JP5187262B2 - Brazing composite material and method for producing the same - Google Patents

Description

  The present invention relates to a brazing composite material having a low melting temperature (melting point) and a method for producing the same.

  Brazing materials such as stainless steel clad brazing materials are used as structural materials for oil coolers for automobiles. In the stainless steel clad brazing material, copper having a function as a brazing material is clad on one surface or both surfaces of a stainless steel plate. Further, as a brazing material for parts such as stainless steel, nickel base and cobalt base alloy, various nickel brazing materials having excellent oxidation resistance and corrosion resistance of the brazed portion are defined by JIS standards.

  Further, the nickel brazing material for brazing the heat exchanger is constituted by adding 4 wt% to 22 wt% of a metal powder selected from nickel, chromium and nickel-chromium alloy to a powdered nickel brazing material. A nickel brazing material is disclosed in Patent Document 1.

  Further, Patent Document 2 discloses a method for producing a self-brazing composite material.

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

  The composite material obtained by the manufacturing method of Patent Document 2 has the following problems.

  In the above composite material, when the ratio of titanium to nickel is large, the brazing material dissolves at 1000 ° C. or less, but the brazed portion is hard and brittle, so that cracks are likely to occur and there is a problem in brazing strength. On the other hand, when the ratio of titanium to nickel is small, the brazing strength after the brazing material is melted is sufficiently ensured, but the brazing temperature is required to be 1150 ° C. or higher. When mass production of brazing is carried out industrially at a brazing temperature of 1150 ° C, the heat load applied to the heat treatment furnace is very large, and the lifetime of the furnace is shortened due to thermal fatigue of the furnace components and corrosion such as high-temperature oxidation. Is done.

  Therefore, an object of the present invention is to solve the above-mentioned problems and provide a brazing composite material having a low melting temperature and a method for producing the same.

In order to achieve the above object, a brazing composite material of the present invention comprises a laminated brazing material layer comprising a titanium component layer having a brazing material of titanium or a titanium alloy and a nickel component layer having a brazing material of nickel or a nickel alloy. A base material layer joined to the laminated brazing filler metal layer and comprising a base material; and a melting temperature lowering material layer made of a melting temperature lowering material interposed between the base material layer and the laminated brazing filler metal layer. The melting temperature lowering material is silicon particles or silicon powder, and the mass ratio of the entire laminated brazing material layer to the brazing material is 4% by mass or more and 10% by mass or less .

  The laminated brazing material layer may include a third brazing material layer using iron or an iron alloy as a brazing material.

The melting temperature lowering material has a particle size may even under 5μm or less than a diameter of 1 [mu] m.

  The base material may be stainless steel.

  The manufacturing method of the present invention is a method for manufacturing a brazing composite material in which a laminated brazing material layer is bonded to a base material layer, wherein silicon particles are mixed with an organic solvent, and this mixture is mixed with titanium or a titanium alloy. After applying to a laminated brazing material layer or a base material layer containing a titanium component layer and a nickel component layer using nickel or a nickel alloy as a brazing material, the laminated brazing material layer and the base material layer are joined together. .

  The organic solvent that volatilizes at 70 ° C. or higher and 100 ° C. or lower is used as the organic solvent, and the time from applying the mixture to bonding the laminated brazing filler metal layer and the base material layer is less than 70 ° C. The laminated brazing filler metal layer and the base material layer may be joined by cold rolling, and may be annealed at over 100 ° C. after cold rolling.

  The present invention provides a brazing composite material having a low melting temperature and a method for producing the same.

It is sectional drawing of the composite material for brazing which shows one Embodiment of this invention. It is sectional drawing of the composite material for brazing which shows one Embodiment of this invention. It is sectional drawing of the composite material for brazing which shows one Embodiment of this invention. It is an enlarged image figure of the cross section of the base material layer in this invention, a melting temperature reduction material layer, and a lamination brazing material layer.

  Hereinafter, an embodiment of the present invention will be described in detail with reference to the accompanying drawings.

  As shown in FIGS. 1 to 3, the brazing composite materials 1, 2, and 3 according to the present invention include a titanium component layer 4 that uses titanium or a titanium alloy as a brazing material and nickel or a nickel alloy as a brazing material. A laminated brazing filler metal layer 6 including a nickel component layer 5, a base material layer 7 joined to the laminated brazing filler metal layer 6 and made of a base material, and between the base material layer 7 and the laminated brazing filler metal layer 6 And a melt temperature reducing material layer 8 made of a melt temperature reducing material.

  The melting temperature lowering material used for the melting temperature lowering material layer 8 is, for example, silicon. Here, silicon particles (which may be silicon powder) are used.

  The base material used for the base material layer 7 is, for example, stainless steel.

