JP3996050B2 - Alloy for sheathed heater tube - Google Patents
Alloy for sheathed heater tube Download PDFInfo
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- JP3996050B2 JP3996050B2 JP2002364022A JP2002364022A JP3996050B2 JP 3996050 B2 JP3996050 B2 JP 3996050B2 JP 2002364022 A JP2002364022 A JP 2002364022A JP 2002364022 A JP2002364022 A JP 2002364022A JP 3996050 B2 JP3996050 B2 JP 3996050B2
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Description
【0001】
【発明の属する技術分野】
本発明は、放射率の高い黒色保護皮膜で覆われたシーズヒーターの被覆管(シース)用合金に関するものである。
【0002】
【従来の技術】
シーズヒーターは、抵抗発熱体をアルミナ+酸化マグネシウムの如き耐熱性電気絶縁体を介して、管(シース)内に収容し、その被覆管を溶接密閉することにより構成されている。その被覆管用の材料(合金)としては、高温、たとえば600 ℃〜900 ℃の温度域において、耐酸化性、耐応力腐食割れ性あるいは溶接性に優れていることが求められているため、NCF800やNCF600などの、高Ni耐熱合金(Ni:20〜80 wt%)が広く用いられている。しかし、この高Ni耐熱合金は、加工性や溶接性が悪く、また高価で経済的でないという問題があった。これに対し、従来、これらの問題を解消するための種々の提案がなされている。
【0003】
例えば、Ni濃度を19〜23 mass%まで低減した上で、Ti/C比およびSi、Ti濃度の関係を規制することにより溶接性を改善した提案(特許文献1)がある。また、Ni濃度を8.75〜15.5 mass%まで低減し、∂フェライト量を制御して溶接性を改善した合金についての提案(特許文献2)もある。
【0004】
【特許文献1】
特開昭63−121641号公報
【特許文献2】
特公平7−103450号公報
【0005】
【発明が解決しようとする課題】
しかし、特許文献1に記載の合金では、放射率に優れた黒色保護皮膜を形成するために、必要なだけのTi濃度を含有していないので、必ずしも黒化性に優れた合金とはいえないものであった。しかも、Ni濃度がなお高いレベルにあることから、経済性がよいとは言い難い。一方、特許文献2に記載の合金は、Ti濃度が高いため、黒化性にすぐれており、Ni濃度も低いため、特許文献1に記載の合金より経済性に優れているといえる。しかし、この特許文献2の合金は、Al濃度(≧0.25 mass%)が高いため、介在物が発生し易く溶接部に欠陥を発生し易いという問題がある。しかも、Al濃度が高いため、合金を製造するとき、鋳造工程や熱間加工時に割れや庇を生じやすく、歩留まりを低下させるため、必ずしも経済性が十分とはいえなかった。
【0006】
そこで、本発明の目的は、黒化性と溶接性がともに優れると共に、表面疵等が発生しにくく加工性の良好なシーズヒータの被覆管用合金を提案することにある。
【0007】
【課題を解決するための手段】
従来技術が抱えている前記問題点を解決し、上記の目的を達成するために開発した本発明は、C≦0.05mass%、Si:0.1〜1.5mass%、Mn:0.05〜1.0mass%、Ni:8〜15mass%、Cr:18〜23mass%、Al:0.05〜0.25mass%未満、Ti:0.2〜0.7mass%、P≦0.02mass%、S≦0.005mass%を含有し、かつAlとTiはAl+Ti≦0.8mass%満足して含み、残部がFeおよび不純物からなるシーズヒーターの被覆管用合金である。
【0008】
【発明の実施の形態】
この発明合金開発の基本的な考え方は、Ni濃度を下げて溶接性と経済性とを改善する一方で、TiとAlの濃度を好適範囲内に制御することで、黒化性の維持と加工性の改善をも図り、これらの諸特性が互いに他を犠牲にすることなく、バランスよく実現・維持できるシース用合金を提供することにある。この合金についての成分組成を前記のように限定した理由を以下に説明する。
【0009】
C:0.05 mass%以下
