JP5709602B2 - Stainless steel material with good insulation and its manufacturing method - Google Patents
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- 229910001220 stainless steel Inorganic materials 0.000 title claims description 63
- 239000010935 stainless steel Substances 0.000 title claims description 57
- 239000000463 material Substances 0.000 title claims description 43
- 238000009413 insulation Methods 0.000 title claims description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 238000007747 plating Methods 0.000 claims description 47
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 40
- 238000010438 heat treatment Methods 0.000 claims description 32
- 239000000758 substrate Substances 0.000 claims description 24
- 229910000831 Steel Inorganic materials 0.000 claims description 18
- 239000010959 steel Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 90
- 239000010408 film Substances 0.000 description 50
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
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- 229910017060 Fe Cr Inorganic materials 0.000 description 4
- 229910002544 Fe-Cr Inorganic materials 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 4
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- 239000011810 insulating material Substances 0.000 description 3
- 239000012212 insulator Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- 229910000859 α-Fe Inorganic materials 0.000 description 2
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- 150000004706 metal oxides Chemical class 0.000 description 1
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- 229910052596 spinel Inorganic materials 0.000 description 1
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- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、塗膜を形成することなく良好な絶縁性を付与したステンレス鋼材、およびその製造法に関する。 The present invention relates to a stainless steel material imparted with good insulating properties without forming a coating film, and a method for producing the same.
ステンレス鋼は耐食性や耐熱性が要求される種々の用途に広く使用されている。ただし、ステンレス鋼自体は導電性材料であるため、絶縁性が要求される用途に適用するためには表面を絶縁皮膜で覆う必要がある。絶縁皮膜の形成方法としては絶縁性の塗料をコーティングする手法が一般的である。 Stainless steel is widely used in various applications that require corrosion resistance and heat resistance. However, since stainless steel itself is a conductive material, it is necessary to cover the surface with an insulating film in order to apply it to applications that require insulation. As a method for forming an insulating film, a technique of coating an insulating paint is common.
塗料の多くは有機樹脂を主成分としている。一般に有機樹脂の耐熱温度は２００〜３００℃である。このため、それより高温に曝される用途では一般的な有機樹脂塗系塗料を使用することができない。例えば、絶縁性の太陽電池基板を想定した場合、成膜工程（硫化処理、セレン化処理など）での５００℃程度の温度への加熱に耐える材料が要求される。 Many paints are based on organic resins. Generally, the heat-resistant temperature of the organic resin is 200 to 300 ° C. For this reason, general organic resin coating materials cannot be used in applications exposed to higher temperatures. For example, when an insulating solar cell substrate is assumed, a material that can withstand heating to a temperature of about 500 ° C. in a film forming process (sulfurization treatment, selenization treatment, etc.) is required.
比較的良好な耐熱性を有する有機樹脂としてはポリイミド樹脂が知られている。特許文献１には表面のＦｅ酸化物の厚みを薄くすることによってポリイミドフィルムとの密着性を高めたステンレス鋼箔が開示されている。しかし、ポリイミド樹脂であっても３５０℃程度が使用温度の限界であり、上記のような成膜工程に適用することは困難である。 A polyimide resin is known as an organic resin having relatively good heat resistance. Patent Document 1 discloses a stainless steel foil having improved adhesion to a polyimide film by reducing the thickness of the surface Fe oxide. However, even if it is a polyimide resin, about 350 degreeC is the limit of use temperature, and it is difficult to apply to the above film forming processes.
特許文献２にはシロキサン結合を主体とするシリカ系の無機ポリマー膜で被覆されたステンレス鋼箔が開示されている。しかし、この場合も５００℃といった高温度域での用途には適用できない。 Patent Document 2 discloses a stainless steel foil coated with a silica-based inorganic polymer film mainly composed of siloxane bonds. However, in this case as well, it cannot be applied to a use in a high temperature range of 500 ° C.
耐熱性の良好な酸化物皮膜をステンレス鋼表面にコーティングする手法も考えられるが、その場合には塗膜の密着性を確保するためにショットブラストや電解処理によってステンレス鋼基材の表面を粗面化しておく必要があり、コストが増大する。 A method of coating a stainless steel surface with an oxide film with good heat resistance is also conceivable, but in this case, the surface of the stainless steel substrate is roughened by shot blasting or electrolytic treatment to ensure adhesion of the coating film. Cost, which increases the cost.
一方、塗料のコーティングによらずにステンレス鋼表面に絶縁性を付与する手法として、特許文献３にはＡｌを含有するステンレス鋼の表面を酸化させて全表面をα−Ａｌ2Ｏ3で被覆する技術が開示されている。しかし、鋼成分であるＡｌを酸化させるのであるから絶縁皮膜の膜厚を短時間で急速に厚くすることが困難である。例えば９００〜１３００℃で１時間未満〜１６時間加熱しても絶縁皮膜の膜厚は１.５μｍ程度にとどまり、絶縁性を持たせるための熱処理に長時間を要するという欠点がある。また、表面疵に対して高い信頼性を有する絶縁皮膜とするためには、より膜厚の厚い皮膜（例えば厚さ数μｍ以上）が望まれるが、特許文献３の手法ではそのような膜厚の絶縁皮膜を工業的に得ることは困難である。 On the other hand, as a method for imparting insulation to the surface of stainless steel without depending on coating, Patent Document 3 discloses that the surface of stainless steel containing Al is oxidized and the entire surface is coated with α-Al 2 O 3 . Technology is disclosed. However, since the steel component Al is oxidized, it is difficult to rapidly increase the thickness of the insulating film in a short time. For example, even if it is heated at 900 to 1300 ° C. for less than 1 hour to 16 hours, the film thickness of the insulating film is limited to about 1.5 μm, and there is a drawback that it takes a long time for the heat treatment to provide insulation. Further, in order to obtain an insulating film having high reliability with respect to surface defects, a film having a larger film thickness (for example, a thickness of several μm or more) is desired. It is difficult to obtain this insulating film industrially.
