖ、Ｗ、Ｐの１種または２種以
上を含有した合金メツキをほどこし、酸化性雰
囲気で再結晶温度以上、1000℃以下の温度範囲
において焼鈍をおこなうことを特徴とするステ
ンレス薄板の製造方法。
(3) 第１項の方法に、薄板を酸洗または表面研磨
して表面酸化膜を除去することを付加した方
法。
(4) 第２項の方法に、薄板を酸洗または表面研磨
して表面酸化膜を除去することを付加した方
法。
以下本発明を詳細に説明する。
本発明は冷延後のステンレス薄板にCrメツキ
を施して酸化性雰囲気で焼鈍するものであるが、
一般にCrは酸素との親和力が強くBA（光輝）焼
鈍が難しい。AXガス（H2：75％、N2：25％）で
も露点が−40℃程度に上ると酸化してテンパーカ
ラーが生じる。反面Cr2O3の緻密な皮膜は酸化膜
の成長を押えO2の存在する酸化雰囲気で焼鈍し
ても、連続焼鈍炉のような短時間加熱であれば酸
化膜を1000〜2000Åのきれいな青色にとどめるこ
とができる。
このような事情より、本発明は0.1μｍ以上、
好ましくは0.5μｍ程度迄のCrメツキをしたステ
ンレス薄板を酸化性雰囲気（酸素又は水蒸気を含
む雰囲気）で再結晶温度以上1000℃以下の温度範
囲で通常の連続焼鈍の条件で焼鈍する。この結果
を示したのが、第２図であるが、同図Ａは焼鈍前
の板厚最表面から0.5〜0.6μｍ迄に100％のCrメ
ツキを施した状態を示し、同図Ｂでは850℃×２
分の焼鈍後の状態を示している。該図で明らかな
のように0.1〜0.2μｍの酸化膜と、Crが拡散して
形成したCr―FeのCr富化合金層があり、酸化ス
ケールを酸洗または研磨でデスケールしても高
Cr高耐食性表面層を残すことができるのであ
る。
次に、本発明が対象とするステンレス薄板につ
いて考察する。
Crメツキするステンレス薄板のCr量がどの程
度必要であるか、鋼中のCr量を０〜９％まで変
えた試験材をつくり、Crメツキ厚さ0.3μｍをほ
どこし、空気比1.2の直火炉（O2：約５％）で850
℃まで焼鈍し、酸化スケールを金属光沢がでるま
で研磨して、耐食試験をおこなつた。結果を表１
に示す。
The present invention relates to surface treatment of thin stainless steel plates. Conventional stainless steel sheets are manufactured by adding additive elements such as Cr, Ni, or small amounts of Mo, Al, and Ti to Fe, and then proceeding through the following steps: steel billet → hot rolling → hot rolled plate annealing pickling → bright annealing or oxidation annealing →It is made into a finished product by pickling, temper rolling, or polishing. By the way, Cr, the main component of stainless steel
Since Fe has a much stronger affinity for oxygen than Fe, it is easily oxidized, and Fe is easily oxidized during hot rolling and oxidative annealing.
After repeated oxidation and descaling several times, the Cr content in the surface layer becomes considerably smaller than that in the center of the plate thickness. This forms a so-called Cr-free layer. When the present inventors investigated a thin plate of SUS430, a typical ferrite stainless steel, the Cr content at the center of the plate thickness was 17.1%, as shown in Figure 1, but the Cr content at the outermost surface was only 8.6%. Nakatsuta. A feature of stainless steel sheets is their corrosion and rust resistance, which greatly affects the amount of Cr in the steel, but the lack of Cr on the outermost surface of the steel is a major problem. Moreover, what influences the corrosion resistance and rust resistance is the components of the outermost surface ranging from tens of angstroms to several micrometers and the density of the Cr 2 O 3 film. Scale formation is unavoidable several times in the manufacturing process of stainless steel thin plates, and to that extent, the surface should not be removed.
