JP5236535B2 - Joining material for Al alloy-ceramic composite material and method for producing the same - Google Patents

Description

The present invention relates to a bonding material for bonding an Al alloy-ceramic composite material having an Al alloy as a matrix.

Al alloy is a material that is lightweight and excellent in corrosion resistance, and is excellent in thermal conductivity and conductivity, and thus has been used in various fields so far. Also in the field of ceramics, an Al alloy-ceramic composite material, in which an Al alloy is used for the matrix and ceramics is used for the reinforcing material, is a lightweight and highly rigid material that takes advantage of the above characteristics of the Al alloy. It has come to be used.

Furthermore, in order to apply and expand the Al alloy-ceramic composite material for various applications, it is essential to have a joining technique that can cope with an increase in size, a complicated shape, and a hollow structure. In other words, it is possible to produce an Al alloy-ceramic composite joined body that is tightly bonded so that the Al alloy-ceramic composite material can withstand practical use, and that the joint has good airtightness to prevent gas leakage. However, there are few examples of such reports.

So far, as a joining technique, for example, a diffusion material that can be joined even at a temperature lower than the melting point of the matrix alloy by filling an insert material such as Cu between Al alloy-ceramic composite material and heat-treating it with a predetermined temperature and pressure. Although a bonding method (see Patent Document 1) has been proposed, the diffusion bonding method can perform strong bonding, but must be heat-treated at a considerably high pressure, for example, about 1 MPa, and is large in order to pressurize. There is a problem that a device such as a press machine is required and the cost is increased. In addition, when the shape is complicated, there is a problem that it is difficult to apply pressure itself and joining becomes difficult. Therefore, as a method for producing an Al alloy-ceramic composite material assembly having such a satisfactory hermeticity that gas leakage can be prevented without a large pressure device, the present applicant has made glass containing lead borate as a main component. Has proposed a joining method (see Patent Document 2) in which is used as a joining material.

In addition, as a method of joining a metal-ceramic composite material that can be easily and firmly joined, the present applicant has 40 masses of Al between a metal-ceramic composite material using an Al alloy as a matrix and the same or different material. % And containing a brazing filler metal having a liquid phase generation temperature of 500 ° C. or less, and heat-treating it at a temperature of 500 ° C. or more in a non-oxidizing atmosphere and a melting point or less at which the metal in the composite material melts. A metal-ceramic composite material joining method was proposed (see Patent Document 3).

JP-A-6-1555044 JP 2002-263851 A JP 2000-271737 A

With the joining method of Patent Document 2, an Al alloy-ceramic composite material assembly having good airtightness that can prevent gas leakage can be obtained without a large pressure device, but boric acid is used as the joining material. Since lead glass is used, there is a problem that the strength of the joint is low and the size and application of the material to be joined are limited. In addition, in recent years, the toxicity of lead has been regarded as a problem, and since there are regulations on the use of lead in many industries, there is a high possibility that lead borate glass cannot be used in the future. Met. On the other hand, lead-free glass can solve the problem related to toxicity, but there is a problem in that the wettability is poor as compared with glass containing lead, so that a defect is likely to occur in the bonded portion, and the bonded portion cannot be hermetically sealed.

In the method of Patent Document 3, Al—Si—Cu—Sn, Al—Zn, Al—Si—Cu—Zn, and the like are listed as the bonding material. Thus, when an Al alloy-ceramic composite material joined body is produced, there is a problem because the joint strength may be significantly smaller than the strength of the Al alloy-ceramic composite material to be joined.

The present invention has been made in view of the problem in joining of such an Al alloy-ceramic composite material, and can be easily joined without using a large pressure device, and an Al alloy capable of obtaining a joining strength that can withstand practical use. -It aims at providing the bonding material for ceramics composite materials.

As a result of intensive studies to achieve the above object, the present inventors have found that the bonding material can be firmly bonded by using a layer structure, and have completed the present invention.

