JPH10251824A - Al alloy powder brazing filler metal for thermal spraying, thermal spraying method therefor and brazing filler metal-coated extruded porous flat tube obtainable by this - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an Al alloy powder brazing filler metal excellent in brazability and corrosion resistance for obtaining an Al alloy member for brazing by thermal spraying coating of a brazing filler metal and to provide a thermal spraying method therefor. SOLUTION: This Al alloy brazing filler metal for thermal spraying is the one having a compsn. contg., by weight, 6.0 to 20.0% Si, contg. one or two kinds of 0.10 to 1.8% Fe and 0.10 to 1.8% Ni, furthermore contg. 0.5 to 40.0% Zn or one or two kinds of 0.0005 to 0.3% In and 0.0005 to 0.3% Sn, and the balance Al with inevitable impurities. The method for thermal-spraying an Al alloy powder brazing filler metal is the one in which this Al alloy powder brazing filler metal for thermal spraying is used, and high speed gas flame thermal spraying is executed, by which the surface of an Al alloy material is coated with the brazing filler metal to obtain an Al alloy member for brazing excellent in brazability and corrosion resistance. The tube can be obtd. by this.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an Al alloy powder brazing material for thermal spraying, a thermal spraying method thereof, and a brazing material-coated extruded multi-hole flat tube obtained by the method. More specifically, a member such as a heat exchanger manufactured by a brazing (brazing) method has an A surface on various Al alloy materials.
Although the present invention is applied to a case where the coating of a brazing material is difficult by rolling or the like, for example, an Al alloy powder for thermal spraying at the time of coating by spraying a brazing material onto an Al alloy extruded member or the like. The present invention relates to a brazing material, a thermal spraying method thereof, and a brazing material-coated extruded multi-hole flat tube obtained by the method.
In this specification, the composition of all Al alloys is wt%, but will be simply abbreviated to%.

[0002]

2. Description of the Related Art A condenser is shown in FIG. 1 as an example of an aluminum alloy heat exchanger. The tube of this heat exchanger is a multi-hole flat tube formed by extrusion, and brazing sheet fins clad with brazing material are used for the fins, and are integrally manufactured by a brazing method. In recent years, in order to reduce the size and weight of heat exchangers, fins, which have a limit in thinning, are made thinner using bare fins, brazing material is coated on the outside of the extruded tube by thermal spraying, and these are combined and integrated by brazing. (For example, JP-A-63-34495, JP-A-2-84261, etc.). However, in such a method of spraying an Al brazing alloy material on an extruded tube, the alloy composition of the brazing material has not been sufficiently studied, so that there is a problem in brazing properties and corrosion resistance. The method of spraying the material has not been industrialized.

[0003]

An Al alloy heat exchanger or the like needs to have brazing properties and corrosion resistance. However, in view of the above-mentioned circumstances, the object of the present invention is to braze an Al brazing alloy powder by thermal spraying. An object of the present invention is to find an Al alloy powder brazing material for thermal spraying having excellent brazing property and corrosion resistance of an Al alloy member for thermal spraying and a thermal spraying method thereof.

[0004]

According to a first aspect of the present invention, there is provided a method for manufacturing a semiconductor device, comprising: Si: 6.0 to 20.0%;
0 to 1.8% and Ni: 0.10 to 1.8%
Further, an Al alloy brazing powder for thermal spraying, characterized by containing Zn: 0.5 to 40.0%, and the balance consisting of Al and unavoidable impurities.

The invention of claim 2 contains Si: 6.0 to 20.0%, contains one or two of Fe: 0.10 to 1.8% and Ni: 0.10 to 1.8%, and further contains In: 0.0005 to 0.3%. , Sn: An aluminum alloy powder brazing filler metal for thermal spraying, comprising one or two types of 0.0005 to 0.3%, the balance consisting of Al and unavoidable impurities,

A third aspect of the present invention is an Al alloy powder brazing material for thermal spraying, characterized in that the Al alloy powder brazing material according to the second aspect further contains Zn: 0.5 to 40.0%.