Cr cannot be avoided. Therefore, it is possible to improve the corrosion resistance of the surface by plating the final product with Cr, but plating alone does not necessarily lead to improved corrosion resistance because microscopically, cracks and point defects occur. In addition, recently, stainless steel sheets have been increasingly used as exterior materials such as roofs and exterior walls.
In this case, it is often used as a paint rather than as a shiny white metal. By the way, no matter how high-quality paint you use, as it is an organic material, it cannot prevent aging and must be repainted every 5 to 10 years. Even if you use highly corrosion-resistant stainless steel, it is a waste to repaint it. Furthermore, conventional colored stainless steel is subjected to a wet chemical conversion treatment followed by a pore sealing treatment, but like plating, it was not possible to completely prevent point defects. Therefore, maintenance-free inorganic coatings can maintain the color tone permanently. So-called colored stainless steel has these properties, but due to the long processing time of conventional wet chemical conversion treatments, it was impossible to continuously chemically treat strip-shaped stainless steel sheets, and it also required equipment. It was never manufactured because it was too expensive. As a result of various experiments, the present inventors found that before final annealing, that is, after cold rolling, stainless steel sheets were plated with Cr and the surface was removed by annealing and thermal diffusion.
We found a way to make a high-quality stainless steel sheet with high corrosion resistance by supplementing the Cr layer with Cr, or rather enriching it, and by performing the above annealing in an oxidizing atmosphere, we were able to adjust the atmosphere, annealing temperature, and annealing time. They discovered that colors can be selected from gold to brown, reddish-purple, blue, bluish-purple, and black, making it possible to produce colored stainless steel at a much lower cost than conventional wet chemical conversion treatments. That is, the gist of the present invention is as follows. (1) Cr plating is applied to the cold-rolled stainless steel sheet, and then heated above the recrystallization temperature in an oxidizing atmosphere.
A method for manufacturing thin stainless steel sheets, characterized by annealing in a temperature range of 1000°C or less. (2) An alloy plating containing Cr as the main component and one or more of Mo, V, W, and P is applied to the cold-rolled thin stainless steel sheet, and the plate is heated at 1000°C above the recrystallization temperature in an oxidizing atmosphere. A method for manufacturing a thin stainless steel plate, characterized by annealing in the following temperature range. (3) A method in which the thin plate is pickled or surface polished to remove the surface oxide film in addition to the method described in item 1. (4) A method in which the thin plate is pickled or surface polished to remove the surface oxide film in addition to the method described in item 2. The present invention will be explained in detail below. The present invention applies Cr plating to a stainless steel sheet after cold rolling and annealing it in an oxidizing atmosphere.
In general, Cr has a strong affinity for oxygen and is difficult to perform BA (bright) annealing. Even with AX gas (H 2 : 75%, N 2 : 25%), if the dew point rises to around -40°C, it will oxidize and cause temper color. On the other hand, the dense film of Cr 2 O 3 suppresses the growth of the oxide film, and even when annealing is performed in an oxidizing atmosphere containing O 2 , the oxide film can be reduced to a beautiful blue color with a thickness of 1000 to 2000 Å if heated for a short time such as in a continuous annealing furnace. can be kept at Under these circumstances, the present invention provides a
Preferably, a thin stainless steel plate plated with Cr up to about 0.5 μm is annealed in an oxidizing atmosphere (atmosphere containing oxygen or water vapor) at a temperature range from the recrystallization temperature to 1000° C. under normal continuous annealing conditions. This result is shown in Figure 2. Figure A shows a state in which 100% Cr plating has been applied from the outermost surface of the plate to 0.5 to 0.6 μm before annealing, and Figure B shows a state in which 100% Cr plating has been applied to 0.5 to 0.6 μm from the outermost surface of the plate before annealing. ℃×2
The state after annealing for 30 minutes is shown. As is clear from the figure, there is an oxide film of 0.1 to 0.2 μm and a Cr-rich alloy layer of Cr-Fe formed by diffusion of Cr, and even if the oxide scale is descaled by pickling or polishing, the high
This allows a highly corrosion-resistant Cr surface layer to remain. Next, a stainless steel thin plate to which the present invention is directed will be considered. To find out how much Cr is required in stainless steel sheets to be plated with Cr, we made test materials with varying amounts of Cr in the steel from 0 to 9%, applied Cr plating to a thickness of 0.3 μm, and heated them in a direct-fired furnace with an air ratio of 1.2. O2 : about 5%) at 850
It was annealed to ℃, the oxide scale was polished until it had a metallic luster, and a corrosion resistance test was conducted. Table 1 shows the results.
