JP2011041956A - Clad material and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a clad material which inhibits higher melting point of a filler metal composition layer to avoid lowering of strength and generation of thermal deformation of a metallic material, which reduces manufacturing cost, which thins a filler metal composition layer to prevent the filler metal from sagging during brazing, and which further improves machinability such as press formability, and also to provide a method of manufacturing the clad material. <P>SOLUTION: Phosphorus copper alloy powder is stuck by pressing to a base material 1 to form a filler metal composition layer 11, and the clad material 8 in which the filler metal composition layer 11 is formed is heated for a required time at a temperature at least equal to or higher than the solidus temperature of the phosphorus copper alloy and lower than the liquidus temperature. Thus, in the phosphorus copper alloy (Cu<SB>3</SB>P phase) containing 5% or more phosphorus component in weight ratio, there is formed the filler metal composition layer 11 in which copper (α phase) containing 2% or less phosphorus component in weight ratio is dispersed in a dotted manner. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a clad material and a manufacturing method thereof.

  In general, there is a brazing method using a brazing material as a metal joining method. Examples of the brazing material include various types of brazing materials depending on the type of metal to be joined, such as phosphor copper brazing and nickel brazing.

  The phosphor copper braze is generally a brazing material dedicated to copper and copper alloy in which 4 to 9% by weight of phosphorus is added to copper to lower the melting point. Among them, JIS standard Z3264 is referred to as BCuP-2. Phosphorus copper brazing is an alloy in which 6.8 to 7.5% phosphorus is added to copper, and is widely used for brazing gas appliances, refrigerators, and other copper products.

  In the case of phosphorous copper wax called BCuP-2 in the JIS standard, because it is a metal that is not ductile at room temperature, workability is poor, and it is difficult to roll and form into a sheet, It is commercially available as a wire, rod or powder.

  However, for example, when a metal plate is press-molded into corrugated plates and fins and valleys are brazed together, such as fins of a plate heat exchanger, a wire rod or powdered phosphor copper solder is used as a metal plate. This requires a process for setting the brazing material so that it is difficult to increase productivity because it takes time and effort.

  For this reason, if a clad material in which a brazing material composition layer is formed on the surface of a metal plate as a base material is manufactured, and the clad material can be used as a fin material to be brazed in the plate heat exchanger as described above, The brazing material setting process can be omitted, and the entire production process can be continued and automated, which can be expected to improve productivity and reduce costs.

  FIG. 7 is a schematic view showing an apparatus for producing a clad material by a general rolling method. The manufacturing apparatus includes a base material rewinding machine 3 for rewinding a base material coil 2 on which a base material 1 made of a metal plate is wound, and a dissimilar material coil on which a dissimilar material 4 made of a different type of metal plate is wound. A rewinding machine 6 for dissimilar material that unwinds 5, a rolling machine 7 for clad forming that rolls the base material 1 and the dissimilar material 4 on top of each other, and a clad material 8 ′ rolled by the rolling machine 7. The clad material coil 9 is provided with a clad material winder 10 for winding.

  In the clad material manufacturing apparatus shown in FIG. 7, the base material 1 is rewound from the base material coil 2 by the base material rewinding machine 3, and the dissimilar material from the dissimilar material coil 5 by the dissimilar material rewinding machine 6. 4 is unwound, the base material 1 and the dissimilar material 4 are overlapped and rolled by a rolling mill 7 for clad forming, and the clad material 8 'rolled by the rolling mill 7 for clad forming is wound on the clad material. The clad material coil 9 is wound up by the machine 10.

  As shown in FIG. 8, the cross-section of the clad material 8 'rolled by the clad forming rolling mill 7 is such that the dissimilar material 4 is pressed against the surface of the base material 1 to form a brazing material composition layer 11'. Become so.

  By the way, various kinds of metals are used as the base material 1. Among them, for example, a copper plate is used as the base material 1, and the dissimilar material 4 has a phosphorus content so that it does not break even when rolled. A metal composed of a phosphor copper alloy formed into a sheet shape with a phosphorus content outside the JIS standard having a weight ratio lower than 4.5% which is the JIS standard of the phosphor copper brazing material BCuP-1 (about 3%) It has been proposed to produce the adopted cladding material 8 '.

  For example, Patent Document 1 shows a general technical level related to the clad material as described above.

JP 2004-114158 A

  However, as described above, as the dissimilar material 4, the use of the phosphor copper alloy formed into a sheet with the phosphorus content lowered to about 3% by weight, the amount of the phosphorus content is reduced. When the liquidus temperature of the brazing material composition layer 11 ′ in the finished clad material 8 ′ becomes high, and the brazing temperature becomes higher than the temperature of the JIS standard product, the strength of the base material 1 is reduced, It has the disadvantage of causing deformation.

