JP4196776B2 - Brazing composite material and method for producing the same - Google Patents

Description

  The present invention relates to a composite material used for brazing a heat exchanger and a fuel cell member, and a method for producing the same.

  Stainless steel-based clad materials are used as joining materials for automobile oil coolers. In this case, a Cu material having a function as a brazing material is clad on one side or both sides of a stainless steel plate as a base material.

  As a brazing material for members made of stainless steel, Ni-base or Co-base alloy, various Ni brazing materials excellent in oxidation resistance and corrosion resistance of joints are defined by JIS standards. Moreover, as Ni brazing filler metal used for joining of heat exchangers, powder obtained by adding 4 to 22 wt% of metal powder selected from Ni, Cr, or Ni—Cr alloy to powder Ni brazing filler metal Ni brazing filler metal has been proposed (see, for example, Patent Document 1). Furthermore, there is a self-brazing composite material having a brazing layer made of Ni and Ti on the surface of stainless steel as a base material, that is, a brazing layer structure of Ni / Ti / stainless steel (for example, Patent Document 2). reference).

  Also, a brazing composite material having a brazing layer having a multilayer structure composed of at least two kinds of layers of Ti or Ti alloy, Ni or Ni alloy, or Cu or Cu alloy on the surface of the base material (For example, refer to Patent Document 3).

JP 2000-107883 A Japanese Patent Laid-Open No. 7-299592 JP 2003-117678 A

  By the way, when performing plastic working such as press working on the brazing composite material described in Patent Documents 2 and 3, it is preferable that the material is soft (low hardness) and large in elongation. In order to satisfy these characteristics, after brazing the brazing composite material, it may be annealed before plastic working. Here, in order to improve the plastic workability, it is necessary to perform an annealing treatment at a high temperature for a long time.

  However, when the brazing composite material is subjected to an annealing treatment at a high temperature for a long time, a diffusion reaction proceeds at the interface of each metal layer. Thereby, a diffusion reaction layer of an intermetallic compound is generated between Ti / Ni, between Ti / Cu, or between Ni / Cu. Since these diffusion reaction layers are very hard and brittle as compared with each metal layer, the hardness of the entire brazing composite material increases and the elongation decreases after annealing. As a result, there is a problem that the plastic workability is lowered. In addition, when a brazing composite material is subjected to an annealing treatment at a high temperature for a short time, in addition to the influence of the mechanical properties of the base material and the diffusion reaction layer, there is a factor that the hardness decrease of the Ti or Ti alloy layer is small. Therefore, it has been difficult to control the hardness and elongation of the brazing composite material by annealing at a high temperature for a short time.

  In addition, since the annealing temperature and annealing time in the annealing process are greatly influenced by various factors such as the heating method of the heating furnace and the size of the heating furnace, they are not decisive conditions for managing and controlling the annealing process. There was a problem.

  An object of the present invention created in view of the above circumstances is to provide a brazing composite material having good plastic workability and a method for producing the same.

In order to achieve the above object, a brazing composite material according to the present invention is a brazing composite material having a brazing layer on the surface of the base material, and a multilayer comprising a Ti layer and an Ni layer on the base material surface. After superposing the above brazing layers of the structure , the superposition body was subjected to an annealing treatment under a reducing atmosphere at a temperature condition of 820 to 1000 ° C. × 1 to 3 min, and at the interface of each metal layer of the brazing layer, A diffusion reaction layer composed of an intermetallic compound and having a layer thickness of 0.5 to 10% is provided with respect to a layer thickness of 100 to 200 μm of the entire brazed layer after processing .

Further, the brazing composite material according to the present invention is the brazing composite material having a brazing layer on the surface of the base material, wherein the brazing material has a multilayer structure composed of a Ti layer and an Ni layer on the base material surface. After superimposing the brazing layer, the superposition body is subjected to an annealing treatment in a reducing atmosphere under a temperature condition of 820 to 1000 ° C. for 1 to 3 min. A diffusion reaction layer having a layer thickness of 1.0 to 10.0 μm is provided with respect to a layer thickness of 100 to 200 μm of the entire brazed layer after processing .

