WO2016139860A1 - ろう付け用合金粉末および接合部品 - Google Patents
ろう付け用合金粉末および接合部品 Download PDFInfo
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- WO2016139860A1 WO2016139860A1 PCT/JP2015/084284 JP2015084284W WO2016139860A1 WO 2016139860 A1 WO2016139860 A1 WO 2016139860A1 JP 2015084284 W JP2015084284 W JP 2015084284W WO 2016139860 A1 WO2016139860 A1 WO 2016139860A1
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- brazing
- alloy powder
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/3033—Ni as the principal constituent
- B23K35/304—Ni as the principal constituent with Cr as the next major constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
- B23K35/0244—Powders, particles or spheres; Preforms made therefrom
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/07—Alloys based on nickel or cobalt based on cobalt
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/02—Amorphous alloys with iron as the major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/04—Amorphous alloys with nickel or cobalt as the major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2200/00—Crystalline structure
- C22C2200/02—Amorphous
Definitions
- the present invention relates to a brazing alloy powder and a joined part.
- one particle is referred to as “particle”, and an aggregate of the particles is referred to as “powder”.
- An alloy particle containing an amorphous phase is referred to as “amorphous alloy particle”, and an alloy powder that is an aggregate of alloy particles configured to contain 10% by volume or more of the amorphous alloy particle is referred to as “amorphous alloy powder”.
- alloy particles composed of a crystal phase that does not substantially include an amorphous phase are referred to as “crystal alloy particles”, and an alloy powder that is an aggregate of the crystal alloy particles is referred to as “crystal alloy powder”.
- a heat exchanger (EGR cooler) of an exhaust gas recirculation system (EGR: Exhaust Gas Recycling System) configured using various stainless steels, a gas turbine configured using various heat-resistant alloys,
- EGR Exhaust Gas Recycling System
- brazing brazing joining
- brazing joint parts used in highly corrosive environments such as exhaust gas, combustion gas, steam, etc.
- brazing material using Ni-based alloy powder containing Cr having an effect of enhancing corrosion resistance.
- a brazing material containing B or P having an effect of lowering the melting point is also used.
- Ni alloy brazing materials include, for example, BNi-2 and BNi-5 containing B, and BNi-7 containing P, which are standardized in JIS and AWS standards. These brazing materials are so brittle that plastic working such as rolling is difficult, and are generally used in the form of alloy powder.
- the Ni alloy heat-resistant brazing materials described in Patent Documents 1 and 2 contain Cr, P, Si (silicon), etc., and are said to have good wettability and salt water corrosion resistance and can be brazed at about 1050 ° C. (Patent Document 1).
- brazing materials are said to be usable in the form of powders, foils, rods and the like produced by a normal atomizing method.
- the brazing material described above has an appropriate melting point.
- a powder having the above-described composition is prepared, and an appropriate amount of a binder is mixed with the powder to prepare a paste.
- a method of applying and heating a “powder brazing material” to the bonded portion is common.
- defects are likely to occur in the brazed portion (brazed portion).
- there is dissatisfaction with the bonding strength (brazing strength, brazing strength) of the bonded portion there is dissatisfaction with the bonding strength (brazing strength, brazing strength) of the bonded portion, and further improvement of the bonding strength is desired.
- One of the objects of the present invention is to provide an alloy powder for brazing in which the occurrence of defects in the brazed portion is suppressed and the bonding strength of the bonded portion can be improved.
- Another object of the present invention is to provide a joined part that is brazed using the brazing alloy powder of the present invention and that has a high joining strength at the joined part.
- the brazing alloy powder of the present invention is an alloy powder composed of particles containing 55% by mass or more of at least one element selected from Ni, Fe, and Co, and the alloy powder is amorphous. D90 ⁇ 60 ⁇ m when the particle size containing 10% or more of the phase-containing alloy particles and 90% in the integrated volume distribution curve by the laser diffraction scattering method is d90.
- the said alloy powder contains 40% or more of alloy particles containing an amorphous phase.
- the alloy powder has a particle size indicating 10%, 50%, and 90% in an integrated volume distribution curve by a laser diffraction scattering method, where d10, d50, and d90 are (d90 ⁇ d10) / d50 ⁇ It is preferably 1.5.
- the component of the alloy powder is represented by a composition formula: M 100-xyz Cr x Q y Si z (mass%), and the M is at least one selected from Ni, Fe, and Co.
