JPH06158276A - Al oxide-coated iron material excellent in insulation property and high-temperature oxidation resistance - Google Patents
Al oxide-coated iron material excellent in insulation property and high-temperature oxidation resistanceInfo
- Publication number
- JPH06158276A JPH06158276A JP4333869A JP33386992A JPH06158276A JP H06158276 A JPH06158276 A JP H06158276A JP 4333869 A JP4333869 A JP 4333869A JP 33386992 A JP33386992 A JP 33386992A JP H06158276 A JPH06158276 A JP H06158276A
- Authority
- JP
- Japan
- Prior art keywords
- base material
- iron
- film
- al2o3
- oxide
- 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.)
- Withdrawn
Links
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000000463 material Substances 0.000 title claims abstract description 50
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 36
- 238000009413 insulation Methods 0.000 title abstract description 11
- 230000003647 oxidation Effects 0.000 title abstract description 11
- 238000007254 oxidation reaction Methods 0.000 title abstract description 11
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 239000011888 foil Substances 0.000 abstract description 16
- 238000010438 heat treatment Methods 0.000 abstract description 16
- 238000001816 cooling Methods 0.000 abstract description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 6
- 229910052593 corundum Inorganic materials 0.000 abstract 6
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 6
- 239000010410 layer Substances 0.000 abstract 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract 2
- 239000002344 surface layer Substances 0.000 abstract 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 28
- 229910000831 Steel Inorganic materials 0.000 description 26
- 239000010959 steel Substances 0.000 description 23
- 238000000034 method Methods 0.000 description 12
- 239000000919 ceramic Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- 239000011810 insulating material Substances 0.000 description 3
- 239000012212 insulator Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000010891 electric arc Methods 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Landscapes
- Physical Vapour Deposition (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、表面が絶縁化されてお
り、しかも高温加熱を繰り返しても絶縁性が失われるこ
とがなく、また、耐高温酸化性が高い絶縁性表面を有す
る鉄基材料に関する。BACKGROUND OF THE INVENTION The present invention relates to an iron-based material which has an insulating surface, does not lose its insulating property even when repeatedly heated at high temperatures, and has an insulating surface with high high-temperature oxidation resistance. Regarding materials.
【０００２】[0002]
【従来の技術】ヒーター用などの電気発熱材料には耐熱
性を必要とするためＮｉ−Ｃｒ系合金、Ｆｅ−Ｃｒ−Ａ
ｌ系合金またはＰｔなどが用いられている。これらは電
気的に絶縁しなければならないことが多く、その場合に
は、セラミックスなどの材料で絶縁している。線状また
は板状などの発熱体では表面全体を絶縁しなければなら
ない場合があり、その場合には耐熱性のガラス繊維やセ
ラミックス繊維でできた絶縁物やアスベストなどで覆っ
たり、管状の絶縁物の中を通したりしている。高温用の
耐熱絶縁材料としてはセラミックスが多用されている。2. Description of the Related Art Electric heating materials for heaters and the like require heat resistance, so that Ni--Cr alloys, Fe--Cr--A are used.
An l-based alloy or Pt is used. These often have to be electrically insulated, in which case they are insulated with a material such as ceramics. In the case of a linear or plate-shaped heating element, it may be necessary to insulate the entire surface.In that case, it should be covered with heat-resistant glass fiber or ceramic fiber insulation, asbestos, or tubular insulation. I am passing through. Ceramics is often used as a heat-resistant insulating material for high temperatures.