本発明は、塗膜の形成によらずに耐熱性の良い絶縁皮膜を形成したステンレス鋼材であって、工業的に比較的低コストにて製造可能なものを提供することを目的とする。 An object of this invention is to provide the stainless steel material which formed the insulating film with favorable heat resistance irrespective of formation of a coating film, and can be manufactured industrially at comparatively low cost.
上記目的は、質量％で、Ｃ：０.０００１〜０.１５％、Ｓｉ：０.００１〜１.２％、Ｍｎ：０.００１〜２.０％、Ｐ：０.００１〜０.０５％、Ｓ：０.０００５〜０.０３％、Ｎｉ：０〜２.０％，Ｃｕ：０〜１.０％、Ｃｒ：１１.０〜３２.０％、Ｍｏ：０〜３.０％、Ａｌ：０〜０.１％未満、Ｎｂ：０〜１.０％、Ｔｉ：０〜１.０％、Ｎ：０〜０.０２５％、Ｂ：０〜０.０１％，Ｖ：０〜０.５％、Ｗ：０〜０.３％、Ｃａ、Ｍｇ、Ｙ、ＲＥＭ（希土類元素）の合計：０〜０.１％、残部Ｆｅおよび不可避的不純物からなるステンレス鋼を基材として、その基材表面上に、Ｎｉ層を介して、厚さ１.０μｍ以上好ましくは５０.０μｍ以下のＮｉＯとＮｉＦｅ2Ｏ4の混合層が形成されている絶縁性の良好なステンレス鋼材によって達成される。 The above-mentioned purpose is mass%, C: 0.0001 to 0.15%, Si: 0.001 to 1.2%, Mn: 0.001 to 2.0%, P: 0.001 to 0.05. %, S: 0.0005 to 0.03%, Ni: 0 to 2.0%, Cu: 0 to 1.0%, Cr: 11.0 to 32.0%, Mo: 0 to 3.0% , Al: 0 to less than 0.1%, Nb: 0 to 1.0%, Ti: 0 to 1.0%, N: 0 to 0.025%, B: 0 to 0.01%, V: 0 ~ 0.5%, W: 0-0.3%, Ca, Mg, Y, REM (rare earth elements) total: 0-0.1%, balance Fe and stainless steel consisting of unavoidable impurities as a base material This is achieved by a stainless steel material with good insulation, in which a mixed layer of NiO and NiFe 2 O 4 having a thickness of 1.0 μm or more, preferably 50.0 μm or less, is formed on the surface of the substrate via a Ni layer. Is done.
上記の絶縁性の良好なステンレス鋼材の製造法として、ステンレス鋼基材の表面に電気Ｎｉめっき法にて厚さ１.０〜３０.０μｍのＮｉめっき層を形成したのち、その鋼材をＮｉめっき層の表面が大気に曝される環境で８００〜１２００℃に加熱し、厚さ１.０μｍ以上のＮｉＯとＮｉＦｅ2Ｏ4の混合層が生成し且つＮｉめっき層の一部が残存する時間範囲で前記加熱を終了する手法が適用できる。 As a method for producing the above-described stainless steel material with good insulation, a Ni plating layer having a thickness of 1.0 to 30.0 μm is formed on the surface of a stainless steel substrate by an electric Ni plating method, and then the steel material is Ni-plated. Heating to 800-1200 ° C. in an environment where the surface of the layer is exposed to the atmosphere, a time range in which a mixed layer of NiO and NiFe 2 O 4 having a thickness of 1.0 μm or more is formed and a part of the Ni plating layer remains The method of terminating the heating can be applied.
本発明によれば、塗膜によらずに良好な絶縁性を有する皮膜を形成したステンレス鋼材が提供された。その絶縁皮膜は金属酸化物を主体とするものであり、有機系の塗膜と比べ耐熱性に優れることから、ＣＩＳ系太陽電池用絶縁基板、薄膜Ｓｉ太陽電池基板、面状発熱体など、特に高温での成膜処理を必要とする絶縁部材や、高温で使用される絶縁部材へのステンレス鋼材の適用が可能となる。また、その絶縁皮膜はＮｉめっきステンレス鋼材を熱処理することによって形成できるものであり、数μｍ以上の膜厚を有する耐久性の高い絶縁皮膜を有するものを工業的に比較的低コストで量産可能である。 ADVANTAGE OF THE INVENTION According to this invention, the stainless steel material which formed the film | membrane which has favorable insulation irrespective of a coating film was provided. The insulating film is mainly composed of a metal oxide, and is superior in heat resistance as compared with an organic coating film. Therefore, an insulating substrate for a CIS solar cell, a thin film Si solar cell substrate, a planar heating element, etc. The stainless steel material can be applied to an insulating member that requires film formation at a high temperature and an insulating member that is used at a high temperature. In addition, the insulating film can be formed by heat-treating Ni-plated stainless steel material, and it is possible to industrially mass-produce what has a highly durable insulating film having a film thickness of several μm or more at a relatively low cost. is there.
図１に、本発明のステンレス鋼材における表面付近の断面構造を模式的に示す。ステンレス鋼基材（以下単に「基材」ということがある）の表面上にＮｉ層を介してＮｉＯとＮｉＦｅ2Ｏ4の混合層（以下「ＮｉＯ＋ＮｉＦｅ2Ｏ4混合層」ということがある）が形成されている。ＮｉＯとＮｉＦｅ2Ｏ4の各酸化物が絶縁物質であることから、このＮｉＯ＋ＮｉＦｅ2Ｏ4混合層によってステンレス鋼表面に絶縁性が付与される。 In FIG. 1, the cross-sectional structure of the surface vicinity in the stainless steel material of this invention is shown typically. A mixed layer of NiO and NiFe 2 O 4 (hereinafter also referred to as “NiO + NiFe 2 O 4 mixed layer”) is formed on the surface of a stainless steel substrate (hereinafter sometimes simply referred to as “substrate”) via a Ni layer. Is formed. Since each of the oxides of NiO and NiFe 2 O 4 is an insulating material, the NiO + NiFe 2 O 4 mixed layer provides insulation to the stainless steel surface.