Shown below.
【表】
Crメツキする鋼板中のCr量が２％以下に少な
くなると、メツキしたCrは鋼中に拡散してしま
つて、表面のCr濃度が薄くなり耐食性を保つこ
とができない。本実験の結果は鋼中のCr量4.3％
でほぼSUS430並、７％Cr以上になるとSUS430
以上の耐食性を示すことがわかつた。
一般にステンレスとは12％Cr以上といわれて
いるが、ステンレス薄板の最表面はCrが少なく
なつている。そこでステンレスとしての耐食性を
保つように最表面のCr成分を12％以上にするに
は本発明法のCrメツキ・焼鈍法を用いても、鋼
中のCr量が４〜５％以上は必要である。
以上本発明についてCrメツキについて説明し
たが、CrにMo、Ｖ、Ｗ、Ｐ等の元素を１種又は
２種以上、１〜10％の範囲で含有させた合金メツ
キは、実施例にも示すように耐食性により優れ、
カラーステンレスとしてもまつたく新しい製品を
提供できるのである。
なお、CrおよびCr合金をメツキする方法は、
別に限定する必要はない。すなわち、Crメツキ
においては６価Crだけでなく３価Crを使用した
メツキ法でもよく、また合金メツキにおいては通
常の直流電解だけでなくパルスメツキでもよい。
いずれにしろ本発明は、Cr量４％以上の薄鋼
板に0.1μｍ以上のCr又はCr合金のメツキを施し
て焼鈍し熱拡散により表面にCrを富化せしめた
ステンレス薄板の製造法を提供し得るものであ
る。
これまでも普通鋼にCrメツキまたは粉末金属
Crを塗布して熱拡散する、いわゆるクロマイジ
ングはよく知られているが、熱拡散の時間が長時
間であり、帯鋼のように広い面積にわたつておこ
なうことは例がなかつた。これまでのクロマイジ
ングは普通鋼や特殊鋼の小さな工具や部品の耐熱
性を高めるために高価についても特殊な用途に使
われてきたにすぎない。
本発明のステンレス薄板にCrまたはCr合金を
メツキし、焼鈍―熱拡散させる方法は従来のクロ
マイジングと違つてステンレス薄板の表面脱Cr
層にCrを補い、逆にCr富化するものであるため
極薄メツキ（0.1〜0.5μｍ程度）と通常の焼鈍時
間で十分である。
次に本発明法を用いてステンレス薄板を製造し
た実施例について述べる。
実施例 １
SUS409（11％Cr）の冷延板に0.5μｍのCrメ
ツキをほどこし普通鋼の連続焼鈍炉（H2：1.5
％、N2：98.5％、露点−20℃）で850℃×2min加
熱した。得られた鋼板は黒灰色となり酸化膜厚み
は約2000Åであつた。
同一焼鈍条件でメツキしないSUS409の冷延板
を通板したときの表面酸化膜は青紫色で約1500Å
の厚みであつた。この両種の鋼板を合金光沢が出
るまで研磨して耐食試験をおこなつた結果を表２
に示す。[Table] When the amount of Cr in a Cr-plated steel sheet decreases to 2% or less, the plated Cr will diffuse into the steel, and the Cr concentration on the surface will become thinner, making it impossible to maintain corrosion resistance. The result of this experiment was that the amount of Cr in the steel was 4.3%.
It is almost the same as SUS430, and when it becomes 7% Cr or more, it becomes SUS430.
