JPH0674481B2 - Fe-Cr-Ni-Al ferrite alloy - Google Patents
Fe-Cr-Ni-Al ferrite alloyInfo
- Publication number
- JPH0674481B2 JPH0674481B2 JP5564792A JP5564792A JPH0674481B2 JP H0674481 B2 JPH0674481 B2 JP H0674481B2 JP 5564792 A JP5564792 A JP 5564792A JP 5564792 A JP5564792 A JP 5564792A JP H0674481 B2 JPH0674481 B2 JP H0674481B2
- Authority
- JP
- Japan
- Prior art keywords
- alloy
- alumina
- base material
- film
- alumina film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000956 alloy Substances 0.000 title claims description 53
- 229910045601 alloy Inorganic materials 0.000 title claims description 52
- 229910000859 α-Fe Inorganic materials 0.000 title claims description 15
- 229910003310 Ni-Al Inorganic materials 0.000 title claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 45
- 239000000463 material Substances 0.000 description 23
- 239000011651 chromium Substances 0.000 description 19
- 239000011248 coating agent Substances 0.000 description 19
- 238000000576 coating method Methods 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 17
- 229910000943 NiAl Inorganic materials 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 5
- 239000010953 base metal Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 208000019300 CLIPPERS Diseases 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910002060 Fe-Cr-Al alloy Inorganic materials 0.000 description 2
- 229910001566 austenite Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 208000021930 chronic lymphocytic inflammation with pontine perivascular enhancement responsive to steroids Diseases 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910001151 AlNi Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910019590 Cr-N Inorganic materials 0.000 description 1
- 229910019588 Cr—N Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910017060 Fe Cr Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910002544 Fe-Cr Inorganic materials 0.000 description 1
- -1 NiAl compound Chemical class 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- CYUOWZRAOZFACA-UHFFFAOYSA-N aluminum iron Chemical compound [Al].[Fe] CYUOWZRAOZFACA-UHFFFAOYSA-N 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Other Surface Treatments For Metallic Materials (AREA)
Description
【０００１】[0001]
【産業上の利用分野】この発明は、高温酸化雰囲気中で
合金の表面に密着性に優れ緻密かつ均一なアルミナを主
成分とする皮膜が生成でき、母材の高硬度化も図れ、電
気カミソリやバリカンなどの刃物や電動工具のチャッ
ク、ギア、シャフト等の部品に適するＦｅ−Ｃｒ−Ｎｉ
−Ａｌ系フェライト合金に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is capable of producing a dense and uniform coating containing alumina as a main component on the surface of an alloy in a high temperature oxidizing atmosphere, which is capable of increasing the hardness of the base material and also the electric razor. Fe-Cr-Ni suitable for parts such as blades and clippers, chucks for electric tools, gears, shafts, etc.
-Al-based ferrite alloy.
【０００２】[0002]
【従来の技術】高温酸化によりアルミナ皮膜を生成でき
る合金として、特開昭54-141314 号公報、特開昭60-262
943 号公報、特開平2-254136号公報にみられるようなＦ
ｅ−Ｃｒ−Ａｌ系合金がある。これらの合金はＮｉを含
まないものである。このＦｅ−Ｃｒ−Ａｌ系合金は、強
度がフェライト系ステンレスと略同程度であり、また、
何らかの熱処理を施しても、その機械的性質を大幅に改
善することが出来ない。それに、厚み数μｍ以上のアル
ミナ皮膜を生じさせるには、数時間以上１１００℃以上
の高温にさらさねばならず、この間に合金の結晶粒が著
しく成長し機械的性質の低下をもたらす。2. Description of the Related Art As an alloy capable of forming an alumina film by high temperature oxidation, Japanese Patent Laid-Open Publication Nos. 54-141314 and 60-262 are known.
F as seen in 943 and JP-A-2-254136
There is an e-Cr-Al alloy. These alloys do not contain Ni. The strength of this Fe-Cr-Al alloy is about the same as that of ferritic stainless steel, and
Even if some heat treatment is applied, its mechanical properties cannot be significantly improved. In addition, in order to form an alumina coating having a thickness of several μm or more, it has to be exposed to a high temperature of 1100 ° C. or more for several hours or more, during which the crystal grains of the alloy remarkably grow and the mechanical properties deteriorate.