〔ＮｉＯとＮｉＦｅ2Ｏ4の混合層〕
ＮｉＯとＮｉＦｅ2Ｏ4の混合層は、ステンレス鋼基材の表面に形成されたＮｉめっき層を大気中で酸化処理することによって形成できる。そのＮｉめっき層は例えば公知の電気Ｎｉめっき法によって形成できる。Ｎｉめっき層を形成した鋼材を大気中で所定温度に加熱すると、表面の金属Ｎｉが空気中の酸素と化合してＮｉＯを主体とした酸化物が生成する。また、基材の成分であるＦｅがＮｉ層中に拡散して大気に由来する酸素と反応し、ＮｉＦｅ2Ｏ4が生成する。ＮｉＯはモット絶縁体またはザン・ライス束縛状態における絶縁体と言われており、金属や半導体の性質をもつものではない。ＮｉＦｅ2Ｏ4はスピネル構造の絶縁体である。
[Mixed layer of NiO and NiFe 2 O 4 ]
The mixed layer of NiO and NiFe 2 O 4 can be formed by oxidizing the Ni plating layer formed on the surface of the stainless steel substrate in the atmosphere. The Ni plating layer can be formed by, for example, a known electric Ni plating method. When the steel material on which the Ni plating layer is formed is heated to a predetermined temperature in the atmosphere, the metal Ni on the surface combines with oxygen in the air to generate an oxide mainly composed of NiO. Further, Fe, which is a component of the base material, diffuses into the Ni layer and reacts with oxygen derived from the atmosphere to produce NiFe 2 O 4 . NiO is said to be a Mott insulator or an insulator in a Zan-Rice bound state and does not have metal or semiconductor properties. NiFe 2 O 4 is an insulator having a spinel structure.
発明者らの検討によれば、ＮｉＯ＋ＮｉＦｅ2Ｏ4混合層は例えば厚さ１.０μｍ程度の薄い膜厚であっても表面抵抗率１.０×１０-6 Ω／□以上という良好な絶縁性を呈する。ＮｉＯとＮｉＦｅ2Ｏ4のそれぞれの絶縁物質が共存することにより、電子がより動きにくくなり、このような高い表面抵抗率が実現できるのではないかと推察される。 According to the study by the inventors, even if the NiO + NiFe 2 O 4 mixed layer has a thin film thickness of about 1.0 μm, for example, the surface resistivity is 1.0 × 10 −6 Ω / sq . Presents. By coexisting the insulating materials of NiO and NiFe 2 O 4 , electrons are more difficult to move, and it is assumed that such a high surface resistivity can be realized.
ＮｉＯとＮｉＦｅ2Ｏ4の混合層の厚さは１.０μｍ以上であることが望まれる。それより薄いと絶縁材料として多くの用途に適用可能となる表面抵抗率１.０×１０-6 Ω／□以上の絶縁性を安定して得ることが難しくなる場合がある。部品の取り扱い時などに表面疵が生じた場合でも良好な絶縁性を維持するためには、当該混合層は２.０μｍ以上の厚さであることがより好ましく、５.０μｍ以上であることが一層好ましい。特に耐疵性の高い皮膜とする場合には１０μｍ以上、あるいは２０μｍ以上といった膜厚とすることもできる。ただし、あまり厚くても表面抵抗率は飽和し、耐疵性も過剰となりやすいので、通常は５０.０μｍ以下の範囲とすればよい。このＮｉＯ＋ＮｉＦｅ2Ｏ4混合層の膜厚は、大気中での加熱処理に供する材料のＮｉめっき層の厚さおよび加熱条件によってコントロールできる。 The thickness of the mixed layer of NiO and NiFe 2 O 4 is desirably 1.0 μm or more. If it is thinner than that, it may be difficult to stably obtain an insulating property of a surface resistivity of 1.0 × 10 −6 Ω / □ that can be applied to many uses as an insulating material. In order to maintain good insulation even when surface flaws occur when handling parts, the mixed layer is more preferably 2.0 μm or more in thickness, and preferably 5.0 μm or more. Even more preferred. In particular, when the film has a high weather resistance, the film thickness can be 10 μm or more, or 20 μm or more. However, even if it is too thick, the surface resistivity is saturated and the weather resistance is likely to be excessive, so the range of 50.0 μm or less is usually sufficient. The thickness of the NiO + NiFe 2 O 4 mixed layer can be controlled by the thickness of the Ni plating layer of the material used for the heat treatment in the air and the heating conditions.
ＮｉＯとＮｉＦｅ2Ｏ4の混合層の厚さは、例えばＥＤＸによる深さ方向の分析によってＮｉ，ＦｅおよびＯの存在が確認され、そのＮｉおよびＯの検出強度がいずれも基材中の強度よりも高く、かつＣｒの検出強度が基材中よりも低い領域の厚さとして把握することができる。また、ＮｉＯとＮｉＦｅ2Ｏ4の存在はＸ線回折によって同定可能である。 As for the thickness of the mixed layer of NiO and NiFe 2 O 4 , for example, the presence of Ni, Fe, and O is confirmed by analysis in the depth direction by EDX, and the detected intensity of Ni and O is higher than the strength in the substrate. And the thickness of the region where the Cr detection intensity is lower than that in the base material. The presence of NiO and NiFe 2 O 4 can be identified by X-ray diffraction.