- Q is at least one element selected from B and P, x satisfies 15 ⁇ x ⁇ 30, y satisfies 1 ⁇ y ⁇ 12, and z satisfies 0 ⁇ z. It is preferable that ⁇ 8 is satisfied and 7 ⁇ y + z ⁇ 15 is satisfied.
- a part of the M may be substituted with 5% by mass or less of Mo.
- a part of the M may be substituted with 2% by mass or less of Cu.
- the brazing alloy powder of the present invention hardly causes defects in the brazed part (brazed part), it can contribute to the improvement of the joining strength of the joined part. Moreover, by applying the brazing material constituted by using the brazing alloy powder of the present invention to brazing (brazing) a plurality of members, it is possible to obtain a joined component having a high joining strength at the joined portion. .
- the brazing alloy powder of the present invention is an alloy powder composed of particles (alloy particles) containing 55% by mass or more of at least one element selected from Ni, Fe, and Co. The elements constituting the alloy particles will be described later.
- the brazing alloy powder according to the present invention contains 10% or more of amorphous alloy particles in a ratio of the number of particles, and d90 in an integrated volume distribution curve (hereinafter referred to as “cumulative distribution”) by a laser diffraction scattering method is 60 ⁇ m. It is important that: By including such an amorphous alloy particle containing an amorphous phase at a predetermined ratio and constituting the alloy powder having a specific particle size distribution, the occurrence of defects in the brazed portion using the alloy powder is suppressed, It is possible to improve the bonding strength of the bonded portion.
- Amorphous alloy particles have a smoother particle surface than crystalline alloy particles. Therefore, if the amorphous alloy particles have the same particle size, the surface area (total surface area) is smaller than that of the crystal alloy particles, and the amount (volume value) of the oxide layer formed on the surface of the particles is small. Therefore, the oxygen content contained in the amorphous alloy particles is smaller than that of the crystal alloy particles if they have the same particle size.
- Amorphous alloy particles are more uniform in chemical composition between particles than crystal alloy particles and have less variation. Therefore, even when the amorphous alloy particles are crystallized by heating, the structure tends to be more homogeneous and less variable than the structure after the crystalline alloy particles are similarly heated. is there.
- brazing alloy powders would have melted into a liquid state by heating when the amount of oxide layer (volume value) was large, or when the uniformity of the structure after heating was low and the component variation was large It has been confirmed that the wettability of the material (hereinafter referred to as “wax”) tends to decrease. Therefore, when the crystal alloy powder is used as a brazing material (brazing material), the solder melts into a liquid state by heating, but bubbles are likely to be entrained when wetting and spreading on the surface to be joined.
- the amorphous alloy powder configured to include 10% or more of the amorphous alloy particles described above tends to exhibit good wettability with respect to an object (base material) when melted by heating and becomes liquid. There is. Therefore, when such an amorphous alloy powder is used for the brazing material, the braze smoothly wets and spreads on the surface to be joined, and the entrainment of bubbles in the brazing layer portion of the joined portion is suppressed. Therefore, the brazing material using the amorphous alloy powder suppresses the occurrence of defects due to residual bubbles in the brazing layer portion of the joined portion, prevents the mechanical strength of the joined portion from being lowered, and the joined strength of the joined portion. It is possible to obtain a high-joint component.
- the brazing alloy powder (amorphous alloy powder) of the present invention contains 10% or more of alloy particles (amorphous alloy particles) containing an amorphous phase. If the content ratio of the amorphous alloy particles is less than 10%, the effect of improving the wettability described above can hardly be expected, so that the effect of improving the joint strength of the joined portion after brazing is hardly obtained. From the viewpoint of obtaining the above-described wettability improving effect, it is preferable to include 40% or more of alloy particles including an amorphous phase, and the bonding strength is further improved. More preferably, it contains 80% or more of alloy particles containing an amorphous phase, and the bonding strength is further improved.
- the brazing alloy powder of the present invention is an aggregate of alloy particles including amorphous alloy particles.
- the content ratio (number ratio) of amorphous alloy particles in the brazing alloy powder is determined by structure observation. Specifically, first, a plurality of particles randomly selected from the brazing alloy powder (hereinafter referred to as “powder”) are embedded in a resin, polished to form a flat surface, and then a marble liquid. The observation surface including the cross section of the powder is produced by etching using Next, the number of amorphous alloy particles (particle number NA) and the total number of alloy particles (total particle number N) present in the range of 0.5 mm square are counted on the observation surface observed at an appropriate magnification with an optical microscope.
