JP2012241219A - Member for heat treatment furnace excellent in carburization resistance - Google Patents
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- 238000010438 heat treatment Methods 0.000 title claims abstract description 27
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 56
- 239000000956 alloy Substances 0.000 claims abstract description 56
- 229910003310 Ni-Al Inorganic materials 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 23
- 239000012535 impurity Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 238000005255 carburizing Methods 0.000 abstract description 12
- 239000000758 substrate Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 19
- 239000007789 gas Substances 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 238000007747 plating Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910002061 Ni-Cr-Al alloy Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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Abstract
Description
本発明は、ガス浸炭雰囲気で使用される熱処理炉用部材、特にラジアントチューブに関するものである。 The present invention relates to a member for a heat treatment furnace used in a gas carburizing atmosphere, particularly a radiant tube.
浸炭雰囲気の熱処理炉の熱源として、ラジアントチューブが使用されている。炉内に設置されたラジアントチューブは、そのチューブ内にバーナーの高温燃焼炎を噴射してチューブが加熱される。炉内で赤熱したチューブの輻射熱が熱源となる。一方、被処理物への浸炭を目的とする炉内雰囲気は、ＣＯ並びにプロパン、 メタン、エタン等の炭化水素系ガスが混合された還元性雰囲気となる。高温の還元雰囲気かつＣＯや炭化水素系ガス雰囲気では、金属表面に酸化物が生成しにくくなり、金属表面で気体分子が分解し原子化したＣが金属内に浸入することとなる。ラジアントチューブは長期間に渡り浸炭環境に曝されることとなる。浸炭が進むことにより、チューブ全体が脆化し、使用中に破壊に至ることが懸念される。そのため、高温強度にすぐれ、かつ耐浸炭性にすぐれるＮｉ合金である６００合金（ＵＮＳ Ｎ０６６００）や６０１合金（ＵＮＳ Ｎ０６６０１）が使用されてきた。しかし、それらは十分な耐浸炭性が得られず、より一層の耐浸炭性を追求して、以下のような対策が提案されてきた。
例えば、特許文献１に開示された技術では、Ａｌを１．５−４％含有するＦｅ−Ｃｒ−Ｎｉ−Ａｌ系合金を用いることによって、ラジアントチューブの耐浸炭性を向上させている。
また、特許文献２に開示された技術では、ＮｉまたはＣｏ系めっき皮膜中にＡｌとＣｒを拡散させてなるＮｉ−Ｃｒ−Ａｌ系合金皮膜またはＣｏ−Ｃｒ−Ａｌ系合金皮膜によって基材への浸炭を防止している。
Radiant tubes are used as a heat source for a heat treatment furnace in a carburizing atmosphere. The radiant tube installed in the furnace is heated by injecting a high-temperature combustion flame of a burner into the tube. The radiant heat of the tube that is red hot in the furnace becomes the heat source. On the other hand, the furnace atmosphere for the purpose of carburizing the workpiece is a reducing atmosphere in which hydrocarbon gases such as CO and propane, methane, ethane are mixed. In a high-temperature reducing atmosphere and CO or hydrocarbon-based gas atmosphere, it is difficult for oxides to be formed on the metal surface, and gas molecules decomposed and atomized on the metal surface enter the metal. Radiant tubes will be exposed to the carburizing environment for a long time. As carburization progresses, the entire tube becomes brittle, and there is a concern that it will break during use. Therefore, 600 alloy (UNS N06600) and 601 alloy (UNS N06601), which are Ni alloys having excellent high-temperature strength and carburization resistance, have been used. However, they cannot obtain sufficient carburization resistance, and the following measures have been proposed in pursuit of further carburization resistance.
For example, in the technique disclosed in Patent Document 1, the carburization resistance of the radiant tube is improved by using an Fe—Cr—Ni—Al alloy containing 1.5 to 4% Al.
In the technique disclosed in Patent Document 2, the Ni-Cr-Al alloy film or the Co-Cr-Al alloy film formed by diffusing Al and Cr in the Ni or Co plating film is applied to the substrate. Carburization is prevented.
ところが、特許文献１に開示された技術は、雰囲気中で表面にアルミナを分散させることを意図して、基材そのもののＡｌ含有量を高めた発明であるが、基材のＡｌ含有量を高めることにより、基材の伸びが低下しチューブを製造する際の曲げ加工中に割れるなどの懸念があった。さらに、加工が可能だとしても、最大４％のＡｌ含有量では表面を完全なアルミナ皮膜で覆うことが出来ず、高真空状態でない還元性の浸炭ガス環境では耐浸炭性が十分でないという課題があった。
また、特許文献２に開示された技術は、めっき皮膜を改質することにより、浸炭を防止する発明であるが、めっき皮膜は皮膜に欠陥が多くあり、浸炭ガスは欠陥を通じて基材／めっき皮膜界面に到達し、局部的に基材の浸炭が進み、めっき膜が剥がれてしまう。これにより、長期間に亘り高い耐浸炭性を維持することができないという課題があった。
However, the technique disclosed in Patent Document 1 is an invention in which the Al content of the base material itself is increased with the intention of dispersing alumina on the surface in an atmosphere, but the Al content of the base material is increased. As a result, there has been a concern that the elongation of the base material is reduced and cracking occurs during bending when the tube is manufactured. Furthermore, even if processing is possible, the maximum 4% Al content cannot cover the surface with a complete alumina film, and there is a problem that the carburization resistance is not sufficient in a reducing carburizing gas environment that is not in a high vacuum state. there were.