【０００３】上記Ｆｅ−Ｃｒ−Ａｌ系合金の他に、特開
昭62-174352 号公報や米国特許第 4144380号明細書にみ
られるようなＦｅ−Ｃｒ−Ｎｉ−Ａｌ系を主構成要素と
するオーステナイト合金がある。しかし、この合金は、
アルミナ皮膜が均一でないし剥がれ易い。そこで、発明
者等は、特開平3-150337号公報にみるようなＦｅ−Ｃｒ
−Ｎｉ−Ａｌ系フェライト合金を提案している。この合
金は、高温の酸化性雰囲気中で加熱された場合、表面に
密着性に優れたアルミナ皮膜を生成する。また、合金生
地中には微細かつ均一な分散状態でＮｉＡｌ系金属間化
合物が析出して母材の硬度が高く、アルミナ皮膜形成時
高温にさらされても、ＮｉＡｌの存在により結晶粒粗大
化が抑制される。In addition to the Fe-Cr-Al-based alloys described above, Fe-Cr-Ni-Al-based alloys as disclosed in JP-A-62-174352 and US Pat. No. 4,144,380 are the main constituent elements. There is an austenitic alloy. But this alloy
Alumina film is not uniform and easily peels off. Therefore, the inventors have found that Fe-Cr as disclosed in Japanese Patent Laid-Open No. 3-150337.
-Ni-Al ferrite alloy is proposed. This alloy, when heated in a high temperature oxidizing atmosphere, forms an alumina film with excellent adhesion on the surface. In addition, NiAl-based intermetallic compounds are precipitated in a fine and uniform dispersed state in the alloy material, and the hardness of the base material is high. Even when exposed to high temperature during the formation of the alumina film, the presence of NiAl causes coarsening of crystal grains. Suppressed.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、発明者
等の提案にかかる合金においても、アルミナ皮膜の密着
性と母材硬度は必ずしも十分とは言えず、使用中にアル
ミナ皮膜が部分的に剥離したり、母材が磨耗するなどの
問題がある。この発明は、上記事情に鑑み、アルミナ皮
膜と合金の密着性および母材硬度の向上が図れるＦｅ−
Ｃｒ−Ｎｉ−Ａｌ系フェライト合金を提供することを課
題とする。However, even in the alloys proposed by the inventors, the adhesion and base material hardness of the alumina coating are not always sufficient, and the alumina coating partially peels off during use. Or the base material is worn out. In view of the above circumstances, the present invention provides an Fe-based alloy that improves the adhesion between the alumina coating and the alloy and the base metal hardness.
An object is to provide a Cr-Ni-Al ferrite alloy.
【０００５】[0005]
【問題を解決するための手段】発明者らは、前記事情に
鑑み、アルミナ皮膜の密着力と母材硬度の両方を同時に
向上させられる方途を求めて、様々な角度から検討を行
った。中でも、構成元素の含有量、すなわち組成の点に
まで逆上って改めて鋭意検討した。そして、その結果、
以下のような知見を得ることができた。[Means for Solving the Problems] In view of the above circumstances, the inventors have studied from various angles in search of a way to simultaneously improve both the adhesion of the alumina coating and the hardness of the base material. Above all, the content of the constituent elements, that is, the point of the composition, was backtracked and the result of intensive research was conducted again. And as a result,
The following findings were obtained.
【０００６】第１の知見は、高温酸化で生成したアルミ
ナ皮膜（Ａｌ2 Ｏ3 皮膜）が母材に根を生やしたように
成長することが密着性向上に不可欠なのであるが、Ｃｒ
の含有量が３５重量％（wt％）を越えるようになると、
根が十分に密で適切な状態で生えるようになるというこ
とである。第２の知見は、Ｃｒの含有量を固定しＮｉ，
Ａｌの含有量を増していくとＮｉＡｌ系化合物の量が増
加し母材硬度は高くなるが、Ｎｉの含有量が２０重量％
となるあたりからその効果は飽和してゆくが、逆に、Ｎ
ｉ，Ａｌの含有量を固定しＣｒの含有量を増していくと
前者の場合よりも硬度化が大きくできるが、Ｃｒの含有
量が４０重量％を越すと極端に脆くなるということであ
る。The first finding is that it is essential for improving the adhesion that the alumina film (Al 2 O 3 film) formed by high temperature oxidation grows like rooting on the base material.