- particles in which a crystal structure such as dendrite is not observed in a cross section of a particle having a focused part (a clear outline of the surroundings) are determined as crystal alloy particles.
- the alloy particle in which the crystal structure mentioned above is not observed is an amorphous state.
- the powder constituted by mixing the alloy particles in which the crystal structure is not observed and the particles in which the crystal structure is observed corresponds to the amorphous alloy particles 1 as shown in FIG.
- the halo pattern 4 indicating the amorphous phase and the crystal peak 3 corresponding to the crystal alloy particle 2 can be confirmed.
- the brazing alloy powder of the present invention has d90 ⁇ 60 ⁇ m, where d90 is a particle size indicating 90% in an accumulated volume distribution curve (cumulative distribution) by a laser diffraction scattering method.
- d90 is a particle size indicating 90% in an accumulated volume distribution curve (cumulative distribution) by a laser diffraction scattering method.
- An alloy powder having a small d90 value tends to have a small void volume between particles due to a small content of coarse particles in the powder layer. Even when such an alloy powder is used for brazing as a paste-like brazing material, in the brazing filler metal layer arranged on the surface to be joined, there is moisture that easily evaporates by heating in the voids between the particles. .
- the brazing alloy powder of the present invention is d90 ⁇ 60 ⁇ m.
- d90 ⁇ 45 ⁇ m is preferable.
- d90 ⁇ 20 ⁇ m from the viewpoint of practicality such as the manufacturing cost of the alloy powder. The degree is considered to be sufficient.
- the brazing alloy powder of the present invention has a particle size of 10%, 50%, and 90% in the cumulative volume distribution curve obtained by the laser diffraction scattering method when d10, d50, and d90 are (d90 ⁇ ). It is preferable that d10) /d50 ⁇ 1.5 is satisfied.
- the (d90-d10) / d50 value may be considered as a sharpness indicating the degree to which the particle size distribution of particles containing many particles is sharp, and the smaller the value, the sharper the particle size distribution of the powder. Represents that. Powders having a sharp particle size distribution are generally preferred because they are easy to handle and do not require further operations such as sieving. Accordingly, the (d90-d10) / d50 value of the brazing alloy powder is preferably small for practical use, and is preferably, for example, 1.35 or less.
- the brazing alloy powder of the present invention is composed of particles (alloy particles) containing 55% by mass or more of at least one element selected from Ni, Fe, and Co.
- Ni, Fe, and Co may be contained alone by 55 mass% or more, or when Fe or Co is contained in 55 mass% or more of Ni, or Ni is contained in 55 mass% or more of Fe. In some cases, Ni or Fe may be contained with respect to Co of 55 mass% or more.
- the brazing material contains 55% by mass or more of Ni
- it is suitable for brazing a member using, for example, stainless steel, carbon steel, pure Ni, Ni-base alloy, pure Co, Co-base alloy, etc., for example, EGR cooler, In addition to general heat exchangers, it can be used for brazing metal catalysts, food handling components, medical devices, marine and automotive applications, etc.
- the brazing material contains Fe in an amount of 55% by mass or more, there is basically the same usefulness as when the main component is Ni.
- Such a brazing material using an Fe-based alloy powder is used for brazing automobile EGR coolers, industrial / household heat exchangers, metal honeycomb catalysts, and the like.
- the inclusion of Fe tends to increase the brazing liquid liquidus temperature and increase the brazing temperature, but it is cheaper than Ni and Co, so the brazing material manufacturing cost (raw material cost) is reduced. There is also an advantage that can be done.
- the brazing material contains Co in an amount of 55% by mass or more, there is basically the same usefulness as when the main component is Ni.
- the brazing material using such Co-based alloy powder is used for brazing of heat-resistant alloys such as turbines. Further, by containing Co, further improvement in heat resistance of the brazed joint component can be expected.
- the constituent elements of the brazing alloy powder of the present invention include Ni (nickel), Fe (iron), and Co (cobalt) depending on the purpose and application such as corrosion resistance, oxidation resistance, heat resistance, and low melting point.
- a plurality of elements can be combined.
- Cr chromium
- Mo mobdenum
- Cu copper
- V vanadium
- Nb niobium
- Ta tantalum
- C carbon
- N nitrogen
- B boron
- P phosphorus
- Si silicon
- the brazing alloy powder of the present invention is preferably represented by a composition formula: M 100-xyz Cr x Q y Si z (mass%), and the M is at least selected from Ni, Fe, and Co.