The technique disclosed in Patent Document 2 is an invention for preventing carburization by modifying the plating film. However, the plating film has many defects in the film, and the carburizing gas passes through the substrate / plating film. It reaches the interface, the carburizing of the substrate proceeds locally, and the plating film is peeled off. Thereby, there existed a subject that high carburization resistance could not be maintained over a long period of time.
そこで、本発明が解決しようとする技術的課題、すなわち、本発明の目的は、浸炭環境で使用される熱処理炉部材、特にラジアントチューブの素材に適した耐浸炭性にすぐれた熱処理炉用部材を提供することにある。 Therefore, the technical problem to be solved by the present invention, that is, the object of the present invention is to provide a heat treatment furnace member used in a carburizing environment, particularly a heat treatment furnace member excellent in carburization resistance suitable for a radiant tube material. It is to provide.
そこで、前記課題を解決すべく本発明者らが鋭意研究を重ねた結果、最表面にＮｉ−Ａｌ合金層を、その直下にＣｒ濃縮層を有するニッケル基合金製部材を、ガス浸炭雰囲気で使用される熱処理炉用部材、特にラジアントチューブとして適用することにより、長期間に亘り高い耐浸炭性を維持することを可能とし、前記課題を解決できるという知見を得たのである。 Therefore, as a result of repeated extensive research by the present inventors to solve the above-mentioned problems, a nickel-based alloy member having a Ni-Al alloy layer on the outermost surface and a Cr-enriched layer directly below it is used in a gas carburizing atmosphere. As a result, it has been found that by applying as a heat treatment furnace member, particularly a radiant tube, it is possible to maintain a high carburization resistance for a long period of time and to solve the above-mentioned problems.
本発明の構成は、
「（１） Ｎｉ基合金からなる基材の表面にＣｒ濃縮層およびＮｉ−Ａｌ合金層を形成した熱処理炉用部材であって、
前記基材を構成するＮｉ基合金が、Ｃｒ：１４．０−３５．０重量％，Ｆｅ：０．１−２５．０重量％，Ａｌ：０．１−１．５重量％未満，Ｔｉ：０．００１−０．４重量％，Ｃ：０．００５−０．１５重量％，Ｍｎ：０．１−１．０重量％， Ｓｉ：０．１−１．０重量％を含有し、残部がＮｉおよび不可避不純物からなる組成を有するＮｉ基合金であり、
前記Ｎｉ−Ａｌ合金層が、厚さ：１０〜２００μｍ、組成：Ａｌ；１０〜６０重量％とし、残りをＮｉと不可避不純物からなり、
前記Ｃｒ濃縮層が、前記Ｎｉ−Ａｌ合金層の直下に形成されていることを特徴とする耐浸炭性にすぐれた熱処理炉用部材。
（２） 前記基材を構成するＮｉ基合金が、さらに、
（ａ）Ｃｏ：０．１−４．０重量％，
（ｂ）Ｍｏ：７．０−１７．０重量％，
（ｃ）Ｗ：０．１−４．５重量％，
（ｄ）Ｎｂ：０．１−４重量％，Ｔａ：０．１−４重量％の内の１種または２種，
前記（ａ）〜（ｄ）の内の１種または２種以上を含有することを特徴とする（１）に記載の耐浸炭性にすぐれた熱処理炉用部材。
（３）前記熱処理炉部材が、ラジアントチューブであることを特徴とする（１）または（２）に記載の耐浸炭性にすぐれた熱処理炉用部材。」
である。
次に、各構成要素の限定理由について詳述する。
Ｎｉ−Ａｌ合金層：
Ａｌは酸素との親和性が高いため、還元性環境であっても極低分圧の酸素により高温環境においてアルミナを形成する。これにより、浸炭ガスに対する耐浸炭性を発揮できる。また、表面に形成されるアルミナは、合金からの形成したものであるため、密着性が非常に高く簡単に剥離しない。さらに、Ｎｉ−Ａｌ層／Ｃｒ濃縮層と基材は後述する方法により、拡散による金属結合のため一体化しており、すぐれた耐剥離性を発揮する。
１）厚さ：１０〜２００μｍ
厚さが、１０μｍ未満では、高温での保護性の高い緻密なアルミナを形成するのには不十分である。一方、２００μｍを超えると基材との熱膨張差などにより、高温での繰り返し使用中にＮｉ−Ａｌ合金層に亀裂などが発生し易くなるため好ましくない。そこで、Ｎｉ−Ａｌ合金層の厚さは、１０〜２００μｍと定めた。
２）組成：Ａｌ；１０〜６０重量％とし、残りをＮｉと不可避不純物
Ａｌが１０重量％未満だと、保護性の高い緻密なアルミナを形成するのには不十分である。一方、６０重量％を超えるとアルミニウムに近い挙動となり、高温環境でＮｉ−Ａｌ合金層が溶融してしまうため好ましくない。
The configuration of the present invention is as follows:
“(1) A heat treatment furnace member in which a Cr-concentrated layer and a Ni—Al alloy layer are formed on the surface of a base material made of a Ni-based alloy,
The Ni base alloy constituting the base material is Cr: 14.0-35.0% by weight, Fe: 0.1-25.0% by weight, Al: less than 0.1-1.5% by weight, Ti: 0.001-0.4 wt%, C: 0.005-0.15 wt%, Mn: 0.1-1.0 wt%, Si: 0.1-1.0 wt%, the balance Is a Ni-based alloy having a composition consisting of Ni and inevitable impurities,
The Ni—Al alloy layer has a thickness of 10 to 200 μm, a composition of Al; 10 to 60% by weight, and the rest is made of Ni and inevitable impurities.