When the content of exceeds 35% by weight (wt%),
This means that the roots will grow densely and properly. The second finding is that the content of Cr is fixed and Ni,
As the Al content increases, the amount of NiAl-based compound increases and the base metal hardness increases, but the Ni content is 20% by weight.
From that point, the effect becomes saturated, but conversely, N
If the content of i and Al is fixed and the content of Cr is increased, the hardness can be made larger than in the former case, but if the content of Cr exceeds 40% by weight, it becomes extremely brittle.
【０００７】以上のことから、Ｃｒの含有量を３５重量
％を越して多くすることが、アルミナ皮膜の密着性と母
材硬度の同時向上を図れるようにするのであるが、Ｃｒ
の増量には脆化の点から限界があるということが分か
り、これにより、この発明を完成させることが出来たの
である。したがって、この発明にかかるＦｅ−Ｃｒ−Ｎ
ｉ−Ａｌ系フェライト合金はＣｒ：３５〜４０重量％
（３５重量％は含まず）、Ｎｉ：１５〜２５重量％、Ａ
ｌ：４〜８重量％、Ｔｉ：０〜０．５重量％、Ｚｒ，
Ｙ，Ｈｆ，Ｃｅ，Ｌａ，ＮｄおよびＧｄのうちのいずれ
か１種または２種以上：０．０５〜１．０重量％、残
部：実質的にＦｅからなるという構成をとるようにして
いる。From the above, increasing the Cr content above 35% by weight makes it possible to simultaneously improve the adhesion of the alumina coating and the hardness of the base material.
It was found that there was a limit to the increase in the amount from the viewpoint of embrittlement, and this enabled the completion of the present invention. Therefore, Fe-Cr-N according to the present invention
The i-Al ferrite alloy is Cr: 35 to 40% by weight.
(Not including 35% by weight), Ni: 15 to 25% by weight, A
1: 4 to 8% by weight, Ti: 0 to 0.5% by weight, Zr,
Any one or more of Y, Hf, Ce, La, Nd and Gd: 0.05 to 1.0% by weight, the balance: substantially Fe.
【０００８】以下、この発明をより具体的に説明する。
まず、この発明のＦｅ−Ｃｒ−Ｎｉ−Ａｌ系フェライト
合金の含有元素について、その含有量とその限定理由を
説明する。この発明の合金は、フェライト生成元素であ
るＣｒおよびＡｌと、オーステナイト生成元素であるＮ
ｉを多量に含有したＦｅ基合金であり、合金が主として
フェライト相となるように各元素の量が選ばれている。
この発明の合金を主としてフェライト相にする理由は、
次の通りである。フェライト相の合金は、酸化加熱処理
により、緻密で下地との密着性の良い厚いアルミナ（Ａ
ｌ2 Ｏ3 ）皮膜を形成し易いが、オーステナイト相の合
金はアルミナ皮膜が均一に生じず、剥離するからであ
る。合金をフェライト相にする場合、Ｎｉ量を増加させ
ると、（Ｃｒ＋Ａｌ）量を増加させるようにする。The present invention will be described in more detail below.
First, the contents of the elements contained in the Fe-Cr-Ni-Al ferrite alloy of the present invention and the reasons for limiting the contents will be described. The alloy of the present invention has a ferrite forming element of Cr and Al and an austenite forming element of N.
It is a Fe-based alloy containing a large amount of i, and the amount of each element is selected so that the alloy mainly becomes a ferrite phase.
The reason why the alloy of the present invention is mainly in the ferrite phase is
It is as follows. Ferrite phase alloys are thick and dense (A
l 2 O 3) film is formed easily, but an alloy of austenite phase does not occur uniformly alumina film is because peeling. When making the alloy into a ferrite phase, the amount of (Cr + Al) is increased when the amount of Ni is increased.