Cは、高温強度を確保するのに有効な元素であるが、過剰に含有すると粒界にCrの炭化物を形成し耐食性を劣化させるので、0.05 mass%以下に限定した。なお、C含有量は0.03 mass%以下に抑えることが望ましい。
【0010】
Si:0.1〜1.5 mass%
Siは、塩化物の存在する高温環境での耐食性を改善する作用があり、本発明合金の必須添加元素の1つである。その含有量が0.1 mass%未満では、上記環境において、十分な耐食性改善効果が得られないため0.1 mass%以上とした。一方、含有量が1.5 mass%を超えると、合金が凝固割れを起こし、溶接性を阻害するので、Si含有量は0.1〜1.5 mass%と定めた。好ましくは0.1〜1.0 mass%とする。さらに好ましくは、0.1〜0.5 mass%とする。
【0011】
Mn:0.05〜1.0 mass%
Mnは、熱間加工性を維持するために必要な元素であるが、1.0 mass%超含有すると曲げ加工時に溶接部に割れが発生し易くなる。一方、0.05 mass%未満では、熱間加工時に割れを発生し、著しく歩留りが低下することから、その成分範囲を0.05 mass%〜1.0 mass%の範囲に限定した。
なお、このMnは、図1に示す、35%引張り後、ビードに発生した割れ個数とMn濃度との関係を示すグラフから明らかなように、0.5 mass%以下に制御することが好ましく、それはこの範囲であれば凝固時に粒界へのMn偏析が抑制され、シーズヒーターのシース管の曲げ加工時に、溶接ビードに発生する微割れを大幅に低減できるからである。ただし、このMn含有量はできれば、上記の作用効果をより顕著なものとするために0.05〜0.3 mass%程度に調整することがより好ましい。
【0012】
Ni:8〜15 mass%
Niは、オーステナイト相を安定させ、高温耐食性と高温強度を維持するために必須の成分であり、この意味において8 mass%以上含有される。しかし、このNiの濃度が高くなると、経済性が劣る他、溶接割れ感受性が劣化する。特に、Ni含有量が15 mass%を超えると、溶接割れ感受性の劣化が大きくなるため、Ni含有量は8〜15 mass%と定めた。好ましくは10〜15 mass%とする。
【0013】
Cr:18〜23 mass%
Crは、耐食性を得るための必須の元素であるが、その含有量が23 mass%超では、熱間加工性と溶接割れ感受性が劣化する。一方、このCr含有量が18 mass%未満では十分な耐食性が得られないため、Crの含有量は18〜23 mass%と定めた。
【0014】
Al::0.05〜0.25mass%
Alは、本発明において重要な元素の1つであり、耐酸化性の向上に効果的に作用する。しかし、このAlは、図2、図3に示すように、黒色保護皮膜の形成に有効であるばかりでなく、表面疵発生の抑制にも有効であるため、少なくとも0.05mass%は含有させる必要がある。しかし、その含有量があまり多くなると、図3に示すとおり、溶接時にA12O3介在物を形成してクラスターを生成し、溶接欠陥が増大するため、表面庇の原因になる。そこで、本発明では、このAlの含有量を0.25mass%未満に制限することにした。それは、上述した介在物クラスターの生成を抑制し、溶接欠陥を低減すると同時に、合金製造時の表面庇を大幅に低減させるためである。なお、このAl含有量は、0.1〜0.2mass%とすることが好ましい。
【0015】
Ti:0.2〜0.7mass%
Tiは、図2に示す放射率との関係に明らかなように、黒色保護皮膜の生成に有効な元素であり、0.2mass%以上含有しないとその効果が期待できない。しかし、このTi含有量が0.7mass%超になると、製造時に表面庇が発生し易くなる。従って、Tiの含有量は0.2〜0.7mass%と定めた。
【0016】
Al+Ti:0.8 mass%以上
AlならびTiは、上述したように、黒化性に着目したときには、共通した作用効果を示し、ときには、それらが相乗的に作用するので、これらの一方のみを制御するだけでは不十分であり、一体として制御しなければならない。即ち、放射率や表面疵の発生とAlおよびTi濃度との関係を示す図3のグラフから明らかなように、これらの元素は、ともに含有量が多くなればなるほど、製造時に表面庇が発生し易くなる。一方で、Alは耐食性を改善するために有効である。そこで、これらの知見を下に、本発明では、AlとTiの総量を規制する必要があると考え、それぞれの元素の制御とともに、Al+Ti≦0.8 mass%を満足するように合金設計を行うことにしたのである。その結果、黒化性を常に望ましいレベルに維持することができると同時に、耐食性や、さらには製造時の表面庇の発生を阻止して、高歩留で望ましい合金材料を製造することができるようになる。