  The brazing composite material 1 in FIG. 1 has a melting temperature lowering material layer 8 on the surface (upper side in the drawing) of a base material layer 7 and a laminated brazing material layer 6 on the surface of the melting temperature lowering material layer 8. The laminated brazing material layer 6 is obtained by laminating the nickel component layer 5 on the surface of the titanium component layer 4.

  The brazing composite material 2 in FIG. 2 has a melting temperature lowering material layer 8 on the surface (upper side in the drawing) of the base material layer 7 and a laminated brazing material layer 6 on the surface of the melting temperature lowering material layer 8. The laminated brazing material layer 6 is obtained by laminating the titanium component layer 4 on the surface of the nickel component layer 5 and further laminating the nickel component layer 5 on the surface of the titanium component layer 4.

  The brazing composite material 3 in FIG. 3 has a melting temperature lowering material layer 8 on the surface (upper side in the drawing) of the base material layer 7 and a laminated brazing material layer 6 on the surface of the melting temperature lowering material layer 8. The laminated brazing material layer 6 is obtained by laminating a nickel component layer 5 on the surface of the titanium component layer 4 and further laminating a third brazing material layer 9 on the surface of the nickel component layer 5. The third brazing material layer 9 uses iron or an iron alloy as a brazing material.

  In order to explain the effect of the brazing composite material of the present invention, a case where the brazing composite material 1 of FIG. 1 is brazed to a target member made of stainless steel will be described as an example.

  The laminated brazing material layer 6 includes a titanium component layer 4 using titanium or a titanium alloy as a brazing material and a nickel component layer 5 using nickel or a nickel alloy as a brazing material. In the temperature increase process of the brazing heat treatment, the titanium component layer 4 and the nickel component layer 5 start a diffusion reaction from the interface between them, and the titanium component diffuses to the surface of the laminated brazing material layer 6.

Since titanium is a metal that is easily oxidized, if a small amount of oxygen remains in the brazing atmosphere, the titanium component that has diffused to the surface of the laminated brazing material layer 6 will be oxidized to form an oxide. The oxide formed on the surface of the laminated brazing filler metal layer 6 greatly hinders the flow of the brazing filler metal after the entire laminated brazing filler metal layer 6 reaches the melting temperature, and the brazing flow is remarkably deteriorated. Therefore, the heat treatment atmosphere is preferably in a vacuum of 7 × 10 ⁻² Pa or less in order to suppress surface oxidation before melting the brazing material.

  After the start of brazing heat treatment, alloying by mutual diffusion of the base metal and the metal constituting the brazing material proceeds, and the entire brazing material is melted at the brazing temperature, and the brazing composite material 1 and the target member It flows in the contact area, gaps, and valleys, and solidifies when the temperature falls below the brazing temperature by cooling to complete brazing.

  When the brazing material is melted, the melting temperature of the brazing material composed mainly of a nickel component and a titanium component is reduced by the silicon component, which is a melting temperature lowering material. Brazing at a temperature lower than ℃ is possible.

  As described above, according to the brazing composite material 1 of the present invention, the melting temperature lowering material layer 8 is interposed between the base material layer 7 and the laminated brazing material layer 6 regardless of the ratio of nickel and titanium. Therefore, the melting temperature of the brazing material can be lowered.

  Moreover, according to the brazing composite material 1 of the present invention, the melting temperature of the brazing material can be lowered without impairing the high corrosion resistance of the titanium component in the brazing material.

  Moreover, according to the composite material 1 for brazing of this invention, the lifetime of a brazing heat treatment furnace can be extended because the melting temperature of brazing material becomes low.

  The effects of the brazing composite material of the present invention are not limited to the brazing composite material 1 of FIG. 1, but are the same as the brazing composite materials 2 and 3 of FIGS.

  In the above embodiment, the concentration of the melting temperature lowering material in the melting temperature lowering material layer 8 is not limited, but the melting temperature lowering material (silicon) is the brazing material (titanium or titanium alloy and nickel) of the laminated brazing material layer 6 as a whole. (Or nickel alloy), the mass ratio is desirably 4% by mass or more and 10% by mass or less. When the mass ratio of silicon is less than 4% by mass, the melting temperature of the brazing material is 1080 ° C. or higher, and the brazing temperature is 1100 ° C., so the effect of lowering the brazing temperature is not sufficient. When the mass ratio of silicon exceeds 10 mass%, the thickness of the melting temperature lowering material layer 8 becomes thick, and it becomes difficult to join the base material layer 7 and the laminated brazing material layer 6. That is, by limiting the concentration of the melting temperature lowering material as described above, the melting temperature of the brazing material can be sufficiently lowered, and the joining of the base material layer 7 and the laminated brazing material layer 6 is facilitated. Become.

