JPH02182884A - Stainless steel material coated with ceramic and production thereof - Google Patents
Stainless steel material coated with ceramic and production thereofInfo
- Publication number
- JPH02182884A JPH02182884A JP87889A JP87889A JPH02182884A JP H02182884 A JPH02182884 A JP H02182884A JP 87889 A JP87889 A JP 87889A JP 87889 A JP87889 A JP 87889A JP H02182884 A JPH02182884 A JP H02182884A
- Authority
- JP
- Japan
- Prior art keywords
- stainless steel
- steel material
- ceramic
- layer
- oxide layer
- 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
Links
- 239000000463 material Substances 0.000 title claims abstract description 56
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 54
- 239000010935 stainless steel Substances 0.000 title claims abstract description 53
- 239000000919 ceramic Substances 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 238000001035 drying Methods 0.000 claims abstract description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 16
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims abstract description 12
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- 238000011282 treatment Methods 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 19
- 238000005524 ceramic coating Methods 0.000 claims description 14
- 238000007654 immersion Methods 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000002048 anodisation reaction Methods 0.000 claims description 2
- PYRZPBDTPRQYKG-UHFFFAOYSA-N cyclopentene-1-carboxylic acid Chemical compound OC(=O)C1=CCCC1 PYRZPBDTPRQYKG-UHFFFAOYSA-N 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 21
- 238000005260 corrosion Methods 0.000 abstract description 21
- 229910000831 Steel Inorganic materials 0.000 abstract description 6
- 239000010959 steel Substances 0.000 abstract description 6
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 26
- 238000005868 electrolysis reaction Methods 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- -1 25 g/A to 600 g/j2 Chemical compound 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005422 blasting Methods 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- KPVWDKBJLIDKEP-UHFFFAOYSA-L dihydroxy(dioxo)chromium;sulfuric acid Chemical compound OS(O)(=O)=O.O[Cr](O)(=O)=O KPVWDKBJLIDKEP-UHFFFAOYSA-L 0.000 description 2
- 238000010849 ion bombardment Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 210000001951 dura mater Anatomy 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
Landscapes
- Other Surface Treatments For Metallic Materials (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、ドライプロセスによりセラミックスをコーテ
ィングしたステンレス鋼材に関し、特にステンレス鋼材
に特定の前処理を行って、ステンレス鋼とセラミックス
との密着性を良好にした耐食性・加工性の優れたセラミ
ックコーティング鋼材およびその製造方法に関する。[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a stainless steel material coated with ceramics by a dry process. This invention relates to a ceramic coated steel material with improved corrosion resistance and workability, and a method for producing the same.
〈従来の技術〉
従来、ステンレス鋼材を基板として、イオンプレイティ
ング、化学蒸着、スパッタリングなどのドライプロセス
によりセラミックスをコーティングする際、ステンレス
鋼材とセラミックスとの密着性、耐食性を向上させるた
めの前処理としてイオンボンバード処理、あるいは硝酸
電解（特開昭６３−６２８６０号参照）による表面改質
が行われていた。<Conventional technology> Conventionally, when coating ceramics on a stainless steel substrate using a dry process such as ion plating, chemical vapor deposition, or sputtering, it was used as a pretreatment to improve the adhesion and corrosion resistance between the stainless steel material and the ceramic. Surface modification was performed by ion bombardment treatment or nitric acid electrolysis (see JP-A-63-62860).
〈発明が解決しようとする課題〉
しかし、これらの処理によって密着性は改善されるもの
の、表面改質とともに欠陥が生じやすくなり、欠陥部か
らの腐食が進み耐食性が低下する可能性が多くなり、セ
ラミックスコーティングスチレン鋼材を建材用として使
用するには耐食性が不充分である。<Problems to be solved by the invention> However, although adhesion is improved by these treatments, defects are more likely to occur along with surface modification, and there is a greater possibility that corrosion will progress from the defective parts and the corrosion resistance will decrease. Corrosion resistance is insufficient for ceramic-coated styrene steel materials to be used as building materials.