【０００９】〔Ｃｒ：３５〜４０wt％（但し、３５wt％
は含まず）〕 Ｃｒは、合金表面に緻密で均一なアルミ
ナ皮膜を形成させるために必要であるが、アルミナ皮膜
が根を母材に密に生やして密着性が向上するようになる
には、Ｃｒの含有量が３５wt％を越す必要がある。た
だ、Ｃｒの含有量が４０wt％を越すと極端に脆くなって
しまい、製品として適当でなくなる。それに、上記範囲
だと母材硬度の向上も図れるようになる。そのため、Ｃ
ｒの含有量は、３５wt％を越え、４０wt％以下とするの
である。[Cr: 35-40 wt% (however, 35 wt%
Cr is necessary in order to form a dense and uniform alumina film on the alloy surface, but in order for the alumina film to grow roots densely on the base material and improve the adhesion, It is necessary that the content exceeds 35 wt%. However, if the content of Cr exceeds 40 wt%, it becomes extremely brittle and is not suitable as a product. Besides, in the above range, the hardness of the base material can be improved. Therefore, C
The content of r is more than 35 wt% and 40 wt% or less.
【００１０】〔Ｎｉ：１５〜２５wt％〕 Ｎｉは、微細
なＮｉＡｌを合金中に析出させ、母材の機械的性質の向
上を図っているが、Ａｌとの共存下でＮｉＡｌを析出さ
せるのに不可欠の元素である。機械的性質の向上に十分
効果的であるだけのＮｉＡｌを析出させるためには１５
wt％以上のＮｉを必要とする。Ｎｉ量が増加すれば、Ｎ
ｉＡｌの析出による機械的性質の向上には好都合である
が、２０wt％を越すとその効果は飽和傾向を示し２５wt
％付近では一定となる。それ故、Ｎｉの上限値は２５wt
％である。[Ni: 15 to 25 wt%] Ni precipitates fine NiAl in the alloy to improve the mechanical properties of the base material. However, Ni is not coexisted in the presence of Al. It is an essential element. In order to precipitate NiAl which is sufficiently effective for improving the mechanical properties, 15
Requires more than wt% Ni. If the amount of Ni increases, N
It is convenient for improving the mechanical properties by precipitation of iAl, but when it exceeds 20 wt%, its effect tends to be saturated and 25 wt%.
It becomes constant around%. Therefore, the upper limit of Ni is 25wt
%.
【００１１】〔Ａｌ：４〜８wt％〕 Ａｌは、微細なＮ
ｉＡｌを合金中に析出させ、さらに、高温酸化処理によ
り合金表面にアルミナ皮膜を形成させるために不可欠な
元素である。緻密で均一な皮膜を形成させるためには、
４wt％以上のＡｌを含有することが必要である。Ａｌ含
有量の増加は、ＮｉＡｌの析出やアルミナ皮膜の形成に
有利であるが、８wt％を越えると合金の加工性が低下す
るので、Ａｌの上限は８wt％である。[Al: 4-8 wt%] Al is a fine N
It is an essential element for precipitating iAl in the alloy and for forming an alumina film on the alloy surface by high temperature oxidation treatment. In order to form a dense and uniform film,
It is necessary to contain 4 wt% or more of Al. An increase in the Al content is advantageous for the precipitation of NiAl and the formation of an alumina film, but if it exceeds 8 wt%, the workability of the alloy decreases, so the upper limit of Al is 8 wt%.
【００１２】〔Ｚｒ，Ｙ，Ｈｆ，Ｃｅ，Ｌａ，Ｎｄおよ
びＧｄのうちのいずれか１種または２種以上：０．０５
〜１．０重量％〕 これらの各元素（およびＴｉ）はア
ルミ皮膜内に混入して皮膜の脆さを改善するとともに皮
膜直下の合金内に内部酸化物粒子として分散し、皮膜の
密着性を著しく向上させる。これらの効果を発揮させる
には、０．０５wt％以上で含有させる必要がある。他
方、１wt％を越えて含有すると、合金の加工性が急激に
低下するので、上限は１wt％である。[Any one or more of Zr, Y, Hf, Ce, La, Nd and Gd: 0.05
~ 1.0 wt%] Each of these elements (and Ti) is mixed in the aluminum film to improve the brittleness of the film and disperse as internal oxide particles in the alloy immediately below the film to improve the adhesion of the film. Significantly improve. In order to exert these effects, it is necessary to contain at 0.05 wt% or more. On the other hand, if the content exceeds 1% by weight, the workability of the alloy sharply deteriorates, so the upper limit is 1% by weight.