〔Ｎｉ層〕
ステンレス鋼基材と、ＮｉＯ＋ＮｉＦｅ2Ｏ4混合層との間に介在するＮｉ層は、ＮｉＯ＋ＮｉＦｅ2Ｏ4混合層の密着性を確保する上で重要である。Ｎｉ層はステンレス鋼基材とＮｉＯ＋ＮｉＦｅ2Ｏ4混合層の間に存在していればよく、極めて薄い状態であっても構わない。例えば平均膜厚が０.１μｍ程度であっても、Ｎｉ層が存在していればその上のＮｉＯ＋ＮｉＦｅ2Ｏ4混合層の密着性は確保できる。このＮｉ層は、Ｎｉめっき層の全部を酸化させず、一部を金属Ｎｉのまま残存させることによって存在させることができる。全ての表面部分にＮｉ層を安定して残存させるために、Ｎｉ層の平均厚さは１.０μｍ以上とすることがより好ましい。ＮｉＯ＋ＮｉＦｅ2Ｏ4混合層が所定の厚さで形成できている限り、Ｎｉ層の厚さは厚くても構わないが、経済性を考慮すると例えば平均膜厚２０.０μｍ以下程度の範囲とすればよい。
[Ni layer]
The Ni layer interposed between the stainless steel substrate and the NiO + NiFe 2 O 4 mixed layer is important for ensuring the adhesion of the NiO + NiFe 2 O 4 mixed layer. The Ni layer only needs to exist between the stainless steel substrate and the NiO + NiFe 2 O 4 mixed layer, and may be in a very thin state. For example, even if the average film thickness is about 0.1 μm, the adhesion of the NiO + NiFe 2 O 4 mixed layer on the Ni layer can be ensured if the Ni layer is present. This Ni layer can be present by not oxidizing the entire Ni plating layer but leaving a portion of the metal Ni as it is. In order to stably leave the Ni layer on all the surface portions, the average thickness of the Ni layer is more preferably 1.0 μm or more. As long as the NiO + NiFe 2 O 4 mixed layer can be formed with a predetermined thickness, the thickness of the Ni layer may be large, but considering the economy, for example, if the average film thickness is in the range of about 20.0 μm or less. Good.
Ｎｉ層の存在は、例えばＥＤＸによる深さ方向の分析によって、Ｎｉの検出強度がＮｉＯ＋ＮｉＦｅ2Ｏ4混合層中の強度よりも高く、Ｃｒの検出強度が基材中よりも低く、かつＯの検出強度が基材中と同等あるいはそれ以下である領域が、基材の領域に隣接して存在することにより確認することができる。Ｎｉ層を存在させるためには、大気中での加熱処理に供する材料のＮｉめっき層の厚さを十分に確保し、かつ、それが消失しないように加熱条件を設定すればよい。 The presence of the Ni layer is determined by, for example, analysis in the depth direction by EDX, the Ni detection intensity is higher than that in the NiO + NiFe 2 O 4 mixed layer, the Cr detection intensity is lower than that in the base material, and O detection This can be confirmed by the presence of a region having strength equal to or lower than that in the substrate adjacent to the region of the substrate. In order to make the Ni layer exist, the heating conditions may be set so that the thickness of the Ni plating layer of the material to be subjected to the heat treatment in the atmosphere is sufficiently secured and does not disappear.
〔基材〕
本発明では、鋼の中でも熱膨張係数の小さいフェライト系ステンレス鋼を適用対象とする。用途に応じて種々のフェライト系ステンレス鋼種が適用可能であるが、代表的な成分元素の含有量範囲について説明する。以下、鋼組成における「％」は特に断らない限り「質量％」を意味する。
〔Base material〕
In the present invention, ferritic stainless steel having a small thermal expansion coefficient among the steels is applied. Various ferritic stainless steel types are applicable depending on the application, but the content ranges of typical component elements will be described. Hereinafter, “%” in the steel composition means “% by mass” unless otherwise specified.
Ｃ、Ｎは、鋼の強度を確保するうえで有効な元素であるが、多量に含有するとステンレス鋼の加工性、低温脆性に悪影響を及ぼす場合がある。本発明ではＣ含有量が０.０００１〜０.１５％、Ｎ含有量が０〜０.０２５％の鋼を対象とする。 C and N are effective elements for securing the strength of the steel, but if contained in a large amount, C and N may adversely affect the workability and low temperature brittleness of the stainless steel. In the present invention, steel having a C content of 0.0001 to 0.15% and an N content of 0 to 0.025% is targeted.
Ｓｉは、多量に含有すると鋼を硬質化して加工性を阻害する場合がある。本発明ではＳｉ含有量が０.００１〜１.２％の鋼を対象とする。Ｓｉ含有量は０.５％以下の範囲に管理してもよい。 If Si is contained in a large amount, it may harden the steel and impair the workability. In the present invention, steel having a Si content of 0.001 to 1.2% is targeted. The Si content may be controlled within a range of 0.5% or less.
Ｍｎは、多量に含有すると加工性低下、耐食性低下を招く場合がある。本発明ではＭｎ含有量が０.００１〜２.０％の鋼、より好ましくは０.００１〜１.５％の鋼を対象とする。 If Mn is contained in a large amount, it may cause deterioration in workability and corrosion resistance. In the present invention, steel having a Mn content of 0.001 to 2.0%, more preferably 0.001 to 1.5% is intended.
Ｐ、Ｓは、不純物として不可避的に混入するが、鋼の諸特性に悪影響を及ぼすので含有量は少ない方がよい。ただし、極度の脱Ｐ、脱Ｓは製鋼での負荷を増大させ好ましくない。本発明では、Ｐ含有量が０.００１〜０.０５％、Ｓ含有量が０.０００５〜０.０３％の鋼を対象とする。 P and S are inevitably mixed as impurities, but since they adversely affect various properties of steel, it is better that the content is small. However, extreme removal P and removal S are not preferable because they increase the load in steelmaking. In the present invention, steel having a P content of 0.001 to 0.05% and an S content of 0.0005 to 0.03% is an object.
Ｎｉ、Ｃｕは、フェライト系ステンレス鋼において酸性雰囲気での耐全面腐食性を改善し、また低温靭性を改善する作用があるため、必要に応じてこれらの１種以上を含有させることができる。上記作用を十分に発揮させるには、Ｎｉの場合は０.１５％以上、Ｃｕの場合は０.２％以上の含有量を確保することがより効果的である。種々検討の結果、Ｎｉ、Ｃｕの１種以上を含有させる場合は、Ｎｉは２.０％以下、Ｃｕは１.０％以下の範囲で行う。 Ni and Cu have the effect of improving the general corrosion resistance in an acidic atmosphere and improving the low-temperature toughness in ferritic stainless steel, and therefore can contain one or more of these as required. In order to sufficiently exhibit the above action, it is more effective to secure a content of 0.15% or more in the case of Ni and 0.2% or more in the case of Cu. As a result of various studies, when one or more of Ni and Cu are contained, the Ni content is 2.0% or less and the Cu content is 1.0% or less.