A member for a heat treatment furnace excellent in carburization resistance, wherein the Cr enriched layer is formed immediately below the Ni-Al alloy layer.
(2) The Ni-based alloy constituting the base material further includes:
(A) Co: 0.1-4.0% by weight,
(B) Mo: 7.0-17.0% by weight,
(C) W: 0.1-4.5% by weight,
(D) One or two of Nb: 0.1-4 wt% and Ta: 0.1-4 wt%,
The heat treatment furnace member having excellent carburization resistance according to (1), comprising one or more of (a) to (d).
(3) The heat treatment furnace member having excellent carburization resistance according to (1) or (2), wherein the heat treatment furnace member is a radiant tube. "
It is.
Next, the reasons for limiting each component will be described in detail.
Ni-Al alloy layer:
Since Al has a high affinity with oxygen, alumina is formed in a high-temperature environment by oxygen having an extremely low partial pressure even in a reducing environment. Thereby, the carburization resistance with respect to the carburizing gas can be exhibited. Moreover, since the alumina formed on the surface is formed from an alloy, it has very high adhesion and does not easily peel off. Furthermore, the Ni—Al layer / Cr enriched layer and the base material are integrated for metal bonding by diffusion by the method described later, and exhibit excellent peeling resistance.
1) Thickness: 10-200 μm
If the thickness is less than 10 μm, it is insufficient to form dense alumina that is highly protective at high temperatures. On the other hand, if it exceeds 200 μm, the Ni—Al alloy layer is liable to be cracked during repeated use at a high temperature due to the difference in thermal expansion from the substrate, etc., which is not preferable. Therefore, the thickness of the Ni—Al alloy layer is set to 10 to 200 μm.
2) Composition: Al; 10 to 60% by weight, and the balance of Ni and inevitable impurities Al being less than 10% by weight is insufficient to form dense alumina with high protective properties. On the other hand, if it exceeds 60% by weight, the behavior is close to that of aluminum, and the Ni—Al alloy layer melts in a high temperature environment, which is not preferable.
Ａｌと不可避不純物以外はＮｉであるが、基材成分に含まれるＣｒ＋Ｍｏ＋Ｆｅ＋Ｗの合計値が２５重量％以下含有することは許容される。合計値を超えた場合、Ｎｉ−Ａｌ合金層が脆化し亀裂発生の原因となってしまうため好ましくない。
Ｃｒ濃縮層：
基材とＮｉ−Ａｌ合金層の間にＣｒ−ｒｉｃｈな合金層（Ｃｒ濃縮層）を有することにより、Ｎｉ−Ａｌ合金層からＡｌが基材に拡散して、基材のＡｌ含有量が増加することによる脆化を抑制できる。同時に表面でのＮｉ−Ａｌ合金層を維持することにも役立ち、それにより環境中で形成されたアルミナ層が欠損した場合でも自己再生可能とさせる。Ｃｒ濃縮層中に含有するＣｒ含有量は、４０％以上であることが望ましい。
基材のＮｉ基合金：
Ｃｒ：１４．０−３５．０重量％，Ｆｅ：０．１−２５．０重量％，Ａｌ：０．１−１．５重量％未満，Ｔｉ：０．００１−０．４重量％，Ｃ：０．００５−０．１５重量％，Ｍｎ：０．１−１．０重量％，Ｓｉ：０．１−１．０重量％を含有し、さらに必要に応じて
（ａ）Ｃｏ：０．１−４．０重量％，
（ｂ）Ｍｏ：７．０−１７．０重量％，
（ｃ）Ｗ：０．１−４．５重量％，
（ｄ）Ｎｂ：０．１−４重量％，Ｔａ：０．１−４重量％の内の１種または２種、