  In the above embodiment, the particle size of the silicon particles used as the melting temperature lowering material of the melting temperature lowering material layer 8 is not limited, but the particle size of the melting temperature lowering material (silicon) is 1 μm or more and 5 μm or less in diameter. Is desirable. When the particle diameter of the silicon particles is less than 1 μm in diameter, the inside of the melting temperature lowering material layer 8 becomes too dense, and when the base material layer 7 and the laminated brazing material layer 6 are joined, the base material layer 7 and the laminated brazing material layer are combined. There is almost no contact area in contact with 6, and joining becomes difficult. When the particle size of the silicon particles exceeds 5 μm, the unevenness of the melting temperature lowering material layer 8 due to the silicon particles is reflected on the surface of the laminated brazing filler metal layer 6, the surface of the laminated brazing filler metal layer 6 becomes rough, and the flatness deteriorates. That is, by limiting the particle size of the silicon particles as described above, as shown in FIG. 4, in the melting temperature lowering material layer 8 interposed at the interface between the base material layer 7 and the laminated brazing filler metal layer 6, A gap 42 having an appropriate width is formed between the silicon particles 41, the joining between the base material layer 7 and the laminated brazing filler metal layer 6 is easy, and the flatness of the surface of the laminated brazing filler metal layer 6 is improved.

  The brazing composites 1, 2, and 3 according to the present invention can improve the brazing performance and the heat resistance and the corrosion resistance. Also, the brazing composite materials 1, 2, and 3 of the present invention are applied to heat exchangers (exhaust gas recirculation (EGR) coolers and fuel cell reformer coolers) and fuel cell members.

  Next, in the method for producing the brazing composite material 1 according to the present invention, when the laminated brazing material layer 6 is joined to the base material layer 7, the melting temperature is lowered at the interface between the laminated brazing material layer 6 and the base material layer 7. The material layer 8 is interposed.

  As a method of interposing the melting temperature lowering material layer 8 at the interface between the laminated brazing filler metal layer 6 and the base material layer 7, for example, in a pre-process performed before performing the composite process of the laminated brazing filler metal layer 6 and the base material layer 7. Then, there is a method of applying the melting temperature lowering material to the base material layer 7 or the laminated brazing material layer 6. Hereinafter, it demonstrates as what applies a melting temperature decreasing material to the base material layer 7. FIG.

  In order to uniformly apply the silicon particles as the melting temperature lowering material to the surface of the base material layer 7, the silicon particles are placed on the base material layer 7 so that the silicon particles are arranged at predetermined positions on the surface of the base material layer 7. May be directly injected. An organic solvent may be used as a binder for collecting silicon particles. That is, silicon particles are mixed with an organic solvent, and this mixture is applied to the base material layer 7. Thereby, the silicon particles can be uniformly applied to the surface of the base material layer 7.

  At this time, when the base material layer 7 on which the mixture temperature was applied and the melting temperature lowering material layer 8 was formed was joined to the laminated brazing filler metal layer 6 as it was, it was heated in an annealing process for material refining after the joining process. At this time, since the organic solvent present in the melting temperature lowering material layer 8 volatilizes and expands, surface swelling occurs in the manufactured brazing composite material 1. When the annealing process is not performed, a gas is generated in the melting temperature lowering material layer 8 during brazing, and the gas reacts with the titanium component in the brazing material to form a compound. Inhibits. Therefore, it is desirable that the organic solvent is volatilized before the annealing step or before brazing.

  Therefore, in the present invention, the organic solvent is volatilized in the bonding step. For example, in the joining step (clad joining step) by cold rolling, the laminated brazing filler metal layer 6 and the base material layer 7 to be joined generate heat and exceed 100 ° C. If the volatilization temperature of the organic solvent is 100 ° C. or lower, the organic solvent is volatilized in the bonding step, and thus it is possible to prevent gas generation during the annealing step or brazing.

  In order to prevent the organic solvent from volatilizing during the storage from the time when the mixture of the silicon particles and the organic solvent is applied to the base material layer 7 until the laminated brazing filler metal layer 6 and the base material layer 7 are joined. The volatilization temperature of the organic solvent may be higher than room temperature (storage atmosphere temperature; less than 70 ° C.). Since the silicon particles are fixed to the surface of the base material layer 7 by an organic solvent, if the organic solvent volatilizes during storage, there is a problem that the fixing of the silicon particles is hindered.

  For these reasons, in the present invention, an organic solvent that volatilizes at 70 ° C. or higher and 100 ° C. or lower is used.

  Thus, after apply | coating the mixture of a silicon particle and an organic type solvent to the base material layer 7, the laminated brazing filler metal layer 6 and the base material layer 7 were cold-rolled and joined, and it annealed above 100 degreeC after that. To do.

  According to the production method of the present invention, when silicon particles are used as the melting temperature lowering material, an organic solvent is used as a binder for collecting silicon particles, the silicon particles are mixed in the organic solvent, and this mixture is used as a base. Since it applied to the material layer 7, the silicon particles can be uniformly applied to the surface of the base material layer 7.