  In addition, the thickness t ′ of the brazing material composition layer 11 ′ needs to be repeatedly rolled in order to make it 100 μm or less in view of manufacturing the sheet-like dissimilar material 4 itself by rolling. However, repeated rolling leads to an increase in manufacturing cost, which is not preferable for commercial use. On the other hand, when the number of rolling is reduced and the thickness of the brazing material composition layer 11 ′ is stopped to about 100 μm in order to reduce the manufacturing cost, the brazing material is not brazed during actual brazing because the brazing material composition layer 11 ′ is thick. On the other hand, when the clad material 8 ′ is press-molded, there is a risk that the brazing material composition layer 11 ′ may crack.

  For this reason, the present inventors have developed a clad material manufacturing method and a clad material that can solve the above-mentioned problems and have already filed an application (see Japanese Patent Application Laid-Open No. 2008-49371). It was rare.

  In view of such a situation, the present invention can suppress the increase in the melting point of the brazing material composition layer to avoid the strength reduction of the metal material and the occurrence of thermal deformation, and reduce the manufacturing cost, It is an object of the present invention to provide a clad material that can reduce the thickness of the layer and prevent dripping of the brazing material during brazing, and can further improve workability such as press formability, and a method for manufacturing the same. .

  The present invention relates to a clad material in which a brazing material composition layer composed of at least two kinds of metal phases is coated on a metal material.

  In the clad material, at least one metal phase of at least two metal phases constituting the brazing material composition layer is a brazing material composition layer dispersed in another metal phase, A clad material in which a brazing material composition layer is coated with a metal material can be used.

  In the clad material, among the at least two kinds of metal phases constituting the brazing material composition layer, the dispersed metal layer is copper containing a phosphorus component of 2% or less by weight, and other metal phases Can be a clad material which is a phosphor copper alloy containing a phosphorus component of 5% or more by weight.

  Further, the present invention provides a brazing material composition layer formed by pressure bonding a phosphoric copper alloy powder to a metal material, and the clad material on which the brazing material composition layer is formed has at least a solidus temperature of the phosphoric copper alloy and A brazing material composition layer in which copper containing a phosphorus component of 2% or less by weight is dispersed in a phosphorus copper alloy containing a phosphorus component of 5% or more by weight by heating to a temperature lower than the liquidus temperature for a required time. The present invention relates to a method for producing a clad material characterized in that

  In the method for producing the clad material, it is effective to maintain the temperature in the non-oxidizing atmosphere at a temperature higher than the solidus temperature of the phosphor copper alloy and lower than the liquidus temperature for 20 seconds or more. The non-oxidizing atmosphere is, for example, a mixed gas atmosphere of nitrogen gas and hydrogen gas, a reducing atmosphere such as a DX gas atmosphere containing carbon monoxide, an inert gas atmosphere such as an argon gas atmosphere, or a vacuum atmosphere. Is mentioned.

According to the clad material of the present invention and the manufacturing method thereof, it is possible to prevent the strength of the metal material from being lowered and the occurrence of thermal deformation by suppressing the melting point of the brazing material composition layer from being increased, and to reduce the manufacturing cost. The brazing material composition layer can be thinned to prevent dripping of the brazing material during brazing, and high ductility copper (α phase) is scattered in the phosphor copper alloy (Cu ₃ P phase). By forming the brazing material composition layer by dispersing as described above, it is possible to achieve an excellent effect that workability such as press formability can be further improved.

It is the schematic which shows an example of the manufacturing apparatus used in order to manufacture the clad material of this invention. It is a Cu-P binary alloy standard state figure. It is a diagram which shows the temperature change with respect to the time of the heating and cooling performed in the heating-cooling furnace in order to manufacture the clad material of this invention. It is an expanded sectional view showing an example of the clad material of the present invention. (A) is an enlarged sectional view showing a state in which a pipe as a wire joining test piece is joined to the surface of the clad material, and (b) is an enlarged cross section showing a state in which a plate as a surface joining test piece is joined to the surface of the cladding material. FIG. (A) is a figure which shows the female metal mold | die and male metal mold | die used for the press test of a clad material, (b) is a figure which shows the state which implements a press test, (c) is a clad as a test piece by which the press process was carried out It is a figure which shows material. It is the schematic which shows an example of the manufacturing apparatus used in order to implement the manufacturing method of the clad material by the general rolling method. It is an expanded sectional view showing an example of the conventional clad material.