前記（ａ）〜（ｄ）の内の１種または２種以上を含有し、残部がＮｉおよび不可避不純物からなる組成を有するＮｉ基合金。
Ｃｒ：
Ｃｒは、Ｎｉ−Ａｌ合金層と基材の間にＣｒ濃縮層を形成させるために必須である。前述したように、Ｃｒ濃縮層の中間層を有することにより、Ｎｉ−Ａｌ合金層からのＡｌの拡散消失を防ぐことができる。ところが、Ｃｒを１４．０重量％未満含有しても中間層に十分なＣｒが濃縮せず、結果、Ａｌの拡散消失を防止する効果が得られない。一方、３５．０重量％を超えて含有すると加工が困難となり、ラジアントチューブの形成が困難となる。したがって、Ｃｒの含有量は１４．０〜３５．０重量％とした。一層好ましくは、１５．０〜３２．０重量％である。
Ｆｅ：
Ｆｅは、基材であるＮｉ基合金を所望の部材に加工する際の熱間加工性を向上させる効果がある。ところが、０．１重量％未満含有しても所望の効果が得られず、一方、２５．０重量％を超えて含有すると表面のＮｉ−Ａｌ合金層にＦｅが許容範囲を超えて含有するので好ましくない。したがって、Ｆｅの含有量は０．１〜２５．０重量％とした。一層好ましくは、１５．０〜２２．０重量％である。
Ａｌ：
Ａｌは、表面側にあるＮｉ−Ａｌ合金層が欠落した際に、Ｃｒ濃縮層と基材の間に内部酸化によるアルミナ層を形成することにより長寿命化に寄与するために添加される。ところが、その含有量が０．１重量％未満では所望の効果が得られず、１．５重量％以上では加工性が著しく劣化し、ラジアントチューブ製造に必要な曲げ加工性を損なうため好ましくない。したがって、Ａｌの含有量を０．１〜１．５重量％未満とした。一層好ましくは、０．２〜０．８重量％である。
Ｔｉ：
Ｔｉは、浸炭で浸入する炭素をＴｉＣとして固定することにより、基材の脆化を抑制する効果がある。ところが、その含有量が０．００１重量％未満では所望の効果が得られず、０．４重量％を超えると高温での使用中に脆化し易くなるため好ましくない。したがって、Ｔｉの含有量を０．００１〜０．４重量％とした。一層好ましくは、０．００２〜０．０１重量％である。
Ｃ：
Ｃは、Ｃｒ炭化物などを析出させることにより高温強度向上に寄与するため含有する。ところが、０．００５重量％未満を含有しても所望の効果が得られず、一方、０．１５重量％を越えて含有すると、合金が脆化し、部材の素材となる板などへの形状付与が困難となるので好ましくない。したがって、Ｃの含有量を０．００５〜０．１５重量％に定めた。一層好ましい範囲は０．０１〜０．０８重量％ である。
Ｍｎ：
Ｍｎは、母相の結晶構造であるオーステナイト構造を安定化させることにより、熱間加工性を向上させるので、形状付与を容易にする作用がある。ところが、Ｍｎが０．１重量％未満含有しても所望の効果が得られず、一方、１．０重量％を超えて含有すると逆に熱間加工性が劣化するので好ましくない。したがって、Ｍｎの含有量を０．１〜１．０重量％とした。一層好ましくは、０．２〜０．８重量％である。
Ｓｉ：
Ｓｉは、高温強度を高める効果がある。それにより、高温下で使用中に変形することを防止できる。ところが、Ｓｉを０．１重量％未満含有しても所望の効果が得られず、一方、１．０重量％を越えて含有すると、合金の脆化が顕在化し、部材の素材となる板などへの形状付与が困難となるので好ましくない。したがって、Ｓｉの含有量を０．１〜１．０重量％とした。一層好ましい範囲は０．２〜０．８重量％である。
Ｃｏ：
Ｃｏは、高温強度／高温クリープ強度を高める効果がある。それにより、必要に応じて添加する。ところが、０．１重量％未満含有しても所望の効果が得られず、一方、４．０重量％を越えて含有すると、冷間加工性が悪化するのでチューブへの成形性を損なうため好ましくない。したがって、Ｃｏの含有量を０．１〜４．０重量％とした。一層好ましい範囲は０．２〜３．０重量％である。
Ｍｏ：
Ｍｏは、高温におけるクリープ強度を高める効果がある。そのため、高温環境下で荷重が加わることによる変形を防止する必要がある場合に、添加される。ところが、Ｍｏを７．０重量％未満添加しても所望の効果が得られず、一方、１７．０重量％を越えて含有すると加工性の著しい低下をもたらすので好ましくない。したがって、Ｍｏの含有量を７．０〜１７．０重量％に定めた。一層好ましい範囲は８．０〜１４．０重量％である。
Ｗ：
Ｗは、熱膨張係数を下げる効果がある。そのため、高温〜低温の熱サイクル疲労に対して効果があるため、必要に応じて添加される。ところが、Ｗを０．１重量％未満添加しても所望の効果が得られず、一方、４．５重量％を越えて含有すると加工性の著しい低下をもたらすので好ましくない。したがって、Ｗの含有量を０．１〜４．５％とした。一層好ましい範囲は０．２〜１．０重量％である。
ＮｂおよびＴａ：
これら成分は、浸炭の原因となるＣを固定化する効果がある。ところが、Ｎｂの含有量が０．１重量％未満では所望の効果が得られず、一方、４．０重量％を越えて含有すると、加工性が劣化するので好ましくない。したがって、Ｎｂの含有量を０．１〜４．０重量％とした。一層好ましい範囲は０．５〜３．０重量％である。
同様に、Ｔａの含有量が０．１重量％未満では所望の効果が得られず、一方、４．０重量％を越えて含有すると、加工性が劣化するので好ましくない。したがって、Ｔａの含有量を０．１〜４．０重量％に定めた。Ｔａの含有量の一層好ましい範囲は０．５〜３．０重量％である。
不可避不純物：
不可避不純物としてはＰ，Ｓなどが挙げられるが、これら不純物は、高温加工などの合金製造時における割れや溶接部における高温割れの原因となる。したがって、できるだけ低減することが望ましい。
Ni other than Al and unavoidable impurities is Ni, but the total value of Cr + Mo + Fe + W contained in the base material component is allowed to be 25% by weight or less. Exceeding the total value is not preferable because the Ni—Al alloy layer becomes brittle and causes cracking.