【０００３】[0003]
【発明が解決しようとする課題】鉄基材を絶縁体などで
覆うことは体積が大きくなり使用に際して制限が大きく
なる。絶縁体がセラミックスの場合は加工なども大型に
なると困難になるという問題もある。発熱体の場合は、
絶縁材料で物理的に表面を覆うと直接熱が伝わらず、発
熱体から空気層を介して絶縁材料に熱が伝わり、その熱
が被加熱物に伝わるため被加熱物の昇温が遅くなったり
する。表面を覆った絶縁物が放射熱の反射体となるた
め、被加熱物の昇温がさらに遅くなる。これらの問題を
解決するため、絶縁性のセラミックスで表面を被覆すれ
ばよいが、発熱材料である金属との熱膨張率の差から被
覆のセラミックス層にクラックや剥離が生じたり、それ
によって絶縁性の低下、クラックおよび剥離の発生の部
分から急速に酸化が進んだりする。高温用の絶縁性セラ
ミックスを用いる場合、セラミックスが熱衝撃に弱いた
めセラミックスが割れたりして使用不能になったりする
ことが多い。Covering the iron base material with an insulator or the like has a large volume and limits the use thereof. In the case where the insulator is ceramics, there is also a problem that it becomes difficult when the processing becomes large in size. For heating elements,
When the surface is physically covered with an insulating material, the heat is not directly transferred, but the heat is transferred from the heating element to the insulating material through the air layer, and the heat is transferred to the heated object. To do. Since the insulator covering the surface serves as a radiant heat reflector, the temperature rise of the object to be heated is further delayed. In order to solve these problems, the surface should be coated with insulating ceramics, but cracks or peeling may occur in the ceramic layer of the coating due to the difference in the coefficient of thermal expansion from the metal that is the heat generating material The oxidation progresses rapidly from the part where the deterioration of temperature, cracks and peeling occur. When using insulating ceramics for high temperatures, the ceramics are often vulnerable to thermal shock, and the ceramics often crack and become unusable.
【０００４】[0004]
【問題点を解決するための手段】前記の問題はＡｌを含
有する鉄基材の表面を酸化Ａｌで被覆することによって
解決される。The above problems are solved by coating the surface of an Al-containing iron substrate with Al oxide.
【発明の構成】本発明は、Ａｌを含有する鉄基材とその
表面を酸化Ａｌの被覆からなる材料を提供する。本発明
の材料の鉄基材は ０.５〜８ｗｔ％のＡｌを含有する。
酸化Ａｌ層の厚さは、特に限定されない。厚い程絶縁性
は高いが、厚すぎると可撓性は制限される。本発明の材
料の鉄基材はＡｌに加えて８〜３５ｗｔ％のＣｒ、およ
び合計で０.２ｗｔ％以下の希土類とＹの少なくとも一
種を含んでいてもよい。BEST MODE FOR CARRYING OUT THE INVENTION The present invention provides a material comprising an Al-containing iron base material and a surface thereof coated with Al oxide. The iron substrate of the material of the present invention contains 0.5-8 wt% Al.
The thickness of the Al oxide layer is not particularly limited. The thicker it is, the higher the insulation, but if it is too thick, the flexibility is limited. The iron base material of the material of the present invention may contain, in addition to Al, 8-35 wt% of Cr, and 0.2 wt% or less in total of at least one of rare earth elements and Y.
【０００５】[0005]
【作用】本発明の材料は、鉄基材中にＡｌが含有されて
いることにより、Ａｌ2０3膜にクラックや剥離が生じて
も加熱中に鉄基材中のＡｌが酸化しそのクラック部にＡ
ｌ2Ｏ3膜が生じてクラック部分が自然に修復（自己修
復）される。鉄基材中のＡｌの含有量は ０.５ｗｔ％以
上でないと自己修復作用は現われない。上限は８ｗｔ％
であり、８ｗｔ％を超えると熱衝撃に弱くなる。In the material of the present invention, since Al is contained in the iron base material, even if cracks or peeling occur in the Al 2 O 3 film, Al in the iron base material is oxidized during heating and the cracks are generated. Part A
The l 2 O 3 film is generated, and the cracked portion is naturally repaired (self-healing). The self-repairing action does not appear unless the content of Al in the iron base material is 0.5 wt% or more. The upper limit is 8 wt%
If it exceeds 8 wt%, it becomes vulnerable to thermal shock.