【0017】
P:0.02 mass%以下
Pは、多量に含有すると熱間加工性を阻害するので、0.02 mass%以下とする。
【0018】
S:0.005 mass%以下
Sは、多量に含有すると熱間加工性を阻害するので、0.005 mass%以下とする。しかし、溶接時の湯流れを向上させる働きがあるので、好ましくは0.0003〜0.003 mass%に調整することが望ましい。
【0019】
その他の元素
本発明の合金は、上記のような成分組成を有するものであるが、上記の成分に加えて、合金の耐食性を改善する目的でMo,Cu,NbについてはMo≦1.0 mass%、Cu≦1.0 mass%、Nb≦1.0 mass%、さらに、耐酸化性を改善する目的で、Co,Ca,B,Mg,YおよびLaの中から選ばれるいずれか少なくとも1種類以上を単独、または合計で1.5 mass%以下含有させることが好ましい。これらの元素の添加は、合金材料の特性には格別に弊害を招くことなく、本発明の所期した目的を達成することができるので好ましい。
【0020】
【実施例】
表1は、本発明合金と比較合金の化学成分、ならびに放射率、表面庇、溶接性の評価結果である。
黒色保護皮膜の放射率測定は、供試材を1050 ℃で5分間、電気炉にて加熱して保護皮膜を生成させ、生成したその保護皮膜の放射率を、サーモスポットセンサー(ジャパンセンサー株式会社製)により、赤外線放射率を測定して求めた。良好な黒色保護皮膜とは、放射率の値が0.3以上のものを言う。そして、本発明でいう黒化性とは、供試材に所定の熱処理を施したときの、放射率の高い黒色保護皮膜の生成のしやすさのことである。
【0021】
表面庇は、0.5 mm厚まで圧延したときに、合金長さ1mあたりについて、欠陥長さ1mm以上の庇の発生量が2箇所以下のものを表面庇が良好と判断した。
溶接性は、0.5 mm厚の合金板に電流値60 mA、送り速度150 mm/分で長さ10 cmのTIG溶接ビードを作製し、その合金板を溶接ビード長手方向に35%引張った後、ビード上に発生した微割れの個数を数え、100μm以上の微割れが2箇所以内のものを溶接性が良好と判断した。
【0022】
この評価試験において、放射率0.3以上の優れた黒色保護皮膜を得るには、Alが0.05mass%以上、Tiが0.2mass%以上必要であることがわかった(図2)。
また、表面庇を抑制するには、Alが0.25mass%未満、Tiが0.7mass%以下に制御する必要があることがわかった(図3)。
従って、放射率0.3以上の優れた黒色保護皮膜を形成し、表面庇を抑制するには、図4に示すように、AlおよびTiの濃度を所定の範囲制御する必要があることがわかる。
【0023】
溶接部の曲げ加工時の割れは、Mn濃度に関係する。図1に示すように、35%引張り後ビードに発生した割れ個数を2以下にするには、Mn濃度を1.0%以下に制御することが有効であり、このことにより、曲げ加工による割れを抑制できることがわかる。とくに、Mn含有量は、0.5mass%、0.3mass%と低減するほど効果が大きい。
【0024】
また、表1に示す結果からわかるように、本発明に係る合金はいずれも、黒化性(照射率)に優れると共に、表面庇の発生がなく溶接割れ特性の良好なシーズヒーター被覆管用合金が得られる。これに対し、比較材は、黒化性、表面庇、溶接性のいずれか、あるいは複数の特性において本発明合金より劣っていた。
【0025】
【表1】
【0026】
【発明の効果】
以上説明したように、この発明に係る合金は、黒化性と溶接性がともに優れる他、さらには表面疵の発生が少ない点で、従来合金に比べて、シーズヒーターの被覆管用合金として好ましく、さらには安価なシースを提供するのに効果がある。
【図面の簡単な説明】
【図1】 35%引張り後、ビードに発生した割れ個数とMn濃度の関係を示すグラフである。
【図2】 放射率測定値とAl,Ti濃度の関係を示すグラフである。
【図3】 表面疵の発生量とAl,Ti濃度の関係を示すグラフである。
【図4】 本発明合金のAl,Ti濃度範囲を示すグラフである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an alloy for a sheathed tube (sheath) of a sheathed heater covered with a high emissivity black protective film.