Ｃｒは、ステンレス鋼の耐食性を確保するために重要な元素であり、本発明においては１１.０％以上のＣｒ含有量を確保する必要がある。ただし、多量のＣｒ含有は加工性の低下を招くので、Ｃｒ含有量は３２.０％以下に制限され、３０.０％以下とすることがより好ましい。２５.０％以下に管理しても構わない。 Cr is an important element for ensuring the corrosion resistance of stainless steel, and in the present invention, it is necessary to ensure a Cr content of 11.0% or more. However, since a large amount of Cr causes a decrease in workability, the Cr content is limited to 32.0% or less, and more preferably 30.0% or less. You may manage to 25.0% or less.
Ｍｏは、Ｃｒとの共存によりステンレス鋼の耐食性を向上させる元素であり、必要に応じて含有させることができる。その作用を十分に得るためには０.３％以上のＭｏ含有量を確保することがより効果的である。ただし、多量のＭｏ含有はステンレス鋼を硬質化させ加工性劣化を招き、またコスト的にも不利となるので、Ｍｏを含有させる場合は３.０％以下の範囲で行う。２.０％以下に管理しても構わない。 Mo is an element that improves the corrosion resistance of stainless steel by coexistence with Cr, and can be contained as required. In order to obtain the effect sufficiently, it is more effective to secure a Mo content of 0.3% or more. However, if a large amount of Mo is contained, the stainless steel is hardened, resulting in deterioration of workability and disadvantageous in terms of cost. Therefore, when Mo is contained, the content is within a range of 3.0% or less. You may manage to 2.0% or less.
Ａｌは、鋼の脱酸に有効であり、必要に応じて含有させることができる。その作用を十分に得るためには０.０４％以上のＡｌ含有量を確保することがより効果的である。ただし、過剰に含有させるとその作用は飽和し不経済となるのでＡｌを含有させる場合は０.１％未満の範囲で行う。 Al is effective for deoxidation of steel and can be contained as necessary. In order to obtain the effect sufficiently, it is more effective to secure an Al content of 0.04% or more. However, if it is contained excessively, its action is saturated and uneconomical. Therefore, when Al is contained, it is performed in a range of less than 0.1%.
Ｎｂ、Ｔｉは、Ｃ、Ｎを固定し加工性を改善する作用があり、必要に応じて含有させることができる。上記作用を十分に得るには、Ｎｂ：０.０３％以上、Ｔｉ：０.０３％以上の１種以上を含有させることがより効果的である。ただし、Ｔｉ、Ｎｂの１種以上を含有させる場合は、Ｎｂ、Ｔｉとも１.０％以下、より好ましくは０.５％以下の範囲で行う。 Nb and Ti have an action of fixing C and N and improving workability, and can be contained as necessary. In order to sufficiently obtain the above action, it is more effective to contain one or more of Nb: 0.03% or more and Ti: 0.03% or more. However, when one or more of Ti and Nb are contained, both Nb and Ti are carried out within a range of 1.0% or less, more preferably 0.5% or less.
その他、鋼の各種特性を改善するために、必要に応じてＢ、Ｖ、Ｗ、Ｃａ、Ｍｇ、Ｙ、ＲＥＭ（希土類元素）の１種以上を含有させることができる。その場合、Ｂは０.１％以下、Ｖは０.５％以下、Ｗは０.３％以下の範囲とし、Ｃａ、Ｍｇ、Ｙ、ＲＥＭ（希土類元素）の合計含有量は０.１％以下の範囲とする。 In addition, in order to improve various properties of the steel, one or more of B, V, W, Ca, Mg, Y, and REM (rare earth elements) can be included as necessary. In this case, B is 0.1% or less, V is 0.5% or less, W is 0.3% or less, and the total content of Ca, Mg, Y, and REM (rare earth elements) is 0.1%. The following range.
〔製造法〕
本発明に従う絶縁性の良好なステンレス鋼材は、ステンレス鋼基材の表面上に電気Ｎｉめっきを施し、そのＮｉめっき層の表面が大気に曝される環境で所定温度に加熱する手法によって得ることができる。具体的には以下のような条件が好適に採用できる。
[Production method]
The stainless steel material with good insulation according to the present invention can be obtained by a method in which electric Ni plating is applied on the surface of a stainless steel substrate and the surface of the Ni plating layer is heated to a predetermined temperature in an environment exposed to the atmosphere. it can. Specifically, the following conditions can be suitably employed.
〔電気Ｎｉめっき〕
ステンレス鋼基材の表面に公知の電気Ｎｉめっき法によりＮｉめっき層を形成させる。Ｎｉめっき層の厚さは、後述の加熱によりＮｉめっき層の上層部を所定厚さのＮｉＯ＋ＮｉＦｅ2Ｏ4混合層とし、かつＮｉめっき層の下層部（基材側の一部分）を金属Ｎｉ層として残存させるに足る厚さを確保する必要がある。種々検討の結果、厚さ１.０μｍ以上のＮｉめっき層を形成させることが望ましい。それより薄いと加熱処理によって「所定厚さのＮｉＯ＋ＮｉＦｅ2Ｏ4混合層を生成させ、かつＮｉ層を残存させること」が難しくなりやすい。Ｎｉめっき厚さは３.０μｍ以上とすることがより好ましい。一方、過剰のＮｉめっきは不経済となるので、３０.０μｍ以下の範囲とすればよい。１５μｍ以下の範囲に管理してもよい。
[Electric Ni plating]
A Ni plating layer is formed on the surface of the stainless steel substrate by a known electric Ni plating method. The thickness of the Ni plating layer is such that the upper layer portion of the Ni plating layer is a NiO + NiFe 2 O 4 mixed layer having a predetermined thickness and the lower layer portion of the Ni plating layer (part on the substrate side) is a metal Ni layer by heating described later. It is necessary to ensure a sufficient thickness to remain. As a result of various studies, it is desirable to form a Ni plating layer having a thickness of 1.0 μm or more. If it is thinner than that, it tends to be difficult to “generate a NiO + NiFe 2 O 4 mixed layer having a predetermined thickness and leave the Ni layer” by heat treatment. The Ni plating thickness is more preferably 3.0 μm or more. On the other hand, since excessive Ni plating becomes uneconomical, it may be in the range of 30.0 μm or less. You may manage in the range below 15 micrometers.
