JP2018094620A - Stainless steel material for diffusion joining jig - Google Patents

Stainless steel material for diffusion joining jig Download PDF

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JP2018094620A
JP2018094620A JP2016244820A JP2016244820A JP2018094620A JP 2018094620 A JP2018094620 A JP 2018094620A JP 2016244820 A JP2016244820 A JP 2016244820A JP 2016244820 A JP2016244820 A JP 2016244820A JP 2018094620 A JP2018094620 A JP 2018094620A
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JP7033847B2 (en
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芳明 堀
Yoshiaki Hori
芳明 堀
一成 今川
Kazunari Imagawa
一成 今川
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Nippon Steel Nisshin Co Ltd
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Abstract

PROBLEM TO BE SOLVED: To provide a stainless steel material for a diffusion joining jig, that suppresses deformation of materials to be joint while maintaining a diffusion joinability of the materials to be joint, and that is superior in releasability (detachability of the materials to be joint and a release member) after diffusion joining treatment.SOLUTION: Provided is a stainless steel material for a diffusion joining jig, which is a stainless steel material containing Si by 1.5 mass% or more, and in which a ratio (Fr/Fp) is 0.9 or higher between high temperature strength (Fr) of the stainless steel material at 1000°C and high temperature strength (Fp) at 1000°C of the materials to be joint by diffusion joining, and which is superior in deformation inhibition and detachability. The stainless steel material preferably comprises a composition containing, in mass%: 0.1% or less of C; 1.5-5.0% of Si; 2.5% or less of Mn; 0.06% or less of P; 0.02% or less of S; 8.0-15.0% of Ni; 13.0-23.0% of Cr; 0.2% or less of N; and the remainder consisting of Fe and inevitable impurities.SELECTED DRAWING: Figure 1

Description

本発明は、変形抑制および離型性に優れた拡散接合治具用ステンレス鋼材に関する。また、本発明は、拡散接合による製造方法に適した離型部材に関する。   The present invention relates to a stainless steel material for a diffusion bonding jig excellent in deformation suppression and releasability. The present invention also relates to a release member suitable for a manufacturing method using diffusion bonding.

熱交換器には、種々のタイプのものが存在する。そのうち、プレート式熱交換器(平板型熱交換器)は、熱交換性能が高く、設置や保守点検が容易であるため、電気給湯機、産業用機器、自動車の空調装置等に広く使用されている。プレート式熱交換器は、複数の金属薄板(プレート)を重ね合わせた構造を備えており、積層したプレート間で高温媒体の通路と低温媒体の通路とを交互に隣接して形成し、個々のプレートを介して高温媒体と低温媒体との間で熱交換作用を行うように構成されている。   There are various types of heat exchangers. Among them, plate heat exchangers (flat plate heat exchangers) are widely used in electric water heaters, industrial equipment, automotive air conditioners, etc. because of their high heat exchange performance and easy installation and maintenance. Yes. The plate heat exchanger has a structure in which a plurality of thin metal plates (plates) are stacked, and a hot medium passage and a cold medium passage are alternately formed adjacent to each other between the stacked plates. A heat exchange action is performed between the high temperature medium and the low temperature medium through the plate.

複数のプレートを積層させて組み立てる方法としては、例えば、特許文献1には、ガスケットとネジによる締結、溶接、ろう付け等の接合方法が記載されている。小中型の熱交換器については、耐圧性を考慮して、ろう付けで接合されることが多い。しかしながら、波形状が付与されたプレートを積層し、ろう付けで接合すると、接合時に生じる溶損、ろう部の割れ、溶融したろうによる流路埋没等、ろう材特有の接合不具合が生じる場合がある。   As a method of stacking and assembling a plurality of plates, for example, Patent Document 1 describes a joining method such as fastening with a gasket and a screw, welding, brazing, or the like. Small and medium-sized heat exchangers are often joined by brazing in consideration of pressure resistance. However, if plates with corrugated shapes are stacked and joined by brazing, there may be cases where joining problems peculiar to brazing materials occur, such as melting damage during cracking, cracking of the brazing part, channel burial due to molten brazing, etc. .

そこで、ろう付け法に替えて、拡散接合法の適用が検討されている。拡散接合は、真空または不活性雰囲気中の高温圧力下で接合界面に生じる母材原子の相互拡散を利用して接合する方法である。拡散接合された接合部は、母材なみの強度および耐食性が得られる。   Therefore, the application of a diffusion bonding method instead of the brazing method has been studied. Diffusion bonding is a method of bonding by utilizing mutual diffusion of base material atoms generated at a bonding interface under a high temperature pressure in a vacuum or an inert atmosphere. The joint part that has been diffusion-bonded has the same strength and corrosion resistance as the base material.

拡散接合を行うときは、積層した被接合部材を加圧手段で押圧し、加圧された状態を所定時間保持する。被接合部材と加圧手段との間には、当て板やスペーサ等の離型部材を挟んで拡散接合することがある。この離型部材としては、拡散接合時の温度に対して耐熱性があって破損しないことが求められるので、カーボン材が使用される。例えば、特許文献2には、弾力性を有するカーボンシートを用いた拡散接合手段が記載されている。   When performing diffusion bonding, the stacked members to be bonded are pressed by a pressing means, and the pressed state is held for a predetermined time. In some cases, diffusion bonding is performed between a member to be bonded and a pressurizing unit with a release member such as a contact plate or a spacer interposed therebetween. As the mold release member, a carbon material is used because it is required to have heat resistance against the temperature during diffusion bonding and not to be damaged. For example, Patent Document 2 describes diffusion bonding means using a carbon sheet having elasticity.

特開2010−85094号公報JP 2010-85094 A 特開2014−128815号公報JP 2014-128815 A

ところで、熱交換器の耐久性向上の観点から、金属板として耐食性に優れたステンレス鋼板が用いられている。ステンレス鋼板からなるプレート材を積層させて拡散接合させるとき、プレート材に隣接する離型部材としてカーボン材を用いると、ステンレス鋼とカーボンとの反応が生じるため、拡散接合処理を完了した後、プレート材から離型部材を取り外すことが難しくなり、両部材の離型性が低下する。また、ステンレス鋼中にカーボンが浸透する浸炭に起因して、プレート材の耐食性が低下したり、プレート材の表面粗さが大きくなって表面性状が低下するという問題があった。   By the way, from the viewpoint of improving the durability of the heat exchanger, a stainless steel plate having excellent corrosion resistance is used as a metal plate. When laminating plate materials made of stainless steel plates for diffusion bonding, if a carbon material is used as a release member adjacent to the plate material, the reaction between stainless steel and carbon occurs, so after completing the diffusion bonding process, the plate It becomes difficult to remove the release member from the material, and the release properties of both members are lowered. Further, due to the carburization of carbon permeating into the stainless steel, there is a problem that the corrosion resistance of the plate material is lowered, or the surface roughness of the plate material is increased and the surface properties are lowered.

また、拡散接合では、ホットプレス装置等を用いて、被接合材に加圧および加熱を施すことが必要であるため、被接合材のプレートは、高圧および高温下に保持される。また、熱交換器の本体内に流路を形成するプレート材は、流路側に非接合面の部分を有するので、他のプレート材に比べて周囲から拘束される程度が小さい(図3の(A)を参照)。そのため、例えば図3の(B)に示すように、拡散接合処理の加熱により、上記の非接合面部分においてプレート材を流路側へ膨張させる熱変形が起きることがあり、その熱膨張の程度によっては、拡散接合処理の完了後に冷却しても、変形部分が復元しないという問題があった。   In addition, in diffusion bonding, it is necessary to apply pressure and heat to a material to be bonded using a hot press apparatus or the like, and therefore the plate of the material to be bonded is held under high pressure and high temperature. In addition, the plate material that forms the flow channel in the main body of the heat exchanger has a non-joint surface portion on the flow channel side, and therefore is less constrained from the surroundings than other plate materials ((( See A)). Therefore, for example, as shown in FIG. 3 (B), the heat of the diffusion bonding process may cause thermal deformation that causes the plate material to expand to the flow path side at the non-bonding surface portion, depending on the degree of the thermal expansion. However, even after cooling after completion of the diffusion bonding process, there was a problem that the deformed portion was not restored.

