Patent Application
20190358751
The present invention relates to a solder alloy for preventing growth of intermetallic compounds, preform solder, flux-cored solder, and a solder joint.
White goods such as an air conditioner and a refrigerator include a cooling device. The cooling device mainly includes a compressor, a condenser, an expansion valve, an evaporator, and pipes that supply a refrigerant to each device. As a cooling cycle generated by the cooling device, first, a gas refrigerant is compressed by the compressor, and the compressed high-temperature and high-pressure gas passes through the condenser and liquefies. The liquefied refrigerant passes through the expansion valve, and a boiling point thereof decreases due to a sudden drop in pressure. Then, the liquefied refrigerant is vaporized by the evaporator. Finally, the vaporized refrigerant is compressed again by the compressor, and the cycle is repeated. The temperature in the surroundings decreases by endotherm during vaporization of the liquefied refrigerant by the evaporator.
Machines constituting the above-described cooling device are disposed in the white goods after the machines are connected with the pipe that supplies a refrigerant. As described in JP-A-561-49974, for example, a method of connecting by brazing is adopted as a connection method of pipes. JP-A-S61-49974 describes that brazed parts are reduced since reliability may be reduced due to leakage of the refrigerant if the number of the brazed parts is large.
However, a skill of a brazing worker is necessary in pipe joining by brazing, and the quality of the joint portion depends on skill level of the worker. Due to differences in skill level, a pipe temperature may be excessively high when a pipe is heated, causing the pipe to deform, or a void may be generated in a brazing material, and refrigerant leakage defects may occur. In addition, the brazing material may not penetrate into the entire circumference of the pipe gap if the pipe temperature is too low, and thus the refrigerant leakage defects may occur. Further, the pipe is annealed in brazing, resulting in softening the pipe, which may cause deformation. In addition, the brazing potentially causes a fire during pipe joining since a high temperature and long heating time are required in the brazing.
Therefore, JP-A-H02-34295 describes a lead-free solder alloy composition suitable for joining metallic pipe such as a Cu pipe or a brass pipe at a low temperature. The solder alloy described in JP-A-H02-34295 contains 3 mass % to 5 mass % of Cu in order to widen a range of a solidus temperature and a liquidus temperature of a Sn—Sb—Cu solder alloy. Further, in the present invention described in JP-A-H02-34295, by heating the solder alloy to a temperature slightly higher than the solidus temperature to cause a liquid phase and a solid phase to coexist, liquid flows into a part where a gap between a pipe and the other pipe is small, and solid is filled in a part having a large gap, thereby joining the pipes.
The solder alloy described in JP-A-H02-34295 includes an alloy composition for soldering which can be performed at a low temperature, in order to solve the problems in the joining by brazing described in JP-A-S61-49974. However, the solder alloy described in JP-A-H02-34295 has a large amount of Cu, so that there is a concern over deposition of an intermetallic compound such as Cu6Sn5 (hereinafter, appropriately referred to as “InterMetallic Compound” (IMC)) and growth of an IMC layer when a solder joint that joins Cu pipes is formed. In addition, not only a Cu pipe but also a Fe pipe is used in a recent cooling device. Therefore, when the Cu pipe is joined with the Fe pipe, a refrigerant may leak out from a joint portion when the Cu pipe and the Fe pipe underwent a temperature cycle caused by circulation of the refrigerant, which may cause a failure.
In addition, JP-A-H02-34295 also discloses that the solder alloy described herein contains Ni. It is common that Cu6Sn5 becomes (CuNi)6Sn5 when Ni is added to the solder alloy, so that rupture at a joint interface is prevented. However, when the Cu pipe and the Fe pipe undergo a temperature cycle caused by circulation of the refrigerant in the future, it is difficult to sufficiently prevent rupture at the joint interface when only Ni is added as described in JP-A-H02-34295.
Recent white goods have a long service life due to improvement in performance Accordingly, a pipe of the cooling device mounted on the white goods is exposed to a long-term temperature cycle. In order to prevent the refrigerant from leaking out of a pipe joint portion, it is required to prevent IMC growth in low-temperature joining of the pipes using the solder alloy.