Further, the invention of claim 4 provides the above-mentioned claim 1,
By performing high-speed gas flame spraying using the Al alloy powder brazing material for thermal spraying described in any one of 2 and 3, the surface of the Al alloy material is coated with the brazing material, and is excellent in corrosion resistance and brazing property. Characterized in that an Al alloy member for brazing is obtained.
A method of spraying brazing alloy powder,

According to a fifth aspect of the present invention, the Al alloy material is A
5. The method of claim 4, wherein the tube is an extruded multi-hole flat tube made of 1 or Al alloy.

Further, the invention according to claim 6 is a brazing material-coated extruded multi-hole flat tube obtained by the thermal spraying method according to claims 4 and 5.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, each of the above inventions will be described in detail. First, the invention of claim 1 will be described.
The invention according to claim 1 contains Si: 6.0 to 20.0%, and Fe: 0.10%.
Al alloy powder brazing material for thermal spraying containing 1 or 2 types of Ni: 0.1% to 1.8% and Ni: 0.10% to 1.8%, further contains Zn: 0.5 to 40.0%, the balance being Al and unavoidable impurities. It is an abstract.

The role of each additive element in the Al alloy powder brazing material is as follows. Si is an essential element for lowering the melting point of the alloy and making it a brazing filler metal. The amount is
If it is less than 6.0% or more than 20.0%, the melting point does not decrease sufficiently, and it is not suitable as a brazing filler metal. Therefore, the range is set to 6.0 to 20.0%, but the range of 8.0 to 14.0% is preferable in consideration of the wax flowability.

Fe and Ni are important addition elements for brazing brazing materials to be coated by thermal spraying, and are the most important elements for the present invention. In describing the role of Fe and Ni, thermal spraying will first be briefly described. When spraying a brazing alloy material industrially, a spraying device is installed immediately after extrusion in an extrusion line. It is desirable that the extrusion rate of the material be high in order to affect productivity, but the higher the extrusion rate, the thinner the brazing material layer formed by thermal spraying. If a large number of thermal spraying devices are installed in series, it is possible to increase the thickness of the brazing material layer formed by thermal spraying, but there is a limit in terms of the cost of the device. In addition, the yield of the wax by thermal spraying is 10
About 60%, which is also a cause of thinning the brazing material layer. For these reasons, when the brazing material layer is coated by thermal spraying, it is usually about 40 g / m ² , which is about 15 μm in terms of thickness, and is generally used in a heat exchanger as an electric resistance welded tube. It is less than half of the brazing material coverage of the brazing sheet of 0.4 mm of 10% (40 μm). Thus, when coating the Al alloy braze by thermal spraying,
Since the amount of brazing material is small, it is necessary to use a brazing alloy capable of securing sufficient strength and corrosion resistance of the fillet portion by brazing.

Furthermore, in the case of thermal spraying, unlike brazing sheets, brazing does not reach (microscopically) uniformly, so it is necessary to use a brazing material having higher brazing properties than brazing sheets. That is, the amount of the brazing material deposited differs in the width direction of the tube, and the amount of the brazing material at the center in the width direction is larger than the amount of the brazing material at the end. Further, microscopic spraying is not uniform microscopically because a very fine brazing alloy adheres to the tube surface. For this reason, the brazing property of the sprayed brazing material particularly requires the brazing property, and if the brazing property is enhanced, the brazing property can be ensured even if the brazing is unevenly attached. Here, when thermal spraying is performed as powder, Fe and Ni have the function of improving the flowability of brazing and enhancing the brazing performance. In other words, the brazing material is rapidly cooled during thermal spraying,
At that time, when Fe and Ni are added to the brazing material, Fe and Ni become fine compounds and crystallize. Since the crystallization of Fe and Ni occurs before the Si generated by the eutectic reaction, the crystallization of Si at the time of solidification during thermal spraying occurs after the Fe and Ni-based intermetallic compounds are finely generated. Coarse in the brazing material
No Si occurs. Therefore, when the brazing material to which Fe and Ni are added is sprayed, since coarse Si is not generated, the melting of the brazing occurs promptly, and the flowability of the brazing is improved. Such a characteristic is a phenomenon peculiar to the thermal spray brazing material. Where F
If the amounts of e and Ni are less than 0.10%, such effects are insufficient. As described above, from the viewpoint of brazing properties, the addition of Fe and Ni is effective in the thermal spray brazing alloy, but if the addition amount of Fe and Ni is excessively increased, the amount of Fe and Ni-based intermetallic compounds increases, Since it remains unmelted at the time of brazing and conversely impairs the flow of the braze and lowers the brazing properties, the addition amounts of Fe and Ni are each 1.8% or less, but from the point of the braze flow, % Or more and 1.2% or less is particularly recommended.