【０００６】鉄基材が箔などの場合はクラックの発生と
自己修復の繰り返しによって含有しているＡｌが枯渇す
る場合がある。このようになると導電性のＦｅ酸化物が
急速に成長し、Ａｌ2Ｏ3膜が剥離し、絶縁性が喪失す
る。Ｆｅ酸化物の成長は鉄基材中に８ｗｔ％以上のＣｒ
を含有させることによって防止することができる。これ
は鉄基材中にＣｒを含有させることによって、Ａｌが枯
渇する場合にＣｒ2Ｏ3やＦｅＯ・Ｃｒ2Ｏ3が緻密にで
き、その後の酸化物の成長を抑え、Ａｌ2Ｏ3膜の剥離が
急速に進むことがないためである。Ｃｒ含有量の上限は
３５ｗｔ％である。３５ｗｔ％を超えると鉄基材が３０
０℃以下で極めて脆くなり加工ができなくなる。鉄基材
中にＣｒを含有させることによって鉄基材中のＡｌが枯
渇した場合においてもＦｅ酸化物の成長による急速なＡ
ｌ2Ｏ3膜の剥離およびそれによる絶縁性、耐高温酸化性
の喪失がなくなる。また、Ｃｒを含有させることによっ
て素材の靭性および加工性も高まる。When the iron base material is a foil or the like, the contained Al may be depleted due to repeated occurrence of cracks and self-repair. In this case, the conductive Fe oxide grows rapidly, the Al 2 O 3 film is peeled off, and the insulating property is lost. The growth of Fe oxide is 8 wt% or more of Cr in the iron base material.
Can be prevented. This by inclusion of Cr in the iron substrate, Cr 2 O 3 and FeO · Cr 2 O 3 can be densely when Al is depleted, reducing the growth of subsequent oxide, Al 2 O 3 film This is because the peeling off of does not proceed rapidly. The upper limit of the Cr content is 35 wt%. When the content exceeds 35 wt%, the iron base material is 30
Below 0 ° C, it becomes extremely brittle and cannot be processed. Even when Al in the iron base material is depleted by including Cr in the iron base material, rapid A due to growth of Fe oxide
The peeling of the l 2 O 3 film and the resulting loss of insulation and high temperature oxidation resistance are eliminated. Moreover, the toughness and workability of the material are increased by including Cr.
【０００７】鉄基材とＡｌ2Ｏ3膜の間には熱膨張率の差
によってＡｌ2Ｏ3膜の剥離が生じる場合があるが、鉄基
材中に希土類元素とＹの少なくとも１種を含有させるこ
とによってＡｌ2Ｏ3膜の密着性が高まり、剥離が少なく
なる。このことによってＡｌ2Ｏ3膜の剥離後の自己修復
作用による鉄基材中のＡｌの消耗が少なくなる。これは
鉄基材が箔などの場合には特に有効であり、絶縁性が早
期に失われることがなくなる。しかし、希土類元素およ
び／またはＹの合計が ０.２ｗｔ％を越えると介在物と
して鉄基材中に析出するため、Ａｌ2Ｏ3膜が剥離しやす
くなる。このため、希土類元素および／またはＹの含有
量の合計は ０.２ｗｔ％以下にすべきである。希土類お
よび／またはＹの含有により、Ａｌ2Ｏ3膜の密着性が高
まり、加熱、冷却を繰り返してもＡｌ2Ｏ3膜が剥離する
ことが少なくなる。これによって鉄基材中のＡｌの消費
速度が小さくなり、長期に渡り絶縁性が維持される。ま
た、耐高温酸化性も維持される。[0007] While between iron substrate and the Al 2 O 3 film in some cases separation of the Al 2 O 3 film by the difference in thermal expansion occurs, at least one rare earth element and Y in the iron substrate By including it, the adhesion of the Al 2 O 3 film is enhanced and peeling is reduced. This reduces the consumption of Al in the iron base material due to the self-repairing action after the peeling of the Al 2 O 3 film. This is particularly effective when the iron base material is a foil or the like, and the insulating property is not lost early. However, when the total amount of rare earth elements and / or Y exceeds 0.2 wt%, the Al 2 O 3 film is easily peeled off because it is precipitated as an inclusion in the iron base material. Therefore, the total content of rare earth elements and / or Y should be 0.2 wt% or less. The content of the rare earth and / or Y, increases the adhesion of the Al 2 O 3 film, heat, the Al 2 O 3 film even after repeated cooling is less likely to be peeled off. This reduces the consumption rate of Al in the iron base material and maintains the insulating property for a long period of time. Further, the high temperature oxidation resistance is maintained.