That is, the present inventor provides the following (1) and (2) as means for solving the above problems.
(1) The Al alloy as a matrix, Al alloy was used ceramic reinforcing material - a bonding material for bonding the ceramic composite material to each other, the main component is Zn, a core material constituting the core, the main The component is Al and contains 0.5 to 2.5% by mass of Mg and is composed of a surface layer material constituting the surface layer , an alloy containing Al and Zn, and is formed between the core material and the surface layer material. bonding material for ceramic composite material - was an intermediate layer, only including, Al alloy mass ratio Al / Zn of Al and Zn contained in the bonding material, characterized in that a 0.25 to 2.33.
(2) A method for manufacturing a bonding material for bonding Al alloy-ceramic composite materials using Al alloy as a matrix and ceramics as a reinforcing material, and containing 0.5 to 2.5% by mass of Mg and the thin Al alloy, a step of preparing a sheet of Zn, and the thin plate before Symbol a l alloy, a step of roll-bonding by superposing the sheet of the Zn, and Ri by the heat treatment a l alloy and Zn Al alloy but that seen containing a step of forming an intermediate layer diffused into each other, the weight ratio Al / Zn of Al and Zn contained in the bonding material, characterized in that a 0.25 to 2.33 - A method for manufacturing a bonding material for bonding ceramic composite materials.

The present invention provides a bonding material for an Al alloy-ceramic composite material that can be easily bonded without using a large-sized pressurizing device and that can provide a bonding strength that can withstand practical use.

Schematic sectional view showing the bonding material of the present invention Schematic sectional view showing an application example of the bonding material of the present invention Schematic sectional view of the joined body Top view of concave material

Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a schematic sectional view showing a bonding material of the present invention.

The bonding material of the present invention has a structure including a core material 11 constituting a core, a surface layer material 12 constituting a surface layer, and an intermediate layer 13 formed between the core material and the surface material.

The core material 11 contains Zn as a main component. This is because it is possible to prevent a decrease in bonding strength by arranging Zn in the center of the bonding material.

In Patent Document 3, as an Al—Zn-based bonding material, after a metal is mixed, it is heated and melted at a temperature of 650 ° C. in a graphite crucible, and it is obtained by pouring it out to a metal rotating two roll. Things are listed. Such a method seems to be preferable because the composition of the bonding material is made uniform. However, when such a bonding material is used, the bonding strength may be significantly reduced. This is thought to be due to the fact that as the diffusion of Zn into the material to be joined progresses, voids are formed in the joining layer, so that the joining strength is significantly reduced. In order to solve this problem, in the present invention, Zn is disposed at the center of the bonding material. With such a configuration, the voids in the bonding layer can be eliminated.

In addition, in the method of mixing and melting metals as described in Patent Document 3, it is difficult to integrally produce a bonding material having a large area exceeding 300 × 300 mm (hereinafter, □ 300 mm). It was. When a non-integral bonding material is used, it is inevitable that a seam is formed in the bonding layer. Therefore, there is a problem that it is difficult to produce an Al alloy-ceramic composite material joined body having a large size exceeding □ 300 mm and having good airtightness. In this invention, since it was set as the joining material containing a core material, surface layer material, and an intermediate | middle layer, a large-sized joining material exceeding □ 300 mm is producible.

The main component of the surface layer material 12 is Al. By disposing the core material mainly composed of the surface layer material Al and Zn as the main component at the center of the bonding material, the voids in the bonding layer can be eliminated.

An intermediate layer 13 is formed between the core material 11 and the surface layer material 12. The intermediate layer is made of an alloy containing Al and Zn. The intermediate layer 13 is mainly formed by diffusing Zn on the core material side having a low melting point and easily diffusing into Al on the surface material side. At this time, Al on the surface layer side is also diffused into Zn on the core side, though less than the diffusion of Zn.