【００１３】なお、Ｔｉは合金中に０．５wt％程度含有
されている場合、適当な熱処理により微細な金属間化合
物を形成し、合金の強靱化に役立つ。この発明の合金
は、Ｔｉを含んでいないものであってもよいが、このよ
うな理由によりＴｉを含んでいてもよい。ただし、Ｔｉ
の含有量が０．５wt％を越えるアルミナ皮膜の密着性や
緻密性が損なわれる恐れがあるため、Ｔｉの含有量の上
限は０．５wt％である。 〔Ｆｅ：残部〕 以上の成分の他をＦｅが占める。ただ
し、残部が完全にＦｅである場合のみに限定されず、不
可避的に不純物としてＦｅ中に存在する場合も含む。な
お、不純物の中でも、Ｓｉ、Ｃ、Ｎの３元素は、下記の
理由により、下記の範囲となるようにするのが好まし
い。When Ti is contained in the alloy in an amount of about 0.5 wt%, a fine intermetallic compound is formed by an appropriate heat treatment, which helps strengthen the toughness of the alloy. Although the alloy of the present invention may not contain Ti, it may contain Ti for such a reason. However, Ti
The upper limit of the Ti content is 0.5 wt% because the adhesion and the denseness of the alumina coating containing more than 0.5 wt% may be impaired. [Fe: balance] In addition to the above components, Fe occupies. However, it is not limited to the case where the balance is completely Fe, and includes the case where it is inevitably present in Fe as an impurity. Of the impurities, the three elements of Si, C, and N are preferably in the following range for the following reasons.
【００１４】Ｓｉは高温酸化処理中にＳｉＯ2 となり、
アルミナ皮膜に混入して皮膜の緻密性を損なう恐れがあ
ることから、０．３wt％以下とすることが望ましい。０
wt％であってもよい。Ｃは高温でＣｒと反応してＣｒ炭
化物を形成し、合金を脆化させる。また、ＣＯがＣＯ2
ガスとなり、アルミナ皮膜を破壊する。さらに、稀土類
元素と容易に反応し皮膜の密着性向上に対する稀土類元
素の効果を低下させる。これらのことから、Ｃは０．０
１wt％以下が望ましい。０wt％であってもよい。Si becomes SiO 2 during the high temperature oxidation treatment,
Since it may be mixed in the alumina coating and impair the denseness of the coating, it is preferably 0.3 wt% or less. 0
It may be wt%. C reacts with Cr at high temperatures to form Cr carbides and embrittles the alloy. Also, CO is CO 2
It becomes a gas and destroys the alumina film. Further, it easily reacts with the rare earth element and reduces the effect of the rare earth element on improving the adhesion of the coating. From these, C is 0.0
It is preferably 1 wt% or less. It may be 0 wt%.
【００１５】Ｎは合金の靱性を低下させ、また、高温加
熱中にＣｒと反応してＣｒ系窒化物となり、合金の脆化
の原因となりうる。このため、Ｎは０．０１５wt％以下
が望ましい。０wt％であってもよい。続いて、この発明
の合金の表面にアルミナ皮膜を形成する場合について説
明する。N reduces the toughness of the alloy, and reacts with Cr during heating at high temperature to form a Cr-based nitride, which may cause embrittlement of the alloy. Therefore, N is preferably 0.015 wt% or less. It may be 0 wt%. Next, the case of forming an alumina film on the surface of the alloy of the present invention will be described.
【００１６】アルミナ皮膜の形成は、この発明の合金を
高温の大気中あるいは酸素ガス等の酸化性雰囲気中で加
熱処理することにより実現できる。加熱温度は、通常、
７００℃以上、１３００℃以下の範囲が好ましい。７０
０℃未満だと表面に均一なアルミナ皮膜が形成されない
傾向がみられ、１３００℃を越えると母材が脆化するこ
とがあるからである。また、加熱温度が１０００℃以下
の場合は、加熱時間が０．５時間以上であることが好ま
しい。０．５時間よりも短いと全面に均一なアルミナ皮
膜が形成されないことがある。生成されるアルミナ皮膜
の厚みは特定の厚みに限定されるようなことはない。The formation of the alumina film can be realized by heating the alloy of the present invention in a high temperature atmosphere or an oxidizing atmosphere such as oxygen gas. The heating temperature is usually
The range of 700 ° C or higher and 1300 ° C or lower is preferable. 70
This is because if the temperature is lower than 0 ° C, a uniform alumina film tends not to be formed on the surface, and if the temperature exceeds 1300 ° C, the base material may become brittle. When the heating temperature is 1000 ° C. or lower, the heating time is preferably 0.5 hours or longer. If it is shorter than 0.5 hours, a uniform alumina film may not be formed on the entire surface. The thickness of the alumina coating produced is not limited to a particular thickness.