本発明は、上記のような問題点を解決するために案出されたものである。被接合材の拡散接合性を維持したまま、被接合材の変形が抑制され、拡散接合処理後の離型性(被接合材と離型部材との剥離性)に優れる拡散接合治具用ステンレス鋼材を提供することを目的とする。   The present invention has been devised to solve the above problems. Stainless steel for diffusion bonding jigs that suppresses deformation of the material to be bonded while maintaining the diffusion bonding property of the material to be bonded, and has excellent releasability after the diffusion bonding process (peelability between the material to be bonded and the release member). The purpose is to provide steel.

本発明者らは、被接合材(プレート材)に直接接触する離型部材の材質や特性に着目した。離型部材の構成材料として、被接合材と反応しない材質であって、拡散接合後の変形抑制に適した材質を選択することにより、上記の目的を達成できることを見出し、本発明を完成するに至った。具体的には、本発明は、以下のものを提供する。   The inventors paid attention to the material and characteristics of the release member that is in direct contact with the material to be joined (plate material). As a constituent material of the release member, it is found that the above object can be achieved by selecting a material that does not react with the material to be joined and is suitable for suppressing deformation after diffusion joining, and the present invention is completed. It came. Specifically, the present invention provides the following.

(1)本発明は、Siを1.5質量%以上含有するステンレス鋼材であって、前記ステンレス鋼材の1000℃における高温強度(Fr)と拡散接合によって接合される被接合材の1000℃における高温強度(Fp)との比(Fr/Fp)が0.9以上である、変形抑制および離型性に優れた拡散接合治具用ステンレス鋼材である。 (1) The present invention is a stainless steel material containing 1.5 mass% or more of Si, and the high temperature strength (Fr) of the stainless steel material at 1000 ° C. and the high temperature at 1000 ° C. of the materials to be joined by diffusion bonding. It is a stainless steel material for a diffusion bonding jig having a ratio (Fr / Fp) to strength (Fp) of 0.9 or more and excellent deformation control and releasability.

(2)本発明は、前記ステンレス鋼材は、C:0.1質量%以下、Si:1.5〜5.0質量%、Mn:2.5質量%以下、P:0.06質量%以下、S:0.02質量%以下、Ni:8.0〜15.0質量%、Cr:13.0〜23.0質量%、N:0.2質量%以下を含み、残部がFeおよび不可避的不純物からなる組成を有する、上記(1)に記載の変形抑制および離型性に優れた拡散接合治具用ステンレス鋼材である。 (2) In the present invention, the stainless steel material is C: 0.1% by mass or less, Si: 1.5 to 5.0% by mass, Mn: 2.5% by mass or less, P: 0.06% by mass or less. S: 0.02% by mass or less, Ni: 8.0-15.0% by mass, Cr: 13.0-23.0% by mass, N: 0.2% by mass or less, with the balance being Fe and inevitable The stainless steel material for a diffusion bonding jig having excellent composition for suppressing deformation and releasability according to the above (1), which has a composition composed of mechanical impurities.

(3)本発明は、前記ステンレス鋼材は、さらに、Mo:3.0質量%以下、Cu:4.0質量%以下、Nb:0.8質量%以下、Ti:0.5質量%以下、V:1.0質量%以下、B:0.02質量%以下から選択される1種以上を含む、上記(2)に記載の変形抑制および離型性に優れた拡散接合治具用ステンレス鋼材である。 (3) In the present invention, the stainless steel material further includes Mo: 3.0 mass% or less, Cu: 4.0 mass% or less, Nb: 0.8 mass% or less, Ti: 0.5 mass% or less, V: 1.0 mass% or less, B: One or more types selected from 0.02 mass% or less, and the stainless steel material for a diffusion bonding jig excellent in deformation suppression and releasability according to (2) above It is.

(4)本発明は、前記ステンレス鋼材は、さらに、Al:0.2質量%以下、REM:0.2質量%以下、Y:0.2質量%以下、Ca:0.1質量%以下、Mg:0.1質量%以下から選択される1種以上を含む、上記(2)または(3)に記載の変形抑制および離型性に優れた拡散接合治具用ステンレス鋼材である。 (4) In the present invention, the stainless steel material further includes Al: 0.2% by mass or less, REM: 0.2% by mass or less, Y: 0.2% by mass or less, Ca: 0.1% by mass or less, Mg: The stainless steel material for a diffusion bonding jig according to (2) or (3), which includes one or more selected from 0.1% by mass or less and excellent in deformation suppression and releasability.

(5)本発明は、上記(1)〜(4)のいずれかに記載のステンレス鋼材で構成された離型部材である。 (5) This invention is a mold release member comprised with the stainless steel material in any one of said (1)-(4).

本発明は、上記の構成を備える被接合材と離型部材との組み合わせを使用することにより、被接合材の拡散接合性を維持したまま、被接合材の変形が抑制され、拡散接合処理をした後の離型性に優れる拡散接合治具用ステンレス鋼材を提供することができる。   By using a combination of a material to be bonded and a release member having the above-described configuration, the present invention suppresses the deformation of the material to be bonded while maintaining the diffusion bonding property of the material to be bonded. Thus, it is possible to provide a stainless steel material for a diffusion bonding jig that is excellent in releasability after being applied.

ホットプレス装置内での被接合材の実施形態を説明するための模式図である。It is a schematic diagram for demonstrating embodiment of the to-be-joined material in a hot press apparatus. 実施例における拡散接合処理の加熱および冷却のパターンを示す図である。It is a figure which shows the pattern of the heating and cooling of the diffusion bonding process in an Example. 実施例における変形量の測定方法を説明するための模式図である。(A)は、拡散接合前の試験組立体をセットした状態を示す図であり、(B)は、拡散接合後のプレート材が変形した状態を示す図である。It is a schematic diagram for demonstrating the measuring method of the deformation amount in an Example. (A) is a figure which shows the state which set the test assembly before diffusion joining, (B) is a figure which shows the state which the plate material after diffusion joining deform | transformed. 実施例における離型性に関する測定方法を説明するための模式図である。It is a schematic diagram for demonstrating the measuring method regarding the mold release property in an Example.

以下、本発明の実施形態について説明する。本発明は、これらの記載により限定されるものではない。   Hereinafter, embodiments of the present invention will be described. The present invention is not limited by these descriptions.

本実施形態は、ステンレス鋼からなる複数の被接合材を積層し、加熱及び加圧を行い、前記被接合材を拡散接合させる熱交換器の製造方法において使用される拡散接合用治具に関する。上記の製造方法は、前記被接合材の両面に離型部材を配置するとともに、前記離型部材を介して前記被接合材を挟むように押え治具を配置した後、前記押え治具を介して加圧装置で押圧することにより、被接合材であるプレート材を拡散接合させて熱交換器を製造するものである。本実施形態では、拡散接合用治具の離型部材をプレート材と押え治具との間に配置している。   The present embodiment relates to a diffusion bonding jig used in a method of manufacturing a heat exchanger in which a plurality of materials to be bonded made of stainless steel are stacked, heated and pressurized, and diffusion bonded to the materials to be bonded. In the manufacturing method described above, a release member is disposed on both surfaces of the material to be bonded, a press jig is disposed so as to sandwich the material to be bonded via the release member, and then the press jig is interposed. By pressing with a pressurizing device, the plate material, which is the material to be joined, is diffused and joined to produce a heat exchanger. In this embodiment, the release member of the diffusion bonding jig is disposed between the plate material and the holding jig.