【０００８】酸化Ａｌで被覆する手段として、ＰＶＤ
法、ＣＶＤ法、溶射法など種々の方法を採用することが
できる。緻密で密着性のよいＡｌ2Ｏ3層を得るためには
ＰＶＤ法またはＣＶＤ法を採用する方がよい。緻密で密
着性がよくなることによって薄い被覆膜で高い絶縁性が
得られるようになる。ＰＶＤ法とＣＶＤ法を比較すると
ＰＶＤ法の方が高速度で被覆することが可能である。ま
たＰＶＤ法の中でも特開平３−７２０６９号および特開
平４−１２４２６３号に記載されているイオン化蒸着法
が生産性よく高速度で被覆することが可能である。イオ
ン化蒸着法とはるつぼ中の金属とるつぼ上方の電極との
間でアーク放電を発生させ、そのアーク放電中で蒸発し
た金属を一部もしくは全部をイオン化させ、その蒸気を
酸素が存在する真空中で基板に蒸着させる方法である。
金属蒸気の一部もしくは全部がイオン化しているため、
金属蒸気と酸素との反応性が高くなり、高速に酸化Ａｌ
膜が蒸着できる。PVD is used as a means for coating with Al oxide.
Various methods such as a CVD method, a CVD method and a thermal spraying method can be adopted. In order to obtain a dense and adherent Al 2 O 3 layer, it is better to adopt the PVD method or the CVD method. Due to the denseness and good adhesion, high insulation can be obtained with a thin coating film. Comparing the PVD method and the CVD method, the PVD method can coat at a higher speed. Among the PVD methods, the ionization vapor deposition method described in JP-A-3-72069 and JP-A-4-124263 can be used for high productivity and high-rate coating. Ionization vapor deposition is a method in which arc discharge is generated between the metal in the crucible and the electrode above the crucible, the metal evaporated in the arc discharge is partially or completely ionized, and the vapor is in a vacuum containing oxygen. It is a method of vapor-depositing on a substrate.
Because some or all of the metal vapor is ionized,
The reactivity between metal vapor and oxygen becomes high, and Al oxide is rapidly formed.
The film can be deposited.
【０００９】被覆する酸化Ａｌ膜は完全に酸化されたＡ
ｌ2Ｏ3でなければならない。完全に酸化されていない酸
化Ａｌ（不飽和酸化Ａｌ）は絶縁性がないので、それで
被覆した場合は絶縁性を付与するため、空気中または酸
化雰囲中で加熱し、完全に酸化したＡｌすなわちＡｌ2
Ｏ3にしなければならない。すなわち最終的には鉄基材
表面はＡｌ2Ｏ3膜で覆われていなければならない。不飽
和酸化Ａｌ膜は酸化工程で体積膨張をし、クラックが生
じたり剥離する場合があるため、最初の酸化膜形成にお
いて酸素濃度が３０原子％以上になるように不飽和酸化
Ａｌ層で被覆しなければならない。The coating Al oxide film is completely oxidized A
must be l 2 O 3 . Al oxide that has not been completely oxidized (unsaturated Al oxide) has no insulating property, and therefore, when it is coated with it, it is heated in air or an oxidizing atmosphere so that fully oxidized Al Al 2
Must be O 3 . That is, finally, the surface of the iron base material must be covered with the Al 2 O 3 film. The unsaturated Al oxide film expands in volume in the oxidation process, and cracks or peeling may occur. Therefore, in the first oxide film formation, the unsaturated Al oxide film should be coated so that the oxygen concentration becomes 30 atomic% or more. There must be.
