JP2990778B2 - Corrosion resistant metal composite and method of manufacturing the same - Google Patents
Corrosion resistant metal composite and method of manufacturing the sameInfo
- Publication number
- JP2990778B2 JP2990778B2 JP2271629A JP27162990A JP2990778B2 JP 2990778 B2 JP2990778 B2 JP 2990778B2 JP 2271629 A JP2271629 A JP 2271629A JP 27162990 A JP27162990 A JP 27162990A JP 2990778 B2 JP2990778 B2 JP 2990778B2
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- Prior art keywords
- resistant
- thickness
- metal composite
- heat
- 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.)
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- Other Surface Treatments For Metallic Materials (AREA)
Description
本発明は、耐食性とくに耐高温酸化性が高く、耐熱性
であってかつ耐摩耗性の良好な金属複合材と、その製造
方法に関する。The present invention relates to a metal composite material having high corrosion resistance, particularly high-temperature oxidation resistance, heat resistance and good wear resistance, and a method for producing the same.
高温かつ腐食性の雰囲気中で使用する機器を構成する
材料、とくに自動車排ガス淨化装置の触媒担体用素材、
反応器の内張板、あるいは電熱線などの材料としては、
それぞれ所要の耐食性や耐熱性をもった合金が使用され
ている。しかし、耐食耐熱性の合金は一般に加工性が低
いことと、耐食性は主として表面の問題であることか
ら、加工性のよい基材を使用してその表面に耐食性をも
った材料を組み合わせた複合材料や、基材の表面に耐食
性を向上させる処理を施した材料が種々提案されてい
る。 自動車の排ガス淨化装置に用いる触媒担体用メタルハ
ニカム素材に例をとると、発明者らは、15Cr−3Al−Fe
（いわゆるエレマン鋼）を基本組成とする合金の板にAl
箔をクラッドし、圧延、真空焼鈍および酸化性雰囲気中
での加熱を行なうことにより、表面のAlを酸化してAl2O
3に変え、耐食性を高めた材料を発明し、すでに提案し
た（特願平２−192090）。エレマン鋼は加工性がよく、
その表面の耐食性を保護被膜Al2O3の生成で高めたこと
により、任意の形状の耐食耐熱性部品を製作することが
可能になった。 発明者らはまた、NiまたはNi−Cr合金のヒーター材の
高温耐食性を向上させる方策として、その表面にAl箔を
クラッドして前記と同様に真空焼鈍および酸化性雰囲気
中の加熱を行ない、Al2O3を生成させる技術を確立し
て、これもすでに開示した（特願平２−148158）。この
ヒーター材は耐久性が高い。その理由は、クラッドした
Alと基材のNiとの間で、熱処理により金属間化合物Ni3A
l（一部NiAlも）が生成し、これが強固に基材を被覆す
るためであると考えられる。 上記した二つの技術に共通のAl2O3層の形成にして
も、後の技術におけるNi3Al層の形成にしても、難点は
加熱処理に長い時間を必要とすることであって、これら
保護層の形成による効果を確実に得ようとするならば、
真空焼鈍のために数時間、酸化のために１時間以上の加
熱を行なわなければならない。このため、上記の技術は
大量生産には不向きであるし、製造コストも高くなる。Materials for equipment used in high-temperature and corrosive atmospheres, especially materials for catalyst carriers in automobile exhaust gas purification equipment,
As a material for the reactor lining plate or heating wire,
Alloys having the required corrosion resistance and heat resistance are used. However, since corrosion-resistant and heat-resistant alloys generally have low workability and corrosion resistance is mainly a surface problem, a composite material that combines a material with corrosion resistance on the surface using a base material with good workability Also, various materials have been proposed in which the surface of a substrate is subjected to a treatment for improving corrosion resistance. Taking an example of a metal honeycomb material for a catalyst carrier used in an exhaust gas purification device for automobiles, the inventors have found that 15Cr-3Al-Fe
(So-called Eleman steel) on an alloy plate with a basic composition of Al
By cladding the foil, rolling, vacuum annealing and heating in an oxidizing atmosphere, the surface Al is oxidized to Al 2 O
3 and invented a material with improved corrosion resistance, which has already been proposed (Japanese Patent Application No. 2-192090). Eleman steel has good workability,
By increasing the corrosion resistance of the surface by the formation of the protective coating Al 2 O 3 , it became possible to manufacture a corrosion-resistant and heat-resistant part having an arbitrary shape. The inventors have also proposed a method of improving the high-temperature corrosion resistance of a heater material of Ni or a Ni-Cr alloy by cladding an Al foil on the surface thereof and performing vacuum annealing and heating in an oxidizing atmosphere in the same manner as described above. A technique for producing 2 O 3 has been established and has also been disclosed (Japanese Patent Application No. 2-148158). This heater material has high durability. The reason was clad
Heat treatment between Al and Ni as intermetallic compound Ni 3 A
It is considered that l (also NiAl) is generated, and this is because the substrate is firmly coated. Regardless of the formation of the Al 2 O 3 layer common to the above two technologies or the formation of the Ni 3 Al layer in the later technology, the difficulty is that the heat treatment requires a long time, If you want to ensure the effect of forming the protective layer,
Heating must be performed for several hours for vacuum annealing and for one hour or more for oxidation. For this reason, the above technique is not suitable for mass production, and the manufacturing cost increases.