すなわち、ドライプロセスでセラミックをコーティング
する際、前処理としてイオンボンバード処理、硝酸電解
等を行ったセラミックスコーテイング材について耐食性
試験を行った結果、発銹箇所が点在している状態であっ
た。 走査電子顕微鏡で表面を観察すると、セラミック
スがポーラスに形成されていることがわかった。 そこ
で、セラミックスをコーティングする前処理としてステ
ンレス鋼とセラミックスとの間に、密着性、耐食性の良
好な、かつ均一な処理層を形成する必要がある。That is, when a ceramic coating material was subjected to ion bombardment treatment, nitric acid electrolysis, etc. as a pretreatment when coating ceramic by a dry process, a corrosion resistance test was conducted, and as a result, rusting spots were scattered. Observation of the surface with a scanning electron microscope revealed that the ceramic was porous. Therefore, as a pretreatment for coating ceramics, it is necessary to form a uniform treatment layer with good adhesion and corrosion resistance between stainless steel and ceramics.
本発明は、ステンレス鋼とセラミックスとの密着性が良
く耐食性の良好な処理層を、ステンレス鋼とセラミック
スとの間に生成させることを特徴とするドライプロセス
によるセラミックスコーティングステンレス鋼材および
その製造方法を提供することを目的としている。The present invention provides a ceramic-coated stainless steel material using a dry process, which is characterized by forming a treated layer with good adhesion and corrosion resistance between stainless steel and ceramics, and a method for manufacturing the same. It is intended to.
〈課題を解決するための手段〉
上記目的を達成するために、本発明の第１の態桜はステ
ンレス鋼材と、
該表面に形成されるＣｒとＦｅを有する５０〜３０００
人の酸化物層と、
該酸化物層上に形成される０、３〜５μｍのセラミック
ス層とを有することを特徴とするセラミックコーティン
グステンレス鋼材を提供する。<Means for Solving the Problems> In order to achieve the above object, the first embodiment of the present invention comprises a stainless steel material, and a stainless steel material having 50 to 3000 Cr and Fe formed on the surface.
Provided is a ceramic-coated stainless steel material characterized by having a human oxide layer and a ceramic layer of 0.3 to 5 μm formed on the oxide layer.
本発明の第２の態様は、ステンレス鋼材を酸化性雰囲気
中で、温度１００〜８００℃、時間３０秒〜３０分で加
熱処理し、さらにドライプロセスによりセラミックコー
ティング処理することを特徴とするセラミックコーティ
ングステンレス鋼材の製造方法を提供する。A second aspect of the present invention is a ceramic coating characterized in that a stainless steel material is heat treated in an oxidizing atmosphere at a temperature of 100 to 800°C for a time of 30 seconds to 30 minutes, and further subjected to a ceramic coating treatment by a dry process. A method for manufacturing stainless steel material is provided.
本発明の第３の態様は、ステンレス鋼材を、クロム酸２
５ｇ／Ｊｌ〜ａ ｏ ｏ ｇ／ｆＬおよび硫酸Ｏ１１〜
ａ ｏ ｏ ｇ／ｊ！を含む水溶液中で浸漬処理および
／または陽極処理と陰極処理とを所望の組合わせによっ
て行う交番電流電解処理し、
その後、該ステンレス鋼材を乾燥し、ドライプロセスに
よりセラミックコーティングＩＡ理することを特徴とす
るセラミックコーティングステンレス鋼材の製造方法を
提供する。A third aspect of the present invention is to treat stainless steel material with chromic acid 2
5g/Jl~a o o g/fL and sulfuric acid O11~
a o o g/j! The stainless steel material is subjected to an alternating current electrolytic treatment in which a desired combination of immersion treatment and/or anodic treatment and cathodic treatment is performed in an aqueous solution containing the stainless steel material, and then the stainless steel material is dried and subjected to a ceramic coating IA treatment by a dry process. Provided is a method for manufacturing ceramic coated stainless steel material.
以下に本発明の構成を詳細に説明する。The configuration of the present invention will be explained in detail below.
本発明者等は、耐食性、加工性の良好なセラミックスコ
ーティングステンレス鋼材を得るために種々研究した結
果、ドライプロセスによりセラミックスをコーチイブす
る前処理つまりステンレス鋼材とセラミックス層との間
に、酸化物層を形成することで耐食性、加工性が著しく
向上することを見い出した。As a result of various studies to obtain a ceramic-coated stainless steel material with good corrosion resistance and workability, the present inventors have discovered that an oxide layer is formed between the stainless steel material and the ceramic layer in pre-treatment for coating ceramics using a dry process. It has been found that corrosion resistance and workability are significantly improved by forming a steel sheet.