  According to the above, it is possible to obtain a brazing composite material having a diffusion reaction layer composed of an intermetallic compound in a brazing layer and having good plastic workability.

On the other hand, the method for producing a brazing composite material according to the present invention is a method for producing a brazing composite material having a brazing layer on a substrate surface, and is composed of a Ti layer and a Ni layer on the substrate surface. After the above-mentioned brazing layer having a multilayer structure is overlaid and cold-rolled , the laminated body is subjected to an annealing treatment in a reducing atmosphere under a temperature condition of 820 to 1000 ° C. × 1 to 3 minutes , A diffusion reaction layer composed of an intermetallic compound and having a layer thickness of 0.5 to 10% with respect to a layer thickness of 100 to 200 μm of the entire brazed layer after processing is formed at the interface of each metal layer. is there.

Moreover, the method for producing a brazing composite material according to the present invention is a method for producing a brazing composite material having a brazing layer on a substrate surface. The brazing composite material comprises a Ti layer and a Ni layer on the substrate surface. After the above-mentioned brazing layer having a multilayer structure is overlaid and cold-rolled , the laminated body is subjected to an annealing treatment in a reducing atmosphere under a temperature condition of 820 to 1000 ° C. × 1 to 3 minutes , What is formed of an intermetallic compound at the interface of each metal layer and generates a diffusion reaction layer having a layer thickness of 1.0 to 10.0 μm with respect to a layer thickness of 100 to 200 μm of the entire brazed layer after processing It is.

  According to the above, the diffusion reaction layer composed of the intermetallic compound in the brazing layer can be easily formed with a predetermined layer thickness.

  According to the present invention, an excellent brazing composite material having excellent plastic workability can be obtained by adjusting the thickness of the diffusion reaction layer composed of an intermetallic compound in the brazing layer. Demonstrate the effect.

  In order to obtain a brazing composite material having good plastic workability, it is necessary to specify optimum annealing treatment conditions. However, in the past, in order to identify the optimal annealing treatment conditions, it was obtained by conducting an experiment with various parameters (furnace heating method, furnace size, annealing temperature, annealing time, etc.) as parameters. It was necessary to measure and analyze the hardness and elongation data of the composite material one by one, which took time and effort.

  Therefore, as a result of intensive studies by the present inventors, it is easy to produce a brazing composite material having good plastic workability without depending on parameters of various processing conditions by paying attention to the layer thickness of the diffusion reaction layer. I found out that

  DESCRIPTION OF EXEMPLARY EMBODIMENTS Hereinafter, a preferred embodiment of the invention will be described with reference to the accompanying drawings.

  As shown in FIG. 2, the brazing composite material 20 according to a preferred embodiment of the present invention is composed of two metal layers on the surface of the base material 11 (only the upper surface in FIG. 2). A brazing layer 12 having a three-layer structure is provided. The brazing layer 12 is composed of a layer of at least two metals of Ti or Ti alloy, Ni or Ni alloy, or Cu or Cu alloy, and preferably includes a Ni or Ni alloy layer and a Ti or Ti alloy layer. It is formed by alternately laminating. The surface of the base material 11 here refers to all surfaces exposed to the outside.

  Specifically, the brazing layer 12 is made of a clad material in which a Ti or Ti alloy layer 14 is sandwiched between Ni or Ni alloy layers 13a and 13b and overlapped. The formation method of the clad material is not particularly limited, and all conventional methods for forming the clad material can be applied. For example, a method of repeatedly forming and rolling the plate material, or after laminating all the plate materials The method of rolling collectively is mentioned.