  Moreover, according to the manufacturing method of the present invention, since the organic solvent that volatilizes at 70 ° C. or more and 100 ° C. or less is used, the organic solvent can be volatilized in the joining process, and gas is generated during the annealing process or brazing. This can prevent the organic solvent from volatilizing during storage.

Example 1
A coiled pure nickel plate having a thickness of 1.64 mm is used as the brazing material for the nickel component layer 5, and a coiled pure titanium plate having a thickness of 2.0 mm is used as the brazing material for the titanium component layer 4. In addition, a clad plate having a two-layer structure with a thickness of 1.4 mm was obtained by cold rolling. Subsequently, the clad plate having a thickness of 0.15 mm was finished by cold rolling, and this was used as the laminated brazing material layer 6.

A stainless steel strip (SUS304, thickness 1.5 mm) is used as the base material layer 7, and a mixture of silicon particles and an organic solvent is applied to the base material layer 7 so that the weight of silicon particles per 1 cm ² is 0.86 mg. Then, the melting temperature lowering material layer 8 was formed. The laminated brazing filler metal layer 6 was disposed so that the titanium component layer 4 was in contact with the melting temperature lowering material layer 8 with respect to the base material layer 7, and the laminated brazing filler metal layer 6 and the base material layer 7 were joined by cold rolling. Thereafter, cold rolling was further performed to produce a brazing composite material 1 having a thickness of 0.3 mm.

(Example 2)
A coiled pure nickel plate having a thickness of 1.64 mm is used as the brazing material for the nickel component layer 5, and a coiled pure titanium plate having a thickness of 2.0 mm is used as the brazing material for the titanium component layer 4. In addition, a clad plate having a two-layer structure with a thickness of 1.4 mm was obtained by cold rolling. Subsequently, the clad plate having a thickness of 0.15 mm was finished by cold rolling, and this was used as the laminated brazing material layer 6.

A stainless steel strip (SUS304, thickness 1.5 mm) is used as the base material layer 7, and a mixture of silicon particles and an organic solvent is applied to the base material layer 7 so that the weight of silicon particles per cm ² is 1.29 mg. Then, the melting temperature lowering material layer 8 was formed. The laminated brazing filler metal layer 6 was disposed so that the titanium component layer 4 was in contact with the melting temperature lowering material layer 8 with respect to the base material layer 7, and the laminated brazing filler metal layer 6 and the base material layer 7 were joined by cold rolling. Thereafter, cold rolling was further performed to produce a brazing composite material 1 having a thickness of 0.3 mm.

(Example 3)
A coiled pure nickel plate having a thickness of 0.82 mm is used as a brazing material for the nickel component layer 5, a coiled pure titanium plate having a thickness of 2.0 mm is used as a brazing material for the titanium component layer 4, and a coiled shape having a thickness of 0.82 mm A pure nickel plate was used as another brazing material for the nickel component layer 5, and these three layers of brazing material were superposed, and a clad plate having a thickness of 1.4 mm was obtained by cold rolling. Subsequently, the clad plate having a thickness of 0.15 mm was finished by cold rolling, and this was used as the laminated brazing material layer 6.

A stainless steel strip (SUS304, thickness 1.5 mm) is used as the base material layer 7, and a mixture of silicon particles and an organic solvent is applied to the base material layer 7 so that the weight of silicon particles per 1 cm ² is 1.08 mg. Then, the melting temperature lowering material layer 8 was formed. The laminated brazing filler metal layer 6 was disposed so that the nickel component layer 5 was in contact with the melting temperature lowering material layer 8 with respect to the base material layer 7, and the laminated brazing filler metal layer 6 and the base material layer 7 were joined by cold rolling. Thereafter, cold rolling was further performed to produce a brazing composite material 2 having a thickness of 0.3 mm.

Example 4
A coiled pure nickel plate having a thickness of 0.82 mm is used as a brazing material for the nickel component layer 5, a coiled pure titanium plate having a thickness of 2.0 mm is used as a brazing material for the titanium component layer 4, and a coiled shape having a thickness of 0.82 mm A pure nickel plate was used as another brazing material for the nickel component layer 5, and these three layers of brazing material were superposed, and a clad plate having a thickness of 1.4 mm was obtained by cold rolling. Subsequently, the clad plate having a thickness of 0.15 mm was finished by cold rolling, and this was used as the laminated brazing material layer 6.

A stainless steel strip (SUS304, thickness 1.5 mm) is used as the base material layer 7, and a mixture of silicon particles and an organic solvent is applied to the base material layer 7 so that the weight of silicon particles per 1 cm ² is 2.15 mg. Then, the melting temperature lowering material layer 8 was formed. The laminated brazing filler metal layer 6 was disposed so that the nickel component layer 5 was in contact with the melting temperature lowering material layer 8 with respect to the base material layer 7, and the laminated brazing filler metal layer 6 and the base material layer 7 were joined by cold rolling. Thereafter, cold rolling was further performed to produce a brazing composite material 2 having a thickness of 0.3 mm.