Cr enriched layer:
By having a Cr-rich alloy layer (Cr enriched layer) between the base material and the Ni-Al alloy layer, Al diffuses from the Ni-Al alloy layer to the base material, and the Al content of the base material increases. The embrittlement by doing can be suppressed. At the same time, it helps to maintain the Ni—Al alloy layer on the surface, thereby enabling self-regeneration even when the alumina layer formed in the environment is lost. The Cr content contained in the Cr enriched layer is preferably 40% or more.
Base Ni-based alloy:
Cr: 14.0-35.0 wt%, Fe: 0.1-25.0 wt%, Al: less than 0.1-1.5 wt%, Ti: 0.001-0.4 wt%, C : 0.005-0.15 wt%, Mn: 0.1-1.0 wt%, Si: 0.1-1.0 wt%, and (a) Co: 0. 1-4% by weight,
(B) Mo: 7.0-17.0% by weight,
(C) W: 0.1-4.5% by weight,
(D) One or two of Nb: 0.1-4 wt%, Ta: 0.1-4 wt%,
A Ni-based alloy containing one or more of (a) to (d), with the balance being composed of Ni and inevitable impurities.
Cr:
Cr is essential for forming a Cr enriched layer between the Ni-Al alloy layer and the substrate. As described above, by having the intermediate layer of the Cr enriched layer, it is possible to prevent Al from diffusing and disappearing from the Ni—Al alloy layer. However, even if Cr is contained in an amount of less than 14.0% by weight, sufficient Cr is not concentrated in the intermediate layer, and as a result, the effect of preventing the diffusion and disappearance of Al cannot be obtained. On the other hand, when it contains exceeding 35.0 weight%, a process will become difficult and formation of a radiant tube will become difficult. Therefore, the content of Cr is set to 14.0 to 35.0% by weight. More preferably, it is 15.0-32.0 weight%.
Fe:
Fe has an effect of improving hot workability when a Ni-based alloy as a base material is processed into a desired member. However, even if the content is less than 0.1% by weight, a desired effect cannot be obtained. It is not preferable. Therefore, the content of Fe is set to 0.1 to 25.0% by weight. More preferably, it is 15.0 to 22.0% by weight.
Al:
Al is added to contribute to a longer life by forming an alumina layer by internal oxidation between the Cr enriched layer and the substrate when the Ni—Al alloy layer on the surface side is missing. However, if the content is less than 0.1% by weight, the desired effect cannot be obtained, and if it is 1.5% by weight or more, the workability is remarkably deteriorated and the bending workability required for the production of the radiant tube is impaired, which is not preferable. Therefore, the Al content is set to less than 0.1 to 1.5% by weight. More preferably, it is 0.2 to 0.8% by weight.
Ti:
Ti has an effect of suppressing embrittlement of the base material by fixing carbon that enters by carburization as TiC. However, if the content is less than 0.001% by weight, the desired effect cannot be obtained, and if it exceeds 0.4% by weight, it tends to become brittle during use at high temperatures. Therefore, the Ti content is set to 0.001 to 0.4% by weight. More preferably, it is 0.002 to 0.01% by weight.
C:
C is contained because it contributes to improving the high-temperature strength by precipitating Cr carbide and the like. However, even if it contains less than 0.005% by weight, the desired effect cannot be obtained. On the other hand, if it contains more than 0.15% by weight, the alloy becomes brittle and imparts a shape to a plate or the like as a material of the member Is not preferable because it becomes difficult. Therefore, the content of C is set to 0.005 to 0.15% by weight. A more preferred range is 0.01 to 0.08% by weight.
Mn:
Since Mn improves the hot workability by stabilizing the austenite structure, which is the crystal structure of the parent phase, it has the effect of facilitating shape provision. However, even if Mn is contained in an amount of less than 0.1% by weight, the desired effect cannot be obtained. On the other hand, if it contains more than 1.0% by weight, the hot workability is adversely deteriorated. Therefore, the Mn content is set to 0.1 to 1.0% by weight. More preferably, it is 0.2 to 0.8% by weight.
Si:
Si has the effect of increasing the high temperature strength. Thereby, deformation during use at high temperatures can be prevented. However, even if Si is contained in an amount of less than 0.1% by weight, a desired effect cannot be obtained. This is not preferable because it is difficult to impart a shape to the surface. Therefore, the Si content is set to 0.1 to 1.0% by weight. A more preferable range is 0.2 to 0.8% by weight.