    The brazing layer 12 is composed of an intermetallic compound (NiTi) at the interface between the layers, that is, between the layer 13a and the layer 14 and between the layer 14 and the layer 13b. The diffusion reaction layers 21 and 21 have a layer thickness of 0.5 to 10%, preferably 0.7 to 7% of the layer thickness t. Here, the layer thickness of each diffusion reaction layer 21 is set to 0.5 to 10% of the layer thickness t of the entire brazing layer 12 if less than 0.5% (if the diffusion is insufficient) This is because the annealing treatment of the base material 11 is insufficient, the hardness of the base material 11 is high, the elongation is reduced, and cracking occurs when the composite material 20 is plastically processed. On the other hand, if it exceeds 10% (excessive diffusion), the hardness of the brazing layer 12 is remarkably increased and the elongation is remarkably lowered. This is because peeling occurs. For example, when the layer thickness t of the entire brazing layer 12 is 100 to 200 μm, the layer thickness of each diffusion reaction layer 21 is 1.0 to 10.0 μm, and the mechanical properties of the substrate 11 and the brazing layer 12 In order to achieve both a high level of brittleness suppression, the thickness is preferably 1.5 to 8 μm, and particularly preferably 2.0 to 7 μm.

  The constituent material of the substrate 11 is preferably an Fe-based alloy containing Fe as a main component, and particularly stainless steel.

  As Ni alloy which comprises Ni or Ni alloy layer 13a, 13b, a Ni-P type alloy and a Ni-Cr-Fe type corrosion-resistant heat-resistant superalloy (for example, Inconel (trademark) etc.) are preferable. By using these alloys, it is possible to improve the flowability and wettability of brazing during brazing. When an Fe-based alloy (for example, stainless steel) is used as the base material 11, The elution of the Fe component into the brazing layer 12 can be reduced.

  Further, the Ni or Ni alloy layer 13b which is the outermost layer (the layer exposed on the surface) of the brazing layer 12 may be composed of a Ni alloy containing at least one selected from P, B, or Si. Good. By adding these elements to the Ni alloy and adjusting the content of these elements, the melting point, wettability, toughness, and bonding strength of the brazing material can be adjusted. In particular, by containing 0.02 to 10 wt% of P in the Ni alloy, the hot metal flow, wettability, and corrosion resistance of the brazing material can be remarkably improved. The reason why the content of P is limited to 0.02 to 10 wt% is that if it is less than 0.02 wt%, an inconvenience that improvement in hot water flow cannot be expected occurs. This is because the adhesive layer becomes brittle and the vibration fatigue characteristics and the bonding strength are remarkably lowered, and the preferred content is 0.5 to 8 wt%.

  In the brazing composite material 20 according to the present embodiment, the brazing layer 12 of the composite material 20 and a brazing member (not shown) for joining are superposed and heated, or one piece for joining. A brazing product is obtained by forming a composite material 20 using one brazing member as a base material 11 and heating the composite material 20 and the other brazing member in a superposed manner. .

  In the brazing composite material 20 according to the present embodiment, the case where the brazing layer 12 is formed only on one surface (the upper surface in FIG. 2) of the base material 11 has been described. Brazing layers 12 and 12 may be formed on the upper and lower surfaces in FIG. Moreover, although the brazing composite material 20 according to the present embodiment has been described with respect to the case where the brazing layer 12 is formed on the surface of the plate-like substrate 11, the brazing composite material 20 is formed on the surface of the rod-like or wire-like substrate. The brazing layer 12 may be formed. In this case, the brazing layer 12 is formed by a plating method, an extrusion method, a pipe making method, or the like. Furthermore, in the brazing composite material 20 according to the present embodiment, the case where the layer structure of the brazing layer 12 is three layers has been described, but a two-layer structure or a structure of four or more layers may be used. .

  Next, a method for manufacturing a brazing composite material according to a preferred embodiment of the present invention will be described.

  First, a Ti or Ti alloy plate is sandwiched between two Ni or Ni alloy plates and stacked, and then the stacked plate materials are subjected to rolling (for example, hot rolling) to produce a first cladding material. . The first cladding material is subjected to a rolling process (for example, a cold rolling process) to form a desired plate thickness.

  Next, the first clad material formed to a desired plate thickness is overlaid on the surface of the stainless steel plate, and then the laminated plate material is subjected to rolling (for example, hot rolling) to produce a second clad material. To do. The second cladding material is subjected to a rolling process (for example, a cold rolling process) to form a desired plate thickness. Thereby, as shown in FIG. 1, the preform material 10 which has the brazing layer 12 comprised by the layers 13a, 14, 13b on the surface of the base material 11 is obtained.