An object of the present invention is to provide a solder alloy, preform solder, flux-cored solder, and a solder joint, with which joining reliability during joining of metallic pipe and long term joining reliability can be ensured by preventing growth of an intermetallic compound layer generated at the joint interface during low-temperature joining of the metallic pipes.
From the viewpoint of cost reduction, the present inventors used soldering instead of brazing in order to adopt a joining method using a pipe according to the related art rather than a pipe of a special material, and studied a solder alloy composition suitable for the soldering. Generally, in joining of metallic pipes, an end portion of one pipe is inserted into the other pipe, and on an outer periphery of the one pipe and an inner periphery of the other pipe, a portion where the two pipes face to each other and an area in vicinity thereof are heated by high-frequency heating or flame. Therefore, an IMC layer at a joint interface is likely to grow since heating conditions are varied and heating area and joining area are widely spread, compared with the case where a fine electrode part such as a semiconductor device is joined in an environment with controlled temperature and atmosphere.
In view of the pipe joining conditions as described above, the present inventors studied an element that prevents the growth of the IMC layer during pipe joining by using the Sn—Sb—Cu solder alloy described in JP-A-H02-34295 as a basic composition. Here, although the metallic pipe of a cooling device used for white goods is usually a Cu pipe, a Fe pipe may be used as described above. Therefore, it is required to select an element that prevents growth of the IMC layer in joining with the Fe pipe. From the viewpoint of preventing diffusion of Fe into the solder alloy with respect to the Fe pipe, Fe, Co, and Ni are sometimes treated equivalently as elements that can be contained in the solder alloy. However, Fe is not preferable since Fe significantly increases a melting point of a solder alloy for a Sn-based solder alloy. Co and Ni also have high melting points. Therefore, it is considered that it is difficult to use these elements that are handled equivalently as described in the related art when pipe joining at a low temperature is performed.
As a result of further studies, the present inventors intentionally added Ni, which was commonly considered unsuitable for pipe joining at a low temperature and attempted to join a Fe pipe with a Cu pipe by using a Sn—Sb—Cu—Ni based solder alloy. As a result, the growth of the IMC layer could not be prevented by only adding Ni. However, the following findings were obtained: when pipes are joined, an increase in melting point falls in an allowable range as long as the Ni content is within a predetermined range.
Therefore, the following findings were obtained: an increase in melting point can be unexpectedly prevented and the IMC layer at the joint interface can be 1.5 times or more thinner than the solder alloy composition according to the related art to which Co is not added, when a predetermined amount of Co, which is avoided to be added like Ni, was further added to the alloy composition.
As a result of further detailed investigations, the following findings were obtained: the growth of the IMC layer is reduced when the content ratio of the Co content to the Ni content is within a predetermined range.
The present invention obtained based on these findings is as follows.
(1) A solder alloy for joining a Cu pipe and/or a Fe pipe, the solder alloy having an alloy composition comprising in mass %: Sb: 5.0% to 15.0%; Cu: 0.5% to 8.0%; Ni: 0.025% to 0.7%; and Co: 0.025% to 0.3%, with the balance being Sn,
wherein the alloy composition satisfies the following relationship (1):
0.07≤Co/Ni≤6 (1)
wherein Co and Ni represent Co and Ni in mass %, respectively.
(2) The solder alloy for joining a Cu pipe and/or a Fe pipe according to (1), wherein the alloy composition further comprises, in mass %, Sb: 5.0% to 9.0%.
(3) The solder alloy for joining a Cu pipe and/or a Fe pipe according to (1) or (2), wherein the alloy composition further comprises, in mass %, Cu: 0.5% to 3.0%.
(4) The solder alloy for joining a Cu pipe and/or a Fe pipe according to any one of (1) to (3), wherein the alloy composition further comprises, in mass %, Ni: 0.025% to 0.1%.
(5) The solder alloy for joining a Cu pipe and/or a Fe pipe according to any one of (1) to (4), which has a liquidus temperature of 450° C. or lower.