〔加熱処理〕
Ｎｉめっき層を形成させたステンレス鋼材を、そのＮｉめっき層表面が大気に曝される状態で加熱することによりＮｉＯ＋ＮｉＦｅ2Ｏ4混合層を生成させる。その際、厚さ１.０μｍ以上のＮｉＯとＮｉＦｅ2Ｏ4の混合層が生成し、かつＮｉめっき層の一部が残存する時間範囲で前記加熱を終了する。加熱温度は８００〜１２００℃の範囲とすることが望ましい。８００℃より低いとＮｉＯ＋ＮｉＦｅ2Ｏ4混合層の厚さを短時間で十分に確保することが難しくなる。１２００℃を超えるとＮｉめっき層が急速に酸化され、Ｎｉめっき層の厚さが比較的薄い場合には基材とＮｉＯ＋ＮｉＦｅ2Ｏ4混合層の間にＮｉ層を残存させる加熱時間を設定することが難しくなる。また、１２００℃を超える高温では基材であるステンレス鋼の結晶粒が粗大化し強度レベルが低下することがある。加熱時間は、Ｎｉめっき層の厚さと加熱温度に応じて調整される。工業的には例えば１〜１０ｍｉｎの範囲で設定することが望ましい。
[Heat treatment]
The NiO + NiFe 2 O 4 mixed layer is generated by heating the stainless steel material on which the Ni plating layer is formed in a state where the surface of the Ni plating layer is exposed to the atmosphere. At that time, the heating is finished within a time range in which a mixed layer of NiO and NiFe 2 O 4 having a thickness of 1.0 μm or more is formed and a part of the Ni plating layer remains. The heating temperature is preferably in the range of 800 to 1200 ° C. When the temperature is lower than 800 ° C., it is difficult to sufficiently secure the thickness of the NiO + NiFe 2 O 4 mixed layer in a short time. When the temperature exceeds 1200 ° C., the Ni plating layer is rapidly oxidized. When the thickness of the Ni plating layer is relatively thin, a heating time for leaving the Ni layer between the base material and the NiO + NiFe 2 O 4 mixed layer should be set. Becomes difficult. Further, at a high temperature exceeding 1200 ° C., the crystal grains of the stainless steel as a base material may become coarse and the strength level may be lowered. The heating time is adjusted according to the thickness of the Ni plating layer and the heating temperature. Industrially, for example, it is desirable to set in the range of 1 to 10 min.
図２に、本発明に従って絶縁皮膜を形成したステンレス鋼材の表面についてのＸ線回折パターン（ＭｏＫα線使用）を示す。このステンレス鋼材は、ステンレス鋼基材の表面に厚さ１０μｍのＮｉめっき層を形成させた後、大気中１０００℃×５ｍｉｎの加熱処理を施したものである（表２のＮｏ.１８）。基材のステンレス鋼（フェライト相；図中Ｆｅ−Ｃｒと表示）の回折ピーク、金属Ｎｉの回折ピークの他、ＮｉＯおよびＮｉＦｅ2Ｏ4の回折ピークが観測される。 FIG. 2 shows an X-ray diffraction pattern (using MoKα rays) on the surface of a stainless steel material on which an insulating film is formed according to the present invention. This stainless steel material is obtained by forming a Ni plating layer having a thickness of 10 μm on the surface of a stainless steel substrate and then performing a heat treatment at 1000 ° C. for 5 minutes in the atmosphere (No. 18 in Table 2). A diffraction peak of NiO and NiFe 2 O 4 is observed in addition to a diffraction peak of stainless steel (ferrite phase; expressed as Fe—Cr in the figure) and a diffraction peak of metallic Ni.
図３に、図２に示した本発明例のステンレス鋼材の断面における表面から深さ方向へのＥＤＸによる元素分析プロファイルを例示する。断面のＳＥＭ像とそのＳＥＭ像中のライン分析位置を図中に重ねて示してある。図中、Ｆｅ−Ｃｒと表示した領域がステンレス鋼基材に相当し、それに隣接してＮｉ層があり、その上（図中の左側）にＮｉＯ＋ＮｉＦｅ2Ｏ4混合層がある。 FIG. 3 illustrates an elemental analysis profile by EDX from the surface to the depth direction in the cross section of the stainless steel material of the example of the present invention shown in FIG. The cross-sectional SEM image and the line analysis position in the SEM image are shown superimposed in the figure. In the figure, the region indicated as Fe—Cr corresponds to the stainless steel substrate, there is a Ni layer adjacent to it, and there is a NiO + NiFe 2 O 4 mixed layer above it (on the left side in the figure).
図４に、比較例であるステンレス鋼材の表面についてのＸ線回折パターン（ＭｏＫα線使用）を示す。このステンレス鋼材は、ステンレス鋼基材の表面に厚さ１０μｍのＮｉめっき層を形成させた後、大気中１２００℃×５ｍｉｎの加熱処理を施したものである（表２のＮｏ.２９）。基材のステンレス鋼（フェライト相；図中Ｆｅ−Ｃｒと表示）の回折ピークの他には、ＮｉＯおよびＮｉＦｅ2Ｏ4の回折ピークが観測されるが、Ｎｉ層は見られない。これは、加熱温度が１２００℃と高めであったため、Ｎｉめっき層厚さが１０μｍの場合に加熱時間５ｍｉｎの条件ではＮｉ層を残存させることができなかったことによる。 FIG. 4 shows an X-ray diffraction pattern (using MoKα rays) on the surface of a stainless steel material as a comparative example. This stainless steel material is obtained by forming a Ni plating layer having a thickness of 10 μm on the surface of a stainless steel substrate and then performing a heat treatment at 1200 ° C. for 5 minutes in the atmosphere (No. 29 in Table 2). NiO and NiFe 2 O 4 diffraction peaks are observed in addition to the diffraction peak of the base material stainless steel (ferrite phase; indicated as Fe—Cr in the figure), but no Ni layer is observed. This is because the heating temperature was as high as 1200 ° C., and therefore when the Ni plating layer thickness was 10 μm, the Ni layer could not be left under the condition of a heating time of 5 minutes.