Co:
Co has the effect of increasing the high temperature strength / high temperature creep strength. Thereby, it adds as needed. However, if the content is less than 0.1% by weight, the desired effect cannot be obtained. On the other hand, if the content exceeds 4.0% by weight, the cold workability deteriorates and the formability to the tube is impaired. Absent. Therefore, the content of Co is set to 0.1 to 4.0% by weight. A more preferable range is 0.2 to 3.0% by weight.
Mo:
Mo has the effect of increasing the creep strength at high temperatures. Therefore, it is added when it is necessary to prevent deformation due to application of a load in a high temperature environment. However, even if Mo is added in an amount of less than 7.0% by weight, the desired effect cannot be obtained. Therefore, the Mo content is set to 7.0 to 17.0% by weight. A more preferable range is 8.0 to 14.0% by weight.
W:
W has the effect of lowering the thermal expansion coefficient. Therefore, since it is effective against high-temperature to low-temperature thermal cycle fatigue, it is added as necessary. However, even if W is added in an amount of less than 0.1% by weight, the desired effect cannot be obtained. On the other hand, if it exceeds 4.5% by weight, the workability is remarkably lowered, which is not preferable. Therefore, the W content is set to 0.1 to 4.5%. A more preferable range is 0.2 to 1.0% by weight.
Nb and Ta:
These components have an effect of fixing C which causes carburization. However, if the Nb content is less than 0.1% by weight, the desired effect cannot be obtained. On the other hand, if the Nb content exceeds 4.0% by weight, the workability deteriorates, which is not preferable. Therefore, the Nb content is set to 0.1 to 4.0% by weight. A more preferable range is 0.5 to 3.0% by weight.
Similarly, if the content of Ta is less than 0.1% by weight, the desired effect cannot be obtained. On the other hand, if the content exceeds 4.0% by weight, the workability deteriorates, which is not preferable. Therefore, the content of Ta is set to 0.1 to 4.0% by weight. A more preferable range of the Ta content is 0.5 to 3.0% by weight.
Inevitable impurities:
Inevitable impurities include P, S, etc., but these impurities cause cracks during alloy production such as high-temperature processing and hot cracks in welds. Therefore, it is desirable to reduce as much as possible.
本発明によれば、Ｎｉ基合金からなる基材の表面にＣｒ濃縮層およびＮｉ−Ａｌ合金層を形成した熱処理炉用部材であって、基材を構成するＮｉ基合金が、Ｃｒ：１４．０−３５．０重量％，Ｆｅ：０．１−２５．０重量％，Ａｌ：０．１−１．５重量％未満，Ｔｉ：０．００１−０．４重量％，Ｃ：０．００５−０．１５重量％，Ｍｎ：０．１−１．０重量％， Ｓｉ：０．１−１．０重量％を含有し、残部がＮｉおよび不可避不純物からなる組成を有するＮｉ基合金であり、Ｎｉ−Ａｌ合金層が、厚さ：１０〜２００μｍ、組成：Ａｌ；１０〜６０重量％とし、残りをＮｉと不可避不純物からなり、Ｃｒ濃縮層が、Ｎｉ−Ａｌ合金層の直下に形成されていることによって、耐浸炭性が向上し、熱処理炉の寿命を飛躍的に向上させることが可能となった。 According to the present invention, there is provided a member for a heat treatment furnace in which a Cr-concentrated layer and a Ni—Al alloy layer are formed on the surface of a base material made of a Ni-base alloy, and the Ni-base alloy constituting the base material is Cr: 14. 0-35.0 wt%, Fe: 0.1-25.0 wt%, Al: less than 0.1-1.5 wt%, Ti: 0.001-0.4 wt%, C: 0.005 A Ni-based alloy having a composition containing 0.15% by weight, Mn: 0.1-1.0% by weight, Si: 0.1-1.0% by weight, the balance being Ni and inevitable impurities The Ni—Al alloy layer has a thickness of 10 to 200 μm, a composition of Al; 10 to 60% by weight, the remainder is made of Ni and inevitable impurities, and a Cr-enriched layer is formed immediately below the Ni—Al alloy layer. Therefore, the carburization resistance can be improved and the life of the heat treatment furnace can be dramatically improved. It became Noh.
以下に、本発明について、実施例を用いて説明する Hereinafter, the present invention will be described using examples.