(被接合材)
図1に拡散接合の処理に供される被接合材に関する概要を示す。拡散接合を行う装置としては、所定の雰囲気内で加圧及び加熱を行うことができるホットプレス装置等が用いられる。拡散接合される被接合材(プレート材)は、複数枚のプレート材を重ねて積層された積層体として用意され、加圧加熱装置内に装填される。そして、当該積層体の両面に接するように離型部材が配置される。図1は、4枚のプレート材1を重ねたプレート積層体2を用いた例である。加圧加熱装置内では、プレート積層体2の外側に配置した2枚の離型部材3のそれぞれと接するように押え治具4が配置される。当該押え治具4は、加圧装置の加圧軸5に連結されている。加圧機構(図示なし)を作動すると、加圧軸5を通じて押え治具4がプレート積層体2を挟み込むように押圧し、プレート材1に対して所定の圧力が加わり、加圧状態が所定時間保持される。真空または不活性雰囲気を保持する加圧加熱装置内では、被接合材の上記プレート積層体2に所定条件で加圧と加熱が施されて、プレート材1は拡散接合される。なお、プレート材は、4枚に限られない。複数個のプレート積層体を用いて、各プレート積層体の間に離型部材を挿入した組立体を接合してもよい。また、図1に示したプレート材1は、内側の2枚に流路(図示しない)を設けているため、外側の2枚よりも厚みが大きくなっている。流路の組み合わせについても図1に示した構造に限られない。
(Material to be joined)
FIG. 1 shows an outline of a material to be joined to be subjected to diffusion bonding processing. As an apparatus for performing diffusion bonding, a hot press apparatus that can perform pressurization and heating in a predetermined atmosphere is used. A material to be bonded (plate material) to be diffusion-bonded is prepared as a stacked body in which a plurality of plate materials are stacked and loaded into a pressure heating apparatus. And a release member is arrange | positioned so that both surfaces of the said laminated body may be contact | connected. FIG. 1 shows an example using a plate laminate 2 in which four plate materials 1 are stacked. In the pressure heating apparatus, the holding jig 4 is arranged so as to be in contact with each of the two release members 3 arranged outside the plate laminate 2. The pressing jig 4 is connected to the pressing shaft 5 of the pressing device. When a pressurizing mechanism (not shown) is operated, the presser jig 4 presses the plate stack 2 through the pressurizing shaft 5, a predetermined pressure is applied to the plate material 1, and the pressurization state is maintained for a predetermined time. Retained. In a pressurizing and heating apparatus that maintains a vacuum or an inert atmosphere, the plate laminate 2 of the material to be joined is pressurized and heated under predetermined conditions, and the plate material 1 is diffusion bonded. The plate material is not limited to four. You may join the assembly which inserted the mold release member between each plate laminated body using several plate laminated body. Further, since the plate material 1 shown in FIG. 1 is provided with a flow path (not shown) in the two inner sheets, the thickness is larger than the two outer sheets. The combination of the flow paths is not limited to the structure shown in FIG.

加圧装置は、サーボ、バネ、錘等の加圧機構を備えたものであればよい。拡散接合後に被接合材と離型部材とを容易に取り外すことができるように、拡散接合する前に離型部材の表面に離型剤を塗布してもよい。   The pressurizing device may be any device provided with a pressurizing mechanism such as a servo, a spring, or a weight. A release agent may be applied to the surface of the release member before diffusion bonding so that the material to be joined and the release member can be easily removed after diffusion bonding.

複数のプレート材が積層されてなる熱交換器は、プレート材によって形成された細い流路を流体が通過し、各プレート材を介して高温側流体と低温側流体との間で熱交換が行なわれる。そのため、プレート材には高温域における機械的強度(高温強度)と耐食性が良好であることが要求される。その観点から、本実施形態は、耐熱性と耐久性に優れるステンレス鋼をプレート材に使用している。また、熱交換性能を高める上で薄板形状とすることが望ましい。   In a heat exchanger in which a plurality of plate materials are stacked, the fluid passes through a narrow flow path formed by the plate materials, and heat exchange is performed between the high temperature side fluid and the low temperature side fluid via each plate material. It is. Therefore, the plate material is required to have good mechanical strength (high temperature strength) and corrosion resistance in a high temperature range. From this point of view, this embodiment uses stainless steel having excellent heat resistance and durability for the plate material. Moreover, it is desirable to use a thin plate shape in order to improve the heat exchange performance.

(離型部材)
本実施形態は、Siを1.5質量%以上含有する鋼材で構成された離型部材を使用することが好ましい。離型部材は、拡散接合時の被接合材と接して高温高圧下に置かれているから、高温での破損や腐食が少ないこと、被接合材と反応しないこと等が求められる。本実施形態に係る離型部材は、被接合材との反応を抑制する観点から、Si含有量の多い鋼材を用いて構成することが好ましい。
(Release member)
In the present embodiment, it is preferable to use a release member made of a steel material containing 1.5% by mass or more of Si. Since the release member is placed under high temperature and high pressure in contact with the material to be bonded at the time of diffusion bonding, it is required that there is little damage or corrosion at high temperature and that it does not react with the material to be bonded. The release member according to the present embodiment is preferably configured using a steel material having a high Si content from the viewpoint of suppressing the reaction with the material to be joined.

(Si含有量)
本実施形態に係る離型部材は、Siを1.5質量%以上含有する鋼材を含むものである。Siは、易酸化元素であり、離型部材の表面に強固な酸化膜を形成する。このSi酸化膜を介して離型部材の母材と被接合材とが接触するので、離型部材と被接合材との界面における反応が阻害される。このSi酸化膜の形成により、両方の部材間での接着や界面反応が抑制されるので、拡散接合処理が終了した後に、被接合材から離型部材を小さな引き離し力で容易に取り除くことができる。また、離型部材の含有成分が被接合材の内部に浸透することも上記のSi酸化膜によって阻害されるため、被接合材のステンレス鋼が有する良好な耐熱性や耐食性を維持されるとともに、平滑な表面性状が維持される。このような観点から、離型部材は、Siを1.5質量%以上含有する鋼材を含むことが好ましい。
(Si content)
The release member according to the present embodiment includes a steel material containing 1.5 mass% or more of Si. Si is an easily oxidizable element and forms a strong oxide film on the surface of the release member. Since the base material of the release member and the material to be joined are in contact with each other via the Si oxide film, the reaction at the interface between the release member and the material to be joined is inhibited. By forming this Si oxide film, adhesion and interface reaction between both members are suppressed, so that after the diffusion bonding process is completed, the release member can be easily removed from the material to be bonded with a small pulling force. . In addition, since the above-described Si oxide film also inhibits the components contained in the release member from penetrating into the material to be joined, while maintaining good heat resistance and corrosion resistance of the stainless steel to be joined, Smooth surface texture is maintained. From such a viewpoint, it is preferable that the release member includes a steel material containing 1.5% by mass or more of Si.

また、離型部材の表面にSi酸化膜が形成されても、外的負荷や熱的膨張収縮等による離型部材の形状変化が過大であると、当該酸化膜の部分的破壊が生じる可能性がある。そのときは、被接合材と離型部材とは、当該酸化膜を介さないで密着する箇所が生じるため、両部材の離型性が低下する恐れがある。その観点からも安定で強固な酸化膜を形成できるように、一定以上のSi量を含有する鋼材を離型部材に適用することが望ましい。   In addition, even if a Si oxide film is formed on the surface of the release member, if the shape change of the release member due to an external load or thermal expansion / contraction is excessive, partial destruction of the oxide film may occur. There is. In that case, since the part which adhere | attaches a to-be-joined material and a mold release member without interposing the said oxide film arises, there exists a possibility that the mold release property of both members may fall. From this point of view, it is desirable to apply a steel material containing a certain amount or more of Si to the release member so that a stable and strong oxide film can be formed.

高温環境における機械的強度や耐食性を考慮すると、本実施形態に係る離型部材の構成材料は、耐熱性、耐久性、成形性等に優れるオーステナイト系ステンレス鋼材が好適であり、具体的には、次の組成を有する鋼材を使用できる。   Considering the mechanical strength and corrosion resistance in a high temperature environment, the constituent material of the release member according to this embodiment is preferably an austenitic stainless steel material having excellent heat resistance, durability, formability, etc. A steel material having the following composition can be used.

(1)C:0.1質量%以下、Si:1.5〜5.0質量%、Mn:2.5質量%以下、P:0.06質量%以下、S:0.02質量%以下、Ni:8.0〜15.0質量%、Cr:13.0〜23.0質量%、N:0.2質量%以下を含み、残部がFeおよび不可避的不純物からなるステンレス鋼材。   (1) C: 0.1 mass% or less, Si: 1.5-5.0 mass%, Mn: 2.5 mass% or less, P: 0.06 mass% or less, S: 0.02 mass% or less , Ni: 8.0 to 15.0% by mass, Cr: 13.0 to 23.0% by mass, N: 0.2% by mass or less, with the balance being Fe and inevitable impurities.