【００１０】[0010]
［実施例１］鋼中のＡｌ含有量を変化させて表１に示す
組成の鋼板を作製し、それに特開平３−７２０６９号お
よび特開平４−１２４２６３号に記載のイオン化蒸着法
によって酸素濃度５０原子％の酸化Ａｌを両面に蒸着し
た。その後、加熱冷却試験を行った。鋼板の大きさは３
０×８０ｍｍとし、板厚は ２.５ｍｍとした。蒸着した
酸化Ａｌの膜厚は０.５μｍとした。加熱冷却は １００
〜９００℃まで２℃／秒で昇温、９００℃で６００秒保
持、９００〜１００℃まで放冷のサイクルを１００サイ
クル繰り返した。また、１００サイクル後の鋼板の両面
に銅電極を接触させ、直流電圧を印加して電気絶縁抵抗
を測定した。なお、加熱放冷試験前の試料の絶縁抵抗は
１×１０12Ωｍ以上であった。[Example 1] A steel sheet having the composition shown in Table 1 was prepared by changing the Al content in steel, and the oxygen concentration was 50 by the ionization vapor deposition method described in JP-A-3-72069 and JP-A-4-124263. Atomic percent Al oxide was deposited on both sides. Then, a heating / cooling test was conducted. The size of the steel plate is 3
The plate thickness was 0 × 80 mm and the plate thickness was 2.5 mm. The film thickness of the vapor-deposited Al oxide was 0.5 μm. Heating and cooling is 100
Up to 900 ° C., the temperature was raised at 2 ° C./sec, the temperature was kept at 900 ° C. for 600 seconds, and the system was allowed to cool to 900 to 100 ° C. Further, a copper electrode was brought into contact with both surfaces of the steel sheet after 100 cycles, and a DC voltage was applied to measure electrical insulation resistance. The insulation resistance of the sample before the heating and cooling test was 1 × 10 12 Ωm or more.
【００１１】[0011]
【表１】 [Table 1]
【００１２】結果を鋼板の組成とともに表１に示す。鋼
中の Ａｌ含有量が高い場合、Ａｌ2Ｏ3膜にクラックお
よび剥離が発生してもその部分の鋼中の Ａｌが酸化さ
れて修復されるため、高い絶縁抵抗が維持された。鋼中
のＡｌ濃度が低い場合、初期のＡｌ2Ｏ3膜のクラックお
よび剥離の発生部分から鋼素地は酸化し、Ａｌ2Ｏ3膜は
鋼素地の酸化と加熱冷却の繰り返しによってほとんどが
剥離してしまった。そのため、絶縁抵抗が非常に低くな
った。The results are shown in Table 1 together with the composition of the steel sheet. When the Al content in the steel was high, even if cracks and peeling occurred in the Al 2 O 3 film, Al in the steel in that portion was oxidized and repaired, so that high insulation resistance was maintained. When the Al concentration in the steel is low, the steel base is oxidized from the initial cracking and peeling parts of the Al 2 O 3 film, and most of the Al 2 O 3 film is peeled off due to repeated oxidation and heating / cooling of the steel base. I got it. Therefore, the insulation resistance was very low.
【００１３】［実施例２］厚さ５０μｍ、３０×８０ｍ
ｍの鋼箔を試料とした。これに実施例１と同様にイオン
化蒸着法によってＡｌ2Ｏ3を ０.５μｍずつ両面に蒸着
した。加熱冷却試験は大気中で１００〜１０００℃まで
３℃／秒で昇温、１０００℃での保持時間し、１０００
〜１００℃まで放冷のサイクルを６０００サイクル繰り
返した。加熱冷却試験後のＡｌ2Ｏ3膜の電気絶縁抵抗の
求め方は実施例１と同じである。表２に結果を鋼箔の組
成と共に示す。鋼箔中にＣｒが含有される場合、鋼箔中
のＡｌが枯渇してもクラックまたは剥離の発生部から急
速に鋼箔の酸化が進まないため、Ａｌ2Ｏ3膜が残存し
た。そのため、絶縁性が維持された。Example 2 Thickness 50 μm, 30 × 80 m
m steel foil was used as a sample. Al 2 O 3 of 0.5 μm was vapor-deposited on each side by ionization vapor deposition in the same manner as in Example 1. In the heating and cooling test, the temperature was raised from 100 to 1000 ° C at 3 ° C / sec in the air, and the holding time at 1000 ° C was measured.