通常の高周波溶解炉を用いて溶解し鋳造して表１に示される成分組成を有するＮｉ基合金からなる厚さ：４０ｍｍ、重さ：約５Ｋｇを有するインゴットを作製した。このインゴットを１２３０℃で１０時間均質化熱処理を施し、１０００〜１２３０℃の範囲内に保持しながら、１回の熱間圧延で１ｍｍの厚さを減少させつつ最終的に厚さ：３ｍｍの薄板とし、ついで１２００℃で３０分間保持し水焼入れすることにより固溶化処理を施した。３ｍｍ板を６０℃、１７％ＨＮＯ３−３％ＨＦ溶液中で酸洗し、スケール除去した。次に、溶接管製造装置を用いてこの板から外径５０．８ｍｍ、厚さ３ｍｍ、長さ１０００ｍｍの溶接管を製作した。
各種Ｎｉ合金製パイプの内外面にＮｉ−Ａｌ合金層を形成することにより、ラジアントチューブを模擬する本発明品（表１）および比較品（表２）のラジアントチューブを作製した。Ｎｉ−Ａｌ合金層の形成をしない６００合金（ＵＮＳ Ｎ０６６００）製パイプおよび６０１合金（ＵＮＳ Ｎ０６６０１）を従来品（表３）のラジアントチューブとした。
Ｎｉ−Ａｌ合金層の形成は、カロライジング処理を用いた。基材をＦｅ−Ａｌ合金粉末及びＮＨ４Ｃｌ粉よりなる調合材と共に鋼製ケース内に埋め込み、ケースを密閉し、それを炉内にて９００〜１０５０℃に加熱することによって表面にＮｉ−Ａｌ合金層を、中間層にＣｒ濃縮層を得た。温度や処理時間を変量にすることにより、所定の厚さ・組成の合金層とした。
図１に示すようにラジアントチューブを電気炉に挿入し、さらに管内に１０５０℃の燃焼ガスを通気して、補助的に電気ヒーターによる加熱で１０００℃に保持した浸炭ガス（Ｈ２−３％ＣＨ４）中にラジアントチューブ外面を曝した。５００ｈの試験後、ラジアントチューブを炉から取り出し、中央部となる端から５００ｍｍ付近の肉厚を測定し、最大減肉量を記載した。肉厚測定は、端から５００ｍｍ付近を長手方向に直角となるように切断し、バリ取りを行ったのち、水洗しながらステンレス鋼製のワイヤーブラシを用いて付着物を十分に除去し、さらに水洗・乾燥を行って、測定接触部が球型のマイクロメーターを用いて肉厚測定を円周上の５点について実施した。５点のうち最小値を選定し、初期肉厚よりこの試験後の肉厚を引いた値を減肉量として記載した。なお、初期厚さは、同様の方法で予め端部の肉厚を測定しておき、この肉厚を初期厚さとみなした。
An ingot having a thickness of 40 mm and a weight of about 5 kg made of a Ni-based alloy having the composition shown in Table 1 was prepared by melting and casting using a normal high-frequency melting furnace. The ingot was subjected to a homogenization heat treatment at 1230 ° C. for 10 hours and held within a range of 1000 to 1230 ° C., and the thickness was reduced to 1 mm by one hot rolling and finally a thin plate having a thickness of 3 mm. Then, a solution treatment was performed by holding at 1200 ° C. for 30 minutes and quenching with water. A 3 mm plate was pickled in a 17% HNO 3 -3% HF solution at 60 ° C. and descaled. Next, a welded pipe having an outer diameter of 50.8 mm, a thickness of 3 mm, and a length of 1000 mm was produced from this plate using a welded pipe manufacturing apparatus.
By forming Ni—Al alloy layers on the inner and outer surfaces of various Ni alloy pipes, radiant tubes of the present invention products (Table 1) and comparative products (Table 2) that simulate the radiant tubes were produced. A 600 alloy (UNS N06600) pipe without forming a Ni-Al alloy layer and a 601 alloy (UNS N06601) were used as conventional radiant tubes (Table 3).
The calorizing process was used to form the Ni—Al alloy layer. The base material is embedded in a steel case together with a blended material made of Fe-Al alloy powder and NH 4 Cl powder, the case is sealed, and the surface is heated to 900-1050 ° C. in a furnace, thereby Ni-Al is formed on the surface. An alloy layer was obtained, and a Cr concentrated layer was obtained as an intermediate layer. By varying the temperature and processing time, an alloy layer having a predetermined thickness and composition was obtained.
As shown in FIG. 1, a radiant tube is inserted into an electric furnace, a combustion gas of 1050 ° C. is passed through the tube, and a carburizing gas (H 2 -3% CH) is maintained at 1000 ° C. by heating with an electric heater. 4 ) The radiant tube outer surface was exposed during. After the test for 500 h, the radiant tube was taken out of the furnace, and the thickness near 500 mm from the end which became the central part was measured, and the maximum thickness reduction was described. Thickness measurement is performed by cutting around 500 mm from the end so as to be perpendicular to the longitudinal direction, deburring, sufficiently removing deposits with a stainless steel wire brush while washing with water, and further washing with water. -Drying was performed, and the thickness measurement was carried out at five points on the circumference using a micrometer having a spherical contact portion. The minimum value was selected from the five points, and the value obtained by subtracting the thickness after this test from the initial thickness was described as the thickness reduction. As for the initial thickness, the thickness of the end portion was measured in advance by the same method, and this thickness was regarded as the initial thickness.
以上のとおり、本発明の熱処理炉用部材によれば、耐浸炭性にすぐれているため、より長寿命化が要求される熱処理炉の構成部材、特にラジアントチューブの構成部材として大きな期待が持てるとともに、工業的な価値は極めて大きい。 As described above, according to the heat treatment furnace member of the present invention, since it has excellent carburization resistance, it can be highly expected as a component of a heat treatment furnace that is required to have a longer life, particularly as a component member of a radiant tube. Industrial value is extremely large.