【００１７】そして、この発明の合金は、アルミナ皮膜
形成後、熱処理により母材硬度を向上させることが可能
なのである。母材中に析出しているＮｉＡｌ化合物は約
１２００℃を越えると０．５時間以下で母材中に完全固
溶する。しかる後に急冷を行えば急冷中に核形成・成長
した径が１μｍよりも遙に小さい微細ＡｌＮｉ粒を母材
中に生成できる。この微細ＮｉＡｌ粒の分散析出により
母材は大きく硬化する。但し、１２００℃を越えて２時
間以上加熱すると結晶粒が粗大化する。これは、ＮｉＡ
ｌ粒が消失し結晶粒粗大化を抑制する効果がなくなるか
らである。好ましくは、加熱時間は１時間以下である。
また、急冷は、空冷で１℃／秒以上の速度が望ましい。
１℃／秒より遅い冷却の場合は、再析出ＮｉＡｌ粒のサ
イズが大きくなり、母材硬度を大きく向上させることが
できない。水冷など空冷以外の急冷は熱応力割れが起こ
り易いので好ましくはない。The alloy of the present invention can improve the hardness of the base material by heat treatment after forming the alumina film. The NiAl compound precipitated in the base material completely dissolves in the base material within 0.5 hours when the temperature exceeds 1200 ° C. Then, if the material is rapidly cooled, fine AlNi grains having a diameter of nucleated and grown during the rapid cooling that is much smaller than 1 μm can be generated in the base material. The base material is largely hardened due to the dispersed precipitation of the fine NiAl grains. However, if the heating is performed at over 1200 ° C. for 2 hours or more, the crystal grains become coarse. This is NiA
This is because 1 grain disappears and the effect of suppressing the crystal grain coarsening disappears. Preferably, the heating time is 1 hour or less.
The rapid cooling is preferably air cooling at a rate of 1 ° C./second or more.
In the case of cooling slower than 1 ° C./sec, the size of the reprecipitated NiAl grains becomes large and the base material hardness cannot be greatly improved. Rapid cooling other than air cooling such as water cooling is not preferable because thermal stress cracking easily occurs.
【００１８】以上のことから、比較的厚いアルミナ皮膜
を形成しようとする場合は、１２００℃以下で長時間加
熱処理してから、一旦、室温まで下げてからでもよい
し、そのまま継続してでもよいのであるが、１２００℃
を越えた温度で１時間以下の熱処理を行い最後に急冷す
るようにすればよい。アルミナ皮膜が５μｍ以下程度の
薄いものである場合、始めから１２００℃を越える温度
で１時間以下の熱処理を行い最後に急冷するようにすれ
ばよい。From the above, when a relatively thick alumina film is to be formed, it may be subjected to a heat treatment at 1200 ° C. or lower for a long time and then once cooled to room temperature, or may be continued as it is. However, 1200 ℃
The heat treatment may be performed for 1 hour or less at a temperature exceeding the above temperature, and then the material may be rapidly cooled. When the alumina film is as thin as about 5 μm or less, heat treatment may be performed at a temperature exceeding 1200 ° C. for 1 hour or less from the beginning, and then quenching may be performed at the end.
【００１９】以上により根が密に生えたアルミナ皮膜の
ある高硬度・高強度のものが得られる。このようにして
得られたアルミナ皮膜付のＦｅ−Ｃｒ−Ｎｉ−Ａｌ系フ
ェライト合金の用途としては、耐磨耗性や耐食性が要求
される電気カミソリの内刃、外刃、バリカン刃の固定刃
や可動刃などの刃物や電動工具等の軸、チャックやギア
などの機構部品、内燃機関用あるいは腐食雰囲気用バル
ブなどに応用できる。しかし、用途は、これらに限定さ
れない。アルミナ皮膜形成前に部品の形状に合わせた加
工しておいて、こアルミナ皮膜形成のための熱処理や硬
度上昇のための熱処理を施したものを、そのまま部品に
使うようにすることも可能である。As described above, a product having high hardness and high strength, which has an alumina film with dense roots, can be obtained. The Fe-Cr-Ni-Al ferrite alloy with an alumina coating obtained in this way is used as a fixed blade for the inner blade, outer blade, and clipper blade of an electric razor that requires wear resistance and corrosion resistance. It can be applied to blades such as and movable blades, shafts such as electric tools, mechanical parts such as chucks and gears, valves for internal combustion engines or corrosive atmospheres. However, the application is not limited to these. It is also possible to process the parts according to the shape of the parts before forming the alumina film, and then use the parts that have undergone the heat treatment for forming the alumina film and the heat treatment for increasing the hardness to use the parts as they are. .