The cycle of cooling to -100 ° C was repeated 6000 cycles. The method for obtaining the electrical insulation resistance of the Al 2 O 3 film after the heating / cooling test is the same as in Example 1. Table 2 shows the results together with the composition of the steel foil. When the steel foil contained Cr, the Al 2 O 3 film remained because oxidation of the steel foil did not proceed rapidly from the cracked or peeled portion even when Al in the steel foil was depleted. Therefore, the insulating property was maintained.
【００１４】[0014]
【表２】 [Table 2]
【００１５】鋼箔中に希土類元素あるいは／またはＹが
含有される場合、Ａｌ2Ｏ3膜の密着性が高まり、Ａｌ2
Ｏ3膜の剥離がなくなり、クラックの部分だけが自己修
復され、鋼箔中のＡｌの消費量が少なくなったため絶縁
抵抗が維持された。鋼箔中に希土類元素あるいは／また
はＹが含有されない場合またはＣｒの含有量が少ない場
合は、長期の加熱冷却によって鋼箔の酸化およびＡｌ2
Ｏ3膜の剥離が進み、絶縁性がなくなった。加熱冷却後
の鋼箔中のＡｌ濃度は ０.０５ｗｔ％以下であった。こ
れは、鋼箔などのように表面積に比べて体積が小さい材
料では、長時間の加熱冷却中に自己修復作用によって鋼
箔中のＡｌが消費されＡｌが早期に枯渇し、自己修復作
用が行われなくなったためと考えられる。When the steel foil contains a rare earth element and / or Y, the adhesion of the Al 2 O 3 film is increased and Al 2 O 3 film is increased.
The peeling of the O 3 film was eliminated, only the cracked portion was self-repaired, and the consumption of Al in the steel foil was reduced, so that the insulation resistance was maintained. When the rare earth element or / and Y is not contained in the steel foil or the content of Cr is small, the steel foil is oxidized and Al 2
Peeling of the O 3 film progressed and the insulating property was lost. The Al concentration in the steel foil after heating and cooling was 0.05 wt% or less. This is because in a material such as steel foil whose volume is smaller than its surface area, Al in the steel foil is consumed by the self-repairing action during heating and cooling for a long time, and Al is depleted early and the self-repairing action occurs. It is thought that it was because I was not lost.
【００１６】[0016]
【発明の効果】Ａｌを含有した鉄基材がＡｌ2Ｏ3で被覆
されているため、加熱冷却が繰り返されＡｌ2Ｏ3膜にク
ラックが入ったり、Ａｌ2Ｏ3膜が剥離してもその部分の
鉄基材中のＡｌが酸化してＡｌ2Ｏ3となりＡｌ2Ｏ3膜が
自然に修復される（自己修復作用）。また、そのことに
よって、耐高温酸化性が高まる。最初に表面を被覆する
ものは不飽和の酸化Ａｌでもよい。不飽和酸化Ａｌ膜は
最初の加熱過程で完全に酸化されＡｌ2Ｏ3膜に変化す
る。また、材料として用いる前に酸化性雰囲気で加熱し
てもよい。Ａｌ以外にＣｒが含有されていると鉄基材中
のＡｌが枯渇した場合に鉄基材によるＡｌ2Ｏ3膜の剥離
が生じにくくなる。さらに希土類元素および／またはＹ
が含有されているとＡｌ2Ｏ3膜の密着性が高まり、剥離
が生じなくなる。このため自己修復作用による鉄基材中
のＡｌの消費が少なくなり、寿命が延びる。箔など体積
に比較して表面積が大きい材料には希土類元素、Ｙおよ
びＣｒを含有させることが特に有効である。またこのこ
とによって耐高温酸化性がより高まる。Since the iron-containing base material containing Al is coated with Al 2 O 3 , even if the Al 2 O 3 film is cracked or the Al 2 O 3 film is peeled off by repeated heating and cooling. Al in the iron base material in that portion is oxidized to Al 2 O 3 and the Al 2 O 3 film is naturally restored (self-healing action). In addition, the high temperature oxidation resistance is also enhanced. The first coating on the surface may be unsaturated Al oxide. The unsaturated oxide Al film is completely oxidized in the first heating process and converted into an Al 2 O 3 film. Moreover, you may heat in an oxidizing atmosphere before using it as a material. When Cr is contained in addition to Al, the Al 2 O 3 film is less likely to be peeled off by the iron base material when Al in the iron base material is exhausted. Furthermore, rare earth elements and / or Y