はじめに、第１図に断面図で示す本発明のステンレス鋼
材について説明する。First, the stainless steel material of the present invention shown in cross-sectional view in FIG. 1 will be explained.
本発明は、基板１のステンレス鋼材と、該表面に形成さ
れる酸化物層２と、該酸化物層上にセラミック層３とを
有するセラミックコーティングステンレス鋼材である。The present invention is a ceramic-coated stainless steel material having a stainless steel substrate 1, an oxide layer 2 formed on the surface thereof, and a ceramic layer 3 on the oxide layer.
（１）ステンレス鋼材としてはオーステナイト系ステン
レス鋼材、フェライト系ステンレス鋼材のどちらも適用
でき、表面仕上げは２Ｂ（酸洗肌仕上げ）、２Ｄ、ＢＡ
（光輝焼鈍仕上げ）その他いずれのステンレス鋼材でも
適用できる。(1) As the stainless steel material, both austenitic stainless steel material and ferritic stainless steel material can be applied, and the surface finish is 2B (pickled surface finish), 2D, and BA.
(Bright annealing finish) Any other stainless steel material can be applied.
用いる鋼材の形状は特に限定されるものではなく、板材
、ブロック材、異形材等のいずれでもよい。The shape of the steel material used is not particularly limited, and may be a plate material, a block material, a deformed material, or the like.
（２）このステンレス鋼材の片面あるいは両面にセラミ
ックスコーティング層が形成されるのであるが、ステン
レス鋼材表面とセラミックコーティング層との中間に、
第１層を形成するＣｒとＦｅを有する５０〜３０００人
の酸化物層を有することが本発明の１つの特徴である。(2) A ceramic coating layer is formed on one or both sides of this stainless steel material, but between the surface of the stainless steel material and the ceramic coating layer,
It is a feature of the invention to have 50-3000 oxide layers with Cr and Fe forming the first layer.
この酸化物層のＣｒ量は、最表層において好ましくは４
０〜９０Ｗし％、残りのほとんどがＦｅであり、他にＭ
ｎ％Ｎｉ％Ｓｉなどを本発明の目的を損なわない範囲で
含んでいてもよく、また不可避的不純物を若干量含んで
いてもよい。The amount of Cr in this oxide layer is preferably 4 in the outermost layer.
0~90W%, most of the rest is Fe, and M
It may contain n%Ni%Si and the like within a range that does not impair the object of the present invention, and may also contain some amount of unavoidable impurities.
酸化物層が、５０人未満でうすければ耐食性に効果がな
く、３０００人をこえて厚くなれば皮膜が弱くなり剥離
を生じる。If the oxide layer is thin (less than 50 layers), it has no effect on corrosion resistance, and if it is thicker than 3,000 layers, the film becomes weak and peels off.
（３）第二層を形成するセラミックス層は、Ｔ ｉ
Ｎ ％ Ｔ Ｉ Ｃ％ Ｓ ｉ３ Ｎ
４ 、Ｓ ｔ Ｃｘ Ｃｒ Ｎ等のセラミッ
クスコーティング層であり、好ましくは膜厚は０．３μ
ｍ〜５μｍとする必要がある。 セラミックス層の膜厚
が０．３μｍ未満で薄ければ耐食性が低下し、５μｍを
超えて厚ければ剥離を生じる。(3) The ceramic layer forming the second layer is Ti
N% TIC% Si3 N
4, a ceramic coating layer such as S t Cx Cr N, preferably with a thickness of 0.3μ
It is necessary to set it to 5 micrometers. If the thickness of the ceramic layer is less than 0.3 μm, corrosion resistance will decrease, and if it is thicker than 5 μm, peeling will occur.
次に、本発明のステンレス鋼材の製造方法の好適な例に
ついて説明するが、本発明はこれらに限定されるもので
はない。Next, preferred examples of the method for manufacturing stainless steel materials of the present invention will be described, but the present invention is not limited thereto.