本発明の目的は、Al2O3被覆層の形成による耐食性と
くに耐高温酸化性の改善効果を、長時間の加熱処理を行
なう必要なく実現した板状または線状の金属複合材を提
供すること、およびそのような耐食耐熱性金属複合材の
製造方法を提供することにある。An object of the present invention is to provide a plate-like or linear metal composite material which realizes an effect of improving corrosion resistance, particularly high-temperature oxidation resistance, by forming an Al 2 O 3 coating layer without having to perform a long-time heat treatment. And a method for producing such a corrosion-resistant and heat-resistant metal composite.
本発明の耐食耐熱性金属複合材は、板材の場合は第３
図に、線材の場合は第６図にそれぞれ概念的に示すよう
に、基材金属（１）の表面に、Alの薄層（2C,2G）を介
して、Alの硬質陽極酸化被膜（３）を設けてなる。 基材金属は、使用条件において必要とされる機械的強
度や耐熱性そのほかの物性を有する限り任意である。た
とえば前掲の自動車排気ガス淨化装置の触媒担体用素
材、いわゆるメタルハニカム材を製造するような場合
は、耐熱性とともに良好な加工性を示すFe−15Cr−3Al
（いわゆるエレマン鋼）を使用するとよい。ヒーター材
であれば、Ni−Cr合金がその例となる。 本発明の耐食性金属複合板材の製造方法は、第１図に
示すように、基材金属（１）の表面にAl箔（2A）をクラ
ッドして第２図に示すようなAl層（2B）を有するクラッ
ド材を得、これを陽極として電解浴中で電解し、第３図
に示すように、クラッド材のAl層（2B）表面に少なくと
も50μｍ、好ましくは50〜100μｍの厚さをもった硬質
の陽極酸化被膜（３）を形成することからなる。 Al層（2B）の厚さは、上記の酸化被膜を形成するに足
りるよう、50μｍすなわち0.05mm以上を要する。適当な
厚さは、0.5mmまでの範囲である。この層は、その厚さ
の少なくとも10％を酸化被膜に変えるとよい。Alの硬質
陽極酸化被膜の形成は、アルマイト法としてよく知られ
た技術の中でも、とくに耐摩耗性を得る目的で行なわれ
ている手法を利用すればよい。硬質陽極酸化被膜を得る
代表的な電解操作は、浴温10℃以下の低温で、比較的高
い電流密度で十分長い時間電解を行ない、厚さ50μｍ以
上の酸化被膜を形成することである。 本発明の耐食性金属複合線材の製造方法は、第４図に
示すように、基材金属の線材（１）の表面をAlチューブ
（2E）で被覆して伸線加工によりクラッドして第５図に
示すようなクラッド材とし、これを陽極として、温度10
℃以下の電解浴中で電解し、第６図に示すように、クラ
ッド材のAl層表面に少なくとも50μｍの厚さをもった硬
質の陽極化被膜を形成することからなる。 線材の製造における代表的な例では、基材金属棒の径
が10mm内外で、これを被覆するAlチューブの厚さは、板
材の場合と同様に0.1〜1.0mmでよく、これらに対し減面
率30〜50％の引抜きを数パス行なう伸線加工により、径
0.5〜3mmのクラッド材を得る。 真空焼鈍および酸化性雰囲気中での加熱は、板材につ
いて示したものと同じ条件で行なえばよい。 なお、線材は第６図のような円形断面のものに限ら
ず、正方形や長方形そのほかの断面形状のものも製造可
能である。たとえば第７図に示すような断面形状のクラ
ッド材を、孔型ロールを用いた圧延により得、さらにロ
ール圧延してシートに近い形状の製品とすることもでき
る。この種の製品は、両側縁も被覆されているから、耐
食性がいっそう高い。The corrosion-resistant and heat-resistant metal composite of the present invention has a third
In the figure, in the case of a wire, as shown conceptually in FIG. 6, a hard anodic oxide film (3) of Al is formed on the surface of the base metal (1) via a thin layer of Al (2C, 2G). ). The base metal is optional as long as it has the required mechanical strength, heat resistance, and other physical properties under the use conditions. For example, in the case of manufacturing a material for a catalyst carrier of a car exhaust gas purification apparatus described above, a so-called metal honeycomb material, Fe-15Cr-3Al showing good workability as well as heat resistance.