(2)さらに、上記(1)の組成に、Mo:3.0質量%以下,Cu:4.0質量%以下、Nb:0.8質量%以下、Ti:0.5質量%以下、V:1.0質量%以下、B:0.02質量%以下から選択される1種以上を含むステンレス鋼材。   (2) Further, in the composition of (1), Mo: 3.0% by mass or less, Cu: 4.0% by mass or less, Nb: 0.8% by mass or less, Ti: 0.5% by mass or less, V : Stainless steel material containing 1 or more types selected from 1.0 mass% or less and B: 0.02 mass% or less.

(3)さらに上記(1)または(2)の組成に、Al:0.2質量%以下、REM:0.2質量%以下、Y:0.2質量%以下、Ca:0.1質量%以下、Mg:0.1質量%以下から選択される1種以上を含むステンレス鋼材。   (3) Further, in the composition of (1) or (2), Al: 0.2% by mass or less, REM: 0.2% by mass or less, Y: 0.2% by mass or less, Ca: 0.1% by mass Hereinafter, Mg: a stainless steel material containing at least one selected from 0.1% by mass or less.

上記のステンレス鋼材の含有成分について説明する。   The components contained in the above stainless steel material will be described.

Cは、固溶強化により鋼の強度、硬さを向上させる。他方、C含有量が多くなると、鋼の加工性、靱性を低下させるため、C含有量は、0.1質量%以下が好ましい。   C improves the strength and hardness of steel by solid solution strengthening. On the other hand, when the C content is increased, the workability and toughness of the steel are lowered, so the C content is preferably 0.1% by mass or less.

Siは、上述したとおり、離型部材表面において強固な酸化膜を形成させるために配合され、1.5質量%以上含有することが好ましい。形成されたSi酸化膜により、離型部材と被接合材との界面における反応が阻害されるので、拡散接合後に被接合材から離型部材を小さな引き離し力で容易に取り除くことができる。また、Si酸化膜により、離型部材の含有成分が被接合材の内部に浸透することが阻害されるので、被接合材が有する良好な耐熱性や耐食性が維持されるとともに、平滑な表面性状が維持される。Si含有量が1.5質量%未満であると、酸化膜形成による上記の効果を十分に得られない。なお、5.0質量%を超えて添加しても、上記の効果がほぼ飽和する一方で、硬化により適度な加工性が得られなくなるので、5.0質量%以下で含有すればよい。   As described above, Si is blended in order to form a strong oxide film on the surface of the release member, and is preferably contained in an amount of 1.5% by mass or more. Since the reaction at the interface between the release member and the material to be joined is inhibited by the formed Si oxide film, the release member can be easily removed from the material to be joined with a small pulling force after diffusion bonding. In addition, the Si oxide film prevents the components contained in the release member from penetrating into the material to be joined, so that the good heat resistance and corrosion resistance of the material to be joined are maintained, and smooth surface properties are maintained. Is maintained. When the Si content is less than 1.5% by mass, the above-described effect due to the formation of the oxide film cannot be sufficiently obtained. In addition, even if it adds exceeding 5.0 mass%, while said effect will be substantially saturated, moderate workability will not be acquired by hardening, Therefore It should just contain 5.0 mass% or less.

Mnは、高温酸化特性を向上させる元素である。過多に含有されると、加工硬化して加工性を低下させるため、Mn含有量は、2.5質量%以下が好ましい。   Mn is an element that improves high-temperature oxidation characteristics. If contained in excess, the Mn content is preferably 2.5% by mass or less in order to reduce workability by work hardening.

Crは、不働態被膜を形成して耐食性を付与する元素であり、耐食性の向上をもたらす。13.0質量%未満では、その効果が十分でない。23.0質量%を超えると、加工性が低下する。そのため、Cr含有量は、13.0〜23.0質量%が好ましい。   Cr is an element that forms a passive film and imparts corrosion resistance, and improves corrosion resistance. If it is less than 13.0% by mass, the effect is not sufficient. When it exceeds 23.0 mass%, workability will fall. Therefore, the Cr content is preferably 13.0 to 23.0% by mass.

Niは、オーステナイト相を安定化して耐食性を維持するに必須の元素であり、加工性にも効果的である。8.0質量%未満では、これらの効果が十分でなく、また、15.0質量%を超えると、その効果が飽和しコスト高となることから、Ni含有量は、8.0〜15.0質量%が好ましい。   Ni is an essential element for stabilizing the austenite phase and maintaining the corrosion resistance, and is also effective for workability. If the amount is less than 8.0% by mass, these effects are not sufficient. If the amount exceeds 15.0% by mass, the effect is saturated and the cost is high, so the Ni content is 8.0 to 15. 0% by mass is preferred.

PおよびSは、不可避的不純物として混入する。その含有量は、低いほど望ましく、加工性や材料特性に悪影響を与えない範囲で、P含有量が0.06質量%以下、S含有量が、0.02質量%以下がそれぞれ好ましい。   P and S are mixed as inevitable impurities. The lower the content, the better, and the P content is preferably 0.06% by mass or less and the S content is preferably 0.02% by mass or less as long as the workability and material properties are not adversely affected.

Nは、オーステナイト安定元素として有効であり、さらにCr、Niとともに、ステンレス鋼の高温強度、耐食性を向上させる。一方で、過剰に添加すると、製造性を低下させることから、N含有量は、0.2質量%以下が好ましい。   N is effective as an austenite stable element, and improves the high-temperature strength and corrosion resistance of stainless steel together with Cr and Ni. On the other hand, if added excessively, the productivity is lowered, so the N content is preferably 0.2% by mass or less.

Mo、Cuは、高温強度、耐食性の向上に寄与する元素である。Mo含有量、Cu含有量は、いずれも0.02質量%以上が好ましい。一方で、Moを過多に含有させると、フェライト相を形成して加工性を低下させる可能性があるので、Mo含有量は、3.0質量%以下が好ましい。Cuを過多に含有させると、熱間加工性を低下させる要因となるので、Cu含有量は、4.0質量%以下が好ましい。   Mo and Cu are elements that contribute to improvement in high-temperature strength and corrosion resistance. Both the Mo content and the Cu content are preferably 0.02% by mass or more. On the other hand, if Mo is excessively contained, there is a possibility that the ferrite phase is formed and the workability is lowered. Therefore, the Mo content is preferably 3.0% by mass or less. If Cu is excessively contained, it causes a decrease in hot workability, so the Cu content is preferably 4.0% by mass or less.

Nb、Ti、Vは、高温強度の向上に有効である。Nb含有量は、0.01質量%以上が好ましく、Ti含有量は、0.01質量%以上が好ましく、V含有量は、0.01質量%以上が好ましい。一方で、各元素を過多に含有させると、加工性を低下させるので、Nb含有量は、0.8質量%以下が好ましく、Ti含有量は、0.5質量%以下が好ましく、V含有量は、1.0質量%以下が好ましい。   Nb, Ti, and V are effective in improving the high temperature strength. The Nb content is preferably 0.01% by mass or more, the Ti content is preferably 0.01% by mass or more, and the V content is preferably 0.01% by mass or more. On the other hand, if each element is contained excessively, the workability is lowered, so the Nb content is preferably 0.8% by mass or less, the Ti content is preferably 0.5% by mass or less, and the V content. Is preferably 1.0% by mass or less.

Bは、熱間加工性を改善する元素である。B含有量は、0.0002質量%以上が好ましい。一方で、過多に添加すると、ホウ化物が析出し、加工性を低下させるので、B含有量は、0.02質量%以下が好ましい。   B is an element that improves hot workability. The B content is preferably 0.0002% by mass or more. On the other hand, if added excessively, boride precipitates and deteriorates workability, so the B content is preferably 0.02% by mass or less.

Mo、Cu、Nb、Ti、VおよびBから選択される1種以上を添加してもよい。   One or more selected from Mo, Cu, Nb, Ti, V and B may be added.