(Example 5)
A coiled invar alloy (iron-36 mass% nickel alloy) plate with a plate thickness of 1.0 mm is used as the third brazing material layer 9, and a coiled pure titanium plate with a plate thickness of 2.0 mm is used as the brazing material for the titanium component layer 4, A coil-like pure nickel plate having a thickness of 1.35 mm is used as another brazing material for the nickel component layer 5, and these three layers of brazing material are overlapped, and a clad plate having a thickness of 1.4 mm is obtained by cold rolling. Got. Subsequently, the clad plate having a thickness of 0.15 mm was finished by cold rolling, and this was used as the laminated brazing material layer 6.

A stainless steel strip (SUS304, thickness 1.5 mm) is used as the base material layer 7, and a mixture of silicon particles and an organic solvent is applied to the base material layer 7 so that the weight of silicon particles per 1 cm ² is 0.86 mg. Then, the melting temperature lowering material layer 8 was formed. The laminated brazing filler metal layer 6 was disposed so that the nickel component layer 5 was in contact with the melting temperature lowering material layer 8 with respect to the base material layer 7, and the laminated brazing filler metal layer 6 and the base material layer 7 were joined by cold rolling. Thereafter, cold rolling was further performed to produce a brazing composite material 3 having a thickness of 0.3 mm.

(Example 6)
A coiled invar alloy (iron-36 mass% nickel alloy) plate with a plate thickness of 1.0 mm is used as the third brazing material layer 9, and a coiled pure titanium plate with a plate thickness of 2.0 mm is used as the brazing material for the titanium component layer 4, A coil-like pure nickel plate having a thickness of 1.35 mm is used as another brazing material for the nickel component layer 5, and these three layers of brazing material are overlapped, and a clad plate having a thickness of 1.4 mm is obtained by cold rolling. Got. Subsequently, the clad plate having a thickness of 0.15 mm was finished by cold rolling, and this was used as the laminated brazing material layer 6.

A stainless steel strip (SUS304, thickness 1.5 mm) is used as a base material layer 7, and a mixture of silicon particles and an organic solvent is applied to the base material layer 7 so that the weight of silicon particles per 1 cm ² is 1.72 mg. Then, the melting temperature lowering material layer 8 was formed. The laminated brazing filler metal layer 6 was disposed so that the nickel component layer 5 was in contact with the melting temperature lowering material layer 8 with respect to the base material layer 7, and the laminated brazing filler metal layer 6 and the base material layer 7 were joined by cold rolling. Thereafter, cold rolling was further performed to produce a brazing composite material 3 having a thickness of 0.3 mm.

(Comparative Example 1)
A coiled pure nickel plate having a thickness of 1.64 mm is used as the brazing material for the nickel component layer 5, and a coiled pure titanium plate having a thickness of 2.0 mm is used as the brazing material for the titanium component layer 4. In addition, a clad plate having a two-layer structure with a thickness of 1.4 mm was obtained by cold rolling. Subsequently, the clad plate having a thickness of 0.15 mm was finished by cold rolling, and this was used as the laminated brazing material layer 6.

A stainless steel strip (SUS304, thickness 1.5 mm) is used as a base material layer 7, and a mixture of silicon particles and an organic solvent is applied to the base material layer 7 so that the weight of silicon particles per 1 cm ² is 0.22 mg. Then, the melting temperature lowering material layer 8 was formed. The laminated brazing filler metal layer 6 was disposed so that the titanium component layer 4 was in contact with the melting temperature lowering material layer 8 with respect to the base material layer 7, and the laminated brazing filler metal layer 6 and the base material layer 7 were joined by cold rolling. Thereafter, cold rolling was further performed to produce a brazing composite material having a thickness of 0.3 mm.

  The brazing composite material of Comparative Example 1 has the same structure as the brazing composite material 1 of FIG. 1, but the mass ratio of the melting temperature lowering material to the brazing material of the entire laminated brazing material layer 6 is less than 4% by mass. It becomes.

(Comparative Example 2)
A coiled pure nickel plate having a thickness of 1.64 mm is used as the brazing material for the nickel component layer 5, and a coiled pure titanium plate having a thickness of 2.0 mm is used as the brazing material for the titanium component layer 4. In addition, a clad plate having a two-layer structure with a thickness of 1.4 mm was obtained by cold rolling. Subsequently, the clad plate having a thickness of 0.15 mm was finished by cold rolling, and this was used as the laminated brazing material layer 6.

A stainless steel strip (SUS304, thickness 1.5 mm) is used as the base material layer 7, and a mixture of silicon particles and an organic solvent is applied to the base material layer 7 so that the weight of silicon particles per 1 cm ² is 0.65 mg. Then, the melting temperature lowering material layer 8 was formed. The laminated brazing filler metal layer 6 was disposed so that the titanium component layer 4 was in contact with the melting temperature lowering material layer 8 with respect to the base material layer 7, and the laminated brazing filler metal layer 6 and the base material layer 7 were joined by cold rolling. Thereafter, cold rolling was further performed to produce a brazing composite material having a thickness of 0.3 mm.