It was found that the above corrosion resistance was exhibited. Stainless steel is generally said to have a content of 12% Cr or more, but the outermost surface of a thin stainless steel plate has less Cr. Therefore, in order to maintain the corrosion resistance of stainless steel and increase the Cr content on the outermost surface to 12% or more, even if the Cr plating/annealing method of the present invention is used, the Cr content in the steel must be 4 to 5% or more. be. The present invention has been described above regarding Cr plating, but alloy plating in which Cr contains one or more elements such as Mo, V, W, and P in a range of 1 to 10% is also shown in Examples. Excellent corrosion resistance,
We can also provide new products as colored stainless steel. The method for plating Cr and Cr alloy is as follows:
There is no need to specifically limit it. That is, in Cr plating, a plating method using not only hexavalent Cr but also trivalent Cr may be used, and in alloy plating, not only normal DC electrolysis but also pulse plating may be used. In any case, the present invention provides a method for producing a thin stainless steel plate in which a thin steel plate with a Cr content of 4% or more is plated with Cr or Cr alloy to a thickness of 0.1 μm or more, annealed, and the surface is enriched with Cr by thermal diffusion. It's something you get. Until now, ordinary steel has been coated with Cr plating or powder metal.
So-called chromizing, in which Cr is applied and thermally diffused, is well known, but the thermal diffusion takes a long time, and it has never been performed over a large area like steel strips. Up until now, chromizing has only been used for special and expensive purposes to improve the heat resistance of small tools and parts made of ordinary steel and special steel. Unlike conventional chromizing, the method of plating Cr or Cr alloy on a thin stainless steel plate and annealing and thermal diffusion of the present invention removes Cr from the surface of the thin stainless steel plate, unlike conventional chromizing.
Since the layer is supplemented with Cr and conversely enriched with Cr, extremely thin plating (about 0.1 to 0.5 μm) and normal annealing time are sufficient. Next, an example in which a thin stainless steel plate was manufactured using the method of the present invention will be described. Example 1 A cold-rolled SUS409 (11% Cr) plate was plated with 0.5 μm of Cr and was heated in a continuous annealing furnace (H 2 : 1.5) for ordinary steel.
%, N2 : 98.5%, dew point -20°C) at 850°C for 2 minutes. The obtained steel plate had a blackish gray color and an oxide film thickness of about 2000 Å. When an unplated cold-rolled SUS409 plate is passed through under the same annealing conditions, the surface oxide film is blue-purple and approximately 1500Å thick.
It was thick and warm. Table 2 shows the results of a corrosion resistance test after polishing both types of steel plates until they had an alloy luster.
Shown below.
【表】
Crメツキ―焼鈍―研磨したものは、Crメツキ
をしないSUS409の研磨材、BA材に較べ耐食性が
はるかに優れていた。このCrメツキ―焼鈍材を
焼鈍前と焼鈍後で表面からオージエ分析すると第
２図の結果が得られた。第２図はCrメツキステ
ンレスの焼鈍による熱拡散の状態を示したもの
で、同図Ａは焼鈍前、Ｂは850℃×２分の焼鈍後
の板厚最表面からの深さに応じたFe、Cr、Ｏの
各成分の量を示している。焼鈍前では最表面より
0.5μｍまで100％Cr層であるが、焼鈍後ではＢに
示すようにCrが内部へ拡散し、Crが表面に濃縮
していることがわかる。表面の酸化スケールを除
去した後もCr富化の表面を確保することがで
き、その結果点欠陥を完全に防ぎ、高耐食性を示
すものと思われる。
実施例 ２
ステンレス薄板を屋根や外壁など外装に使用す
るため、焼鈍時のテンパーカラーを利用して安価
なカラーステンレスを製造した。カラーステンレ
スの耐食性を高めるためSUS430のステンレス薄
板の冷延板に表３のような高耐食性のCrおよび