Al、REM(希土類元素)、Y、Ca、Mgは、耐高温酸化性の向上に有効であり、これらの元素から選択される1種以上を添加してもよい。Al含有量は、0.001質量%以上が好ましく、REM含有量は、0.001質量%以上が好ましく、Y含有量は、0.0002質量%以上が好ましく、Ca含有量は、0.0002質量%以上が好ましく、Mg含有量は、0.0002質量%以上が好ましい。しかし、各元素を過剰に含有させると、加工性を低下させるので、Al含有量は、0.2質量%以下が好ましく、REM含有量は、0.2質量%以下が好ましく、Y含有量は、0.2質量%以下が好ましく、Ca含有量は、0.1質量%以下が好ましく、Mg含有量は、0.1質量%以下が好ましい。   Al, REM (rare earth elements), Y, Ca, and Mg are effective in improving high-temperature oxidation resistance, and one or more selected from these elements may be added. The Al content is preferably 0.001% by mass or more, the REM content is preferably 0.001% by mass or more, the Y content is preferably 0.0002% by mass or more, and the Ca content is 0.0002%. The mass content is preferably at least, and the Mg content is preferably at least 0.0002 mass%. However, if each element is excessively contained, the workability is lowered. Therefore, the Al content is preferably 0.2% by mass or less, the REM content is preferably 0.2% by mass or less, and the Y content is 0.2 mass% or less is preferable, Ca content is preferably 0.1 mass% or less, and Mg content is preferably 0.1 mass% or less.

離型部材の形状は、被接合材の形状に応じて適宜選択される。プレート式熱交換器のプレート材は、一般に板状であるから、それに接して配置される離型部材は、離型板として使用される。板厚は、2〜10mmが好ましく、3〜8mmがより好ましい。   The shape of the release member is appropriately selected according to the shape of the material to be joined. Since the plate material of the plate heat exchanger is generally plate-shaped, a release member disposed in contact with the plate material is used as a release plate. The plate thickness is preferably 2 to 10 mm, and more preferably 3 to 8 mm.

(高温強度比)
さらに、本実施形態は、離型部材の1000℃における高温強度(Fr)と被接合材の1000℃における高温強度(Fp)との比(Fr/Fp)が0.9以上である、被接合材と離型部材との組み合わせを用いて拡散接合を行うことが好ましい。
(High temperature strength ratio)
Furthermore, in this embodiment, the ratio (Fr / Fp) of the high temperature strength (Fr) at 1000 ° C. of the release member to the high temperature strength (Fp) at 1000 ° C. of the material to be joined is 0.9 or more. It is preferable to perform diffusion bonding using a combination of a material and a release member.

離型部材は、拡散接合時に被接合材と押し治具との間に挟まれて高圧高温下に曝されているので、離型部材の高温強度が低いと、変形を生じることがある。離型部材が変形すると、それが接する被接合材に対する加圧の均一性が損なわれて、接合部の不良を招く可能性がある。そこで、本実施形態は、拡散接合時の標準的な処理温度として用いられる1000℃での高温強度に基づいて、離型部材の高温特性を検討した。   Since the release member is sandwiched between the material to be joined and the pressing jig during diffusion bonding and exposed to high pressure and high temperature, deformation may occur when the release member has low high temperature strength. If the release member is deformed, the uniformity of the pressure applied to the material to be joined with the release member may be impaired, which may lead to a defective joint. Therefore, in the present embodiment, the high temperature characteristics of the release member were examined based on the high temperature strength at 1000 ° C. used as a standard processing temperature during diffusion bonding.

具体的には、離型部材の1000℃における高温強度(Fr)と被接合材の1000℃における高温強度(Fp)との比(Fr/Fp)に基づいて評価した。離型部材は、1000℃における高温強度比(Fr/Fp)が0.9以上である鋼材を用いると好ましい。離型部材の高温強度が被接合材の高温強度に比して0.9未満であると、離型部材は、押え治具による加圧に対して過度な変形が起きる可能性がある。離型部材の変形により、被接合材に対する加圧状態が不均一となり、被接合材の変形を招く恐れがある。そのため、変形を抑制する観点から、当該高温強度比が0.9以上である離型部材と被接合材との組み合わせを用いることが好ましく、1.0以上がより好ましい。   Specifically, the evaluation was made based on the ratio (Fr / Fp) between the high temperature strength (Fr) at 1000 ° C. of the release member and the high temperature strength (Fp) at 1000 ° C. of the material to be joined. The release member is preferably a steel material having a high temperature strength ratio (Fr / Fp) at 1000 ° C. of 0.9 or more. If the high-temperature strength of the release member is less than 0.9 compared to the high-temperature strength of the material to be joined, the release member may be excessively deformed due to pressurization by the holding jig. Due to the deformation of the release member, the pressure applied to the material to be bonded becomes non-uniform, and the material to be bonded may be deformed. Therefore, from the viewpoint of suppressing deformation, it is preferable to use a combination of a release member having a high temperature strength ratio of 0.9 or more and a material to be joined, and more preferably 1.0 or more.

(熱膨張係数比)
被接合材と離型部材は、30℃〜1000℃における離型部材の熱膨張係数(Tr)と被接合材の熱膨張係数(Tp)との比(Tr/Tp)が0.90〜1.60である組み合わせを用いることが好ましい。被接合材と離型部材は、いずれも加熱時に熱膨張すると弾性変形が生じる。双方の部材に熱膨張差が存在すると、双方が互いの変形を拘束し合うことで歪みが蓄積されて、歪み量の程度によっては塑性変形に至る可能性がある。
(Coefficient of thermal expansion)
In the material to be joined and the release member, the ratio (Tr / Tp) of the thermal expansion coefficient (Tr) of the release member and the thermal expansion coefficient (Tp) of the material to be joined at 30 to 1000 ° C. is 0.90 to 1. It is preferred to use a combination that is .60. If the material to be joined and the release member are both thermally expanded during heating, elastic deformation occurs. If there is a difference in thermal expansion between both members, the two members restrain each other's deformation to accumulate strain, which may lead to plastic deformation depending on the degree of strain.

とくに、熱交換器において熱媒体流路(中空部)を形成する被接合材は、片面側で離型部材と接触していても、反対面側では非接合面となり得る部分を有している。被接合材の接合面が重なり合う箇所では周囲から拘束された状態にあるのに対し、上記のような中空部は、周囲から拘束されていないので、熱膨張による弾性変形が生じる(図3の(B)を参照)。この弾性変形の程度が過大であると、塑性変形に至って形状の復元が困難となる可能性がある。   In particular, the material to be joined that forms the heat medium flow path (hollow part) in the heat exchanger has a portion that can be a non-joint surface on the opposite surface side even if it is in contact with the release member on one surface side. . Whereas the joining surfaces of the materials to be joined are constrained from the surroundings, the hollow part as described above is not restrained from the surroundings, and therefore elastic deformation due to thermal expansion occurs ((( See B)). If the degree of this elastic deformation is excessive, it may become difficult to restore the shape due to plastic deformation.

高温強度比が小さい離型部材を使用する場合は、離型部材の変形抵抗性がプレート材に比べて低いので、被接合材および離型部材における双方の熱膨張係数が同程度であることが好ましい。本実施形態では、この熱的特性に関して、離型部材の熱膨張係数(Tr)と被接合材の熱膨張係数(Tp)との比(Tr/Tp)に基づいて評価できる。高温強度比の小さい離型部材を使用する場合は、当該熱膨張係数比(Tp/Tr)は、1.0を中心として±5%の範囲、すなわち、0.95〜1.05であるとよい。   When using a release member having a small high-temperature strength ratio, since the deformation resistance of the release member is lower than that of the plate material, both the thermal expansion coefficients of the material to be joined and the release member may be approximately the same. preferable. In this embodiment, this thermal characteristic can be evaluated based on the ratio (Tr / Tp) between the thermal expansion coefficient (Tr) of the release member and the thermal expansion coefficient (Tp) of the material to be joined. When using a release member having a small high-temperature strength ratio, the thermal expansion coefficient ratio (Tp / Tr) is in the range of ± 5% centering on 1.0, that is, 0.95 to 1.05. Good.