（１）ステンレス鋼材を酸化性雰囲気中で加熱処理し、
さらにドライプロセスによりセラミックコーティングす
る。(1) Heat treating stainless steel material in an oxidizing atmosphere,
Furthermore, a ceramic coating is applied using a dry process.
第１段の加熱処理の雰囲気としては、酸化性雰囲気であ
ることが、必要であり、酸化性雰囲気としては空気、炭
酸ガス、水蒸気あるいは酸素を窒素やアルゴンなどの不
活性ガスで希釈したガス等の雰囲気が挙げられる。 加
熱温度は１００〜８００℃であることが望ましい。 加
熱温度が１００℃未満では、酸化皮膜生成に時間がかか
り生産性が悪い。 ８００℃を超えて高ければ、酸化皮
膜自身が脆くなり耐食性が低下する。 加熱時間は３０
ｓｅｃ〜３０ｍ１ｎの範囲であることが望ましい。
３０ｓｅｃ未満で短かければ、耐食性・加工性に効果が
なく、３０ｍ１ｎを超えて長ければ、生産性を低下させ
る。The atmosphere for the first heat treatment must be an oxidizing atmosphere, such as air, carbon dioxide, water vapor, or a gas prepared by diluting oxygen with an inert gas such as nitrogen or argon. One example is the atmosphere. It is desirable that the heating temperature is 100 to 800°C. If the heating temperature is less than 100°C, it takes time to form an oxide film, resulting in poor productivity. If the temperature exceeds 800°C, the oxide film itself becomes brittle and corrosion resistance decreases. Heating time is 30
The range is preferably from sec to 30 m1n.
If it is too short (less than 30 sec), it will have no effect on corrosion resistance or workability, and if it is too long (more than 30 m1n), it will reduce productivity.
第１段の加熱処理後、乾燥し、第２段としてドライプロ
セスによりセラミックスをコーティングする。 ドラ
イプロセスとしてはイオンブレーティング法、スパッタ
リング法、化学蒸着等のいずれの方法でも適用できる。After the first stage heat treatment, it is dried, and as a second stage, ceramics are coated by a dry process. As the dry process, any method such as an ion blasting method, a sputtering method, or a chemical vapor deposition method can be applied.
（２）ステンレス鋼材を、クロム酸２５ｇ／１１〜６０
０ ｇ／ｌおよび硫酸０．１〜６００ ｇ／１１を含む
水溶液中で浸漬処理および／または陽極処理と陰極処理
とを所望の組合わせによって行う交番電流電解処理し、
その後、該ステンレス鋼材を乾燥し、ドライブセスによ
りセラミックコーティング処理する。(2) Stainless steel material with chromic acid 25g/11~60
0 g/l and sulfuric acid 0.1 to 600 g/11 in an aqueous solution containing immersion treatment and/or alternating current electrolysis treatment using a desired combination of anodization and cathodic treatment, and then drying the stainless steel material. Then, ceramic coating is applied by dry process.
浸漬処理およびまたは交番電流電解を行う溶液組成とし
ては、クロム酸、２５ｇ／Ａ〜６００ｇ／ｊ２および硫
酸０．１〜６００ ｇ／λを含む水溶液であることが必
要である。The solution composition for performing immersion treatment and/or alternating current electrolysis needs to be an aqueous solution containing chromic acid, 25 g/A to 600 g/j2, and sulfuric acid, 0.1 to 600 g/λ.
クロム酸が２５ｇ／１未満であれば酸化皮膜が生成せず
、６００ ｇ／ｆｌを超えて多ければ溶液中のクロム酸
が溶解しにくくなる。 硫酸は０．１ｇ／ｊ！未満であ
れば酸化皮膜が生成せず、６００ ｇ／ｌを超えて多け
れば、共存するクロム酸が溶解しにくくなる。If the amount of chromic acid is less than 25 g/fl, no oxide film will be formed, and if it is more than 600 g/fl, the chromic acid in the solution will be difficult to dissolve. Sulfuric acid is 0.1g/j! If it is less than 600 g/l, no oxide film will be formed, and if it exceeds 600 g/l, the coexisting chromic acid will be difficult to dissolve.
溶液中には、クロム酸、硫酸以外に、モリブデン酸等の
酸化剤等を加えてもよい。In addition to chromic acid and sulfuric acid, an oxidizing agent such as molybdic acid may be added to the solution.