(6) A preform solder comprising the solder alloy for joining a Cu pipe and/or a Fe pipe according to any one of (1) to (5).
(7) A flux-cored solder comprising the solder alloy for joining a Cu pipe and/or a Fe pipe according to any one of (1) to (5).
(8) A solder joint comprising the solder alloy for joining a Cu pipe and/or a Fe pipe according to any one of (1) to (5).
The present invention is described in detail below. In this description, “%” with respect to a solder alloy composition is “mass %”, unless otherwise specified.
Sb is an element necessary for improving strength of a solder alloy. In addition, Sb is an element that improves temperature cycle properties or fatigue resistance properties.
When the Sb content is less than 5.0%, the above-described effects cannot be sufficiently obtained. As the lower limit of the Sb content, it is 5.0% or more, preferably 6.0% or more, more preferably 6.5% or more, and particularly preferably 7.0% or more. On the other hand, when the Sb content is more than 15.0%, the liquidus temperature is likely to exceed 450° C. Accordingly, workability of soldering is reduced. In addition, the solder alloy becomes hard and a SnSb intermetallic compound is coarsened. As a result, there is a risk that distortion concentrates at a grain boundary, and the solder alloy is ruptured from the grain boundary. As the upper limit of the Sb content, it is 15.0% or less, preferably 14.0% or less, more preferably 13.0% or less, still more preferably 12.0% or less, and particularly preferably 11.0%. In addition, as the upper limit of the Sb content, it is most preferably 9.0% or less, from the viewpoint of improving the wet spreading property and facilitating flow of solder into the gap between pipes.
Cu is an element necessary for improving joining strength of a solder joint. When Cu is less than 0.5%, neither the strength nor a temperature cycle property is improved. As the lower limit of the Cu content, it is 0.5% or more, preferably 0.6% or more, more preferably 0.8% or more, and particularly preferably 1.0% or more. On the other hand, when the Cu content is more than 8.0%, the liquidus temperature exceeds 450° C. Accordingly, workability of soldering is reduced. As the upper limit of the Cu content, it is 8.0% or less, preferably 6.0% or less, more preferably 5.0% or less, and still more preferably 4.0% or less. In addition, the Cu content is particularly preferably 3.0% or less, from the viewpoint of improving the wet spreading property and facilitating flow of solder into the gap between pipes.
Ni is an element necessary for preventing rapture at a joint interface between a metallic pipe and the solder alloy by uniformly dispersing in Cu6Sn5.
In addition, Ni is added together with Co to prevent growth of the IMC layer and to form a uniform and fine IMC layer. When the Ni content is less than 0.025%, the effects of preventing the growth of the IMC layer cannot be sufficiently obtained when Ni is added simultaneously with Co. As the lower limit of the Ni content, it is 0.025% or more, preferably 0.035% or more, and particularly preferably 0.05% or more. On the other hand, when the Ni content is more than 0.7%, the liquidus temperature exceeds 450° C. Accordingly, workability of soldering is reduced. As the upper limit of the Ni content, it is 0.7% or less, preferably 0.6% or less, more preferably 0.5% or less, and still more preferably 0.4% or less.
Further, as the upper limit of the Ni content, it is particularly preferably 0.1% or less, and most preferably 0.07% or less, from the viewpoint of facilitating flow of solder into the gap between pipes.
Co is added together with Ni to prevent the growth of the IMC layer and to form a uniform and fine IMC layer. Co contributes to miniaturization of alloy structure since Co is generated as a large number of solidification nuclei during solidification of the solder alloy and a Sn phase is deposited around the solidification nuclei. Accordingly, the IMC layer at the joint interface can be thinner, and the growth of the IMC layer can be prevented. Further, growth of crystal grains and the growth of the IMC layer are prevented since Ni is uniformly present in Cu6Sn5.
When the Co content is less than 0.025%, such effects cannot be obtained. As the lower limit of the Co content, it is 0.025% or more, preferably 0.035% or more, and particularly preferably 0.050% or more. On the other hand, when the Co content is more than 0.3%, the liquidus temperature exceeds 450° C. Accordingly, workability of soldering is reduced. As the upper limit of the Co content, it is 0.3% or less, preferably 0.2% or less, more preferably 0.1% or less, and particularly preferably 0.07% or less.