  Embodiments of the present invention will be described below with reference to the accompanying drawings.

  FIG. 1 is a schematic view showing an example of a manufacturing apparatus used for manufacturing a clad material of the present invention, and rewinds a base material coil 2 around which a base material 1 as a metal material such as a metal plate is wound. A base material unwinding machine 3, a powder crimping machine 12 for crimping metal powder onto the surface of the base material 1 unwound from the base material coil 2 by the base material unwinding machine 3, and a base material by the powder crimping machine 12 1 is a heating / cooling furnace 13 that heats and cools the clad material 8 on which the metal powder is pressure-bonded, a rolling machine 18 that rolls the clad material 8 that is heated and cooled in the heating / cooling furnace 13, and the rolling machine 18 performs rolling. And a clad material winder 10 for winding the clad material 8 as a clad material coil 9.

  The powder crimping machine 12 includes a pair of rolls 14 arranged in a horizontal direction so as to be rotatable, and a powder supply device 15 for supplying metal powder onto each roll 14, and between the pair of rolls 14. While the base material 1 is introduced from the upper side to the lower side, the metal powder is supplied onto the rolls 14 from the powder supply device 15 and the rolls 14 are rotated so that the metal is applied to both surfaces of the base material 1. The powder is crimped.

  In the manufacturing apparatus as described above, the base material coil 2 on which the base material 1 is wound is rewound by the rewinding machine 3, and the surface of the base material 1 that is rewound from the base material coil 2 by the unwinding machine 3. After the metal powder is pressure-bonded to the powder pressure bonding machine 12, the clad material 8 having the metal powder pressure-bonded to the base material 1 by the powder pressure bonding machine 12 is heated in the heating / cooling furnace 13, cooled, and then heated / cooled furnace 13. The clad material 8 heated and cooled in (1) is rolled by a rolling mill 18, and the clad material 8 rolled by the rolling mill 18 is wound up as a clad material coil 9 by a clad material winder 10.

  In the case of the present embodiment, a copper plate is used as the base material 1, while the metal powder is a mixed powder in which at least two kinds of metal powders are mixed so as to have a required brazing material composition. For example, the composition of the phosphor copper brazing material is used, and the mixed powder constituting the composition of the phosphor copper brazing material is a mixture of copper powder and phosphor copper alloy powder. As is clear from the phase diagram of FIG. 2, the composition of the phosphor copper alloy is such that when the weight ratio of phosphorus to copper is increased, the liquidus indicating the melting point approaches the solidus. .38% P is the eutectic point (714 ° C.) having the lowest liquidus temperature.

  When the clad material 8 is produced using the production apparatus as described above, the clad material 8 is heated and cooled in the heating / cooling furnace 13 in a non-oxidizing atmosphere so that a temperature curve as shown in FIG. 3 is obtained. went. The non-oxidizing atmosphere is, for example, a mixed gas atmosphere of nitrogen gas and hydrogen gas, a reducing atmosphere such as a DX gas atmosphere containing carbon monoxide, an inert gas atmosphere such as an argon gas atmosphere, or a vacuum atmosphere. Is mentioned.

  That is, in the heating and cooling furnace 13, the clad material 8 of less than 50 ° C. is heated to 714 ° C. or more (720 ° C. to 730 ° C.) in about 5 minutes and a half and held for about 30 seconds (20 seconds to 40 seconds), Then, the said clad material 8 was cooled to about 75 degreeC over about 8 minutes.

As a result, as shown in FIG. 4, the thickness t is 100 μm or less (about 25 to 30 μm in the example of FIG. 4) on the surface of the base material 1 (plate thickness is about 150 μm), which is the copper plate, and the weight. A brazing material composition layer 11 dispersed so that copper (α phase) containing 2% or less of a phosphorus component by weight is scattered in a phosphor copper alloy (Cu ₃ P phase) containing 5% or more of a phosphorus component in a proportion. It became possible to form.

This is because a phosphorous copper alloy powder is pressure-bonded to a base material 1 as a metal material to form a brazing material composition layer 11, and the clad material 8 on which the brazing material composition layer 11 is formed is transformed into the phosphoric copper alloy shown in FIG. By heating for a required time to a temperature above the solidus temperature (714 ° C.) and lower than the liquidus temperature, it becomes a solid-liquid coexisting phase, and the brazing material composition layer 11 changes from a powder form to a semi-molten state. Then, the interface between the base material 1 and the brazing material composition layer 11 is welded, and then cooled to below the solidus temperature, so that the brazing material composition layer 11 contains phosphorous copper containing a phosphorus component of 5% or more by weight. This is because copper (α phase) containing a phosphorus component of 2% or less by weight in the alloy (Cu ₃ P phase) is precipitated and dispersed so as to be scattered.