各種Cr合金メツキを0.3〜0.5μｍほどこし、焼鈍
雰囲気は普通鋼の連続焼鈍炉（H2：５％、N2：
95％、露点−40℃および−20℃）と直火酸化炉
（空気比1.20、O2：約５％）で850℃〜900℃まで
加熱して製造した。焼鈍後の色調と耐食性を表３
に示す。[Table] The Cr-plated, annealed and polished material had much better corrosion resistance than the SUS409 abrasive material and BA material without Cr plating. Auger analysis of the surface of this Cr Metski annealed material before and after annealing yielded the results shown in Figure 2. Figure 2 shows the state of thermal diffusion due to annealing of Cr-plated stainless steel, where A is before annealing and B is after annealing at 850°C for 2 minutes. , Cr, and O. From the outermost surface before annealing
Although it is a 100% Cr layer up to 0.5 μm, after annealing, as shown in B, it can be seen that Cr diffuses into the interior and Cr is concentrated on the surface. Even after removing the oxidized scale on the surface, a Cr-enriched surface can be maintained, and as a result, point defects are completely prevented and it is thought to exhibit high corrosion resistance. Example 2 In order to use thin stainless steel plates for exteriors such as roofs and outer walls, inexpensive colored stainless steel was manufactured using the temper color during annealing. In order to improve the corrosion resistance of colored stainless steel, a cold-rolled SUS430 stainless steel sheet is coated with highly corrosion-resistant Cr and various Cr alloy platings of 0.3 to 0.5 μm as shown in Table 3, and the annealing atmosphere is a continuous annealing furnace for ordinary steel (H 2 : 5%, N2 :
95%, dew point -40°C and -20°C) and a direct fire oxidation furnace (air ratio 1.20, O2 : about 5%) by heating to 850°C to 900°C. Table 3 shows the color tone and corrosion resistance after annealing.
Shown below.
【表】
焼鈍雰囲気のH2：５％、N2：95％は普通鋼で
還元雰囲気であるが、SUS430では露点−40℃で
も弱酸化性雰囲気であり、わずかにテンパーカラ
ーが生じる。CrおよびCr合金メツキも同じよう
に酸化する。雰囲気の露点が−20℃程度に上ると
酸化はかなりひどくなり、直火炉のO2を含む雰
囲気よりも酸化膜は厚くなる傾向にある。焼鈍雰
囲気と耐食性の関係はほとんど変らないか、露点
−20℃がやや劣る傾向にある。いずれにしても、
メツキをしないSUS430に較べCrおよびCr合金メ
ツキをほどこして焼鈍したステンレス薄板は耐食
性が著しく向上している。
実施例 ３
実施例２で製造したカラーステンレス（直火炉
酸化焼鈍材）を、酸洗デスケール→調質圧延し、
耐食試験をおこなつた。結果を表４に示す。[Table] The annealing atmosphere containing 5% H 2 and 95% N 2 is a reducing atmosphere for ordinary steel, but for SUS430, it is a weakly oxidizing atmosphere even at a dew point of -40°C, resulting in slight temper color. Cr and Cr alloy plating oxidize in the same way. When the dew point of the atmosphere rises to around -20°C, oxidation becomes quite severe, and the oxide film tends to be thicker than in an atmosphere containing O 2 in a direct-fired furnace. The relationship between annealing atmosphere and corrosion resistance tends to be almost the same, or slightly worse at dew point of -20°C. In any case,
Compared to unplated SUS430, stainless steel sheets plated with Cr or Cr alloy and annealed have significantly improved corrosion resistance. Example 3 The colored stainless steel (direct-fired furnace oxidation-annealed material) produced in Example 2 was pickled and descaled, followed by temper rolling.
A corrosion resistance test was conducted. The results are shown in Table 4.
【表】
この場合の耐食性も研磨の場合と同様に、酸洗
でデスケールされる酸化膜は0.1μｍ以下で、酸
洗後の表面もCr富化層が十分に残り耐食性に優
れていることがわかる。[Table] Similar to the case of polishing, the corrosion resistance in this case is that the oxide film descaled by pickling is less than 0.1 μm, and the surface after pickling also has a sufficient Cr-enriched layer remaining, indicating excellent corrosion resistance. Recognize.