It is necessary to adjust Zn diffusion to the surface material side so as not to be excessive. If the diffusion proceeds excessively, the bonding material becomes brittle, and a bonding material having a large area exceeding □ 300 mm cannot be obtained. Therefore, it is not preferable to diffuse the core material, the intermediate layer, and the surface layer material so that the core material, the intermediate layer, and the surface material are not distinguished. On the other hand, if the diffusion is too small, Zn having a low melting point will be dissolved first at the time of bonding, and since it has a high vapor pressure, it will volatilize quickly and thus will not function as a bonding material. From such a viewpoint, the core material preferably contains 70 mass% or more of Zn, and more preferably 90 mass% or more. The surface layer material Al is preferably contained in an amount of 50% by mass or more, and more preferably 70% by mass or more. The intermediate layer has an intermediate composition between the core material and the surface layer material.

The Al / Zn mass ratio Al / Zn contained in the bonding material is preferably 0.25 to 2.33. This is because when the Al content is low, that is, when the mass ratio Al / Zn is smaller than 0.25, the anodic corrosion of the joint is likely to occur in a corrosive environment, and the temperature rises in an environment where heat is applied. This is because the reliability of the bonded portion is inferior due to problems such as the occurrence of defects due to uneven diffusion at the bonded portion that sometimes occur. On the other hand, when the mass ratio Al / Zn is larger than 2.33, the melting point of the bonding material becomes higher than 600 ° C., so that it is difficult to use it for bonding of an Al alloy-ceramic composite material. . The mass ratio Al / Zn is more preferably 0.85 to 2.33.

Further, the present invention is characterized in that Mg is contained in the component constituting the surface layer material in an amount of 0.5 to 2.5% by mass. Here, the reason why Mg is added to the surface layer material is that Mg plays a role of destroying the oxide film on the surface of the Al alloy that inhibits bonding. Generally, in brazing of an Al alloy, it is known that an oxide film existing on the surface of the Al alloy hinders brazing, and strong brazing cannot be performed unless the oxide film is destroyed by a flux or the like. Similarly, when joining Al alloy-ceramic composite materials, it is necessary to destroy the oxide film on the Al alloy surface of the matrix exposed on the joining surface before the joining material is completely melted by the heat treatment during joining. If Mg contains Mg, it can play its role. That is, when Mg evaporates from the bonding material by heat treatment during bonding, the surface oxide film of the Al alloy is destroyed and the molten Al alloy phase is exposed to the bonding surface. Further, since the evaporated Mg also serves as a getter for removing residual oxygen and moisture in the furnace, the formation of a new Al oxide film is suppressed, so that strong bonding is possible.

The amount of Mg contained in the bonding material is 0.5 to 2.5% by mass. The reason is that if Mg is less than 0.5% by mass, a sufficient amount of Mg is not supplied, so the surface of the Al alloy This is because the oxide film cannot be completely broken and defects remain at the bonding interface, so that strong bonding cannot be achieved. Further, when the amount is more than 2.5% by mass, MgO that inhibits bonding is generated on the bonding surface as in the case of the Al oxide film, so that strong bonding cannot be performed. Furthermore, it was found that when the amount of Mg is in the above range, in addition to the effect of removing the oxide film, the diffusion of Zn and Mg contained in the bonding material is likely to occur, and the adhesion and bonding strength are increased.

The material to be bonded is a bonding material for bonding Al alloy-ceramic composite materials using an Al alloy as a matrix and ceramics as a reinforcing material. What is necessary is just to select required Al alloy according to a manufacturing method and the characteristic made into the objective as Al alloy used for a to-be-joined material. For example, Al alloy for casting and spreading can be used, and among them, JIS standard alloys AC3A, AC8A, 5052, etc. are preferably used. Any Al alloy having a melting point higher than that of the bonding material can be applied.

Various ceramics such as silicon carbide, silicon nitride, alumina, aluminum nitride, and zirconia can be used as the reinforcing material ceramics. The ceramic content of the reinforcing material is preferably 30 to 80% by volume. Such a composite material is excellent in thermal conductivity and electrical conductivity, is lightweight, and is suitable as a highly rigid material.

Next, the manufacturing method of the joining material for Al alloy-ceramic composite material of this invention is demonstrated.