  Next, this preform material 10 is placed in an annealing furnace and subjected to an annealing treatment in a reducing atmosphere. For example, the annealing treatment is performed under a temperature condition of 820 to 1000 ° C. × 1 to 3 minutes, and within this range, the annealing time is lengthened when the annealing temperature is low, and the annealing time is shortened when the annealing temperature is high.

  By this annealing treatment, metal atoms diffuse to each other at the interface of each layer of the brazing layer 12 to form an intermetallic compound, and the diffusion reaction layers 21 and 21 shown in FIG. 2 are formed. The diffusion reaction layers 21 and 21 are inclined layers in which the Ti concentration continuously changes (decreases) from the layer 14 side toward the layers 13a and 13b side. The diffusion reaction layers 21 and 21 are inclined layers in which the Ni concentration continuously changes (decreases) from the layers 13a and 13b to the layer 14 side. Therefore, from the viewpoint of the phase structure, the brazing layer 12 can be regarded as a layer in which the layers 13a, 14 and 13b are substantially integrated via the diffusion reaction layers 21 and 21.

  At this time, when the layer thickness of the diffusion reaction layers 21 and 21 becomes 0.5 to 10% of the layer thickness t of the entire brazing layer 12, the annealing process is finished and the preform material 10 is heated in the heating furnace. From this, the composite material 20 is obtained. The timing at which the preform material 10 is taken out is, for example, when the annealing process is performed under predetermined processing conditions (furnace heating method, furnace size, annealing temperature, etc.) and the processing time and the layer thickness of the diffusion reaction layers 21 and 21. It is determined by obtaining the relationship in advance.

  Next, the operation of the brazing composite material 20 according to the present embodiment will be described.

  The composite material 20 is formed by forming diffusion reaction layers 21 and 21 having a predetermined layer thickness at the interface between the layer 13a and the layer 14 and the interface between the layer 14 and the layer 13b within a range that does not impair plastic workability. The adhesiveness between 13a, 14, 13b is improved, and the composite material 20 can be softened. As a result, the plastic workability of the composite material 20 is improved, and the processing rate at the time of plastic working (at the time of press working) can be increased as compared with the conventional composite material. Pressed products can also be obtained.

  In addition, since each diffusion reaction layer 21 of the composite material 20 is composed of an intermetallic compound having high hardness and excellent heat resistance, in the brazed part of the brazed product using the composite material 20, Tensile strength and heat resistance are improved, and thus high temperature strength can be improved. Therefore, it is possible to obtain a brazed product in which the reliability of the joint portion is good.

  Furthermore, in the composite material 20, the parameter for obtaining good plastic workability is only the layer thickness of the diffusion reaction layers 21 and 21. By setting the layer thickness of the diffusion reaction layers 21 and 21 to 0.5 to 10% of the total thickness t of the brazing layer 12, any processing conditions (furnace heating method, furnace size, annealing temperature, annealing time, etc.) ), The composite material 20 having good plastic workability can be easily obtained if the annealing treatment is finished when the layer thickness of the diffusion reaction layers 21 and 21 reaches a predetermined layer thickness. be able to.

  In addition, since the hardness and elongation of the composite material 20 can be estimated based on the layer thickness of the diffusion reaction layers 21 and 21, it is not necessary to subject the obtained composite material 20 to a hardness test or an elongation test. Therefore, it does not take time and effort to specify the optimum annealing conditions for obtaining the diffusion reaction layers 21 and 21 having a predetermined layer thickness. As a result, the manufacturing cost of the brazing composite material 20 is reduced.

  Furthermore, since the brazing layer 12 is integrally provided on the surface of the base material 11 in the composite material 20, at the time of brazing, powder Ni brazing material is added to each joint portion like various conventional Ni brazing materials. There is no need for a coating operation and no great labor is required for the brazing operation (the brazing workability is improved). As a result, the yield and productivity of the brazed product are improved, and the manufacturing cost can be reduced.