(平均冷却速度)
拡散接合における加熱後の平均冷却速度は、1.2℃/min未満であることが好ましい。被接合材と離型部材は、拡散接合時には熱膨張する一方で、拡散接合後の冷却過程において熱収縮して元の形状に復元される。被接合材と離型部材との間に熱膨張差が存在すると、冷却時の収縮変化を双方部材が拘束し合うため、歪みが蓄積される。この収縮変化が過度の大きさになると、塑性変形を招く可能性がある。そこで、本実施形態は、拡散接合が終了した後の平均冷却速度に着目した。1.2℃/min未満の平均冷却速度で処理すると、冷却後に残存する変形量を抑制することができる。それ以上の冷却速度であると、熱収縮変化が大きくなり、冷却後に残存する変形量が大きくなり好ましくない。上記の平均冷却速度は、拡散接合時の保持温度から400℃程度までの温度範囲で制御すればよい。
(Average cooling rate)
The average cooling rate after heating in diffusion bonding is preferably less than 1.2 ° C./min. While the material to be joined and the release member are thermally expanded at the time of diffusion bonding, they are thermally contracted in the cooling process after diffusion bonding and restored to their original shapes. If there is a difference in thermal expansion between the material to be joined and the release member, both members constrain the shrinkage change during cooling, so that distortion is accumulated. If this shrinkage change becomes excessively large, plastic deformation may occur. Therefore, this embodiment focuses on the average cooling rate after the diffusion bonding is completed. When the treatment is performed at an average cooling rate of less than 1.2 ° C./min, the amount of deformation remaining after cooling can be suppressed. If the cooling rate is higher than that, the heat shrinkage change becomes large, and the amount of deformation remaining after cooling becomes large, which is not preferable. The average cooling rate may be controlled within a temperature range from the holding temperature during diffusion bonding to about 400 ° C.

(押え治具)
押え治具は、加圧装置の加圧機構に連結されて、被接合材に対して押圧力を伝える部材である。拡散接合時の温度において耐熱性があって破損しないことが求められるので、押え治具にはカーボン材を用いることが好ましい。
(Pressing jig)
The holding jig is a member that is connected to the pressurizing mechanism of the pressurizing device and transmits the pressing force to the material to be joined. Since it is required to have heat resistance at the temperature at the time of diffusion bonding and not to be damaged, it is preferable to use a carbon material for the holding jig.

(離型剤)
本発明は、離型部材の両面には離型剤を塗布することが好ましい。例えば、六方晶窒化ホウ素粉末(h−BN)等のボロンナイト(窒化ホウ素)系スプレーを使用できる。離型剤の塗布厚みは、離型剤粉末の平均粒度(例えば約3μm程度)の3倍以上(約10μm程度)であればよい。
(Release agent)
In the present invention, it is preferable to apply a release agent on both surfaces of the release member. For example, a boron night (boron nitride) spray such as hexagonal boron nitride powder (h-BN) can be used. The application thickness of the release agent may be three times or more (about 10 μm) of the average particle size (for example, about 3 μm) of the release agent powder.

以下、本発明の実施例について説明する。本発明は、以下の実施例に限定されるものではなく、適宜変更して実施できる。   Examples of the present invention will be described below. The present invention is not limited to the following examples, and can be implemented with appropriate modifications.

(試験材の作製)
表1に示す成分組成を有する残部Feおよび不可避的不純物からなる鋼材No.1〜鋼材No.9を、30kgの真空溶解で溶製し、得られた鋼塊を厚み30mmの板に鍛造した。次いで、1200℃の熱間圧延を行い、厚み6mmの熱延板とした後、1100℃で60秒の均熱焼鈍を施して熱延焼鈍板を得た。当該熱延焼鈍板を厚み3.0mmまで冷間圧延を行った後、1100℃で均熱30秒の最終焼鈍を施し、最終仕上板厚を3mmとし、表面仕上げ処理を2B仕上または2D仕上で行い、冷延焼鈍板を得た。また、プレートに使用した鋼材5および6については、さらに、冷間圧延、焼鈍を施し、最終仕上板厚を0.4mmおよび1.0mmとし、表面仕上げ処理を2Bまたは2D仕上げで行い、冷延焼鈍材を得た。当該冷延焼鈍板から、210mm×160mmの寸法で板を切り出して試験材を作製した。これらの試験材を被接合材または離型部材に係る試験に供した。
(Production of test materials)
Steel No. 1 composed of the remaining Fe having the composition shown in Table 1 and inevitable impurities. 1 to steel No. 9 was melted by 30 kg of vacuum melting, and the resulting steel ingot was forged into a 30 mm thick plate. Subsequently, hot rolling at 1200 ° C. was performed to obtain a hot-rolled sheet having a thickness of 6 mm, and soaking was performed at 1100 ° C. for 60 seconds to obtain a hot-rolled annealed sheet. After cold rolling the hot-rolled annealed sheet to a thickness of 3.0 mm, a final annealing is performed at 1100 ° C. for 30 seconds soaking, the final finished sheet thickness is 3 mm, and the surface finish treatment is 2B finish or 2D finish The cold-rolled annealed sheet was obtained. Further, the steel materials 5 and 6 used for the plate are further subjected to cold rolling and annealing, the final finished plate thickness is set to 0.4 mm and 1.0 mm, the surface finishing treatment is performed by 2B or 2D finishing, and cold rolling is performed. An annealed material was obtained. From the cold-rolled annealed plate, a plate was cut out with a size of 210 mm × 160 mm to prepare a test material. These test materials were subjected to a test relating to a material to be joined or a release member.

鋼材No.1〜鋼材No.5は、オーステナイト系ステンレス鋼である。鋼材No.6〜鋼材No.9は、フェライト系ステンレス鋼である。   Steel No. 1 to steel No. 1 5 is austenitic stainless steel. Steel No. 6 to Steel No. 9 is ferritic stainless steel.

Figure 2018094620
Figure 2018094620

(高温強度の測定)
得られた試験材を用いて、JIS G 0567に準拠し、1000℃の温度において歪速度:0.3%/minの高温引張試験を行い、0.2%耐力を測定した。本明細書では、この測定値を1000℃における高温強度とした。その測定結果を表1に示す(単位:MPa)。そして、測定された数値に基づき、離型部材の高温強度(Fr)と被接合材の高温強度(Fp)との比(Fr/Fp)を算出した。その結果を表2に示す。
(Measurement of high temperature strength)
The obtained test material was subjected to a high-temperature tensile test at a strain rate of 0.3% / min at a temperature of 1000 ° C. in accordance with JIS G 0567, and 0.2% yield strength was measured. In the present specification, this measured value is the high temperature strength at 1000 ° C. The measurement results are shown in Table 1 (unit: MPa). And based on the measured numerical value, ratio (Fr / Fp) of the high temperature strength (Fr) of a mold release member and the high temperature strength (Fp) of a to-be-joined material was computed. The results are shown in Table 2.

(熱膨張係数の測定)
得られた試験材を用いて、JIS Z 2285に準拠し、示差膨張分析装置(株式会社リガク製、赤外線加熱式熱膨張測定装置(TMA)、標準試料:石英)により昇温速度1℃/秒で30℃〜1000℃に加熱した。その際の試験片の膨張量を測定し、30℃〜1000℃での熱膨張係数(α30−1000℃)として算出した。その測定結果を表1に示す(単位:×10−6/℃)。
(Measurement of thermal expansion coefficient)
Using the obtained test material, in accordance with JIS Z 2285, a temperature increase rate of 1 ° C./second using a differential expansion analyzer (manufactured by Rigaku Corporation, infrared heating thermal expansion measuring device (TMA), standard sample: quartz). At 30 to 1000 ° C. The amount of expansion of the test piece at that time was measured and calculated as a coefficient of thermal expansion (α30-1000 ° C.) at 30 ° C. to 1000 ° C. The measurement results are shown in Table 1 (unit: × 10 −6 / ° C.).

(接合試験)
被接合材(プレート材)の試験材4枚と離型部材(離型板)の試験材1枚とを組み合わせた試験組立体を作製した。表2に示すように、本試験においては、プレート材として鋼材No.5からなる4枚の試験材を使用した。流路になる開口を有する2枚のプレート材(厚み1.0mm/枚)の試験材を使用し、離型部材には鋼材No.1〜No.5からなる厚み3.0mmの試験材を重ねて、その2枚のプレート材を挟むように、上記の開口を有しない伝熱板としての2枚のプレート材(厚み0.4mm/枚)を配置した。押え治具にはカーボン製治具を用いた。離型剤として六方晶窒化ホウ素粉末(株式会社YKイノアス製ボロンスプレー)を離型部材の両面に塗布した。ホットプレス装置により、上記の試験組立体に対して以下の加圧条件および加熱条件で拡散接合処理を施した。
(Joining test)
A test assembly was prepared by combining four test materials for the material to be joined (plate material) and one test material for the release member (release plate). As shown in Table 2, in this test, the steel material No. Four test materials consisting of 5 were used. Two plate materials (thickness: 1.0 mm / sheet) having an opening to be a flow path were used, and a steel material No. 1-No. Two plate materials (thickness 0.4 mm / sheet) as heat transfer plates not having the above-mentioned openings are stacked so that a test material having a thickness of 3.0 mm consisting of 5 is stacked and the two plate materials are sandwiched. Arranged. A carbon jig was used as the holding jig. Hexagonal boron nitride powder (boron spray manufactured by YK Inoas Co., Ltd.) was applied to both surfaces of the release member as a release agent. With the hot press apparatus, the above-mentioned test assembly was subjected to diffusion bonding treatment under the following pressure and heating conditions.