酸化皮膜を生成する方法として浸漬処理を行う場合は、
浸漬時間３ｍ１ｎ〜２０ｍ１ｎで行うことが望ましい。When performing immersion treatment as a method to generate an oxide film,
It is desirable to carry out the immersion for a time of 3 m1n to 20 m1n.
３ｍ１ｎ未満であれば耐食性に効果がなく、２０ｍ
１ｎを超えて長ければ生産性が低下するうえに、皮膜が
脆くなり、耐食性が低下する。 浸漬温度は、７０〜９
０℃であることが望ましい。 ７０℃未満では耐食性
に効果がなく、９０℃を超えて高ければ液の蒸発が激し
く液組成の変化が大きくなるために所望する膜厚に制御
しにくくなる。If it is less than 3 m1n, it will have no effect on corrosion resistance, and if it is less than 20 m
If it is longer than 1 n, not only will productivity decrease, but the film will also become brittle and its corrosion resistance will decrease. The soaking temperature is 70-9
The temperature is preferably 0°C. If it is less than 70°C, there is no effect on corrosion resistance, and if it is higher than 90°C, the liquid will evaporate rapidly and the liquid composition will change greatly, making it difficult to control the desired film thickness.
上記の浸漬処理後、特公昭５３−３１８１７号に示され
ているような硬膜処理すなわちクロム酸２５〜８５０
ｇ／ｆＬ、硫酸０．１〜１０ｇ／ｆｌ水溶液中、液温２
０〜８０℃で、０．６〜３０Ａ／ｄｍ２２〜３０分の陰
極電解を行っても良い。 また硬膜処理として特公昭５
５−４６４７６号に示されているクロム酸０．２６〜７
．５モル／Ｕとクロム酸とイオンのモル比が２０：１〜
５００：１になるような量の塩化物イオン硝酸塩イオン
、リン酸塩イオンおよび酢酸塩の一種または二種以上と
を水溶液状で含む溶液中で陰極電解を行う方法も適用で
とる。After the above immersion treatment, hardening treatment as shown in Japanese Patent Publication No. 53-31817, i.e. chromic acid 25-850
g/fL, in sulfuric acid 0.1-10 g/fl aqueous solution, liquid temperature 2
Cathodic electrolysis may be performed at 0 to 80° C. and 0.6 to 30 A/dm for 22 to 30 minutes. Also, as a treatment for dura mater,
Chromic acid 0.26-7 shown in No. 5-46476
．． 5 mol/U and the molar ratio of chromic acid and ions is 20:1 ~
A method of carrying out cathodic electrolysis in an aqueous solution containing one or more of chloride ions, nitrate ions, phosphate ions and acetates in an amount of 500:1 may also be adopted.
酸化皮膜生成させる方法として交番電流電解処理を行う
場合、好ましくは、特開昭６１−１２７８９９号に示さ
れるように、陽極電流密度０．０１〜３ Ａ／ｄｍ２
陰極電流密度０．０３〜５．ＯＡ／ｄｍ２ａ返し数
１００Ｈｚ以下で交番電流電解を行う方法等が適用でき
る。 交番電流電解処理は、上記の浸漬処理と併用して
行ってもよい。When performing an alternating current electrolytic treatment as a method for forming an oxide film, preferably an anode current density of 0.01 to 3 A/dm2 is used, as shown in JP-A-61-127899.
Cathode current density 0.03-5. A method of performing alternating current electrolysis at an OA/dm2a rate of 100 Hz or less can be applied. The alternating current electrolytic treatment may be performed in combination with the above-mentioned immersion treatment.
以上の処理によって第１段の酸化皮膜を生成させた後、
乾燥し、ドライプロセスによりセラミックスをコーティ
ングする。 ドライプロセスとしては、イオンブレー
ティング法、スパッタリング法、化学蒸着等のいずれの
方法にも適用できる。After generating the first stage oxide film through the above treatment,
Dry and coat the ceramics using a dry process. As the dry process, any method such as an ion blasting method, a sputtering method, or a chemical vapor deposition method can be applied.
〈実施例〉 以下に１本発明を実施例により具体的に説明する。<Example> The present invention will be specifically explained below using examples.