- M is at least selected from Ni, Fe, and Co.
- Q is at least one element selected from B and P, x satisfies 15 ⁇ x ⁇ 30, y satisfies 1 ⁇ y ⁇ 12, and z is 0 ⁇ z ⁇ 8 and 7 ⁇ y + z ⁇ 15.
- M is Ni ⁇ 55 mass%, or when Ni ⁇ (Fe + Co) and (Ni + Fe + Co) ⁇ 55 mass%, the corrosion resistance and heat resistance are further improved.
- the alloy powder for brazing represented by such a composition formula is suitable for brazing of, for example, an EGR cooler for automobiles and various parts for turbines, which particularly require heat resistance.
- the brazing material contains Cr in a range satisfying 15 ⁇ x ⁇ 30 (15% by mass or more and 30% by mass or less).
- the effect of improving the corrosion resistance of the brazed joint is remarkably exhibited.
- Cr is less than 15% by mass, a remarkable improvement in corrosion resistance cannot be expected.
- Cr exceeds 30% by mass, the embrittlement tendency increases, and the mechanical strength of the bonded portion after brazing may be reduced.
- Q y : 1 ⁇ y ⁇ 12 Q is at least one element selected from B and P.
- B and P have an amorphous forming ability. Therefore, when forming an amorphous phase, it is preferable to contain B and P. P can also be expected to reduce the melting point of the alloy powder.
- the brazing material contains at least one selected from B or P, a range satisfying 1 ⁇ y ⁇ 12 (1% by mass or more and 12% by mass or less) is preferable. When such a brazing material is used, since the wettability of the brazing tends to be improved, an effect of improving the mechanical strength of the bonded portion can be expected. If the Q is less than 1% by mass, the formation of the amorphous phase becomes unstable. Moreover, when said Q exceeds 12 mass%, the to-be-joined part after brazing and the corrosion resistance of the vicinity may fall.
- Si z : 0 ⁇ z ⁇ 8 (including 0) Si has an assisting effect on amorphization by B or P. Therefore, when forming an amorphous phase, it is preferable to add Si, but it is not an essential contained element.
- Si is contained in the brazing material, the range satisfying 0 ⁇ z ⁇ 8 (8% or less and including 0), and the sum of Q and Si (y + z) is 7 ⁇ y + z ⁇ 15 (7% by mass or more) 15 mass% or less) is preferable.
- a brazing material since the wettability of the brazing tends to be improved, an effect of improving the mechanical strength of the bonded portion can be expected.
- Si exceeds 8% by mass, the tendency of embrittlement increases, or when (y + z) exceeds 15% by mass, the tendency to embrittlement and the tendency to decrease corrosion resistance increase. The strength may decrease.
- a part of M may be replaced with 5% by mass or less of Mo.
- Mo has an effect of improving the amorphous forming ability in addition to the effect of improving the corrosion resistance and heat resistance.
- an effect of improving the corrosion resistance of the bonded portion after brazing, particularly the corrosion resistance against chloride ions can be expected.
- a part of M may be replaced with 2% by mass or less of Cu.
- Cu has an effect of improving corrosion resistance.
- an effect of improving the corrosion resistance of the bonded portion after brazing, particularly the corrosion resistance against sulfuric acid can be expected.
- the above-described brazing alloy powder of the present invention can be produced by using, for example, a rapid cooling powder manufacturing method such as a water atomizing method, a gas atomizing method, a rotating water atomizing method (Spinning Water Atomization Process).
- a rapid cooling powder manufacturing method such as a water atomizing method, a gas atomizing method, a rotating water atomizing method (Spinning Water Atomization Process).
- These rapid cooling powder manufacturing methods are also called melting process methods, and molten metal (molten metal) containing a necessary amount of elements having an amorphous forming ability is continuously dropped and granulated, and the molten metal (molten metal particles) is granulated. This is a method of rapidly cooling and solidifying to amorphize the solidified structure.
- an amorphous alloy having a cumulative distribution satisfying d90 ⁇ 60 ⁇ m or a particle size distribution satisfying (d90 ⁇ d10) /d50 ⁇ 1.5 can be produced.
- an amorphous alloy powder having a desired cumulative distribution and particle size distribution can be obtained by performing classification processing such as sieving.