(So-called Eleman steel) may be used. Ni-Cr alloy is an example of a heater material. As shown in FIG. 1, the method for manufacturing a corrosion-resistant metal composite plate according to the present invention comprises the steps of cladding an Al foil (2A) on the surface of a base metal (1) and forming an Al layer (2B) as shown in FIG. A clad material having a thickness of at least 50 μm, preferably 50 to 100 μm, was formed on the surface of the Al layer (2B) of the clad material as shown in FIG. Forming a hard anodic oxide coating (3). The thickness of the Al layer (2B) needs to be 50 μm, that is, 0.05 mm or more so as to be sufficient to form the oxide film. Suitable thicknesses range up to 0.5 mm. This layer may convert at least 10% of its thickness to an oxide coating. The formation of the hard anodic oxide film of Al may be performed by a technique well-known as an alumite method, which is performed particularly for the purpose of obtaining wear resistance. A typical electrolytic operation for obtaining a hard anodic oxide film is to perform electrolysis at a low temperature of 10 ° C. or lower at a relatively high current density for a sufficiently long time to form an oxide film having a thickness of 50 μm or more. As shown in FIG. 4, the method for producing a corrosion-resistant metal composite wire according to the present invention is shown in FIG. 5 in which the surface of a base metal wire (1) is covered with an Al tube (2E) and clad by wire drawing. A clad material as shown in Fig.
It consists of forming a hard anodized film having a thickness of at least 50 μm on the surface of the Al layer of the clad material as shown in FIG. In a typical example of manufacturing a wire rod, the diameter of the base metal rod is about 10 mm inside and outside, and the thickness of the Al tube covering this may be 0.1 to 1.0 mm as in the case of the plate material, and the surface area is reduced for these. Wire drawing with several passes at a rate of 30-50%
Obtain 0.5-3mm clad material. Vacuum annealing and heating in an oxidizing atmosphere may be performed under the same conditions as those shown for the sheet material. The wire is not limited to a circular cross-section as shown in FIG. 6, but a square, rectangular or other cross-sectional shape can also be manufactured. For example, a clad material having a cross-sectional shape as shown in FIG. 7 can be obtained by rolling using a grooved roll, and further roll-rolled into a product having a shape close to a sheet. This type of product is even more corrosion resistant because both sides are also coated.
基材金属（１）上にクラッドしたAl層（2B,2F）は、
電解処理および封孔処理により、その厚さの10〜30％以
上、場合によっては大部分がAl2O3（３）に変化する。
このAl2O3は、未変化の残存Al層（2C,2G）に対する密着
性が良好であり、Al層自体は圧延または伸線による基材
へのクラッドの結果よく結合しているから、全体として
複合材表面の硬質陽極酸化被膜は強固に存在する。従っ
て、酸化被膜自体のもつ高い耐食性とくに耐高温酸化性
や耐摩耗性を、この複合材は高度に発揮できる。 在来のアルマイト製品は、Alそれ自身の物性たとえば
低い融点（660℃）のため、その性能および用途に関し
て制約があるが、本発明の複合材は、基材のもつ物性に
加えて硬質陽極酸化被膜の性能をあわせ有することによ
り、耐熱性と高温における耐食性および耐摩耗性とを兼
備する。The Al layer (2B, 2F) clad on the base metal (1)
By the electrolytic treatment and the sealing treatment, the thickness is changed to Al 2 O 3 (3) by 10 to 30% or more, and in some cases, most of the thickness.