The content ratio of Co to Ni in the present invention satisfies the following relationship (1).
0.07≤Co/Ni≤6 (1)
In the relationship (1), “Co” and “Ni” represent contents (mass %) of Co and Ni, respectively.
Co and Ni exert effects particularly when the Cu pipe and the Fe pipe are joined. The two elements prevent diffusion of Fe into the solder alloy. As a result, a brittle intermetallic compound such as FeSn and FeSn2 can be prevented from generating. In addition, Ni is uniformly dispersed in Cu6Sn5 formed at the joint interface to prevent rapture at the joint interface with the Cu pipe, and Co prevents the growth of the IMC layer, as described above. Therefore, the two elements are closely related in the solder alloy of the present invention. That is, in the present invention, it is assumed that the intermetallic compound becomes finer by adding Co with the addition of Ni by which the structure of the intermetallic compound is homogenized.
In order to obtain such effects, Co/Ni, which is the content ratio between the two elements, preferably satisfy the relationship (1). As the lower limit of Co/Ni, it is 0.07 or more, and more preferably 0.09 or more. As the upper limit of Co/Ni, it is 6 or less, more preferably 4 or less, still more preferably 2 or less, and particularly preferably 1 or less.
A preform solder according to the present invention may be used in the form of a ring shape, a cylindrical shape, a shape in which wire solder is wound in three turns or less, and the like. Details are described below with reference to
The solder alloy according to the present invention is suitably used for flux-cored solder in which flux is contained in advance. In addition, the solder alloy may also be used in the form of wire solder, from the viewpoint of supplying solder to soldering iron. Further, the solder alloy may also be suitably used for flux-cored wire solder in which flux is sealed in wire solder. A surface of each solder may be covered with flux. In addition to this, a surface of solder in which flux is not contained may be covered with flux.
The flux content in the solder is, for example, 1 mass % to 10 mass %, and the rosin content in the flux is 70% to 95%. Generally, rosin is an organic compound and contains carbon and oxygen, so that terminal functional groups and the like in the rosin in the present invention is not limited.
The solder joint according to the present invention is suitable for connection between metallic pipes. Solder plating may be applied to the metallic pipe. Here, “solder joint” is referred to as a connection portion of a pipe.
In the joining method of pipes using the solder alloy according to the present invention, for example, a first pipe is joined with a second pipe that includes, at an end portion, an enlarged pipe portion having an inner diameter larger than an outer diameter of the first pipe.
The method includes three steps as follows: a step of fitting preform solder to the first pipe; a step of inserting the first pipe fitted with the preform solder into the enlarged pipe portion of the second pipe and bringing the preform solder into contact with an end surface of the enlarged pipe portion; and a step of heating the preform solder.
Hereinafter, the method is described in detail with reference to the drawings.
The pipes used in the present invention, as shown in
In the second pipe 2, outer diameters of portions other than the enlarged pipe portion 2a are preferably equal to or less than the outer diameter of the first pipe 1, and are more preferably equal to the outer diameter of the first pipe 1. When the outer diameters of portions other than the enlarged pipe portion 2a are equal to or less than the outer diameter of the first pipe 1, the end portion of the first pipe 1 contacts a diameter-reduced portion 2c of the enlarged pipe portion 2a, and a inserted length of the first pipe 1 into the enlarged pipe portion 2a becomes constant, which facilitates the operation, when the first pipe 1 is inserted into the expanded pipe portion 2a. In addition, materials of the two pipes are not particularly limited, and may be, for example, a Cu pipe or a Fe pipe containing Fe as a main component. Solder plating may be applied to these pipes.