- the cooling rate of the molten particles and the alloy particles solidified by the molten particles is generally set in the method for producing the crystalline alloy powder. Set a correspondingly larger cooling rate.
- the amorphous alloy powder containing 50 volume% or more of amorphous alloy particles it is considered that the influence of the component composition of the molten metal particles is large.
- the joining component of the present invention which is formed by joining a plurality of members with a brazing material composed of the brazing alloy powder of the present invention, will be described. Since the joining component of the present invention is brazed using the brazing alloy powder of the present invention, it can have a higher bonding strength than a joining component joined using a conventional crystalline alloy powder.
- a bonded component of the present invention has, for example, a configuration in which two members to be bonded (hereinafter referred to as “base material”) are bonded to each other and one base material. It has a configuration in which a plurality of base materials are bonded to each other with corresponding bonded portions, such as a configuration in which two base materials are bonded to each other.
- the brazing alloy powder of the present invention is placed on the joined surface, heated to be melted, and the molten solder is wet spread on the joined surface. It can be produced by a method of cooling and solidifying later.
- the alloy powder can be arranged on the surface to be joined by a method of sprinkling the binder and the alloy powder, a method of applying a brazing material mixed with the binder and the alloy powder, or the like.
- the above-described heating to solidification process is preferably performed in a vacuum atmosphere, in an inert gas atmosphere of argon or nitrogen with reduced pressure, or in a high-purity dry hydrogen gas atmosphere.
- a strong reducing hydrogen gas atmosphere or a vacuum atmosphere is preferable, and a high effect can be expected for preventing oxidation of the bonded portion and preventing residual bubbles.
- FIG. 1 shows an example of an image observed with an SEM, which was examined for an amorphous alloy powder arbitrarily selected from the manufactured ones.
- FIG. 1 shows a laser diffraction / scattering particle size distribution measuring apparatus (Microtrac (registered trademark)) manufactured by Nikkiso Co.
- FIG. 2 shows an example of a cumulative distribution based on volume using ASVR, and FIG.
- FIG. 3 shows an example of a frequency distribution. From FIG. 2, it was confirmed that the d90 value of this amorphous alloy powder was 46.3 ⁇ m and was within the range of 60 ⁇ m or less. Further, from FIG. 3, it was confirmed that the d50 value of this amorphous alloy powder was 27.3 ⁇ m and the particle size distribution was sharp. In the case of this amorphous alloy powder, it was confirmed that the value of (d90-d10) / d50 was 1.3 (the second decimal place was rounded off).
- amorphous alloy powder (Invention Sample A) is arbitrarily selected, embedded in a resin, polished so that a flat surface is formed, and further etched using marble liquid to include a cross section of the powder.
- a surface was prepared.
- An example of an observation image of the observation surface by an optical microscope is shown in FIG. 4, and an example of an observation image obtained by enlarging a part of the observation image is shown in FIG.
- FIG. 4 An example of an observation image of the observation surface by an optical microscope
- FIG. 4 An example of an observation image obtained by enlarging a part of the observation image is shown in FIG.
- FIG. 6 shows an alloy in which a halo pattern 4 corresponding to an amorphous phase and a crystal peak 3 corresponding to a crystal structure are recognized, and an alloy powder containing an amorphous phase and an alloy powder containing a crystal structure are mixed by X-ray diffraction. It was confirmed to be a powder.
- the number of amorphous alloy particles (particle number NA) and the total number of alloy particles (total particle number N) present in the range of 0.5 mm square were counted on the observation surface observed at an appropriate magnification with an optical microscope.
- the observed cross section is the number of white particles (particle number NA) and the others.
- the total number of alloy particles included (total number of particles N) was determined. Then, when the [NA / N ⁇ 100] value indicating the content ratio of the amorphous alloy particles was determined from the particle number NA and the total particle number N, it was confirmed to be 83.3%.
- two block-shaped base materials made of austenitic stainless steel (SUS304) are prepared, and an appropriate amount of binder is applied to an arbitrarily selected amount of amorphous alloy powder (Invention Example A).
- a paste-like brazing material was prepared by mixing. The brazing material is applied to the bonded surface of one base material, the other base material is placed thereon, heated to 1080 ° C. in a vacuum heat treatment furnace, held for 3 hours, cooled, The base material was brazed (brazed joint) to produce a plurality of joined parts (brazed joints).