（実施例）
ＳＵＳ ３０４光輝焼鈍材、サンプルサイズ７０Ｘ７
２ｍｍ、板厚０．３のステンレス鋼板を用い実験室的に
加熱処理およびクロム酸−硫酸水溶液中で浸漬あるいは
交番電流電解処理後、ドライヤーで乾燥し、イオンブレ
ーティング法によりＴｉＮをコーティングした。(Example) SUS 304 bright annealed material, sample size 70X7
A stainless steel plate having a diameter of 2 mm and a thickness of 0.3 was heated in the laboratory, immersed in an aqueous chromic acid-sulfuric acid solution, or subjected to an alternating current electrolytic treatment, dried with a dryer, and coated with TiN by an ion-blating method.
ＴＩＮの形成条件は表１に示す。The conditions for forming TIN are shown in Table 1.
加熱処理による酸化層生成については処理条件および評
価結果を表２にまとめる。 クロム酸−硫酸水溶液中で
浸漬あるいは交番電流電解処理により酸化層生成につい
ては、処理条件および評価結果を表３にまとめる。Table 2 summarizes the treatment conditions and evaluation results regarding the formation of an oxide layer by heat treatment. Regarding the formation of an oxide layer by immersion in a chromic acid-sulfuric acid aqueous solution or alternating current electrolytic treatment, the treatment conditions and evaluation results are summarized in Table 3.
（比較例）
比較として、実施例と同様に行った。 ただし加熱処理
条件の範囲をはずして表２に示す範囲とした（比較例４
．５）。(Comparative Example) For comparison, the same procedure as in the example was carried out. However, the range of heat treatment conditions was changed to the range shown in Table 2 (Comparative Example 4
．． 5).
べつに、比較として、ステンレス鋼材上に前処理を行わ
ずに直接セラミックコーティングを行フたもの（比較例
６および７）と、表４に示す硝酸電解を用いて前処理を
行ったもの（比較例８）を作成し、同様に評価し、表２
および表３に結果を示した。In addition, as a comparison, ceramic coating was performed directly on the stainless steel material without pretreatment (Comparative Examples 6 and 7), and stainless steel material was pretreated using nitric acid electrolysis shown in Table 4 (Comparative Example 8) was created, evaluated in the same way, and Table 2
The results are shown in Table 3.
塩水噴霧試験および９０°曲げ試験を行い、試駆方法お
よび結果の評価は、下記のとおりとした。A salt spray test and a 90° bending test were conducted, and the trial driving method and evaluation of the results were as follows.
中１）塩水噴霧試験 （５０℃、５ＪＮａＣｕ）評価基
準 評価
ざびが全面に発生したもの ×
さびが一部に発生したもの △
さびが全く発生しないもの Ｏ
中２）９０″曲げ試験
評価基準
外表面に全く変化が起こらないもの
曲げ部分が白っぽく変色したもの
曲げ部分に亀裂が生じたもの
評 価
Δ
×
表 １
表
従来法のステンレス鋼上に硝酸電解処理後、ドライプロ
セスによりセラミックスを直接コーティングする方法で
形成されるセラミックスは、セラミックスがステンレス
鋼との密着性が悪いことにより大変ポーラスであフた。Medium 1) Salt water spray test (50℃, 5JNaCu) Evaluation criteria Evaluation Rust has occurred on the entire surface × Rust has occurred in some areas △ No rust has occurred at all O Medium 2) 90" bending test Evaluation criteria Outer surface No change occurs at all.The bent part has a whitish discoloration.The bent part has cracks.Evaluation Δ The ceramics formed with stainless steel were very porous due to the poor adhesion of the ceramics to the stainless steel.
これに比べ本発明法では、セラミックスコーティング
を行う前処理としてステンレス鋼上に酸化物を生成する
ことでステンレス鋼とセラミックス層の密着性を良好に
する。 この結果セラミックスが緻密に形成されること
で、塩水噴霧の結果かられかるように耐食性が向上した
。 また、９０°曲げ試験の結果かられかるように加工
性が向上した。In contrast, the method of the present invention improves the adhesion between the stainless steel and the ceramic layer by generating oxides on the stainless steel as a pretreatment for ceramic coating. As a result, the ceramics were formed densely, which improved corrosion resistance as seen from the effects of salt spray. Furthermore, the workability was improved as seen from the results of the 90° bending test.