  Then, the clad material 8 was produced by changing the composition of the metal powder to be pressure-bonded to the surface of the base material 1, and the produced clad material 8 was subjected to a brazing test and a press test.

  Here, as described above, from the phase diagram of FIG. 2, the composition of the phosphor copper alloy is basically 8.38% P with the lowest melting point, but in this test, it was manufactured with a width of 7% to 9%. used. That is, as the phosphor copper alloy powder, a so-called Cu-8% P powder in which the weight ratio of phosphorus contained in the phosphor copper alloy powder is in the range of 7% to 9% is used, and the Cu-8% P The weight ratio of the copper powder added to the powder to the entire mixed powder was changed to 12%, 20%, 30%, 40% and 50% as shown in [Table 1] below.

  The brazing material composition layer 11 in the manufactured clad material 8 is composed of a copper component and a phosphorous copper alloy component, and the weight ratio of the average phosphorus is 4.0% to 7.0%. It becomes a range. (Incidentally, 4.0% = 8% × (100% −50%), 7.0% ≈8% × (100% −12%))

  As the brazing test, as shown in FIG. 5A, a test is performed in which a pipe 16 having a diameter of φ2 mm and a wall thickness of 0.5 mm is joined to the surface of the clad material 8 as a wire joining test piece, and FIG. ) And a test of joining a plate 17 having a size of 50 mm × 25 mm and a thickness of 1 mm as a surface joining test piece to the surface of the clad material 8, and the state of the fillet (fillet) in each case The surface state of the clad material 8 after brazing was observed.

The brazing conditions are continuous atmosphere furnace, heating zone set temperature: 850 ° C, 900 ° C
Heating zone length: 600mm
Heating time: about 30 minutes Heating atmosphere: nitrogen.

  The results of the brazing test were as shown in [Table 1] (when the brazing temperature is 850 ° C.) and [Table 2] (when the brazing temperature is 900 ° C.).

  That is, when the brazing temperature is set to 850 ° C., the fillet state becomes slightly worse when the weight ratio of the copper powder to the mixed powder of the copper powder and the phosphorous copper alloy powder is 40%. On the other hand, when the weight ratio of the copper powder in the mixed powder of the copper powder and the phosphorous copper alloy powder is 50%, the fillet state is slightly worsened, and after brazing There is also a tendency that the roughness of the surface of the clad material 8 is conspicuous. This is because when the amount of copper powder added is increased, the concentration of phosphorus in the whole is lowered, and the melting point of the brazing material composition layer 11 is increased (see the Cu-P binary alloy standard state diagram shown in FIG. 2). Therefore, when the brazing temperature is low, it means that the brazing property is deteriorated. However, when the brazing temperature is slightly increased to 900 ° C., a mixed powder of the copper powder and the phosphor copper alloy powder. It was confirmed that when the weight ratio of the copper powder in the range of 12% to 40% is within the range, it is possible to obtain a brazing property without defects. In addition, when the weight ratio of the copper powder in the mixed powder of the copper powder and the phosphorous copper alloy powder is in the range of 12% to 40%, the brazing material composition layer 11 in the manufactured cladding material 8 is a component of copper. And the phosphorous copper alloy component, and the weight ratio of the averaged phosphorus is in the range of 4.2% to 7.9%. (By the way, 4.2% = 7% × (100% −40%), and 7.9% ≈9% × (100% −12%).)

  Further, as shown in FIG. 6 (a), the press test uses a female die 19 having a φ23mm hole 23 and a male die 21 having a φ28mm convex portion 20, and is shown in FIG. 6 (b). As described above, the female member 19 and the male die 21 are disposed with the female material by the vice 22 with the clad material 8 produced by changing the amount of copper powder added and the thickness of the base material 1. The clad material 8 was pressed into a shape as shown in FIG. 6C by tightening the mold 19 and the male mold 21 so as to observe the state of the bent portion.

  The results of the press test were as shown in [Table 3] below.