From the above, in the present brazing material, Fe: 0.10
~ 1.8% and Ni: 0.10 ~ 1.8%, one or two of them are added.
A Fe-Ni based intermetallic compound is generated, a local current is formed around it, and the corrosion resistance of the brazing material is reduced. If the brazing material is thin, the corrosion resistance of the base metal is also reduced. Therefore, from the viewpoint of corrosion resistance, Fe and Ni are desirably added at 0.6% or less, respectively.

[0015] Zn is added to adjust the potential of the brazing material and further increase the corrosion resistance. The amount of addition is
Although it depends on the potential of the alloy, it is usually desirable to add it so that the brazing is lower than that of the Al alloy. Further, when assembling the heat exchanger by brazing, it is preferable to add the heat exchanger so that the potential of the brazing is more noble than the potential of the fins. Here, if Zn is less than 0.5%, the above effect cannot be obtained. Also,
If more than 40.0% of Zn is added, the self-corrosion resistance of the braze decreases. Therefore, the addition of Zn should be 0.5-40.0%.

As unavoidable impurities, other elements (often added to the brazing alloy for the purpose of improving the flowability of the brazing alloy or refining the crystal grains after brazing, etc.), affect the effects of the present invention. ) May be contained as long as each is 0.30% or less, but is preferably 0.05% or less. Here, typical inevitable impurities include Cu, Mn, Mg, and C.
r, Zr, Ti, Bi, Be, Li and the like can be mentioned.

Next, the invention according to claim 2 is characterized in that Si: 6.0 to 20.0%
, Containing one or two of Fe: 0.10 to 1.8% and Ni: 0.10 to 1.8%, In: 0.0005 to 0.3%, Sn: 0.0005
SUMMARY OF THE INVENTION An object of the present invention is to provide an Al alloy powder brazing material for thermal spraying containing about 0.3% of one or two kinds, with the balance being Al and inevitable impurities. Among the alloy compositions of the Al alloy powder brazing material, the meaning and the reason for limiting the range of addition of Si, Fe, and Ni are the same as described above. This Al alloy powder brazing material further contains one or more of In: 0.0005 to 0.3% and Sn: 0.0005 to 0.3%.
Contains seeds. The reason for adding In and Sn in this manner is to adjust the potential of the brazing material and further increase the corrosion resistance. These amounts are determined according to the potential of the Al alloy to be sprayed, but it is usually desirable to add them so as to make the solder less noble than the Al alloy. Further, when assembling the heat exchanger by brazing, it is preferable to add the heat exchanger so that the potential of the brazing is more noble than the potential of the fins. Where 0.0005%
If In is less than 0.005% and Sn is less than 0.0005%, the above effects cannot be obtained. In addition, if more than 0.3% of In and more than 0.3% of Sn are added, the self-corrosion resistance of the braze decreases. Therefore,
One or two kinds of In and Sn are added in the range of 0.0005 to 0.3%. Other unavoidable impurities are the same as those described in the first aspect.