- Example A For comparison with Example A, a crystal alloy powder (Comparative Example A) having substantially the same component composition as Example A was prepared, and a base material having the same material and shape as Example A was prepared. A plurality of joined parts (brazed joints) were produced by brazing (brazing joint) in the same manner.
- test pieces including the bonded portions were cut out from a plurality of bonded parts corresponding to Example A of the present invention, and the tensile strength was measured by a tensile test. As a result, it was confirmed that the average value of the tensile strength of the five test pieces was 282 MPa. Similarly, the average value of the tensile strength of five test pieces measured in the same manner as in Example A using a plurality of joined parts corresponding to Comparative Example A was 231 MPa.
- the joining component using the brazing alloy powder of the present invention is a joining using a crystalline alloy powder (Comparative Example A) substantially free of amorphous alloy particles as a brazing material. It was confirmed that the bonding strength of brazing (brazing joint) was higher than that of the part.
- Example 2 Amorphous alloy powders (Nos. 1 to 15 of the examples of the present invention) and crystal alloy powders (Nos. 16 to 20 of the comparative examples) having the composition shown in Table 1 were prepared by using a gas atomization method. Each of the alloy powders arbitrarily selected from the produced powders was examined, and the d90 obtained from the cumulative distribution by the laser diffraction scattering method (volume basis) and the content ratio of amorphous alloy particles obtained by structural observation ([NA / N ⁇ 100] values) are also shown in Table 1.
- two block-like base materials made of ferritic stainless steel (SUS430) are prepared, and an appropriate amount of binder is mixed with an arbitrarily selected amount of alloy powder to form a paste-like wax A material was prepared.
- the brazing material is applied to the joining surface of one base material, the other base material is placed thereon, heated to 1100 ° C. in a vacuum heat treatment furnace, held for 30 minutes, cooled, The base material was brazed (brazed joint) to produce a plurality of joined parts (brazed joints).
- Such joining parts were produced by brazing materials produced using the respective alloy powders.
- Example 3 As in Example 1, the gas atomization method is used to contain 28.9% Cr, 6.2% P, 3.2% Si, 0.1% Fe, and the balance of Ni and trace elements.
- the brazing alloy powder of the present invention and the alloy powder outside the scope of the present invention were produced. Further, by the same method as in Example 1, the ratio of amorphous phase particles contained in each alloy powder and the particle size distribution of the alloy powder were determined. As a result, the brazing alloy powder of the present invention has 92.5% amorphous phase particles and d90 of 43.2 ⁇ m, and the alloy powder outside the scope of the present invention has 6.5% amorphous phase. With a d90 of 69.5 ⁇ m.
- the melting point was measured from each endothermic peak by changing the heating rate to 5 ° C./min, 10 ° C./min, and 20 ° C./min by differential thermal analysis (DTA).
- the liquidus temperature TL was obtained by extrapolating the rate of temperature increase to 0 ° C./min.
- the liquidus temperature TL was 1006 ° C. for the alloy powder outside the scope of the present invention, but the brazing alloy powder of the present invention was 996 ° C. and 10 ° C. lower.
- the temperature at which the particles are completely melted is high because crystalline particles that are not amorphous phases are relatively coarse and have a high melting point phase.
- the amorphous phase particles do not have substantial segregation, and the structure after crystallization by heating becomes fine and homogeneous. Therefore, it is presumed that the temperature at which the particles are completely melted is lowered.