【００２０】[0020]
【作用】この発明のＦｅ−Ｃｒ−Ｎｉ−Ａｌ系フェライ
ト合金では、Ｃｒの含有量が３５重量％を越えているた
め、アルミナ皮膜の密着力と母材硬度の同時向上が図れ
るとともに、その際、Ｃｒの含有量が４０重量％を越す
ことがないため、脆化で製品適性がなくなるという不都
合もない。In the Fe-Cr-Ni-Al ferrite alloy of the present invention, since the Cr content exceeds 35% by weight, the adhesion of the alumina film and the base metal hardness can be simultaneously improved, and at the same time, Since the Cr content does not exceed 40% by weight, there is no inconvenience that the product suitability is lost due to embrittlement.
【００２１】[0021]
−実施例１〜６および比較例１〜６− 表１，２に示す組成の合金を高周波誘導加熱式真空溶解
炉で溶製し、熱間で１ｍｍの板状に圧延した。すなわ
ち、５×１０-4Torr以上の高真空中で、電解鉄，電解ク
ロムおよびＮｉペレットをアルミナるつぼに入れて溶解
し、溶融液中にアルミニウム鉄合金、ＦｅＺｒ合金、Ｆ
ｅＴｉ合金、ならびに、Ｈｆおよび稀土類元素小片を添
加した。さらに、同じ真空中で炉内にある鉄あるいは銅
鋳型に鋳込んで合金のインゴットを得た。-Examples 1 to 6 and Comparative Examples 1 to 6-The alloys having the compositions shown in Tables 1 and 2 were melted in a high-frequency induction heating type vacuum melting furnace, and hot rolled into a plate shape of 1 mm. That is, electrolytic iron, electrolytic chromium and Ni pellets are put into an alumina crucible and melted in a high vacuum of 5 × 10 −4 Torr or more, and an aluminum iron alloy, FeZr alloy, F
The eTi alloy and Hf and rare earth element flakes were added. Further, it was cast in an iron or copper mold in the furnace in the same vacuum to obtain an alloy ingot.
【００２２】得られたインゴットを軟銅製ケースに入れ
て８００〜１１００℃に加熱し、同温度でパック圧延し
た。ついで、これらの試料を１ｍｍ×１５ｍｍ×２０ｍ
ｍの大きさに切断して、１２００番のエメリーペーパー
で表面を仕上げ、１２５０℃で３０分大気中で加熱処理
を行い、表面に酸化皮膜を形成し、続いて、その温度か
ら空冷で急速冷却（約１０℃／秒前後の冷却速度）し
た。空冷後の母材硬度、アルミナ皮膜厚み、アルミナ皮
膜の根の本数比（面密度比）を測定した。測定結果を、
表３に示す。The obtained ingot was put in a case of annealed copper, heated to 800 to 1100 ° C., and pack-rolled at the same temperature. Then, these samples are 1 mm x 15 mm x 20 m
Cut into m size, finish the surface with No. 1200 emery paper, heat treatment at 1250 ° C for 30 minutes in the atmosphere to form an oxide film on the surface, and then rapidly cool from that temperature by air cooling (Cooling rate of about 10 ° C./sec). The hardness of the base material after air cooling, the thickness of the alumina coating, and the number ratio (area density ratio) of the roots of the alumina coating were measured. The measurement result
It shows in Table 3.
【００２３】アルミナ皮膜の根の本数比に関しては以下
の通りである。図１にみるように、合金１の表面のアル
ミナ皮膜２には母材３中に延びるように根２ａが多数生
えているのであるが、Ａｌの含有量の等しい比較例と実
施例を比較例の場合を１として比べた。なお、４はＮｉ
Ａｌ粒子である。The ratio of the number of roots of the alumina coating is as follows. As shown in FIG. 1, the alumina coating 2 on the surface of the alloy 1 has many roots 2a extending in the base material 3. The case of 1 was compared. 4 is Ni
Al particles.