[0002]
[Prior art]
The sheathed heater is configured by accommodating a resistance heating element in a tube (sheath) via a heat-resistant electrical insulator such as alumina + magnesium oxide and sealing the coated tube by welding. The cladding tube material (alloy) is required to be excellent in oxidation resistance, stress corrosion cracking resistance or weldability at a high temperature, for example, in a temperature range of 600 ° C. to 900 ° C. High Ni heat-resistant alloys (Ni: 20 to 80 wt%) such as NCF600 are widely used. However, this high Ni heat-resistant alloy has problems of poor workability and weldability, and is expensive and not economical. On the other hand, conventionally, various proposals for solving these problems have been made.
[0003]
For example, there is a proposal (Patent Document 1) that improves weldability by reducing the Ni concentration to 19 to 23 mass% and regulating the relationship between the Ti / C ratio and the Si and Ti concentrations. There is also a proposal (Patent Document 2) for an alloy in which the Ni concentration is reduced to 8.75 to 15.5 mass% and the amount of ferrite is controlled to improve weldability.
[0004]
[Patent Document 1]
JP 63-121641 A [Patent Document 2]
Japanese Patent Publication No. 7-103450 [0005]
[Problems to be solved by the invention]
However, since the alloy described in
[0006]
Accordingly, an object of the present invention is to propose an alloy for a sheathed tube of a sheathed heater that is excellent in both blackening property and weldability, is less prone to surface flaws, and has good workability.
[0007]
[Means for Solving the Problems]
The present invention, which was developed to solve the above-mentioned problems of the prior art and achieve the above object, is C ≦ 0.05 mass%, Si: 0.1 to 1.5 mass%, Mn: 0.05 to 1.0 mass%, Ni : 8-15 mass%, Cr: 18-23 mass%, Al: less than 0.05-0.25 mass%, Ti: 0.2-0.7 mass%, P ≦ 0.02 mass%, S ≦ 0.005 mass%, and Al Ti is an alloy for sheathed tubes of sheathed heaters that contain Al + Ti ≦ 0.8 mass % with the balance being composed of Fe and impurities .
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The basic idea behind the development of this alloy is to lower the Ni concentration to improve weldability and economy, while maintaining the blackening property and processing by controlling the Ti and Al concentrations within a suitable range. It is an object of the present invention to provide a sheath alloy that can improve and improve the properties, and can realize and maintain these characteristics in a balanced manner without sacrificing each other. The reason why the component composition of this alloy is limited as described above will be described below.
[0009]
C: 0.05 mass% or less C is an element effective for securing high-temperature strength. However, if excessively contained, Cr carbide is formed at the grain boundary and the corrosion resistance is deteriorated, so the content is limited to 0.05 mass% or less. In addition, it is desirable to suppress C content to 0.03 mass% or less.
[0010]
Si: 0.1-1.5 mass%
Si has the effect of improving the corrosion resistance in a high temperature environment where chloride is present, and is one of the essential additive elements of the alloy of the present invention. If the content is less than 0.1 mass%, a sufficient corrosion resistance improvement effect cannot be obtained in the above environment, so the content was set to 0.1 mass% or more. On the other hand, if the content exceeds 1.5 mass%, the alloy causes solidification cracking and inhibits weldability, so the Si content is determined to be 0.1 to 1.5 mass%. Preferably, the content is 0.1 to 1.0 mass%. More preferably, it is 0.1 to 0.5 mass%.