The present invention is a method of manufacturing a bonding material for bonding Al alloy-ceramic composite materials using Al alloy as a matrix and ceramics as a reinforcing material, and includes a thin plate of Al or Al alloy, a thin plate of Zn, A step of superimposing the Al or Al alloy thin plate and a Zn thin plate on each other and rolling and joining, and a step of forming an intermediate layer in which Al or Al alloy and Zn are diffused to each other by heat treatment, The manufacturing method of the joining material for joining Al alloy-ceramics composite materials characterized by including these is provided.

The bonding material of the present invention has a structure including a core material 11 constituting a core, a surface layer material 12 constituting a surface layer, and an intermediate layer 13 formed between the core material and the surface material. In such a structure, a thin plate of Al or Al alloy (hereinafter referred to as Al foil for convenience) and a thin plate of Zn (hereinafter referred to as Zn foil) are stacked in the order of Al foil / Zn foil / Al foil. It is obtained by clad by hot rolling and thinned to a desired thickness. If the Al foil and the Zn foil are used alone, the rollability is good. However, when Al and Zn are alloyed, it becomes brittle and easily cracked, making it difficult to produce a large joining material. Therefore, Al foil and Zn foil thinned by rolling are superposed in the order of Al foil / Zn foil / Al foil in a ratio so as to have a predetermined composition, and rolled cold or hot, □ A large joining material exceeding 300 mm is produced.

The Al foil is made of Al or an Al alloy. An Al alloy corresponding to the bonding strength and corrosion resistance of the bonding material is used, but an Al alloy having a good rolling property alone may be selected. Of course, pure Al may be selected. For example, a wrought Al alloy can be used, and various alloys such as JIS standard alloys 1000 series to 7000 series can be used. Of these, 1050, 4004, 5052 and the like are preferable.

As the Zn foil, a Zn alloy containing 95% by mass or more of Zn, more preferably, Zn having a purity of 99% or more can be used.

The reason why the Zn foils are overlapped so as to be sandwiched between the Al foils is to form the core material, the intermediate layer and the surface layer material by controlling the diffusion of Zn having a low melting point to the Al foil side. As a result, voids that are likely to occur in the bonding layer during bonding can be eliminated, and the bonding strength can be prevented from significantly decreasing. Conversely, when an Al foil is sandwiched between Zn foils to produce a bonding material, Zn having a low melting point causes partial melting and delamination from Al.

The intermediate layer between the core material and the surface layer material can be formed by subjecting the core material between the surface layer materials and performing a heat diffusion process in the process of rolling into a desired shape. Here, the step of rolling and joining the Al foil and the Zn foil and the step of forming an intermediate layer in which Al or an Al alloy and Zn are mutually diffused by heat treatment may be performed clearly separately. Good or may be done at the same time. For example, after rolling and joining at a temperature that does not cause cold or thermal diffusion, the intermediate layer may be formed by heating and thermal diffusion treatment, or rolling depending on the temperature and time during hot rolling At the same time, the intermediate layer may be formed by thermal diffusion. However, since the intermediate layer generated in the hot rolling process causes a decrease in rolling properties, it is preferable to suppress the temperature as much as possible by adjusting the temperature and time during rolling and controlling the thermal environment. When there is no intermediate layer, that is, when an Al alloy-ceramic composite material is joined only by sandwiching an Al foil and a Zn foil, Zn having a low melting point melts first, but quickly because the vapor pressure is high. Since it volatilizes, it does not function as a bonding material.

Moreover, you may use the method of delaying a spreading | diffusion by pinching the component whose melting | fusing point is higher than both foil between Al foil and Zn foil. For example, low and high melting point Al foils are prepared and sandwiched in the order of low melting point Al foil / high melting point Al foil / Zn foil / high melting point Al foil / low melting point Al foil and rolled hot. Then, the intermediate layer can be easily formed by cladding and thermal diffusion treatment. Various combinations such as 4004 and 1050 and 5052 and 1050 can be applied to the combination of the low melting point Al foil and the high melting point Al foil.