図５に、図４に示した比較例のステンレス鋼材の断面における表面から深さ方向へのＥＤＸによる元素分析プロファイルを例示する。断面のＳＥＭ像とそのＳＥＭ像中のライン分析位置を図中に重ねて示してある。図中、Ｆｅ−Ｃｒと表示した領域がステンレス鋼基材に相当し、それに隣接してＣｒ酸化物層（Ｃｒ−Ｏと表示）があり、その上（図中の左側）にＮｉＯ＋ＮｉＦｅ2Ｏ4混合層がある。Ｎｉめっき層はすべて酸化されたものと考えられ、Ｎｉ層の残存は見られない。このように基材に隣接するＮｉ層が存在しない場合には、ＮｉＯ＋ＮｉＦｅ2Ｏ4混合層の密着性が低下する。 FIG. 5 illustrates an elemental analysis profile by EDX from the surface to the depth direction in the cross section of the stainless steel material of the comparative example shown in FIG. The cross-sectional SEM image and the line analysis position in the SEM image are shown superimposed in the figure. In the figure, the region indicated as Fe—Cr corresponds to the stainless steel substrate, there is a Cr oxide layer (indicated as Cr—O) adjacent to it, and NiO + NiFe 2 O 4 on the upper side (left side in the figure). There is a mixed layer. All of the Ni plating layer is considered to have been oxidized, and no Ni layer remains. Thus, when there is no Ni layer adjacent to the substrate, the adhesion of the NiO + NiFe 2 O 4 mixed layer decreases.
表１に示す組成のフェライト系ステンレス鋼からなる板厚０.４ｍｍの冷延焼鈍鋼板（酸洗仕上げ材）を用意した。 A cold-rolled annealed steel sheet (pickling finish) having a thickness of 0.4 mm made of ferritic stainless steel having the composition shown in Table 1 was prepared.
このステンレス鋼板を基材として、その表面に以下の手順で電気Ｎｉめっきを施し、その後、大気中での加熱処理に供した。
〔電気Ｎｉめっき方法〕
ステンレス鋼板を６０℃の５％オルソ珪酸ナトリウム溶液中に浸せきして、電流密度５Ａ／ｄｍ2で１０ｓｅｃの電解脱脂を行った後、水洗し、５％ＨＣｌ溶液中に５ｓｅｃ浸せきした後、水洗した。次に、２５０ｇ／ＬのＮｉＣｌ2水溶液を塩酸でｐＨ０.１に調整しためっき液を用いて、液温３５℃、電流密度１０Ａ／ｄｍ2で１５ｓｅｃの下地Ｎｉめっきを行った。膜厚は０.１μｍであった。水洗後、２７５ｇ／ＬのＮｉＳＯ4水溶液を塩酸でｐＨ３に調整しためっき液を用いて、液温６０℃、電流密度１０Ａ／ｄｍ2で電解時間を変化させて膜厚０.３〜１５μｍの種々の厚さのＮｉめっき（本めっき）を施した。めっき後水洗して乾燥した。
Using this stainless steel plate as a base material, the surface was subjected to electric Ni plating in the following procedure, and then subjected to heat treatment in the air.
[Electric Ni plating method]
A stainless steel plate was immersed in a 5% sodium orthosilicate solution at 60 ° C., subjected to electrolytic degreasing at a current density of 5 A / dm 2 for 10 seconds, then washed with water, immersed in a 5% HCl solution for 5 seconds, and then washed with water. . Next, using a plating solution in which a 250 g / L NiCl 2 aqueous solution was adjusted to pH 0.1 with hydrochloric acid, a base Ni plating was performed for 15 sec at a liquid temperature of 35 ° C. and a current density of 10 A / dm 2 . The film thickness was 0.1 μm. After washing with water, using a plating solution in which a 275 g / L NiSO 4 aqueous solution was adjusted to pH 3 with hydrochloric acid, the electrolysis time was changed at a solution temperature of 60 ° C. and a current density of 10 A / dm 2. Ni plating (main plating) was applied. After plating, it was washed with water and dried.
〔加熱処理方法〕
各Ｎｉめっき鋼板から７０×５０ｍｍの試験片を切り出し、これをマッフル炉（ヤマト科学製；ＦＭ−３８）に装入し、Ｎｉめっき層の表面が大気に曝される状態で熱処理した。その際、鋼板の温度が７００〜１２００℃の範囲の所定温度となるようにそれぞれ炉温を設定した。試験片を炉内へ装入してから５ｍｉｎ経過後に炉外に取り出すことにより加熱を終了し、常温の大気中で放冷した。
[Heat treatment method]
A test piece of 70 × 50 mm was cut out from each Ni-plated steel sheet, and this was placed in a muffle furnace (manufactured by Yamato Kagaku; FM-38) and heat-treated in a state where the surface of the Ni-plated layer was exposed to the atmosphere. At that time, the furnace temperature was set so that the temperature of the steel sheet would be a predetermined temperature in the range of 700 to 1200 ° C. The test piece was placed in the furnace, and after 5 minutes had passed, the test piece was taken out of the furnace, and then the heating was terminated, and the test piece was allowed to cool in a normal temperature atmosphere.
加熱処理後の各試験片の表面に形成された皮膜について、以下のように絶縁性、皮膜密着性、および皮膜構造を調べた。
〔絶縁性〕
抵抗率計（三菱油化製；ＨＩＲＥＳＴＡ−ＩＰ）を使用し、試験片を絶縁シート（測定台）の上に被測定面（表面皮膜のある面）が上になるように置き、試験片の表面皮膜に測定用の二重リング電極を押し付けて１０Ｖの電圧を印加し、電圧印加開始から３０ｓｅｃ経過時点での表面抵抗率（Ω／□）を測定した。絶縁性が要求される多くの用途では、一般に絶縁抵抗がメガオームすなわち１.０×１０6 Ω／□以上であることが要求されることから、本測定における表面抵抗率が１.０×１０7 Ω／□以上となるものを合格（絶縁性；良好）と評価した。
About the film | membrane formed on the surface of each test piece after heat processing, the insulation, the film | membrane adhesiveness, and the film | membrane structure were investigated as follows.