  In addition, the composite material 20 has a good hot-flow property of the brazing layer 12 by appropriately adding additional elements to the Ni or Ni alloy constituting the Ni alloy layers 13a and 13b. For this reason, when the composite material 20 is applied to brazing of a brazing member having a complicated shape of the brazed joint portion, a good joint surface and sufficient joint strength can be obtained at the joint portion. The reliability of brazed product joints is increased.

  Further, in the composite material 20, the brazing layer 12 is composed of the Ni or Ni alloy layers 13 a and 13 b and the Ti or Ti alloy layer 14. Therefore, during brazing, the Ni brazing material is incorporated into the Ti brazing material. Ni element is mixed (dissolved). This makes it possible to lower the melting point of Ti brazing material made of Ti or Ti alloy, which is excellent in heat resistance and corrosion resistance, but difficult to function as a brazing material due to its high melting point. Brazing can be performed near 1200 ° C. As a result, a Ti-based brazing part having excellent heat resistance, oxidation resistance, and corrosion resistance equivalent to those of a conventional self-brazing composite material (Ni-Ti brazing material) and having excellent brazing properties (Joint part) can be obtained.

  As mentioned above, it cannot be overemphasized that embodiment of this invention is not limited to embodiment mentioned above, and various things are assumed in addition.

  Next, embodiments of the present invention will be described based on examples, but the embodiments of the present invention are not limited to these examples.

(Example 1)
A Ti thin plate with a thickness of 2.0 mm is sandwiched between two Ni thin plates with a thickness of 1.0 mm to form a three-layer structure, and this laminate is hot-rolled to produce a clad plate with a thickness of 1.4 mm did. Subsequently, the clad plate was cold rolled to form a plate thickness of 1.0 mm.

  Next, this clad plate is made of SUS304 (JIS standard) and is laminated on the surface of a stainless steel thin plate having a thickness of 2.5 mm, and then this laminate is clad by a rolling method, followed by cold rolling. To give a preform with a thickness of 0.5 mm.

  This preform material was subjected to an annealing treatment at 900 ° C. × 1 min 20 s in a reducing atmosphere to produce a brazing composite material.

(Example 2)
The same preform material as in Example 1 was subjected to an annealing treatment at 920 ° C. × 2 min in a reducing atmosphere to produce a brazing composite material.

(Comparative Example 1)
The same preform material as in Example 1 was subjected to an annealing treatment at 950 ° C. for 4 minutes in a reducing atmosphere to produce a brazing composite material.

(Comparative Example 2)
The same preform material as in Example 1 was subjected to an annealing treatment at 800 ° C. for 1 min in a reducing atmosphere to produce a brazing composite material.

(Comparative Example 3)
The same preform material as in Example 1 was subjected to an annealing treatment at 820 ° C. × 40 s in a reducing atmosphere to produce a brazing composite material.

(Comparative Example 4)
The same preform material as in Example 1 was subjected to an annealing treatment at 1037 ° C. × 1 min in a reducing atmosphere to produce a brazing composite material.

  Table 1 shows the annealing treatment conditions of each composite material of Examples 1 and 2 and Comparative Examples 1 to 4, and the layer thickness (μm) of the diffusion reaction layer in the cross section of each composite material. Further, after each composite material is cut into 100 mm × 100 mm, each square-shaped thin plate material is pressed, and as shown in FIG. 3 and FIG. 4, it is 100 mm × 100 mm square and 30 mm long × 30 mm wide at the center. X A press-work product 30 having a recess 31 having a depth of 3 mm is produced. Table 1 shows the press working results at this time.

  As shown in Table 1, since each composite material of Examples 1 and 2 has a diffusion reaction layer thickness of 2.5 μm and 3.4 μm and within a limited range (1.0 to 10 μm), press working is performed. In this case, the plastic workability was good, and a sound pressed product 30 could be obtained.

  On the other hand, the composite material of Comparative Example 1 has an annealing time exceeding 4 min and the limited range (1 to 3 min), so that the thickness of the diffusion reaction layer becomes as thick as 12.0 μm. In the concave portion 31 of the object 30, peeling occurred on a part of the surface.