  The brazing composite material of Comparative Example 2 has the same structure as the brazing composite material 1 of FIG. 1, but the mass ratio of the melting temperature lowering material to the brazing material of the entire laminated brazing material layer 6 is less than 4 mass%. It becomes.

(Comparative Example 3)
A coiled pure nickel plate having a thickness of 0.82 mm is used as a brazing material for the nickel component layer 5, a coiled pure titanium plate having a thickness of 2.0 mm is used as a brazing material for the titanium component layer 4, and a coiled shape having a thickness of 0.82 mm A pure nickel plate was used as another brazing material for the nickel component layer 5, and these three layers of brazing material were superposed, and a clad plate having a thickness of 1.4 mm was obtained by cold rolling. Subsequently, the clad plate having a thickness of 0.15 mm was finished by cold rolling, and this was used as the laminated brazing material layer 6.

A stainless steel strip (SUS304, thickness 1.5 mm) is used as a base material layer 7, and a mixture of silicon particles and an organic solvent is applied to the base material layer 7 so that the weight of silicon particles per cm ² is 0.32 mg. Then, the melting temperature lowering material layer 8 was formed. The laminated brazing filler metal layer 6 was disposed so that the nickel component layer 5 was in contact with the melting temperature lowering material layer 8 with respect to the base material layer 7, and the laminated brazing filler metal layer 6 and the base material layer 7 were joined by cold rolling. Thereafter, cold rolling was further performed to produce a brazing composite material having a thickness of 0.3 mm.

  The brazing composite material of Comparative Example 3 has the same structure as the brazing composite material 2 of FIG. 2, but the mass ratio of the melting temperature lowering material to the brazing material of the entire laminated brazing material layer 6 is less than 4% by mass. It becomes.

(Comparative Example 4)
A coiled pure nickel plate having a thickness of 0.82 mm is used as a brazing material for the nickel component layer 5, a coiled pure titanium plate having a thickness of 2.0 mm is used as a brazing material for the titanium component layer 4, and a coiled shape having a thickness of 0.82 mm A pure nickel plate was used as another brazing material for the nickel component layer 5, and these three layers of brazing material were superposed, and a clad plate having a thickness of 1.4 mm was obtained by cold rolling. Subsequently, the clad plate having a thickness of 0.15 mm was finished by cold rolling, and this was used as the laminated brazing material layer 6.

A stainless steel strip (SUS304, thickness 1.5 mm) is used as the base material layer 7, and a mixture of silicon particles and an organic solvent is applied to the base material layer 7 so that the weight of silicon particles per 1 cm ² is 0.43 mg. Then, the melting temperature lowering material layer 8 was formed. The laminated brazing filler metal layer 6 was disposed so that the nickel component layer 5 was in contact with the melting temperature lowering material layer 8 with respect to the base material layer 7, and the laminated brazing filler metal layer 6 and the base material layer 7 were joined by cold rolling. Thereafter, cold rolling was further performed to produce a brazing composite material having a thickness of 0.3 mm.

  The brazing composite material of Comparative Example 4 has the same structure as the brazing composite material 2 of FIG. 2, but the mass ratio of the melting temperature lowering material to the brazing material of the entire laminated brazing material layer 6 is less than 4 mass%. It becomes.

(Comparative Example 5)
A coiled invar alloy (iron-36 mass% nickel alloy) plate with a plate thickness of 1.0 mm is used as the third brazing material layer 9, and a coiled pure titanium plate with a plate thickness of 2.0 mm is used as the brazing material for the titanium component layer 4, A coil-like pure nickel plate having a thickness of 1.35 mm is used as another brazing material for the nickel component layer 5, and these three layers of brazing material are overlapped, and a clad plate having a thickness of 1.4 mm is obtained by cold rolling. Got. Subsequently, the clad plate having a thickness of 0.15 mm was finished by cold rolling, and this was used as the laminated brazing material layer 6.

A stainless steel strip (SUS304, thickness 1.5 mm) is used as the base material layer 7, and a mixture of silicon particles and an organic solvent is applied to the base material layer 7 so that the weight of silicon particles per 1 cm ² is 0.43 mg. Then, the melting temperature lowering material layer 8 was formed. The laminated brazing filler metal layer 6 was disposed so that the nickel component layer 5 was in contact with the melting temperature lowering material layer 8 with respect to the base material layer 7, and the laminated brazing filler metal layer 6 and the base material layer 7 were joined by cold rolling. Thereafter, cold rolling was further performed to produce a brazing composite material having a thickness of 0.3 mm.