A third aspect of the present invention is to provide an Al alloy powder brazing material for thermal spraying, which further comprises 0.5 to 40.0% of Zn in the Al alloy powder brazing material according to the second aspect. Things. That is, it is an Al-Si-Fe.Ni-In.Sn-Zn alloy powder brazing material. Here, 0.5 to 40.0% of Zn is further added.
When adding In or Sn, these elements are segregated, and even if the segregation is minute, these elements greatly change the potential, so that pit-like corrosion may occur, but in order to prevent this. is there. That is, the addition of Zn prevents a local potential difference from occurring, and further enhances the corrosion resistance. If the amount is less than 0.5%, there is no effect, and if it exceeds 40.0%, the self-corrosion resistance of the wax decreases. Other unavoidable impurities are the same as those described in the first aspect.

The above is the description of the composition of the Al alloy powder brazing material for thermal spraying of the present invention. The brazing alloy of the present invention is used as a powder for thermal spraying. When thermal spraying is performed with a wire, the coarse compound does not completely melt during thermal spraying because the coarse intermetallic compound of Fe system is present in the brazing alloy wire, and is directly sprayed to reach the Al alloy material. Therefore, the effect of improving the brazing property by crystallization of Fe and Ni described above is effective.
It cannot be obtained by adding Fe and Ni. In the case of powder, the Fe and Ni-based intermetallic compounds are fine, and the brazing alloy is almost completely melted at the time of thermal spraying. Therefore, the application of the brazing alloy of the present invention is limited to thermal spray powder. The method for producing the powder may be a commonly used method such as an inert gas atomizing method, and the particle size of the powder may be set to a required size according to the conditions of thermal spraying.

Next, a fourth aspect of the present invention relates to the first aspect,
The surface of the Al alloy material is coated with the brazing material by performing high-speed gas flame spraying using the Al alloy powder brazing material for thermal spraying described in any one of 2 and 3, thereby improving corrosion resistance and brazing property. The gist of the present invention is a method of spraying an Al alloy powder brazing material to obtain an excellent brazing Al alloy member.

Typical examples of the metal powder spraying method include powder type flame spraying, explosive spraying, and plasma spraying. The method for spraying the Al alloy brazing material for thermal spraying of the present invention is a powder type. Flame spraying is recommended, especially high-speed gas flame spraying. This is because, in the high-speed gas flame spraying method, the brazing alloy is sprayed at a high speed, so that the molten solder and the base material are surely brought into contact with each other at the time of spraying, and the cooling rate of the solder at the time of spraying is increased. This is because Fe and Ni are effective as fine compounds to improve brazing properties.

The material to be sprayed may be any Al alloy material that is brazed and needs to have corrosion resistance, and is not particularly limited.
Extruded multi-hole flat tubes for Al alloy heat exchangers, various extruded tubes used for piping, drawn tubes, and the like can be used.

The invention according to claim 5 is a preferred embodiment of the aluminum alloy material to be sprayed according to claim 4. That is, as the Al alloy material, an extruded multi-hole flat tube made of Al or an Al alloy is particularly used for a heat exchanger. Specifically, as the pure Al, alloy No. 10
50, 1100, 1200, and the like. 3003, 3203 and the like.

According to a sixth aspect of the present invention, there is provided a brazing material-coated extruded multi-hole flat tube obtained by the thermal spraying method according to the fourth or fifth aspect. That is, it is an extruded multi-hole flat tube made of brazing material-coated Al or an Al alloy, which is obtained by performing high-speed gas flame spraying using the Al alloy brazing material for thermal spraying according to the present invention. This brazed tube
By combining with a bare corrugated fin and brazing, a core such as a capacitor can be manufactured. In this case, since the fin material is a bare material that is not covered with the brazing material, the fin material can be thinned.