In other words, considering the press formability, if the amount of copper powder, which is a metal with high ductility, is increased, cracking will not occur at the bend, but as described above, if the amount of copper powder added is increased, only that much. Since the concentration of phosphorus in the whole is lowered and the melting point of the brazing material composition layer 11 is increased and the brazing property is deteriorated, the copper powder and the phosphor-copper alloy are used in order to satisfy both the brazing property and the press formability. The weight ratio of the copper powder to the mixed powder with the powder is preferably in the range of 20% to 30% in the range of 12% to 40%, and is ductile in the phosphor copper alloy (Cu ₃ P phase). It is effective to form the brazing material composition layer 11 that is dispersed so that high copper (α phase) is scattered.

  Furthermore, since the thickness of the brazing material composition layer 11 obtained by press-bonding the mixed powder to the base material 1 and heating is too thick, normal crimping cannot be performed. As a result of manufacturing experiments, if the thickness is 90 μm or less, normal crimping is not possible. It was confirmed that the brazing material can be prevented from dripping during actual brazing. In order to investigate the relationship between the thickness of the brazing material composition layer 11 and press formability, a press test similar to that described above and a test for bending the clad material 8 by 90 degrees were performed, and the state of each bent portion was observed. did.

  The results of the press test and the 90-degree bending test of the clad material 8 are as shown in [Table 4] below.

That is, when the thickness of the brazing material composition layer 11 is 60 μm, it is considered that the elongation difference from the base material 1 is large and cracks are generated, and it is confirmed that the processing becomes difficult. From the viewpoint of properties, the thickness of the brazing material composition layer 11 is preferably 30 μm or less. However, if the thickness of the brazing material composition layer 11 of 10 μm or more cannot be secured, the possibility of poor brazing increases. Therefore, the thickness of the brazing material composition layer 11 is more preferably 10 μm to 30 μm, It is effective to form the brazing material composition layer 11 that is dispersed so that highly ductile copper (α phase) is scattered in the phosphor copper alloy (Cu ₃ P phase).

  As described above, instead of using a mixture of two types of powders, copper powder and phosphorous copper alloy powder, a single powder in which the weight ratio of the phosphorous component contained in the phosphoric copper alloy powder is adjusted in advance is used. Even if it is used, the same result as described above is obtained.

In this way, using the manufacturing apparatus as described above, the composition of the brazing material and the thickness of the brazing material composition layer 11 are adjusted, and the heating temperature and the heating time in the heating and cooling furnace 13 are adjusted, as shown in FIG. By producing the clad material 8 in which the brazing material composition layer 11 is dispersed so that copper (α phase) having high ductility is scattered in the alloy (Cu ₃ P phase), the melting point of the brazing material composition layer 11 is reduced. The increase in the strength of the metal material and the occurrence of thermal deformation can be avoided by suppressing the increase in the thickness, and the manufacturing cost can be reduced, the thickness of the brazing material composition layer 11 can be reduced, and the brazing material liquid during brazing can be reduced. Sagging can be prevented, and workability such as press formability can be further improved.

  In addition, the clad material and the manufacturing method thereof according to the present invention are not limited to the above-described embodiments, and it goes without saying that various changes can be made without departing from the gist of the present invention.

1 Base material (metal material)
DESCRIPTION OF SYMBOLS 2 Base material coil 3 Base material rewinding machine 8 Clad material 9 Clad material coil 10 Clad material winding machine 11 Brazing material composition layer 12 Powder pressure bonding machine 13 Heating and cooling furnace 14 Roll 15 Powder supply apparatus 18 Rolling mill t Thickness

Claims (5)

  A clad material, wherein a brazing material composition layer composed of at least two kinds of metal phases is coated on a metal material.   The brazing material composition layer of the brazing material composition layer according to claim 1, wherein at least one of the metal phases is a brazing material composition layer dispersed in another metal phase, A clad material in which a material composition layer is coated on a metal material.   Among the at least two kinds of metal phases constituting the brazing material composition layer according to claim 2, the dispersed metal layer is copper containing a phosphorus component of 2% or less by weight, and the other metal phases are A clad material which is a phosphor copper alloy containing a phosphorus component of 5% or more by weight.   A phosphorous copper alloy powder is pressure-bonded to a metal material to form a brazing material composition layer, and the clad material on which the brazing material composition layer is formed is at least above the solidus temperature of the phosphorous copper alloy and lower than the liquidus temperature. A brazing material composition layer in which copper containing 2% by weight or less of a phosphorus component is dispersed in a phosphorus copper alloy containing 5% or more by weight of a phosphorus component by heating to temperature for a required time is formed. A method for producing a clad material.   The method for producing a clad material according to claim 4, wherein the clad material is maintained at a temperature not lower than the liquidus temperature and lower than the liquidus temperature for 20 seconds or more in a non-oxidizing atmosphere.

Images