  The brazing composite material of Comparative Example 5 has the same structure as the brazing composite material 3 of FIG. 3, but the mass ratio of the melting temperature lowering material to the brazing material of the entire laminated brazing material layer 6 is less than 4 mass%. It becomes.

(Comparative Example 6)
A coiled invar alloy (iron-36 mass% nickel alloy) plate with a plate thickness of 1.0 mm is used as the third brazing material layer 9, and a coiled pure titanium plate with a plate thickness of 2.0 mm is used as the brazing material for the titanium component layer 4, A coil-like pure nickel plate having a thickness of 1.35 mm is used as another brazing material for the nickel component layer 5, and these three layers of brazing material are overlapped, and a clad plate having a thickness of 1.4 mm is obtained by cold rolling. Got. Subsequently, the clad plate having a thickness of 0.15 mm was finished by cold rolling, and this was used as the laminated brazing material layer 6.

A stainless steel strip (SUS304, thickness 1.5 mm) is used as the base material layer 7, and a mixture of silicon particles and an organic solvent is applied to the base material layer 7 so that the weight of silicon particles per 1 cm ² is 0.54 mg. Then, the melting temperature lowering material layer 8 was formed. The laminated brazing filler metal layer 6 was disposed so that the nickel component layer 5 was in contact with the melting temperature lowering material layer 8 with respect to the base material layer 7, and the laminated brazing filler metal layer 6 and the base material layer 7 were joined by cold rolling. Thereafter, cold rolling was further performed to produce a brazing composite material having a thickness of 0.3 mm.

  The brazing composite material of Comparative Example 5 has the same structure as the brazing composite material 3 of FIG. 3, but the mass ratio of the melting temperature lowering material to the brazing material of the entire laminated brazing material layer 6 is less than 4 mass%. It becomes.

(Conventional example 1)
A coiled pure nickel plate having a thickness of 1.64 mm is used as the brazing material for the nickel component layer 5, and a coiled pure titanium plate having a thickness of 2.0 mm is used as the brazing material for the titanium component layer 4. In addition, a clad plate having a two-layer structure with a thickness of 1.4 mm was obtained by cold rolling. Subsequently, the clad plate having a thickness of 0.15 mm was finished by cold rolling, and this was used as the laminated brazing material layer 6.

  A stainless steel strip (SUS304, thickness 1.5 mm) is used as a base material layer 7, and a laminated brazing filler metal layer 6 is arranged so that the titanium component layer 4 is in contact with the base material layer 7, and the laminated brazing filler metal layer is formed by cold rolling. 6 and the base material layer 7 were joined. Thereafter, cold rolling was further performed to produce a brazing composite material having a thickness of 0.3 mm.

  The brazing composite material of Conventional Example 1 does not have the melting temperature lowering material layer 8 as compared with the brazing composite material 1 of FIG.

(Conventional example 2)
A coiled pure nickel plate having a thickness of 0.82 mm is used as a brazing material for the nickel component layer 5, a coiled pure titanium plate having a thickness of 2.0 mm is used as a brazing material for the titanium component layer 4, and a coiled shape having a thickness of 0.82 mm A pure nickel plate was used as another brazing material for the nickel component layer 5, and these three layers of brazing material were superposed, and a clad plate having a thickness of 1.4 mm was obtained by cold rolling. Subsequently, the clad plate having a thickness of 0.15 mm was finished by cold rolling, and this was used as the laminated brazing material layer 6.

  A stainless steel strip (SUS304, thickness 1.5 mm) is used as a base material layer 7, and a laminated brazing material layer 6 is disposed so that the nickel component layer 5 is in contact with the base material layer 7, and the laminated brazing material layer is formed by cold rolling. 6 and the base material layer 7 were joined. Thereafter, cold rolling was further performed to produce a brazing composite material having a thickness of 0.3 mm.

  The brazing composite material of Conventional Example 2 does not have the melting temperature lowering material layer 8 as compared with the brazing composite material 2 of FIG.

(Conventional example 3)
A coiled invar alloy (iron-36 mass% nickel alloy) plate with a plate thickness of 1.0 mm is used as the third brazing material layer 9, and a coiled pure titanium plate with a plate thickness of 2.0 mm is used as the brazing material for the titanium component layer 4, A coil-like pure nickel plate having a thickness of 1.35 mm is used as another brazing material for the nickel component layer 5, and these three layers of brazing material are overlapped, and a clad plate having a thickness of 1.4 mm is obtained by cold rolling. Got. Subsequently, the clad plate having a thickness of 0.15 mm was finished by cold rolling, and this was used as the laminated brazing material layer 6.

  A stainless steel strip (SUS304, thickness 1.5 mm) is used as a base material layer 7, and a laminated brazing material layer 6 is disposed so that the nickel component layer 5 is in contact with the base material layer 7, and the laminated brazing material layer is formed by cold rolling. 6 and the base material layer 7 were joined. Thereafter, cold rolling was further performed to produce a brazing composite material having a thickness of 0.3 mm.