第１図はSUS430冷延板の表面から厚さ中心へ
向けてのCr量の変化を示すグラフ、第２図はCr
メツキステンレス薄板の焼鈍による熱拡散の状態
を示すグラフでＡは焼鈍前、Ｂは焼鈍後を示す。
Figure 1 is a graph showing the change in the amount of Cr from the surface to the center of thickness of a cold-rolled SUS430 plate, and Figure 2 is a graph showing the change in Cr content from the surface to the center of thickness of a cold-rolled SUS430 plate.
In the graph showing the state of thermal diffusion due to annealing of a plated stainless steel thin plate, A shows the state before annealing and B shows the state after annealing.
Claims (1)
〜0.6μｍのCrめつきを施し、ついで酸化性雰囲
気下、再結晶温度以上1000℃以下の温度域で連続
焼鈍するようにしたことを特徴とするステンレス
薄板の製造法。 ２ 冷間圧延後のステンレス鋼薄板に、厚さ0.1
〜0.6μｍの、Crを主成分としてこれにMo、Ｖ、
Ｗ、Ｐの１種または２種以上を含有する合金めつ
きを施し、ついで酸化性雰囲気下、再結晶温度以
上1000℃以下の温度域で連続焼鈍するようにした
ことを特徴とするステンレス薄板の製造法。[Claims] 1. A stainless steel thin plate with a thickness of 0.1 after cold rolling.
A method for manufacturing a thin stainless steel plate, characterized in that it is plated with Cr to a thickness of ~0.6 μm, and then continuously annealed in an oxidizing atmosphere at a temperature ranging from a recrystallization temperature to 1000°C. 2. A stainless steel sheet with a thickness of 0.1 after cold rolling.
~0.6μm, with Cr as the main component, Mo, V,
A thin stainless steel sheet, which is plated with an alloy containing one or more of W and P, and then continuously annealed in an oxidizing atmosphere in a temperature range from the recrystallization temperature to 1000°C. Manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1264883A JPS59140392A (en) | 1983-01-31 | 1983-01-31 | Manufacture of stainless steel sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1264883A JPS59140392A (en) | 1983-01-31 | 1983-01-31 | Manufacture of stainless steel sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59140392A JPS59140392A (en) | 1984-08-11 |
| JPS624475B2 true JPS624475B2 (en) | 1987-01-30 |
Family
ID=11811183
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1264883A Granted JPS59140392A (en) | 1983-01-31 | 1983-01-31 | Manufacture of stainless steel sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59140392A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6936567B2 (en) | 2000-06-28 | 2005-08-30 | Sanyo Electric Co., Ltd. | Fuel reformer and manufacturing method of the same |
| JP5335595B2 (en) * | 2009-02-16 | 2013-11-06 | 新日鐵住金ステンレス株式会社 | Chrome-plated stainless steel plate with excellent post-processing corrosion resistance |
| GB2503860B (en) * | 2011-12-29 | 2014-05-07 | Arcanum Alloy Design Inc | Metallurgically bonded stainless steel |
| CN103764388B (en) * | 2011-12-29 | 2016-08-17 | 奥秘合金设计有限公司 | The rustless steel of metallurgical binding |
| CN104109899B (en) * | 2014-06-30 | 2016-08-24 | 江苏兴龙金属制品股份有限公司 | A kind of process of surface treatment of environmental protection gold decoration stainless steel wire rope |
| US20160230284A1 (en) | 2015-02-10 | 2016-08-11 | Arcanum Alloy Design, Inc. | Methods and systems for slurry coating |
| WO2017201418A1 (en) | 2016-05-20 | 2017-11-23 | Arcanum Alloys, Inc. | Methods and systems for coating a steel substrate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5397941A (en) * | 1977-02-07 | 1978-08-26 | Kawasaki Heavy Ind Ltd | Surface treating method for high temperature corrosion resistance and ion plating diffusion treatment furnace |
-
1983
- 1983-01-31 JP JP1264883A patent/JPS59140392A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5397941A (en) * | 1977-02-07 | 1978-08-26 | Kawasaki Heavy Ind Ltd | Surface treating method for high temperature corrosion resistance and ion plating diffusion treatment furnace |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59140392A (en) | 1984-08-11 |
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