・雰囲気: 初期真空度を1×10−2Pa以下
・接合温度: 1080℃
・昇温時間: 常温から接合温度まで約2時間
・均熱(接合)時間: 3時間
・平均冷却速度: 1080℃から400℃までを、3.2℃/min(Aパターン)、または1.1℃/min(Bパターン)
・加圧力: 面圧2MPa
・ Atmosphere: Initial vacuum is 1 × 10 −2 Pa or less ・ Junction temperature: 1080 ° C.
-Temperature rising time: About 2 hours from normal temperature to bonding temperature-Soaking (bonding) time: 3 hours-Average cooling rate: 3.2 ° C / min (pattern A) from 1080 ° C to 400 ° C, or 1. 1 ° C / min (B pattern)
・ Pressure: Surface pressure 2MPa

図2に、上記拡散接合処理に適用された加熱および冷却のパターンを示す。図2のAパターン、Bパターンは、平均冷却速度を変更した上記の2パターンを示している。常温まで冷却した後、試験組立体をホットプレス装置から取り出し、変形抑制および離型性に関して以下の評価試験を行った。   FIG. 2 shows a heating and cooling pattern applied to the diffusion bonding process. The A pattern and B pattern in FIG. 2 show the above two patterns in which the average cooling rate is changed. After cooling to room temperature, the test assembly was taken out of the hot press apparatus and subjected to the following evaluation tests on deformation suppression and mold release.

(変形抑制に関する評価)
変形抑制に関しては、拡散接合されたプレート材の変形量に基づいて評価した。当該変形量を測定する手法を説明する。図3は、試験組立体の断面を示した模式図である。図3の(A)は、拡散接合前の状態であり、4枚のプレート材11a〜11dと2枚の離型板13とを組み合わせた試験組立体14を、カーボン製の押え治具15で挟んだ状態で加圧される形態を示している。図3の(B)は、拡散接合後の試験組立体14の状態を示している。拡散接合後の試験組立体14における空洞部16側に面したプレート材11a,11dは、空洞部側以外を離型板3、他のプレート材11b,11cで拘束されているので、加熱時に膨張すると空洞部側に屈曲するように変形する。冷却時の収縮変化によっても形状が復元しなければ、屈曲形状として残存する。離型板3に接したプレート材11a,11dの面を基準にして変形した最も高い箇所の高さ17を測定し、そのうち最大の数値を求めた。本明細書では、この数値をプレート材の変形量という。この変形量に基づいて、拡散接合後の変形状態を評価した。上記の高さ17は、コムズ製の高速3次元形状システムを用いて測定した。変形抑制の観点から、変形量が30μm未満であるときを良好(◎)、30μm〜50μmであるときを適正(○)、50μm超であるときを不適(×)と評価した。
(Evaluation on deformation suppression)
The deformation suppression was evaluated based on the deformation amount of the diffusion-bonded plate material. A method for measuring the deformation amount will be described. FIG. 3 is a schematic view showing a cross section of the test assembly. FIG. 3A shows a state before diffusion bonding, and a test assembly 14 in which four plate members 11a to 11d and two release plates 13 are combined with a carbon holding jig 15. A form in which pressure is applied while sandwiched is shown. FIG. 3B shows the state of the test assembly 14 after diffusion bonding. Since the plate materials 11a and 11d facing the cavity 16 side in the test assembly 14 after diffusion bonding are constrained by the release plate 3 and the other plate materials 11b and 11c except for the cavity portion side, they expand when heated. Then, it deforms so as to bend toward the cavity side. If the shape is not restored by the shrinkage change during cooling, it remains as a bent shape. The height 17 of the highest portion deformed with reference to the surfaces of the plate materials 11a and 11d in contact with the release plate 3 was measured, and the maximum value was obtained. In the present specification, this numerical value is referred to as a deformation amount of the plate material. Based on this deformation amount, the deformation state after diffusion bonding was evaluated. The height 17 was measured using a high-speed three-dimensional shape system manufactured by Combs. From the viewpoint of suppressing deformation, it was evaluated as good (◎) when the deformation amount was less than 30 μm, appropriate (◯) when it was 30 μm to 50 μm, and inappropriate (×) when it was over 50 μm.

(離型性に関する評価)
試験組立体を用いて、接合後の離型性に関して評価するため、プレート材と離型板との剥離試験を行った。その概要を図4に示す。引張装置(図示なし)と、ワイヤー26の先に吸盤25が取り付けられた治具を2つ用意した。拡散接合後の試験組立体24における2つの離型板23の表面に当該治具の吸盤25を取り付けた。一方の治具のワイヤー26に所定重量の錘27を連結した後、引張装置によって他方の治具のワイヤー26を引き上げた。試験組立体24の両面を錘27の重量で引っ張ることにより、プレート材21と離型板23とが剥離するか否かを目視で観察し、剥離の有無について確認した。錘27の重量を変化させて同様の手順で試験を繰り返した。評価基準に関しては、拡散接合後のプレート材と離型板とを小さい力で外せるのが望ましいことから、5kg以下の錘重量でプレート材と離型板とが剥離した場合は、離型性が良好(○)であり、20kg以下の錘重量でプレート材と離型板とが剥離した場合は、離型性がやや不足(△)であり、20kg超えの錘重量でプレート材と離型板とが剥離しない場合は、離型性が不良(×)であると判定した。
(Evaluation on releasability)
In order to evaluate the releasability after joining using the test assembly, a peel test between the plate material and the release plate was performed. The outline is shown in FIG. Two tensioning devices (not shown) and two jigs each having a suction cup 25 attached to the tip of the wire 26 were prepared. A suction cup 25 of the jig was attached to the surfaces of the two release plates 23 in the test assembly 24 after diffusion bonding. After connecting a weight 27 having a predetermined weight to the wire 26 of one jig, the wire 26 of the other jig was pulled up by a tension device. By pulling both surfaces of the test assembly 24 with the weight 27, whether or not the plate material 21 and the release plate 23 were peeled was visually observed to confirm whether or not peeling occurred. The test was repeated in the same procedure while changing the weight of the weight 27. Regarding the evaluation criteria, it is desirable that the plate material and the release plate after diffusion bonding can be removed with a small force. Therefore, when the plate material and the release plate are peeled off with a weight of 5 kg or less, the release property is If the plate material and the release plate are peeled off with a weight of 20 kg or less, the releasability is slightly insufficient (△), and the plate material and the release plate with a weight weight exceeding 20 kg. When it did not peel, it was determined that the releasability was poor (x).

(試験結果)
本試験では、鋼材No.5のオーステナイト系ステンレス鋼からなるプレート材、および鋼材No.6のフェライト系ステンレス鋼からなるプレート材に対して、それぞれ鋼材No.1〜No.9の各ステンレス鋼からなる離型板を組み合わせた18種の試験組立体を用いて、高温強度、熱膨張係数、変形抑制、離型性に関する試験を行った。その試験結果を表2に示す。変形抑制と離型性については、2種の加熱冷却パターンに対して、それぞれ3個の試験組立体を用いて試験を行った。変形抑制については、3個の変形量の平均値で評価した。離型性については、3個の結果の平均で評価した。
(Test results)
In this test, the steel material No. No. 5 plate material made of austenitic stainless steel, and steel material no. For the plate material made of ferritic stainless steel No. 6, steel No. 1-No. Tests on high temperature strength, coefficient of thermal expansion, deformation suppression, and mold release were performed using 18 types of test assemblies in which release plates made of 9 stainless steels were combined. The test results are shown in Table 2. For deformation suppression and releasability, tests were performed using three test assemblies for two types of heating and cooling patterns. About deformation | transformation suppression, it evaluated by the average value of three deformation amount. The releasability was evaluated by the average of three results.