  The brazing composite material of Conventional Example 3 does not have the melting temperature lowering material layer 8 as compared with the brazing composite material 3 of FIG.

The brazing composite materials of Examples 1 to 6, Comparative Examples 1 to 6, and Conventional Examples 1 to 3 were cut into 20 mm × 25 mm samples, and brazing heat treatment was performed in a vacuum heat treatment furnace capable of visual observation of the samples. (Only the sample was heated). The degree of vacuum is 5.0 × 10 ⁻² Pa, the heating temperature starts from room temperature, the temperature is increased to 20 ° C./min up to 1000 ° C., and the temperature is increased at a rate of 10 ° C./min after exceeding 1000 ° C. did. After confirming melting of the laminated brazing filler metal layer 6, heating was stopped and the observation was terminated.

  Table 1 shows the composition of the brazing composite materials of Examples 1 to 6, Comparative Examples 1 to 6, and Conventional Examples 1 to 3 (elemental symbols representing the main constituent materials of each layer viewed in the order of lamination from the front surface side to the back surface side, It shows the measured values of the silicon concentration (mass ratio of the melting temperature lowering material to the total brazing material) and the melting temperature.

  According to Table 1, the brazing composite materials 1, 2 and 3 of Examples 1 to 6 have a melting temperature of 50 higher than that of the brazing composite materials of Comparative Examples 1 to 6 and Conventional Examples 1 to 3. It is possible to braze at a brazing temperature lower than 1 ° C. and lower than 1100 ° C.

  In the present invention, when a brazing material mainly composed of a nickel component and a titanium component or a brazing material mainly composed of a nickel component, a titanium component and an iron component is melted, the silicon component lowers the melting temperature of the brazing material. It uses the action. Even if the concentration ratio (or plate thickness ratio) of nickel and titanium and the concentration ratio (or plate thickness ratio) of iron alloy, nickel and titanium are different from the ratios in Examples 1 to 6, the present invention can be applied. Equivalent effect is obtained. Further, in the brazing composite material 1 of FIG. 1, the nickel component layer 5 is arranged on the surface side and the titanium component layer 4 is arranged on the base material layer 7 side, but the titanium component layer 4 is arranged on the surface side and the base material is arranged. Even if the nickel component layer 5 is arranged on the layer 7 side, the present invention can be applied and the same effect can be obtained. In Examples 1 to 6, nickel and titanium were used for the brazing material, but the present invention can be applied even if nickel is changed to a nickel alloy or titanium is changed to a titanium alloy, and equivalent effects are obtained. Further, in Examples 5 and 6, the iron alloy layer was provided on the outermost surface, but the stacking order of iron or iron alloy and titanium or titanium alloy and nickel or nickel alloy can be arbitrarily changed, and the same effect can be obtained. can get.

1, 2, 3 Brazing composite material 4 Titanium component layer 5 Nickel component layer 6 Laminated brazing material layer 7 Base material layer 8 Melting temperature lowering material layer 9 Third brazing material layer

Claims (6)

A laminated brazing filler metal layer including a titanium component layer having a brazing material of titanium or a titanium alloy and a nickel component layer having a brazing material of nickel or a nickel alloy;
A base material layer made of a base material joined to the laminated brazing material layer;
It is interposed between the base material layer and the laminated brazing material layer, and comprises a melting temperature lowering material layer made of a melting temperature lowering material ,
The brazing composite material, wherein the melting temperature lowering material is silicon particles or silicon powder, and a mass ratio of the entire laminated brazing material layer to a brazing material is 4% by mass or more and 10% by mass or less .   2. The brazing composite material according to claim 1, wherein the laminated brazing material layer includes a third brazing material layer using iron or an iron alloy as a brazing material. The melting temperature lowering material, brazing composite material according to claim 1 or 2, characterized in that the particle size is below 5μm or less than a diameter of 1 [mu] m. The brazing composite material according to any one of claims 1 to 3 , wherein the base material is stainless steel. In the method for producing a brazing composite material in which a laminated brazing material layer is bonded to a base material layer,
Mix silicon particles with organic solvent,
After this mixture is applied to a laminated brazing material layer or a base material layer including a titanium component layer using titanium or a titanium alloy as a brazing material and a nickel component layer using nickel or a nickel alloy as a brazing material,
A method for producing a brazing composite material, comprising bonding the laminated brazing material layer and the base material layer. For the organic solvent, an organic solvent that volatilizes at 70 ° C. or higher and 100 ° C. or lower is used.
Between applying the mixture and bonding the laminated brazing filler metal layer and the base material layer, store at less than 70 ° C.,
The laminated brazing filler metal layer and the base material layer are joined by cold rolling,
6. The method for producing a brazing composite material according to claim 5 , wherein annealing is performed at a temperature exceeding 100 ° C. after the cold rolling.

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