Claims (3)
前記基材を構成するＮｉ基合金が、Ｃｒ：１４．０−３５．０重量％，Ｆｅ：０．１−２５．０重量％，Ａｌ：０．１−１．５重量％未満，Ｔｉ：０．００１−０．４重量％，Ｃ：０．００５−０．１５重量％，Ｍｎ：０．１−１．０重量％， Ｓｉ：０．１−１．０重量％を含有し、残部がＮｉおよび不可避不純物からなる組成を有するＮｉ基合金であり、
前記Ｎｉ−Ａｌ合金層が、厚さ：１０〜２００μｍ、組成：Ａｌ；１０〜６０重量％とし、残りをＮｉと不可避不純物からなり、
前記Ｃｒ濃縮層が、前記Ｎｉ−Ａｌ合金層の直下に形成されていることを特徴とする耐浸炭性にすぐれた熱処理炉用部材。 A heat treatment furnace member in which a Cr-concentrated layer and a Ni-Al alloy layer are formed on the surface of a base material made of a Ni-based alloy,
The Ni base alloy constituting the base material is Cr: 14.0-35.0% by weight, Fe: 0.1-25.0% by weight, Al: less than 0.1-1.5% by weight, Ti: 0.001-0.4 wt%, C: 0.005-0.15 wt%, Mn: 0.1-1.0 wt%, Si: 0.1-1.0 wt%, the balance Is a Ni-based alloy having a composition consisting of Ni and inevitable impurities,
The Ni—Al alloy layer has a thickness of 10 to 200 μm, a composition of Al; 10 to 60% by weight, and the rest is made of Ni and inevitable impurities.
A member for a heat treatment furnace excellent in carburization resistance, wherein the Cr enriched layer is formed immediately below the Ni-Al alloy layer.
（ａ）Ｃｏ：０．１−４．０重量％，
（ｂ）Ｍｏ：７．０−１７．０重量％，
（ｃ）Ｗ：０．１−４．５重量％，
（ｄ）Ｎｂ：０．１−４重量％，Ｔａ：０．１−４重量％の内の１種または２種，
前記（ａ）〜（ｄ）の内の１種または２種以上を含有することを特徴とする請求項１に記載の耐浸炭性にすぐれた熱処理炉用部材。 The Ni-based alloy constituting the base material further comprises:
(A) Co: 0.1-4.0% by weight,
(B) Mo: 7.0-17.0% by weight,
(C) W: 0.1-4.5% by weight,
(D) One or two of Nb: 0.1-4 wt% and Ta: 0.1-4 wt%,
2. The heat treatment furnace member having excellent carburization resistance according to claim 1, comprising one or more of (a) to (d).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3913101A1 (en) * | 2020-05-22 | 2021-11-24 | Nippon Steel Corporation | Ni-based alloy tube and welded joint |
| CN116287870A (en) * | 2023-03-27 | 2023-06-23 | 昆明理工大学 | A carbon-corrosion-resistant nickel-chromium-based alloy material with rapid response to heating, its preparation method and application |
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| JPS58224161A (en) * | 1982-06-22 | 1983-12-26 | Mitsubishi Heavy Ind Ltd | Material with carburization resistance at high temperature |
| JPH0978204A (en) * | 1995-09-18 | 1997-03-25 | Chiyoda Corp | Metal material |
| JP2001323361A (en) * | 2000-05-16 | 2001-11-22 | Nisshin Steel Co Ltd | Radiant tube excellent in high temperature oxidation resistance and its production method |
| JP2006028566A (en) * | 2004-07-14 | 2006-02-02 | Mitsubishi Kakoki Kaisha Ltd | Components for hydrocarbon reformers |
| JP2010270400A (en) * | 2010-07-21 | 2010-12-02 | Sumitomo Metal Ind Ltd | Steam generator tube for nuclear power plant |
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| JPS5747842A (en) * | 1980-09-01 | 1982-03-18 | Mitsubishi Steel Mfg Co Ltd | Corrosion resistant cast alloy |
| JPS58224161A (en) * | 1982-06-22 | 1983-12-26 | Mitsubishi Heavy Ind Ltd | Material with carburization resistance at high temperature |
| JPH0978204A (en) * | 1995-09-18 | 1997-03-25 | Chiyoda Corp | Metal material |
| JP2001323361A (en) * | 2000-05-16 | 2001-11-22 | Nisshin Steel Co Ltd | Radiant tube excellent in high temperature oxidation resistance and its production method |
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| JP2010270400A (en) * | 2010-07-21 | 2010-12-02 | Sumitomo Metal Ind Ltd | Steam generator tube for nuclear power plant |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP3913101A1 (en) * | 2020-05-22 | 2021-11-24 | Nippon Steel Corporation | Ni-based alloy tube and welded joint |
| CN116287870A (en) * | 2023-03-27 | 2023-06-23 | 昆明理工大学 | A carbon-corrosion-resistant nickel-chromium-based alloy material with rapid response to heating, its preparation method and application |
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| JP5828500B2 (en) | 2015-12-09 |
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