Adjustment of the mass ratio Al / Zn of Al and Zn of the whole bonding material can be adjusted by changing the thickness of the Al foil and the thickness of the Zn foil. Therefore, even if mass ratio Al / Zn changes in the range of 0.25 to 2.33, the composition of the core material and the surface layer material can be adjusted to the above preferable range.

As for a joining material, it is desirable for one side to have a plate shape which has an area of □ 300 mm or more and a thickness of 50 to 500 μm. By using an Al foil and a Zn foil and controlling the formation of the intermediate layer as described above, the thickness of the bonding material can be adjusted appropriately. When the thickness is in such a range, it is possible to obtain sufficient bonding strength and airtightness. In addition, in the method of mixing and heating and melting the metal described in Patent Document 3, since the metal obtained by melting is brittle, the bonding material has a large size exceeding □ 300 mm and the thickness as described above. It is difficult to do.

The material to be joined is obtained by impregnating a metal in a porous ceramic molded body (preform) produced by appropriately adding a binder or the like to a reinforcing material made of ceramics. As the impregnation method, a pressure infiltration method in which molten metal is forcibly impregnated by pressure, a ceramic surface is modified so as to improve the wettability between molten Al and ceramics, and non-capillary using a capillary phenomenon. A non-pressure infiltration method or the like in which the molten metal is impregnated with pressure can be employed.

For joining, a plate-like joining material is inserted into the joining surface of the Al alloy-ceramic composite material, and a load of about 10 to 500 g / cm ² is applied by the weight of the material to be joined or by placing a weight. To. This is installed in a furnace and heated in a vacuum of 0.1 to 50 Pa or in a normal pressure nitrogen atmosphere. The heating is performed at a temperature lower than the melting point of the matrix Al alloy in the composite material and higher than the melting point of the bonding material, held for a predetermined time, and then cooled. Thus, it is preferable to adjust the firing temperature and firing time.

The bonding material of the present invention can be a bonded body having a hollow portion in which ventilation with the outside is blocked by a bonding layer formed of the bonding material. It is suitable not only for the internal space structure for weight reduction but also for obtaining a joined body in which a heat medium flows through the hollow portion.

FIG. 2 is a schematic sectional view showing an application example of the bonding material of the present invention. The plate member 24 to be joined and the concave member 25 having the recess 25b are joined by the joining material 20 of the present invention.

FIG. 3 is a schematic cross-sectional view of the joined body. The joined body 36 includes a hollow portion 37 in which a plate member 34 and a concave mold member 35 are joined via a joining layer 30 and ventilation with the outside is blocked by the joining layer. If bonding is performed using the bonding material of the present invention, bonding can be performed without generating voids in the bonding layer 30, so that a highly airtight bonded body can be obtained.

Here, specifically, whether or not “aeration with the outside is blocked by the bonding layer”, that is, whether the bonding is airtight or not, was determined by performing a He leak test by a bombing method. As a result of the test, those having a leak amount less than 1 × 10 ⁻⁸ Pa · m ³ / sec were considered to have sufficient airtightness because the ventilation was blocked. Needless to say, the leakage amount of the composite material itself, which is the material to be joined, is smaller than the above numerical value. Such evaluation of airtightness was performed in consideration of the corrosion resistance of the bonding layer.

Examples of the present invention will be specifically described below together with comparative examples to describe the present invention in more detail.

(Production No. 3-12)
As the Al alloy-ceramic composite material to be joined, commercially available silicon carbide powder was used as a reinforcing material, and AC3A was used as an aluminum alloy serving as a matrix. A preform was manufactured by adding 100 parts by weight of commercially available ceramic powder, 5 parts by weight of PVB (polyvinyl butyral) as a binder, and 5 parts by weight of colloidal silica, and pressing them into a predetermined size.

Subsequently, an iron plate having a thickness of 1 mm was placed around the manufactured preform with a 1 mm gap between the preform and preheated to 700 ° C. The preheated preform and the iron plate were taken out and placed in the mold of the molten metal pressurizing apparatus so that they were in the same form as in the preheat treatment.