[0011]
Mn: 0.05-1.0 mass%
Mn is an element necessary for maintaining hot workability. However, if it contains more than 1.0 mass%, cracks are likely to occur in the weld during bending. On the other hand, if it is less than 0.05 mass%, cracks occur during hot working and the yield is remarkably reduced. Therefore, the component range is limited to the range of 0.05 mass% to 1.0 mass%.
In addition, it is preferable to control this Mn to 0.5 mass% or less, as is clear from the graph showing the relationship between the number of cracks generated in the bead and the Mn concentration after 35% tension shown in FIG. This is because, within this range, Mn segregation to the grain boundary during solidification is suppressed, and microcracks generated in the weld bead during bending of the sheath tube of the sheathed heater can be greatly reduced. However, if possible, the Mn content is more preferably adjusted to about 0.05 to 0.3 mass% in order to make the above-described effects more remarkable.
[0012]
Ni: 8-15 mass%
Ni is an essential component for stabilizing the austenite phase and maintaining high-temperature corrosion resistance and high-temperature strength. In this sense, Ni is contained in an amount of 8 mass% or more. However, when the Ni concentration is increased, the economic efficiency is deteriorated and the weld crack sensitivity is deteriorated. In particular, when the Ni content exceeds 15 mass%, the deterioration of weld crack sensitivity increases, so the Ni content is determined to be 8 to 15 mass%. Preferably it is 10-15 mass%.
[0013]
Cr: 18-23 mass%
Cr is an essential element for obtaining corrosion resistance. However, if its content exceeds 23 mass%, hot workability and weld cracking susceptibility deteriorate. On the other hand, if the Cr content is less than 18 mass%, sufficient corrosion resistance cannot be obtained, so the Cr content was determined to be 18-23 mass%.
[0014]
Al :: 0.05-0.25mass%
Al is one of the important elements in the present invention, and effectively acts to improve oxidation resistance. However, as shown in FIG. 2 and FIG. 3, this Al is effective not only for forming a black protective film but also for suppressing the occurrence of surface flaws, so it is necessary to contain at least 0.05 mass%. There is. However, if the content is excessively large , as shown in FIG. 3, A1 2 O 3 inclusions are formed during welding to form clusters and increase the number of welding defects, which causes surface defects. Therefore, in the present invention, the Al content is limited to less than 0.25 mass%. The reason for this is to suppress the formation of the inclusion clusters described above, reduce welding defects, and at the same time, greatly reduce the surface defects during alloy production. In addition, it is preferable that this Al content shall be 0.1-0.2 mass%.
[0015]
Ti: 0.2-0.7mass%
As is clear from the relationship with the emissivity shown in FIG. 2, Ti is an element effective for the formation of a black protective film, and its effect cannot be expected unless it is contained by 0.2 mass% or more. However, if this Ti content exceeds 0.7 mass%, surface flaws are likely to occur during production. Therefore, the Ti content is 0.2-0. 7 mass% was determined.
[0016]
Al + Ti: 0.8 mass% or more
As described above, Al and Ti show a common effect when focusing on blackening properties, and sometimes they act synergistically, so it is not sufficient to control only one of these, It must be controlled as a unit. That is, as apparent from the graph of FIG. 3 showing the relationship between the emissivity and the generation of surface flaws and the Al and Ti concentrations, the higher the content of both of these elements, the more the surface flaws are generated during production. It becomes easy. On the other hand, Al is effective for improving the corrosion resistance. Therefore, based on these findings, the present invention considers that it is necessary to regulate the total amount of Al and Ti, and along with the control of each element, to design an alloy to satisfy Al + Ti ≦ 0.8 mass% It was. As a result, the blackening property can always be maintained at a desirable level, and at the same time, the desired alloy material can be produced at a high yield by preventing the occurrence of corrosion resistance and surface flaws during the production. become.
[0017]
P: 0.02 mass% or less P is 0.02 mass% or less because hot workability is impaired when contained in a large amount.
[0018]
S: 0.005 mass% or less S contains 0.005 mass% or less because a large amount of S inhibits hot workability. However, since it has the function of improving the hot water flow during welding, it is desirable to adjust to 0.0003 to 0.003 mass%.