In addition, it is necessary to use thick wire solder in order to increase the amount of solder when a ring-shaped preform solder 3 described below is used. However, this may cause overflow of molten solder. The ring-shaped preform solder 3 has a substantially circular cross section in order to form wire solder in an annular shape, and has small contact area with the end surface 2b of the enlarged pipe portion 2a. Therefore, the molten solder may be difficult to flow into the gap between the enlarged pipe portion 2a and the first pipe 1. From these viewpoints, as shown in
In order to prevent the molten solder from overflowing when the ring-shaped preform solder 3 is used, it is desired that the flare-processed portion 2d has a funnel shape in a longitudinal section of the second pipe 2. The enlarged pipe portion 2a also has a funnel shape in a longitudinal section of the second pipe 2.
The flux may be applied to an outer peripheral surface of the end portion of the first pipe 1 and/or an inner peripheral surface of the enlarged pipe portion 2a of the second pipe 2, when the preform solder 3 is not flux-cored solder. In addition, the flux may be dropped to the preform solder 3 after the first pipe 1 is inserted into the second pipe 2.
A joining method of pipes using these pipes is described in detail below.
In this joining method, first, the preform solder 3 is fitted to the end portion of the first pipe 1 as shown in
Variations in temperature can be reduced when solder having a melting point lower than the brazing metal is used as a joined body. The brazing material is generally heated to a high temperature of 1000° C. to melt by using a burner in joining of the brazing material. Accordingly, a variation of about 900° C. to 1100° C. occurs depending on the skill level, and a difference in quality of the joint portion may occur. On the other hand, the solder may be heated to about 300° C. to 450° C., and a temperature error of 200° C. is unlikely to occur like the case of the brazing material even when the skill level is low. When such a temperature error occurs during soldering, it is difficult to perform soldering.
It is difficult to control the temperature in a short time since brazing is generally performed using a burner even though heating temperature is controlled using a thermometer. Even though the brazing material is heated by a high-frequency induction heating device, it is required to provide a large power supply device and a large cooling mechanism for cooling a coil in order to heat the brazing material to a high temperature of 1000° C., resulting in poor workability. Even through a low temperature brazing material is required to be heated to 500° C. or higher, the above problem is not solved. Further, joining using a brazing material causes a rise in cost due to a necessity of high-temperature heating.
On the other hand, the preform solder 3 having a low melting point and a predetermined size is used in the joining method. Accordingly, the supply amount of the solder is constant, and variation in heating temperature is small. Therefore, the workability is good since no skill degree like the joining by brazing is required.
It is desired that a shape of the preform solder 3 used in the present invention is a hollow cylindrical shape, as shown in
In the case of the hollow cylindrical shape shown in
In addition, the preform solder 3 may be a ring shape as shown in
In addition, it is desired that an inner diameter of the preform solder 3 is substantially equal to the outer diameter of the first pipe 1. In the present invention, it is desired to use own weight of the solder to pour the molten solder into the gap between the enlarged pipe portion 2a and the first pipe 1 when the preform solder 3 is heated. Therefore, as shown in
It is desired that the preform solder 3 is flux-cored solder. The flux may be applied to the end portion of the first pipe 1 in a case where the preform solder 3 is not flux-cored solder. In addition, when an amount of solder provided only by the preform solder 3 is not sufficient, the end portion of the first pipe 1 may be covered with preliminary solder.
(3) Step of Inserting First Pipe Fitted with Preform Solder into Enlarged Pipe Portion of Second Pipe and of Bringing Preform Solder into Contact with End Surface of Enlarged Pipe Portion
As shown in
When the inner diameter of the preform solder 3 is substantially equal to the outer diameter of the first pipe 1 as described above, the preform solder 3 in the state of
As shown in
The solder flows into the gap between the enlarged pipe portion 2a and the first pipe 1 when the preform solder 3 is heated. The first pipe 1 and the second pipe 2 are joined as shown in
The preform solder 3 is heated by heating the pipes. Examples of heating of the pipes include: heating by a near-infrared lamp (NIR), and heating by a high-frequency induction method. The heating by the high-frequency induction method is preferred.
The high-frequency induction heating method is suitable for joining the pipes since the portion corresponding to a coil of a high-frequency induction heating device can be locally heated. A power supply of the high-frequency induction heating device can have a compact size without reducing workability since the melting point of the solder is about 300° C. to 450° C. A large-scale cooling mechanism is not necessary to be provided at the coil of the high-frequency induction heating device since heating temperature may be about 300° C. to 450° C. based on the liquidus temperature.