Separately, the aluminum alloy was melted at 750 ° C., this molten aluminum alloy was put into a mold in which a preform was placed, and a pressure of 30 MPa was applied to infiltrate the molten aluminum alloy into the preform. This infiltration treatment was performed for 10 minutes. Thereafter, the lump containing the Al alloy-ceramic composite material was taken out of the mold. Excess Al alloy adhering to the periphery of the composite material was removed from the mass obtained in this way by grinding to obtain an Al alloy-ceramic composite material having the same shape as the preform.

A sample from this Al alloy-ceramic composite material is a plate-like material having a width of 50 mm, a depth of 100 mm and a thickness of 20 mm as a plate material as shown in FIG. 4, a width of 30 mm at the approximate center of one surface of the plate material as a concave material, A box-shaped material to be joined having a recess having a depth of 80 mm and a depth of 10 mm was cut out and ground with a # 800 grindstone so that the flatness of the joining surface was 5 μm or less. FIG. 4 shows a plan view of the concave material 45 produced. A recess 45b and a joint surface 45a are formed on one side. Grinding dirt on the joint surface was washed with acetone.

JIS alloy 1050 was used for Al as the material of the bonding material, Zn was 99% purity, and Mg was 99% purity. The foil raw material was heated and melted at a temperature of 500 to 700 ° C. in a graphite crucible, and each foil was prepared by pouring it out into a metal two-roll roll. Al foil and Zn foil were prepared so that the mass ratio of Al and Zn and the content of Mg were predetermined values.

Next, the Al foil was subjected to caustic soda etching and acid cleaning, then washed with water and dried. The Zn foil was subjected to sanding and acetone cleaning. Thereafter, the two foils are superposed in the order of Al foil / Zn foil / Al foil, and are subjected to hot rolling at 350 ° C. and cold rolling at room temperature to reduce the thickness to 250 μm. It was heated for a time and subjected to a diffusion treatment to obtain a bonding material having an outer dimension of 450 × 450 mm.

The obtained bonding material was processed into a shape corresponding to the bonding surface shown in FIG. 4, and the surface was washed with acetone. As shown in FIG. 2, the bonding material was inserted between the bonding surfaces of the Al alloy-ceramic composite material, and a weight was placed on the bonding surface so that a load of 300 g / cm ² was applied, and the bonding material was placed in the furnace. This was heated in a vacuum of about 0.1 to 50 Pa at 550 ° C., held at 550 ° C. for 1 hour, then cooled in the furnace, and a hollow portion having a height of about 40 mm, a width of 50 mm, and a depth of 100 mm as shown in FIG. A joined body was obtained.

(Production No. 1, 2, 13-20)
In Production No. 1, a joined body having a hollow part was obtained in the same procedure as in the above production example except that the joining material was not clad and the Zn foil was sandwiched between Al foils. Production No. In No. 2, a bonding material was produced in the same procedure as in the above production example except that an Al foil was sandwiched between Zn foils. Production No. Nos. 13 to 18 except that commercially available alumina, zirconia, aluminum nitride, boron nitride, silicon nitride, and boron carbide powder were used as reinforcing materials for the Al alloy / ceramic composite material to be bonded, respectively. The joined body which has a hollow part was obtained in the same procedure. In Production Nos. 19 and 20, lead borate glass (LS3051 manufactured by Nippon Electric Glass Co., Ltd.) and lead-free glass (BNL115BB manufactured by Asahi Glass Co., Ltd.) were used as the bonding materials. A glass sheet added with an acrylic resin binder into a green sheet with a thickness of 250 μm is used as the bonding material, except that the heat treatment conditions are maintained in the atmosphere at 500 ° C. for 5 minutes and the load on the bonding surface is 30 g / cm ^2. A joined body having a hollow portion was obtained in the same procedure as in the above production example.

(Measurement of bonding material component distribution)
EPMA (JXA-8500F manufactured by JEOL Ltd.) was used to measure the component distribution on the cross section of the bonding material as shown in FIG.