[0019]
Other Elements The alloy of the present invention has the above component composition. In addition to the above components, Mo, Cu, and Nb for the purpose of improving the corrosion resistance of the alloy, Mo ≦ 1.0 mass%, Cu ≦ 1.0 mass%, Nb ≦ 1.0 mass%, and for the purpose of improving oxidation resistance, at least one selected from Co, Ca, B, Mg, Y and La alone or in total It is preferable to contain 1.5 mass% or less. The addition of these elements is preferable because the intended purpose of the present invention can be achieved without causing any particular adverse effect on the characteristics of the alloy material.
[0020]
【Example】
Table 1 shows the evaluation results of the chemical composition, emissivity, surface defects, and weldability of the alloy of the present invention and the comparative alloy.
The emissivity measurement of the black protective coating was performed by heating the test material at 1050 ° C. for 5 minutes in an electric furnace to form a protective coating, and the emissivity of the generated protective coating was measured using a thermo spot sensor (Japan Sensor Co., Ltd.). Infrared emissivity was measured and obtained. A good black protective film is one having an emissivity value of 0.3 or more. And the blackening property as used in the field of this invention is the ease of producing | generating a black protective film with a high emissivity when a test material is given predetermined heat processing.
[0021]
When the surface defects were rolled to a thickness of 0.5 mm, it was judged that the surface defects were good when the number of defects having a defect length of 1 mm or more was 2 or less per 1 m of the alloy length.
Weldability is as follows: A TIG weld bead with a length of 10 cm was produced on a 0.5 mm thick alloy plate at a current value of 60 mA and a feed rate of 150 mm / min, and the alloy plate was pulled 35% in the longitudinal direction of the weld bead. The number of fine cracks generated on the bead was counted, and those having fine cracks of 100 μm or more within two places were judged to have good weldability.
[0022]
In this evaluation test, it was found that in order to obtain an excellent black protective film having an emissivity of 0.3 or more, Al needs to be 0.05 mass% or more and Ti needs to be 0.2 mass% or more (FIG. 2 ).
Moreover, in order to suppress surface flaws, it was found that Al must be controlled to be less than 0.25 mass% and Ti must be controlled to 0.7 mass% or less (FIG. 3 ).
Therefore, to form a good black protective coating over emissivity 0.3, in order to suppress surface eaves, it can be seen that as shown in FIG. 4, it is necessary to control the range of the concentrations of Al and Ti in a predetermined.
[0023]
Cracks during bending of the weld are related to the Mn concentration. As shown in Fig. 1 , it is effective to control the Mn concentration to 1.0% or less in order to reduce the number of cracks generated in the bead after 35% pulling to 2 or less. I understand that I can do it. In particular, the effect is greater as the Mn content is reduced to 0.5 mass% and 0.3 mass%.
[0024]
In addition, as can be seen from the results shown in Table 1, all the alloys according to the present invention are excellent in blackening property (irradiation rate), have no surface flaws, and have excellent weld cracking characteristics. can get. On the other hand, the comparative material was inferior to the alloy of the present invention in any of blackening properties, surface defects, weldability, or a plurality of characteristics.
[0025]
[Table 1]
[0026]
【The invention's effect】
As described above, the alloy according to the present invention is preferable as a cladding tube alloy for a sheathed heater in comparison with a conventional alloy, in addition to being excellent in both blackening and weldability, and further having less surface defects. Furthermore, it is effective in providing an inexpensive sheath.
[Brief description of the drawings]
FIG. 1 is a graph showing the relationship between the number of cracks generated in a bead and the Mn concentration after 35% tension.
FIG. 2 is a graph showing the relationship between emissivity measurement values and Al and Ti concentrations.
FIG. 3 is a graph showing the relationship between the generation amount of surface flaws and Al and Ti concentrations.
FIG. 4 is a graph showing Al and Ti concentration ranges of the alloy of the present invention.
Claims (1)
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JP6875593B1 (en) | 2020-12-23 | 2021-05-26 | 日本冶金工業株式会社 | Fe-Ni-Cr alloy with excellent corrosion resistance, weldability, and oxidation resistance and its manufacturing method |
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