[Insulation]
Using a resistivity meter (manufactured by Mitsubishi Oil Chemical Co., Ltd .; HIRESTA-IP), place the test piece on the insulating sheet (measurement table) so that the surface to be measured (surface with the surface coating) is on top. A double ring electrode for measurement was pressed against the surface film, a voltage of 10 V was applied, and the surface resistivity ( Ω / □ ) was measured after 30 seconds from the start of voltage application. In many applications where insulation is required, the insulation resistance is generally required to be mega ohms, that is, 1.0 × 10 6 Ω / □ or more. Therefore, the surface resistivity in this measurement is 1.0 × 10 7. Those with Ω / □ or higher were evaluated as acceptable (insulating properties; good).
〔皮膜密着性〕
皮膜の表面にＪＩＳ Ｚ１５２２に規定されるセロハン粘着テープを貼付したのち、そのセロハン粘着テープを剥がす方法により、皮膜密着性を調べた。試験数ｎ＝５で試験を行い、目視により皮膜がセロハン粘着テープに付着したサンプルが１つもないものを○（皮膜密着性；良好）、それ以外を×（皮膜密着性；不良）と判定した。
〔皮膜構造〕
試験片の皮膜の表面についてのＸ線回折パターン（図２、図３に例示したのと同様のもの）の測定、および皮膜を含む試験片表層部の断面における表面から深さ方向へのＥＤＸによる元素分析プロファイル（図３、図５に例示したのと同様のもの）の測定により、Ｎｉ層およびＮｉＯ＋ＮｉＦｅ2Ｏ4混合層の厚さを調べた。
これらの結果を表２に示す。
[Film adhesion]
After the cellophane adhesive tape specified in JIS Z1522 was applied to the surface of the film, the film adhesion was examined by a method of peeling the cellophane adhesive tape. The number of tests was n = 5, and when there was no sample in which the film adhered to the cellophane adhesive tape by visual observation, ○ (film adhesion: good) and the others were judged as x (film adhesion: poor). .
[Film structure]
Measurement of X-ray diffraction pattern (similar to those exemplified in FIGS. 2 and 3) on the surface of the test piece coating, and EDX from the surface to the depth direction in the cross section of the test specimen surface layer including the coating The thickness of the Ni layer and the NiO + NiFe 2 O 4 mixed layer was examined by measuring the elemental analysis profile (similar to those exemplified in FIGS. 3 and 5).
These results are shown in Table 2.
表２からわかるように、ステンレス鋼基材の表面にＮｉめっき層を形成した後、その表面を大気に曝して８００〜１２００℃で加熱したものにおいて、Ｎｉ層を介して厚さ１.０μｍ以上のＮｉＯ＋ＮｉＦｅ2Ｏ4混合層を形成させることができた（本発明例）。これらはいずれも表面抵抗率が１.０×１０6 Ω／□以上の良好な絶縁性を呈し、かつ表面の絶縁皮膜の密着性も良好であった。 As can be seen from Table 2, after the Ni plating layer was formed on the surface of the stainless steel substrate, the surface was exposed to the atmosphere and heated at 800 to 1200 ° C., and the thickness was 1.0 μm or more through the Ni layer. NiO + NiFe 2 O 4 mixed layer could be formed (Example of the present invention). All of these exhibited good insulation with a surface resistivity of 1.0 × 10 6 Ω / □ or more, and adhesion of the insulating film on the surface was also good.
これに対し、Ｎｏ.１〜５は加熱処理の温度が低かったことからＮｉＯ＋ＮｉＦｅ2Ｏ4混合層の厚さが１.０μｍに達しておらず、絶縁性に劣った。Ｎｏ.９，２０はそれぞれＮｉめっき層の厚さが薄すぎたものであるが、Ｎｏ.９では９００℃×５ｍｉｎの加熱条件ではＮｉＯ＋ＮｉＦｅ2Ｏ4混合層の厚さを１.０μｍ以上とすることができなかったことから絶縁性に劣り、またＮｏ.２０では１１００℃×５ｍｉｎの加熱条件ではＮｉ層を残存させることができなかったことから皮膜密着性に劣った。Ｎｏ.２１〜２４，２６〜２９はＮｉめっき層の厚さを１.０μｍ以上としたものであるが、それぞれの加熱温度（１１００℃または１２００℃）では加熱終了までの時間を５ｍｉｎとした条件でＮｉ層が残存せず、皮膜密着性に劣った。 On the other hand, Nos. 1 to 5 were inferior in insulating properties because the temperature of the heat treatment was low, so that the thickness of the NiO + NiFe 2 O 4 mixed layer did not reach 1.0 μm. In Nos. 9 and 20, the thickness of the Ni plating layer was too thin. In No. 9, the thickness of the NiO + NiFe 2 O 4 mixed layer was set to 1.0 μm or more under the heating condition of 900 ° C. × 5 min. Insulation was inferior because the film could not be obtained, and in No. 20, the Ni layer could not be left under the heating conditions of 1100 ° C. × 5 min. Nos. 21 to 24 and 26 to 29 are those in which the thickness of the Ni plating layer is set to 1.0 μm or more, but at each heating temperature (1100 ° C. or 1200 ° C.), the time until the heating is completed is 5 min. No Ni layer remained and the film adhesion was poor.
なお、ここでは表１に示したフェライト系ステンレス鋼を基材に用いた例を示したが、上述の組成を有する種々のフェライト系ステンレス鋼種を基材に用いた場合にも、Ｎｉめっき層を形成した後、大気中で加熱する手法にて上記本発明例と同様に絶縁性が良好で、かつ密着性に優れた絶縁皮膜を形成させることができる。 In addition, although the example which used the ferritic stainless steel shown in Table 1 for the base material here was shown, even when various ferritic stainless steel types which have the above-mentioned composition are used for the base material, Ni plating layer is used. After the formation, an insulating film having good insulation and excellent adhesion can be formed in the same manner as in the above-described example of the present invention by heating in the atmosphere.
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