(Bonding strength measurement)
A bonded body having the same conditions and shape as each manufacturing No. was manufactured, a test piece (3 mm × 4 mm × 40 mm) for bonding strength test was cut out, and a four-point bending test (JISR1624 compliant) with a lower span of 30 mm and an upper span of 10 mm ) To obtain the bonding strength.

(He leak test)
A He leak test was performed on a joined body having a hollow portion. The He leak was measured by a bombing method in which a sample in which He was previously pressurized at 0.7 MPa for 30 minutes by a bombing apparatus was placed in a chamber and He that flowed out under a vacuum differential pressure was detected.

Next, in order to confirm the corrosion resistance of the joint, the joined body after the He leak test was left in a high temperature and high humidity (85 ° C.-85% RH) environment for 480 hours, and an acceleration test was performed. The bonded body after the accelerated test was similarly subjected to the He leak test, and the corrosion resistance was confirmed by comparing the amount of He leak before and after the accelerated test.

The test results are shown in Table 1.

Production No. In all of 4-6, 8, 10, 11, 13-18, the joining strength exceeded 100 MPa, and the strength was higher than those of Nos. 19 and 20 using glass powder as the joining material. Further, with respect to He leak, the leak was less than 1 × 10 ⁻⁸ Pa · m ³ / sec, which is a standard for preventing gas leak, and good airtightness was maintained after the corrosion resistance test. .

On the other hand, production No. 1 was simply sandwiched without clad Zn foil and Al foil. In No. 1, since there was no intermediate layer between the Zn foil and the Al foil, Zn was volatilized by the heat treatment during bonding, and bonding could not be performed. Production No. with Al foil sandwiched between Zn foils In No. 2, Zn clad on the surface layer when the Zn foil and the Al foil were clad was partially melted and peeled off, and a bonding material having a target structure could not be obtained. In Production No. 3 in which the Al / Zn mass ratio of the bonding material was small, the bonding layer was corroded during the corrosion resistance test, and hermeticity could not be obtained after the corrosion resistance test. Production No. with a large Al / Zn mass ratio of the bonding material. No. 7 could not be joined because the amount of liquid phase produced at a joining temperature of 550 ° C. was small. Production No. with low Mg content in the surface material of the bonding material. 9 and production No. with a high Mg content. In No. 12, although bonding was possible, the strength was low and airtightness could not be obtained. In production No. 19 using lead borate glass powder as the bonding material, the bonding strength was as low as 45 MPa although it was hermetic. Production No. using lead-free glass as the bonding material. In No. 20, the bonding strength was as low as 30 MPa, and airtightness could not be obtained.

10 Bonding material 11 Core material 12 Surface layer material 13 Intermediate layer

Claims (2)

A bonding material for bonding Al alloy-ceramic composite materials using Al alloy as a matrix and ceramics as a reinforcing material,
A core material whose main component is Zn and constituting the core;
A main layer is Al and contains 0.5 to 2.5% by mass of Mg, and a surface layer material constituting the surface layer;
An intermediate layer made of an alloy containing Al and Zn, and formed between the core material and the surface layer material,
Only including, Al alloy mass ratio Al / Zn of Al and Zn contained in the bonding material, characterized in that a 0.25 to 2.33 - bonding material for ceramic composites. A method of manufacturing a joining material for joining together an Al alloy-ceramic composite material using an Al alloy as a matrix and ceramics as a reinforcing material,
A step of preparing an Al alloy thin plate containing 0.5 to 2.5% by mass of Mg and a Zn thin plate;
A step of roll-bonding superposed and the thin plate before Symbol A l alloy, a thin plate of the Zn,
Forming an intermediate layer and by Ri A l alloy and Zn in a heat treatment are diffused into each other,
Preparation of the bonding material for bonding the ceramic composite material to each other - only contains, Al alloy, wherein the weight ratio Al / Zn of Al and Zn contained in the bonding material is from 0.25 to 2.33 Method.

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