When it contains, the adhesiveness of the Al 2 O 3 film is enhanced and peeling does not occur. Therefore, the consumption of Al in the iron base material due to the self-repairing action is reduced and the life is extended. It is particularly effective to add rare earth elements, Y and Cr to a material such as foil having a large surface area compared to the volume. This also increases the high temperature oxidation resistance.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 松野 雅典 大阪府堺市石津西町５番地 日新製鋼株式 会社鉄鋼研究所表面処理研究部内 (72)発明者 斎藤 実 大阪府堺市石津西町５番地 日新製鋼株式 会社鉄鋼研究所表面処理研究部内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Masanori Matsuno 5 No. 5 Ishizu Nishimachi, Sakai City, Osaka Prefecture Nisshin Steel Co., Ltd. Surface Treatment Research Department, Research Institute of Steel, Japan (72) Minoru Saito 5 No. 5 Ishizu Nishimachi, Sakai City, Osaka Prefecture New Steel Co., Ltd.Steel Research Laboratory, Surface Treatment Research Department
Claims (4)
された酸化Ａｌの被覆からなる材料。1. A material comprising an iron base material containing Al and a coating of aluminum oxide formed on the surface thereof.
していることを特徴とする請求項１に記載の材料。2. The material according to claim 1, wherein the iron base material contains Al of 0.4 to 8 wt%.
含有していることを特徴とする請求項１または請求項２
に記載の材料。3. The iron base material further contains 8-35 wt% Cr.
The material described in.
とも１種を合計で０.２ ｗｔ％以下含有していることを
特徴とする請求項１、請求項２または請求項３に記載の
材料。4. The iron base material further contains at least one kind of rare earth element and Y in a total amount of 0.2 wt% or less, and the iron base material according to claim 1, 2 or 3. material.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4333869A JPH06158276A (en) | 1992-11-20 | 1992-11-20 | Al oxide-coated iron material excellent in insulation property and high-temperature oxidation resistance |
| KR1019930024703A KR100265101B1 (en) | 1992-11-20 | 1993-11-19 | Iron-based material having excellent oxidation resistance at high temperature and manufacturing method thereof |
| EP93118671A EP0599225B1 (en) | 1992-11-20 | 1993-11-19 | Iron-based material having excellent oxidation resistance at elevated temperatures and process for the production thereof |
| DE69318515T DE69318515T2 (en) | 1992-11-20 | 1993-11-19 | Iron-based alloy with high oxidation resistance at elevated temperatures and method of manufacturing the same |
| US08/155,373 US5631090A (en) | 1992-11-20 | 1993-11-22 | Iron-based material having excellent oxidation resistance at elevated temperatures and process for the production thereof |
| US08/467,637 US5612090A (en) | 1992-11-20 | 1995-06-06 | Iron-based material having excellent oxidation resistance at elevated temperatures and process for the production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4333869A JPH06158276A (en) | 1992-11-20 | 1992-11-20 | Al oxide-coated iron material excellent in insulation property and high-temperature oxidation resistance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06158276A true JPH06158276A (en) | 1994-06-07 |
Family
ID=18270862
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4333869A Withdrawn JPH06158276A (en) | 1992-11-20 | 1992-11-20 | Al oxide-coated iron material excellent in insulation property and high-temperature oxidation resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06158276A (en) |
-
1992
- 1992-11-20 JP JP4333869A patent/JPH06158276A/en not_active Withdrawn
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20000201 |