[0025]

EXAMPLES Examples of the present invention (examples of the present invention) will be described below in more detail together with comparative examples and conventional examples. [Embodiment 1] This embodiment corresponds to claims 1, 4, 5, and 6. An aluminum cylindrical billet corresponding to JIS A1050 was hot extruded into a multi-hole flat tube (height 1.8 mm, width 16 mm, 19 holes).
Table 1 shows both sides of this extruded multi-hole flat tube with a width of 16 mm.
Was sprayed by a high-speed gas flame spraying method (Examples Nos. 1 to 12 and Comparative Examples Nos. 13 to 13 in Table 1) of the Al alloy brazing powder (produced by the nitrogen gas atomizing method).
16). The brazing material powder contains 0.04% or less of unavoidable impurity elements.

The high-speed gas flame spraying was performed under the following conditions. -Particle size of powder used: about 20 to 100 m-Fuel gas: mixed gas of propylene and oxygen-Distance between spray gun and tube surface: about 200 mm No. 16 was produced by arc-spraying the brazing alloy wire (diameter 1.5 mm) shown in Table 1 on the tube surface. Conventional example No. 1 in Table 1. No. 17 was produced by arc spraying a brazing alloy wire (diameter 1.5 mm) having the alloy composition (alloy 4343) shown in Table 1. The amount of the brazing material after spraying of these tubes was 35~45g / m ^2.

The obtained multi-hole flat tube is 100 mm in length.
Cut into 0.07mm thick corrugated Al-
In combination with 0.5% Si-1% Fe-0.5% Ni-2% Zn alloy fins, two one-stage cores as shown in FIG. 2 were produced. A fluoride-based flux is applied to the obtained core, and the flux is applied in a nitrogen atmosphere.
Brazing was performed under heating conditions of 5 ° C. × 3.5 minutes.

Using one of the above-mentioned cores, the brazing state of the core was evaluated by the fin adhesion rate. That is, the fins are peeled off from the core, and the adhesion ratio is set to 100% for those completely bonded as shown in FIG. 3, and those having an unbonded portion as shown in FIG. / (Length of bonded portion + Length of non-bonded portion) was multiplied by 100 to obtain an adhesion ratio (%). Table 2 shows the results. The other core was subjected to a CASS test after masking the end face of the tube, and the corrosion resistance was examined. Table 2 shows the results.

[0029]

[Table 1]

[0030]

[Table 2]

As is clear from Tables 1 and 2, all of the examples of the present invention using the brazing alloy powder of the present invention are superior in adhesion rate and corrosion resistance to the conventional examples. Further, in the comparative example having a different composition from the present invention, the adhesion rate and the corrosion resistance are inferior to those of the present invention. Furthermore, in the present invention example No. 5 and Comparative Example No. 5.
Comparative Example No. 16 had the same alloy composition, but was sprayed with a brazing material as a wire. No. 16 is inferior in brazing property as compared with the example of the present invention using the brazing alloy powder of the present invention.

[Embodiment 2] This embodiment is characterized in that:
4, 5, and 6. As in Example 1,
A of the composition shown in Table 3 was applied to both sides of a multi-hole flat tube obtained by hot extrusion of aluminum corresponding to JIS A1050.
1 Alloy brazing powder (produced by nitrogen gas atomizing method)
Was sprayed by a high-speed gas flame spraying method (Examples Nos. 18 to 24 of Table 3 and Comparative Examples Nos. 25 to 28 in Table 3). In addition,
The conditions for the high-speed gas flame spraying are the same as in the first embodiment.

Further, in Comparative Example No. No. 28 was manufactured by arc-spraying the brazing alloy wire (1.5 mm in diameter) shown in Table 3 on the tube surface. The amount of the brazing material after spraying of these tubes was 35~45g / m ^2.

The obtained multi-hole flat tube is 100 mm in length.
2 and a corrugated Al-0.5% Si-1% Fe-0.5% Ni-2% Zn alloy fin having a thickness of 0.07 mm in the same manner as in Example 1. Two of each were made.
A fluoride-based flux was applied to the obtained core and brazed under a heating condition of 595 ° C. × 3.5 minutes in a nitrogen atmosphere. The obtained core was tested and evaluated for the fin adhesion rate and the tube corrosion resistance in the same manner as in Example 1, and the results are shown in Table 4.