This Al 2 O 3 has good adhesion to the unchanged residual Al layer (2C, 2G), and the Al layer itself is well bonded as a result of cladding on the substrate by rolling or drawing. As a result, the hard anodic oxide coating on the surface of the composite material exists firmly. Therefore, this composite material can exhibit the high corrosion resistance of the oxide film itself, especially the high temperature oxidation resistance and the wear resistance. Conventional alumite products are limited in their performance and application due to the physical properties of Al itself, such as a low melting point (660 ° C.). However, the composite material of the present invention is hard anodized in addition to the physical properties of the base material. By having the performance of the film together, it has both heat resistance and corrosion resistance and abrasion resistance at high temperatures.
厚さ0.8mmのFe−15Cr−3Alの薄板の両面にAl箔を圧延
によりクラッドし、全体の厚さが0.4mmでAl層の厚さが
0.02mm（片面0.1mm×２）のクラッド材を得た。 これを、浴温０℃の15％硫酸浴中、電流密度2A/dm2の
直流で陽極酸化し、厚さ50μｍの硬質陽極酸化被膜を形
成した。 この製品を、幅6mm×長さ200mmのリボンにスリットし
た。比較のため、上記Fe−15Cr−3Al鋼そのままの、同
じ厚さのリボンも用意した。 これらの試料について、つぎの耐食性試験を行なっ
た。 （塩水噴霧） 試料を800℃に加熱した状態で一定の張力を加えてお
き、そこへ５％NaCl溶液を２分間に１回噴霧して、試料
の破断に至るまでの塩水噴霧回数をしらべた。 その結果を、第８図に示す。 （酸化増量） 試料を1100℃の大気中に置き、時間の経過に伴う酸化
増量（mg/cm2）を測定した。 その結果は、第９図に示すとおりである。The aluminum foil is clad on both sides of a thin sheet of Fe-15Cr-3Al with a thickness of 0.8 mm by rolling, and the total thickness is 0.4 mm and the thickness of the Al layer is
A clad material of 0.02 mm (0.1 mm × 2 on one side) was obtained. This was anodized in a 15% sulfuric acid bath at a bath temperature of 0 ° C. with a direct current having a current density of 2 A / dm 2 to form a hard anodic oxide film having a thickness of 50 μm. This product was slit into a ribbon having a width of 6 mm and a length of 200 mm. For comparison, a ribbon having the same thickness as the above Fe-15Cr-3Al steel was also prepared. The following corrosion resistance test was performed on these samples. (Salt spray) A constant tension was applied to the sample while heating the sample to 800 ° C., and a 5% NaCl solution was sprayed once every 2 minutes, and the number of times of salt spray until the sample was broken was examined. . The results are shown in FIG. (Oxidation weight increase) The sample was placed in the air at 1100 ° C, and the oxidation weight gain (mg / cm 2 ) over time was measured. The result is as shown in FIG.
本発明により、Al2O3被膜の保護作用を利用した各種
金属の複合材が、長時間にわたる加熱の必要なく製造で
きる。前記のメタルハニカムを代表とする、大量生産の
必要があり、かつコストの低減が至上命令である用途に
向ける複合材の製造にとって、本発明は最適である。According to the present invention, a composite material of various metals utilizing the protective action of the Al 2 O 3 coating can be manufactured without the need for long-time heating. The present invention is most suitable for the production of a composite material such as the above-mentioned metal honeycomb, which is required to be mass-produced and for which the reduction of cost is the highest command.
第１図および第２図は、ともに本発明の耐食性金属複合
板材の製造工程を説明するための、材料の断面図であ
る。 第３図は、本発明の耐食性金属複合板材の構造を示す、
概念的な断面図である。 第４図および第５図は、ともに本発明の耐食性金属複合
線材の製造工程を説明するための、第１図および第２図
に対応する材料の断面図である。 第６図は、本発明の耐食性金属複合線材の構造を示す、
第３図に対応する概念的な断面図である。 第７図は、第６図とは別の態様の線材の構造を示す、同
様な断面図である。 第８図および第９図は、本発明の実施データのグラフで
あって、第８図は塩水噴霧試験、第９図は酸化増量の測
定結果をそれぞれ示す。 １……基材金属板（基材金属線） 2A……Al箔 2E……Alチューブ 2B,2F……クラッドAl層 2C,2G……残存Al層 ３……硬質陽極酸化被膜（Al2O3層）FIG. 1 and FIG. 2 are cross-sectional views of materials for explaining the manufacturing process of the corrosion-resistant metal composite plate of the present invention. FIG. 3 shows the structure of the corrosion-resistant metal composite plate of the present invention.