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Abstract
Description
なお、本明細書では、1つの粒を「粒子」といい、その粒子の集合体を「粉末」という。また、アモルファス相を含む合金粒子を「アモルファス合金粒子」といい、そのアモルファス合金粒子を10体積%以上含むように構成された合金粒子の集合体である合金粉末を「アモルファス合金粉末」という。また、実質的にアモルファス相を含まない結晶相により構成された合金粒子を「結晶合金粒子」といい、その結晶合金粒子の集合体である合金粉末を「結晶合金粉末」という。
本発明の目的の1つは、ろう付け部の欠陥の発生が抑制され、被接合部の接合強度の向上が可能な、ろう付け用合金粉末を提供することである。また、もう1つの目的は、本発明のろう付け用合金粉末を用いてろう付けされた、被接合部の接合強度が高い接合部品を提供することである。
すなわち本発明のろう付け用合金粉末は、Ni、Fe、Coから選ばれた少なくとも1種の元素を55質量%以上含む粒子を用いて構成された合金粉末であって、前記合金粉末は、アモルファス相を含む合金粒子を10%以上含むとともに、レーザー回折散乱法による積算体積分布曲線において90%を示す粒径をd90とするとき、d90≦60μmである。
また、前記合金粉末は、レーザー回折散乱法による積算体積分布曲線において10%、50%、および90%を示す粒径をそれぞれd10、d50、およびd90とするとき、(d90-d10)/d50≦1.5であることが好ましい。
また、前記Mの一部が、5質量%以下のMoに置換されていてもよい。
また、前記Mの一部が、2質量%以下のCuに置換されていてもよい。
また、本発明のろう付け用合金粉末を用いて構成されたろう材を、複数の部材のろう付け(ろう接)に適用することにより、被接合部の接合強度が高い接合部品を得ることができる。
上述したように、本発明のろう付け用合金粉末は、Ni、Fe、Coから選ばれた少なくとも1種の元素を55質量%以上含む粒子(合金粒子)を用いて構成されている。この場合、Ni、Fe、Coが単独で55質量%以上含まれていてもよいし、55質量%以上のNiに対してFeやCoを含む場合や、55質量%以上のFeに対してNiやCoを含む場合や、55質量%以上のCoに対してNiやFeを含む場合があってもよい。
Crは、耐食性の向上効果を有する。よって、ろう材に、15≦x≦30(15質量%以上30質量%以下)を満足する範囲で、Crを含有することが好ましい。こうしたろう材を用いた場合、ろう付け接合部の耐食性の向上効果が顕著に表れる。なお、Crが15質量%未満であると、顕著というほどの耐食性の向上効果が期待できない。また、Crが30質量%を超えると、脆化傾向が強まるため、ろう付け後の被接合部の機械的強度が低下することがある。
前記Qは、BまたはPから選ばれた少なくとも1種の元素である。BやPは、アモルファス形成能を有する。よって、アモルファス相を形成する場合、BやPを含有することが好ましい。また、Pには合金粉末の融点の低減効果も期待できる。BまたはPから選ばれた少なくとも1種をろう材に含む場合、1≦y≦12(1質量%以上12質量%以下)を満足する範囲が好ましい。こうしたろう材を用いた場合、ろうの濡れ拡がり性が向上する傾向があるため、被接合部の機械的強度の向上効果が期待できる。なお、前記Qが1質量%未満であると、アモルファス相の形成が不安定になる。また、前記Qが12質量%を超えると、ろう付け後の被接合部やその近傍の耐食性が低下することがある。
Siは、BやPによるアモルファス化の助勢効果を有する。よって、アモルファス相を形成する場合、Siを加えることが好ましいが、必須の含有元素ではない。Siをろう材に含む場合、0≦z≦8(8質量%以下で0を含む)を満足する範囲、かつ、前記QとSiの合計(y+z)が7≦y+z≦15(7質量%以上15質量%以下)を満足する範囲であることが好ましい。こうしたろう材を用いた場合、ろうの濡れ拡がり性が向上する傾向があるため、被接合部の機械的強度の向上効果が期待できる。なお、Siが8質量%を超えると脆化傾向が強まるため、あるいは(y+z)が15質量%を超えると脆化傾向や耐食性の低下傾向が強まるため、ろう付け後の被接合部の機械的強度が低下することがある。
本発明の接合部品は、本発明のろう付け用合金粉末を用いてろう付けされているため、従来の結晶合金粉末を用いて接合された接合部品よりも高い接合強度を有することができる。こうした本発明の接合部品は、例えば、1箇所の被接合部を有して2つの被接合部材(以下、「基材」という。)が接合された構成や、1つの基材に対して各々被接合部を有して2つの基材が接合された構成など、複数の基材が対応する被接合部を有して接合された構成を有してなる。