【００２４】[0024]
【表１】 [Table 1]
【００２５】[0025]
【表２】 [Table 2]
【００２６】[0026]
【表３】 [Table 3]
【００２７】表３にみるように、実施例の場合、比較例
の場合に比べて母材硬度がＨｖ値で１００程度も上昇し
ている。それに、実施例の場合、アルミナ皮膜の厚さも
約１．５倍程度と増している。アルミナ皮膜の剥がれに
関しては実施例も比較例も外観上からは観察されなかっ
たが、アルミナ皮膜の根の面密度比が実施例の場合、比
較例の約５倍もあり、アルミナ皮膜の密着性が向上して
いることが良く分かる。As shown in Table 3, in the case of the embodiment, the base material hardness is increased by about 100 in Hv value as compared with the case of the comparative example. In addition, in the case of the example, the thickness of the alumina coating is increased to about 1.5 times. Regarding the peeling of the alumina film, neither the example nor the comparative example was observed from the outside, but in the case of the example, the root density of the alumina film was about 5 times that of the comparative example, and the adhesion of the alumina film was high. You can see that is improving.
【００２８】[0028]
【発明の効果】この発明のＦｅ−Ｃｒ−Ｎｉ−Ａｌ系フ
ェライト合金では、Ｃｒの含有量が３５重量％を越えて
いるため、アルミナ皮膜の密着力と母材硬度の同時向上
が図れるとともに、その際、Ｃｒの含有量が４０重量％
を越すことがないため、脆化で製品適性が失われるとい
うような不都合もなく、したがって、非常に有用であ
る。In the Fe-Cr-Ni-Al ferrite alloy of the present invention, since the Cr content exceeds 35% by weight, the adhesion of the alumina film and the base metal hardness can be simultaneously improved, and At that time, the Cr content is 40% by weight.
Therefore, there is no inconvenience that the product suitability is lost due to embrittlement, and therefore it is very useful.
【図１】アルミナ皮膜を形成した合金の構成例をあらわ
す断面図である。FIG. 1 is a cross-sectional view showing a constitutional example of an alloy having an alumina coating formed thereon.
１ 合金 ２ アルミナ皮膜 ２ａ 根 ３ 母材 ４ ＮｉＡｌ粒 1 Alloy 2 Alumina Film 2a Root 3 Base Material 4 NiAl Grain
Claims (1)
含まず）、Ｎｉ：１５〜２５重量％、Ａｌ：４〜８重量
％、Ｔｉ：０〜０．５重量％、Ｚｒ，Ｙ，Ｈｆ，Ｃｅ，
Ｌａ，ＮｄおよびＧｄのうちのいずれか１種または２種
以上：０．０５〜１．０重量％、残部：実質的にＦｅか
らなるＦｅ−Ｃｒ−Ｎｉ−Ａｌ系フェライト合金。1. Cr: 35-40 wt% (not including 35 wt%), Ni: 15-25 wt%, Al: 4-8 wt%, Ti: 0-0.5 wt%, Zr, Y , Hf, Ce,
One or more of La, Nd and Gd: 0.05 to 1.0% by weight, balance: Fe-Cr-Ni-Al ferrite alloy consisting essentially of Fe.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5564792A JPH0674481B2 (en) | 1992-03-13 | 1992-03-13 | Fe-Cr-Ni-Al ferrite alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5564792A JPH0674481B2 (en) | 1992-03-13 | 1992-03-13 | Fe-Cr-Ni-Al ferrite alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05255797A JPH05255797A (en) | 1993-10-05 |
| JPH0674481B2 true JPH0674481B2 (en) | 1994-09-21 |
Family
ID=13004619
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5564792A Expired - Fee Related JPH0674481B2 (en) | 1992-03-13 | 1992-03-13 | Fe-Cr-Ni-Al ferrite alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0674481B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070144622A1 (en) * | 2002-11-04 | 2007-06-28 | Flahaut Dominique M L | High temperature resistant alloys |
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1992
- 1992-03-13 JP JP5564792A patent/JPH0674481B2/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| JPH05255797A (en) | 1993-10-05 |
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