  The composite material of Comparative Example 2 has an annealing temperature of 800 ° C. and less than the limited range (820 to 1000 ° C.), and the composite material of Comparative Example 3 has an annealing time of 40 s and less than the limited range (1 to 3 min). Thus, the thicknesses of the diffusion reaction layers were as thin as 0.4 μm and 0.8 μm, respectively. As a result, the substrate was not sufficiently annealed, the hardness was high, and the elongation was low, so that cracking occurred during the press working.

  Moreover, since the composite material of Comparative Example 4 has an annealing temperature exceeding 1037 ° C. and the limited range (820 to 1000 ° C.), the thickness of the diffusion reaction layer is increased to 16.2 μm, and the pressed product is processed. In the 30 recesses 31, peeling occurred on a part of the surface.

  The brazing composite material according to the present embodiment can be used in a heat exchanger that is exposed to a high-temperature, highly corrosive gas or liquid, such as an EGR cooler. In addition, for example, the present invention can be applied to various uses such as a fuel cell reformer cooler and a fuel cell member. In particular, the composite material formed in a wire shape is used not only for heat exchangers such as EGR coolers, fuel cell reformer coolers, and fuel cell members, but also for oil coolers, radiators, secondary battery members, and the like. Applicable.

It is a cross-sectional view of the composite material for brazing (preform material) before annealing treatment. 1 is a cross-sectional view of a brazing composite material according to a preferred embodiment of the present invention. It is a top view of the press work in an Example. FIG. 4 is a cross-sectional view taken along line 4-4 of FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 11 Base material 12 Brazing layer 13a, 13b Ni or Ni alloy layer 14 Ti or Ti alloy layer 20 Composite material for brazing 21 Diffusion reaction layer

Claims (5)

In a brazing composite material having a brazing layer on a base material surface, the brazing layer having a multilayer structure composed of a Ti layer and a Ni layer is superposed on the base material surface, and then the superposition body is formed. An annealing treatment is performed under a reducing atmosphere under a temperature condition of 820 to 1000 ° C. × 1 to 3 minutes, and the brazing layer is composed of an intermetallic compound at the interface of each metal layer, and the entire brazing layer after processing A brazing composite material provided with a diffusion reaction layer having a layer thickness of 0.5 to 10% with respect to a layer thickness of 100 to 200 µm. In a brazing composite material having a brazing layer on a base material surface, the brazing layer having a multilayer structure composed of a Ti layer and a Ni layer is superposed on the base material surface, and then the superposition body is formed. An annealing treatment is performed under a reducing atmosphere under a temperature condition of 820 to 1000 ° C. × 1 to 3 minutes, and the brazing layer is composed of an intermetallic compound at the interface of each metal layer, and the entire brazing layer after processing A brazing composite material comprising a diffusion reaction layer having a layer thickness of 1.0 to 10.0 μm with respect to a layer thickness of 100 to 200 μm. In the method for producing a brazing composite material having a brazing layer on a substrate surface, the above-mentioned brazing layer having a multilayer structure composed of a Ti layer and an Ni layer is superposed on the substrate surface and cold rolling is performed. After the application , the laminated body is subjected to an annealing treatment under a reducing atmosphere at a temperature condition of 820 to 1000 ° C. for 1 to 3 minutes , and is composed of an intermetallic compound at the interface of each metal layer of the brazing layer, and A method for producing a brazing composite material, characterized in that a diffusion reaction layer having a layer thickness of 0.5 to 10% is produced with respect to a layer thickness of 100 to 200 µm of the entire brazing layer after processing . In the method for producing a brazing composite material having a brazing layer on a substrate surface, the above-mentioned brazing layer having a multilayer structure composed of a Ti layer and an Ni layer is superposed on the substrate surface and cold rolling is performed. After the application , the laminated body is subjected to an annealing treatment under a reducing atmosphere at a temperature condition of 820 to 1000 ° C. for 1 to 3 minutes , and is composed of an intermetallic compound at the interface of each metal layer of the brazing layer, and A method for producing a brazing composite material, characterized in that a diffusion reaction layer having a layer thickness of 1.0 to 10.0 µm is generated with respect to a layer thickness of 100 to 200 µm of the entire brazing layer after processing . A brazed product using the brazing composite material, which is joined using the brazing composite material according to claim 1 .

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