[0035]

[Table 3]

[0036]

[Table 4]

As is clear from Tables 3 and 4, all of the examples of the present invention using the brazing alloy powder of the present invention are superior in adhesion rate and corrosion resistance to the conventional examples. Further, in the comparative example having a different composition from the present invention, the adhesion rate and the corrosion resistance are inferior to those of the present invention. In addition, the comparative example No. 28 is an alloy composition within the range of the invention, but is inferior in brazing properties because the brazing material is sprayed as a wire.

[0038]

As described in detail above, the thermal spraying A according to the present invention is used.
l alloy powder brazing material is an aluminum alloy that requires corrosion resistance, such as a heat exchanger.
It is suitable for thermal spraying on a member, and the thermal sprayed Al alloy member has excellent brazing properties. Further, the thermal spraying method of the present invention can easily obtain a brazing Al alloy member having excellent corrosion resistance and brazing properties. Furthermore, since the brazed filler-coated extruded multi-hole flat tube of the present invention can be brazed in combination with bare corrugated fins, it has an industrially remarkable effect such as realizing a thinner fin material.

[Brief description of the drawings]

FIG. 1 is a perspective view showing an example of a condenser.

FIG. 2 is an explanatory diagram showing a shape of a single-stage core used in an example.

FIG. 3 shows a pattern of a fillet portion 4 having good adhesion formed on the surface of two tubes 1 from which fins have been removed after brazing the core of FIG.

4 shows a pattern of a poorly-filled fillet portion 5 formed on the surface of two tubes 1 from which fins have been removed after the core of FIG. 2 has been brazed. .

[Explanation of symbols]

1: Extruded multi-hole flat tube 2: Fin 3: Nipple 4: Fillet part with good adhesion when fin is peeled off tube material 5: Fillet part with poor adhesion when fin is peeled off tube material

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ Identification code FI F28F 21/08 F28F 21/08 A (72) Inventor Yoshiharu Kinoshita 1-1-1, Showa-cho, Kariya-shi, Aichi Pref. 72) Inventor Taketoshi Toyama 1-1-1, Showa-cho, Kariya-shi, Aichi Prefecture Inside DENSO Corporation (72) Inventor Takaaki Sakane 1-1-1, Showa-cho, Kariya-shi, Aichi Prefecture Inside DENSO Corporation (72) Inventor Etsu Hasegawa Husband Denso, 1-1-1, Showa-cho, Kariya-shi, Aichi (72) Inventor Satoshi Nohira 1-1-1, Showa-cho, Kariya, Aichi, Japan

Claims (6)

[Claims] (1) Si: 6.0 to 20.0 wt% (hereinafter simply referred to as%), Fe: 0.10 to 1.8% and Ni: 0.10 to 1.8%, or
2 types, Zn: 0.5 to 40.0%, the balance being A
A for thermal spraying, comprising A and unavoidable impurities
1 Alloy powder brazing material. 2. The composition contains Si: 6.0 to 20.0 wt% and Fe: 0.10 to
1.8% and Ni: 0.10 to 1.8%
An aluminum alloy powder brazing material for thermal spraying containing one or two of In: 0.0005 to 0.3% and Sn: 0.0005 to 0.3%, with the balance being Al and inevitable impurities. 3. An Al alloy powder brazing material for thermal spraying, wherein the Al alloy powder brazing material according to claim 2 further contains Zn: 0.5 to 40.0%. 4. A high-speed gas flame spraying method using the Al alloy powder brazing material for thermal spraying according to claim 1, whereby the surface of the Al alloy material is coated with the brazing material. ,
A method for spraying an Al alloy powder brazing material, characterized by obtaining an Al alloy material for brazing having excellent corrosion resistance and brazing properties. 5. The method according to claim 4, wherein the Al alloy material is an extruded multi-hole flat tube made of Al or an Al alloy. 6. A flattened brazing material-coated extruded multi-hole tube obtained by the thermal spraying method according to claim 4.