Figure 2018094620
Figure 2018094620

本発明例1〜6は、離型板がそれぞれ鋼材No.1〜No.3で構成された試験組立体で拡散接合された例である。拡散接合後の変形量は、いずれも良好(◎)または適正(○)であって50μm以下の範囲にあり、変形が抑制された拡散接合品が得られた。本発明に相当する被接合材と離型板との組合せを用いると、拡散接合処理時の加熱と冷却による熱的膨張収縮が適度に進行するため、変形が抑制されたものと推測される。   In Invention Examples 1 to 6, the release plates are steel Nos. 1-No. 3 is an example in which diffusion bonding is performed by the test assembly configured by No. 3; The amount of deformation after diffusion bonding was good (◎) or appropriate (○) and was in the range of 50 µm or less, and a diffusion bonded product in which deformation was suppressed was obtained. When the combination of the material to be joined and the release plate corresponding to the present invention is used, it is presumed that deformation is suppressed because thermal expansion and contraction due to heating and cooling during the diffusion bonding process proceed appropriately.

また、本発明例1〜6の離型性に関しては、プレート材と離型板とが小さい引張力で引き剥がされた。本発明に相当する被接合材と離型板との組合せを用いると、拡散接合後の被接合材から容易に離型板を取り外すことができた。離型板の表面に形成されたSi酸化膜により、被接合材と離型板との界面反応が阻害され、両部材の接着が抑制されて離型性が向上したものと推測される。   Moreover, regarding the releasability of Invention Examples 1 to 6, the plate material and the release plate were peeled off with a small tensile force. When the combination of the material to be joined and the release plate corresponding to the present invention was used, the release plate could be easily detached from the material to be joined after diffusion bonding. It is presumed that the Si oxide film formed on the surface of the release plate hinders the interfacial reaction between the material to be joined and the release plate, suppresses the adhesion between both members, and improves the release property.

さらに、拡散接合後の平均冷却速度が、3.2℃/min(Aパターン)、1.1℃/min(Bパターン)で行った結果を本発明例1〜6でみると、平均冷却速度の小さいBパターンで冷却された試験組立体は、Aパターンによる試験組立体に比べて変形抑制が向上していた。冷却速度が小さいと、熱収縮変化の程度が緩和されるため、歪み蓄積が少なくなり、変形が抑制されたものと推測される。   Furthermore, when the average cooling rate after the diffusion bonding is 3.2 ° C./min (A pattern) and 1.1 ° C./min (B pattern), the results of the examples 1 to 6 show that the average cooling rate. The test assembly cooled with a small B pattern had improved deformation suppression compared to the test assembly with the A pattern. If the cooling rate is low, the degree of thermal contraction change is relaxed, so that the strain accumulation is reduced and the deformation is presumed to be suppressed.

それに対し、比較例1〜12は、鋼材No.4〜No.9から構成される離型板を使用したものである。比較例1〜12は、離型板の鋼材のSi含有量が1.5質量%未満であり、本発明の範囲外である。いずれも離型性は、やや不足(△)または不適(×)であり、拡散接合後の取り外しが困難であった。   On the other hand, Comparative Examples 1 to 12 are steel Nos. 4-No. A release plate composed of 9 is used. In Comparative Examples 1 to 12, the Si content of the steel material of the release plate is less than 1.5 mass%, which is outside the scope of the present invention. In either case, the releasability was slightly insufficient (Δ) or unsuitable (×), and removal after diffusion bonding was difficult.

さらに、比較例3〜6、10、12は、高温強度比が0.9未満であるため、拡散接合後の変形が大きく、拡散接合後の変形抑制に関して不適(×)であった。   Furthermore, since Comparative Examples 3-6, 10, and 12 had a high-temperature strength ratio of less than 0.9, the deformation after diffusion bonding was large, and the deformation suppression after diffusion bonding was inappropriate (x).

上記の試験結果によると、本発明の特定された組成を有するステンレス鋼材は、被接合材の拡散接合性を維持したまま、被接合材の変形が抑制され、拡散接合処理後の離型性にも優れる拡散接合治具を提供できること、特に、離型部材に適していることを確認できた。   According to the above test results, the stainless steel material having the specified composition of the present invention can suppress the deformation of the material to be bonded while maintaining the diffusion bonding property of the material to be bonded. It was confirmed that an excellent diffusion bonding jig could be provided, and particularly suitable for a release member.

1 プレート材(被接合材)
2 プレート積層体
3 離型部材
4 押え治具
5 加圧軸
11a、11b、11c、11d プレート材
13 離型板
14 試験組立体
15 押え治具
16 空洞部
17 高さ(変形量)
21 プレート材
23 離型板
24 試験組立体
25 吸盤
26 ワイヤー
27 錘
1 Plate material (material to be joined)
DESCRIPTION OF SYMBOLS 2 Plate laminated body 3 Release member 4 Holding jig 5 Pressurization shaft 11a, 11b, 11c, 11d Plate material 13 Release plate 14 Test assembly 15 Holding jig 16 Cavity part 17 Height (deformation amount)
21 Plate Material 23 Release Plate 24 Test Assembly 25 Suction Cup 26 Wire 27 Weight

Claims (5)

Siを1.5質量%以上含有するステンレス鋼材であって、前記ステンレス鋼材の1000℃における高温強度(Fr)と拡散接合によって接合される被接合材の1000℃における高温強度(Fp)との比(Fr/Fp)が0.9以上である、変形抑制および離型性に優れた拡散接合治具用ステンレス鋼材。   A ratio of the high temperature strength (Fr) at 1000 ° C. of the stainless steel material and the high temperature strength (Fp) at 1000 ° C. of the material to be joined by diffusion bonding, which is a stainless steel material containing 1.5% by mass or more of Si. (Fr / Fp) is 0.9 or more, a stainless steel material for a diffusion bonding jig excellent in deformation suppression and releasability. 前記ステンレス鋼材は、C:0.1質量%以下、Si:1.5〜5.0質量%、Mn:2.5質量%以下、P:0.06質量%以下、S:0.02質量%以下、Ni:8.0〜15.0質量%、Cr:13.0〜23.0質量%、N:0.2質量%以下を含み、残部がFeおよび不可避的不純物からなる組成を有する、請求項1に記載の変形抑制および離型性に優れた拡散接合治具用ステンレス鋼材。   The stainless steel materials are: C: 0.1% by mass or less, Si: 1.5-5.0% by mass, Mn: 2.5% by mass or less, P: 0.06% by mass or less, S: 0.02% by mass %: Ni: 8.0-15.0% by mass, Cr: 13.0-23.0% by mass, N: 0.2% by mass or less, with the balance being composed of Fe and inevitable impurities The stainless steel material for a diffusion bonding jig excellent in deformation suppression and releasability according to claim 1. 前記ステンレス鋼材は、さらに、Mo:3.0質量%以下、Cu:4.0質量%以下、Nb:0.8質量%以下、Ti:0.5質量%以下、V:1.0質量%以下、B:0.02質量%以下から選択される1種以上を含む、請求項2に記載の変形抑制および離型性に優れた拡散接合治具用ステンレス鋼材。   The stainless steel material further includes Mo: 3.0 mass% or less, Cu: 4.0 mass% or less, Nb: 0.8 mass% or less, Ti: 0.5 mass% or less, V: 1.0 mass% Hereinafter, the stainless steel material for a diffusion bonding jig according to claim 2, including at least one selected from B: 0.02% by mass or less and excellent in deformation suppression and releasability. 前記ステンレス鋼材は、さらに、Al:0.2質量%以下、REM:0.2質量%以下、Y:0.2質量%以下、Ca:0.1質量%以下、Mg:0.1質量%以下から選択される1種以上を含む、請求項2または3に記載の変形抑制および離型性に優れた拡散接合治具用ステンレス鋼材。   The stainless steel material is further Al: 0.2 mass% or less, REM: 0.2 mass% or less, Y: 0.2 mass% or less, Ca: 0.1 mass% or less, Mg: 0.1 mass% The stainless steel material for diffusion bonding jigs according to claim 2 or 3, comprising at least one selected from the following, having excellent deformation suppression and releasability. 請求項1〜4のいずれかに記載のステンレス鋼材で構成された離型部材。   The mold release member comprised with the stainless steel material in any one of Claims 1-4.
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