質量%で、Crを29.4%、Pを6.3%、Siを4.1%、残部Niおよび微量元素により構成されたアモルファス合金粉末(本発明例A)を、ガスアトマイズ法を用いて作製した。この場合、Niと微量元素の合計は60.2質量%になり、55質量%以上のNiを含んでいる。作製した中から任意に選んだアモルファス合金粉末を対象として調べた、SEMによる観察像の一例を図1に、日機装株式会社製のレーザー回折・散乱式の粒径分布測定装置(Microtrac(登録商標)ASVR)を用いた体積基準による累積分布の一例を図2に、頻度分布の一例を図3に、それぞれ示す。図2より、このアモルファス合金粉末のd90値が46.3μmであり、60μm以下の範囲内であることが確認された。また、図3より、このアモルファス合金粉末のd50値が27.3μmであるとともに、粒度分布がシャープであることが確認された。なお、このアモルファス合金粉末の場合、(d90-d10)/d50値が1.3(小数点下第2位を四捨五入)であることが確認された。
表1に示す成分組成を有するアモルファス合金粉末(本発明例のNo.1~15)と結晶合金粉末(比較例のNo.16~20)を、ガスアトマイズ法を用いて作製した。作製した中から任意に選んだそれぞれの合金粉末を対象として調べた、レーザー回折散乱法(体積基準)による累積分布から求めたd90と、組織観察により求めたアモルファス合金粒子の含有割合([NA/N×100]値)を、表1に併記する。
実施例1と同様に、ガスアトマイズ法により、質量%で、Crを28.9%、Pを6.2%、Siを3.2%、Feを0.1%含み、残部がNiおよび微量元素からなる、本発明のろう付け用合金粉末と、本発明の範囲外である合金粉末とを製作した。また、実施例1と同様な方法により、それぞれの合金粉末に含まれるアモルファス相の粒子の割合と、その合金粉末の粒度分布とを求めた。その結果、本発明のろう付け用合金粉末は、92.5%がアモルファス相の粒子で、d90が43.2μmであり、本発明の範囲外である合金粉末は、6.5%がアモルファス相の粒子で、d90が69.5μmであった。また、両者の合金粒子について、示差熱分析(DTA:Differential Thermal Analysis)により、昇温速度を5℃/min、10℃/min、20℃/minと変えて、それぞれの吸熱ピークから融点を測定し、液相線温度TLを昇温速度を0℃/minに外挿して求めた。液相線温度TLは、本発明の範囲外である合金粉末は1006℃であったが、本発明のろう付け用合金粉末は996℃で10℃だけ低かった。この点に関しては、アモルファス相でない結晶質の粒子が比較的粗大であって融点の高い相が存在しているため、完全に溶融する温度が高くなったと推察される。これに対し、アモルファス相の粒子は、実質的な偏析が存在せず、加熱によって結晶化した後の組織が微細かつ均質になるため、完全に溶融する温度が低くなったと推察される。
2.結晶合金粒子
3.結晶ピーク
4.ハローパターン(アモルファス相)
Claims (7)
- Ni、Fe、Coから選ばれた少なくとも1種の元素を55質量%以上含む粒子を用いて構成された合金粉末であって、
前記合金粉末は、アモルファス相を含む合金粒子を10%以上含むとともに、レーザー回折散乱法による積算体積分布曲線において90%を示す粒径をd90とするとき、d90≦60μmである、ろう付け用合金粉末。 - 前記合金粉末は、アモルファス相を含む合金粒子を40%以上含む、請求項1に記載のろう付け用合金粉末。
- 前記合金粉末は、レーザー回折散乱法による積算体積分布曲線において10%、50%、および90%を示す粒径をそれぞれd10、d50、およびd90とするとき、(d90-d10)/d50≦1.5である、請求項1または2に記載のろう付け用合金粉末。
- 前記合金粉末の成分は、組成式:M100-x-y-zCrxQySiz(質量%)で表され、前記MはNi、Fe、Coから選ばれた少なくとも1種の元素であり、前記QはB、Pから選ばれた少なくとも1種の元素であり、前記xは15≦x≦30を満たし、前記yは1≦y≦12を満たし、前記zは0≦z≦8を満たし、かつ、7≦y+z≦15を満たす、請求項1乃至3のいずれか1項に記載のろう付け用合金粉末。
- 前記Mの一部が、5質量%以下のMoに置換されている、請求項4に記載のろう付け用合金粉末。
- 前記Mの一部が、2質量%以下のCuに置換されている、請求項4に記載のろう付け用合金粉末。
- 請求項1乃至6のいずれか1項に記載のろう付け用合金粉末を用いて構成されたろう材により、複数の部材が接合されて形成されている、接合部品。
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US15/554,795 US20180015574A1 (en) | 2015-03-05 | 2015-12-07 | Brazing alloy powder and joined component |
JP2017503321A JPWO2016139860A1 (ja) | 2015-03-05 | 2015-12-07 | ろう付け用合金粉末および接合部品 |
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