〈発明の効果〉
本発明のセラミックコーティングステンレス鋼材は、セ
ラミックコーティングの前処理として酸化物層を形成す
ることにより、耐食性、加工性が向上する。<Effects of the Invention> The ceramic coated stainless steel material of the present invention has improved corrosion resistance and workability by forming an oxide layer as a pretreatment for ceramic coating.
本発明のセラミックコーティングステンレス鋼は、外装
用建築材としても幅広い環境下で使用できる。The ceramic coated stainless steel of the present invention can be used as an exterior building material in a wide range of environments.
第１図は、本発明のセラミックスコーティングステンレ
ス鋼材の１例を示す断面図である。
符号の説明
１・・・基板、
２・・・酸化物層、
３・・・セラミック層FIG. 1 is a sectional view showing an example of the ceramic-coated stainless steel material of the present invention. Explanation of symbols 1...Substrate, 2...Oxide layer, 3...Ceramic layer
Claims (3)
Åの酸化物層と、 該酸化物層上に形成される０．３〜５μｍのセラミック
ス層とを有することを特徴とするセラミックコーティン
グステンレス鋼材。(1) Stainless steel material and 50 to 3000 with Cr and Fe formed on the surface.
A ceramic-coated stainless steel material comprising: an oxide layer of 0.3 to 5 μm thick; and a ceramic layer of 0.3 to 5 μm formed on the oxide layer.
〜８００℃、時間３０秒〜３０分で加熱処理し、さらに
ドライプロセスによりセラミックコーティング処理する
ことを特徴とするセラミックコーティングステンレス鋼
材の製造方法。(2) Stainless steel material is heated to 100% in an oxidizing atmosphere.
A method for producing a ceramic-coated stainless steel material, which comprises heating the material at ~800°C for 30 seconds to 30 minutes, and further performing a ceramic coating treatment using a dry process.
ｇ／ｌおよび硫酸０．１〜６００ｇ／ｌを含む水溶液中
で浸漬処理および／または陽極処理と陰極処理とを所望
の組合わせによって行う交番電流電解処理し、 その後、該ステンレス鋼材を乾燥し、ドライプロセスに
よりセラミックコーティング処理することを特徴とする
セラミックコーティングステンレス鋼材の製造方法。(3) Stainless steel material with chromic acid of 25g/l to 600g/l
g/l and sulfuric acid from 0.1 to 600 g/l in an aqueous solution containing immersion treatment and/or anodization and cathodic treatment in a desired combination, followed by drying the stainless steel material, A method for manufacturing ceramic-coated stainless steel material, which is characterized by performing ceramic coating treatment using a dry process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP87889A JPH02182884A (en) | 1989-01-06 | 1989-01-06 | Stainless steel material coated with ceramic and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP87889A JPH02182884A (en) | 1989-01-06 | 1989-01-06 | Stainless steel material coated with ceramic and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02182884A true JPH02182884A (en) | 1990-07-17 |
Family
ID=11485932
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP87889A Pending JPH02182884A (en) | 1989-01-06 | 1989-01-06 | Stainless steel material coated with ceramic and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02182884A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009179878A (en) * | 2008-01-29 | 2009-08-13 | Tokai Carbon Korea Co Ltd | Metal having surface coated with ceramic and method for manufacturing the same |
| JP2011179097A (en) * | 2010-03-03 | 2011-09-15 | Abel Kk | Coated stainless steel and method of manufacturing the same |
| JP2021075747A (en) * | 2019-11-07 | 2021-05-20 | 株式会社永井製作所 | Method for accelerating rust development on bonding surface of splice plate |
-
1989
- 1989-01-06 JP JP87889A patent/JPH02182884A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009179878A (en) * | 2008-01-29 | 2009-08-13 | Tokai Carbon Korea Co Ltd | Metal having surface coated with ceramic and method for manufacturing the same |
| JP2011179097A (en) * | 2010-03-03 | 2011-09-15 | Abel Kk | Coated stainless steel and method of manufacturing the same |
| JP2021075747A (en) * | 2019-11-07 | 2021-05-20 | 株式会社永井製作所 | Method for accelerating rust development on bonding surface of splice plate |
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