It is a conceptual sectional view. 4 and 5 are cross-sectional views of the material corresponding to FIGS. 1 and 2 for explaining the manufacturing process of the corrosion-resistant metal composite wire of the present invention. FIG. 6 shows the structure of the corrosion-resistant metal composite wire of the present invention.
FIG. 4 is a conceptual sectional view corresponding to FIG. 3. FIG. 7 is a similar cross-sectional view showing a structure of a wire rod in another mode different from FIG. FIG. 8 and FIG. 9 are graphs of the working data of the present invention. FIG. 8 shows the results of the salt spray test, and FIG. 9 shows the results of the measurement of the increase in oxidation. 1 Base metal plate (base metal wire) 2A Al foil 2E Al tube 2B, 2F Clad Al layer 2C, 2G Remaining Al layer 3 Hard anodic oxide coating (Al 2 O 3 layers)
Claims (6)
て、Alの硬質陽極酸化被膜を設けてなる耐食耐熱性金属
複合材。1. A corrosion-resistant and heat-resistant metal composite material comprising a hard anodic oxide coating of Al provided on the surface of a heat-resistant base metal via a thin layer of Al.
−Cr−Al合金を使用した請求項１の金属複合材。2. A Ni—Cr alloy or Fe
The metal composite material according to claim 1, wherein a -Cr-Al alloy is used.
ある請求項１の金属複合材。3. The metal composite according to claim 1, wherein the thickness of the hard anodic oxide coating of Al is 50 μm or more.
ドし、得られたクラッド材を陽極として、温度10℃以下
の電解浴中で電解し、クラッド材のAl層表面に少なくと
も50μｍの厚さをもった硬質の陽極化被膜を形成するこ
とからなる耐食耐熱性金属複合板材の製造方法。4. An Al foil is clad on the surface of a plate made of a heat-resistant base material, and the obtained clad is used as an anode and electrolyzed in an electrolytic bath at a temperature of 10 ° C. or less. A method for producing a corrosion-resistant and heat-resistant metal composite plate comprising forming a hard anodized film having a thickness of 1 mm.
被覆して伸線加工によりクラッドし、得られたクラッド
材を陽極として、温度10℃以下の電解浴中で電解し、ク
ラッド材のAl層表面に少なくとも50μｍの厚さをもった
硬質の陽極化被膜を形成することからなる耐食耐熱性金
属複合線材の製造方法。5. The surface of a wire made of a heat-resistant base metal is covered with an Al tube and clad by wire drawing, and the obtained clad is used as an anode and electrolyzed in an electrolytic bath at a temperature of 10 ° C. or less. Forming a hard anodized film having a thickness of at least 50 μm on the surface of the Al layer.
ド材を使用し、この層の厚さの少なくとも10％を酸化被
膜に変えるに足りる時間にわたる電解を続ける請求項４
または５の製造方法。6. A method according to claim 4, wherein a cladding material having a surface Al layer thickness of 0.05 to 0.5 mm is used, and electrolysis is continued for a time sufficient to convert at least 10% of the thickness of the layer to an oxide film.
Or the manufacturing method of 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2271629A JP2990778B2 (en) | 1990-10-09 | 1990-10-09 | Corrosion resistant metal composite and method of manufacturing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2271629A JP2990778B2 (en) | 1990-10-09 | 1990-10-09 | Corrosion resistant metal composite and method of manufacturing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04147984A JPH04147984A (en) | 1992-05-21 |
| JP2990778B2 true JP2990778B2 (en) | 1999-12-13 |
Family
ID=17502738
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2271629A Expired - Fee Related JP2990778B2 (en) | 1990-10-09 | 1990-10-09 | Corrosion resistant metal composite and method of manufacturing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2990778B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110644030A (en) * | 2019-09-20 | 2020-01-03 | 成都阳光铝制品有限公司 | Preparation method of anticorrosive aluminum profile |
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1990
- 1990-10-09 JP JP2271629A patent/JP2990778B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04147984A (en) | 1992-05-21 |
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