The heating time is not particularly limited. However, the heating time may be about 1 to 10 minutes as long as the preform solder 3 is melted. Accordingly, cost reduction can be achieved due to the short heating time. As for a heating atmosphere, the heating is preferably carried out in atmosphere, from the viewpoint of workability. The heating temperature may be appropriately adjusted depending on a composition of the solder, and may be about 250° C. to 450° C. The heating temperature may be controlled, for example, by using an infrared thermometer to adjust an output of the near-infrared lamp or the high-frequency induction heating device.
In order to verify the effect of the present invention, the effect was confirmed by the following alloy compositions. In the present example, a pipe was not used to join with a solder alloy but a plate was used to join with a solder alloy in order to observe a joint interface. The details are as follows.
The solder alloy having the alloy composition shown in Table 1 is molded into a preform solder of 5 mm×5 mm×1 mm, and the preform solder is placed on a Fe plate (carbon steel S50C for machine structure) and heated in the atmosphere of 450° C. for three minutes to form a solder joint.
In the evaluation of “IMC growth prevention”, the cross section was imaged at 3000 times in SEM after heating, and the thicknesses of the IMC layers at five points were measured. When the average thickness of the IMC layers at the specific five points was 4 μm or lower, it was evaluated as “◯”. When the average thickness of the IMC layers was more than 4 μm, it was evaluated as “X”.
In the evaluation of “liquidus temperature”, a DSC measurement was performed at a sample amount of about 30 mg and at a heating rate of about 15° C./min by using EXSTAR DSC 7020 manufactured by SII NanoTechnology Inc. When the liquidus temperature was 450° C. or lower, it was evaluated as “◯”. When the liquidus temperature exceeded 450° C., it was evaluated as “X”.
The case in which both IMC growth prevention evaluation and liquidus temperature evaluation are evaluated as good was evaluated as good in comprehensive evaluation.
The evaluated results are shown in Table 1.
0.8
0.4
0
0
0
As shown in Table 1, in Examples 1 to 19, the heating temperature during joining can be set to 450° C. or lower since the requirements of the present invention were satisfied in any of the alloy compositions. Therefore, growth of the IMC layer during joining was prevented. In addition, the solidus temperature is constant regardless of the composition, so that it is easy to control the solid phase amount and the liquid phase amount in a heating temperature range of the two phase coexisting region including the liquid phase and the solid phase, and a stronger joint portion can be formed. Therefore, it was found that the joint portion of the pipes joined by using the solder alloys in Examples 1 to 19 shows high reliability, and withstands long-time use even when the solder alloys are used for pipe joining for the cooling device. In addition, the similar results were obtained for a Cu plate in the case of using the solder alloys of Examples 1 to 19.
In contrast, it was found that low-temperature joining is difficult in Comparative Example 1 since the Ni content was large and liquidus temperature exceeded 450° C. It is considered that an IMC layer grows and reliability of a joint portion is not obtained in Comparative Example 2 since Ni and Co were not contained. It is considered that an IMC layer grows and reliability of a joint portion is not obtained in Comparative Example 3 sine Co was not contained. The results of Table 1 are further described in detail by using
As shown in
Comparing
As described above, the solder alloy of the present invention is suitable for low-temperature joining between a Cu pipe and the other Cu pipe and for low-temperature joining between a Cu pipe and a Fe pipe, and is particularly suitable for pipe joining of a cooling device mounted in recent white goods.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2017-180660 | Sep 2017 | JP | national |
This application is a U.S. National Phase Application under 35 U.S.C. § 371 of International Patent Application No. PCT/JP2018/021812, filed Jun. 7, 2018, and claims the benefit of Japanese Patent Application No. 2017-180660, filed on Sep. 20, 2017, all of which are incorporated herein by reference in their entirety. The International Application was published in Japanese on Mar. 28, 2019 as International Publication No. WO/2019/058650 under PCT Article 21(2).
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2018/021812 | 6/7/2018 | WO | 00 |
