JP5398293B2 - Joining method and joining structure of aluminum-based material - Google Patents

Description

  The present invention provides a method for joining aluminum-based materials such as aluminum and aluminum alloys, in which a strong oxide film is formed on the surface, thereby significantly impairing the bondability, and joining of aluminum-based materials obtained by such a method. Concerning structure.

  As a typical joining method of the aluminum-based material as described above, there are brazing (brazing) and soldering (soldering).

Among the above methods, in brazing of an aluminum-based material, it is necessary to remove the oxide film using a flux because the oxide film formed on the surface of the material inhibits the wetting and flow of the brazing.
As such a flux, what consists of a chloride type or a fluoride type is used (for example, refer patent document 1).

  On the other hand, in the soldering of an aluminum-based material, an inorganic flux whose main component is a chloride such as zinc chloride is generally used as in the case of brazing.

JP-A-8-323278

However, when brazing aluminum materials, if chloride-based fluxes such as the above remain in the joints, moisture will be absorbed and corrosion will occur in the base metal and joints. It must be made.
In general, most of such a flux can be removed by hot water (80 to 100 ° C.), but in order to further completely remove it, it is necessary to perform an acid treatment.

For such acid treatment, nitric acid is generally widely used, but although it is used for small assemblies, it is dangerous for large assemblies because of the large amount of residual flux that reacts with nitric acid. Since gas is generated and harmful to the aluminum base material, it is rarely applied.
In any case, such an acid treatment and subsequent cleaning process and further equipment are required, which not only increases the production cost, but also allows pickling for complete cleaning depending on the part shape. The problem is that there are restrictions and corrosion occurs if the cleaning is not sufficient.

Furthermore, since the joint obtained by brazing is heated to about 600 ° C., that is, the annealing temperature of the aluminum base metal or higher, the strength of the brazed joint of the non-heat-treatable alloy decreases to the soft base material.
In the first place, in the case of a component having a complicated shape in which thermal stress or thermal shock becomes a problem, the upper limit of the bonding process temperature exists due to restrictions on the manufacturing process, and therefore, the bonding method by brazing, which is a high temperature process, cannot be applied.

  On the other hand, a flux used for soldering an aluminum-based material is also called a reactive flux, and has extremely strong erosion resistance against an aluminum oxide film. Further, such a flux remaining in the joint portion easily absorbs moisture and corrodes aluminum, so that there is a problem that the flux removal process after soldering must be performed completely.

The present invention has been made to solve the above problems in joining aluminum-based materials having a strong oxide film.
The purpose of the aluminum-based material is that it can be bonded at a low temperature without using a flux for removing an oxide film, eliminates the need for a flux cleaning step after bonding, and can reduce costs. It is to provide a joining method. Furthermore, it is providing the joining structure of the aluminum-type material which applied such a method.

  As a result of intensive studies aimed at achieving the above object, the present inventors have, as an intermediate material, a metal glass containing an element that is more easily oxidized than Al, that is, an element whose standard free energy of formation is lower than that of Al. The present inventors have found that the above problems can be solved by interposing them on the joint surface, and have completed the present invention.

  That is, the present invention is based on the above knowledge, and in the joining method of the aluminum-based material of the present invention, the standard free energy for formation of oxidation is smaller than that of Al between the materials to be joined made of aluminum or aluminum alloy. An intermediate material made of metallic glass containing an element is interposed, and in this state, joining is performed by applying pressure while heating to the supercooled liquid region temperature of the metallic glass.

  Moreover, the joining structure of the aluminum-type material of this invention is characterized by joining the new surfaces of the to-be-joined material which consists of aluminum or aluminum alloy through the intermediate material which consists of the above metal glasses.

  According to the present invention, an intermediate material made of a metallic glass containing an element whose standard free energy of oxidation is smaller than that of Al is interposed between the joining surfaces of the aluminum-based materials, and the temperature of the supercooled liquid region of the metallic glass is increased. It is heated and joined. Therefore, the use of flux and cleaning after joining are unnecessary, and the new surfaces are directly joined at a low temperature at which the base material is not annealed, so that high joint strength can be secured and costs can be reduced.

(A)-(e) is explanatory drawing which shows the joining mechanism and joining process of the aluminum-type material by this invention. It is explanatory drawing which shows the joining procedure of the aluminum-type material used in the Example of this invention. It is a photograph which shows the whole high frequency heating apparatus used for joining in the Example of this invention. It is the SEM observation image and EDX mapping image of the joining interface obtained by Example 1 of this invention. It is the SEM observation image and EDX mapping image of the joining interface obtained by Example 2 of this invention.

  Below, the joining method of the aluminum-type material of this invention and the joining structure obtained by this are demonstrated further in detail and concretely.

  In the aluminum-based material joining method of the present invention, as described above, a metal glass containing an element whose standard free energy of oxidation is smaller than that of Al is interposed between the joining surfaces of the materials to be joined. In this state, the metal glass is heated to a temperature at which it becomes a supercooled liquid state, and is pressurized and bonded.

In other words, the metal glass as the intermediate material contains an element whose standard free energy for oxidation is smaller than that of Al, that is, an element that is more easily oxidized than Al. Therefore, in the bonding process, the oxide film (Al ₂ O ₃ ) generated on the surface of the aluminum-based material is reduced by the element, the new surface of the material to be bonded is exposed, and a strong bonding interface is formed. Become.
In addition, the metal glass has a characteristic of being in a supercooled liquid state in a region extremely low in temperature with respect to its melting point. Moreover, in such a supercooled liquid state, the reduction reaction by the above elements is more likely to occur than in the normal solid state, and the oxide film on the surface of the aluminum-based material is more effectively reduced and removed. .

In addition, since the metallic glass in the supercooled liquid state has a higher degree of freedom of deformation than the solid phase state, in the supercooled liquid state, the degree of adhesion with the material to be joined increases, and the intermediate material and the material to be joined are interatomic. The distance can be shortened.
Furthermore, in the supercooled liquid state, as compared with the normal solid phase state, the degree of freedom of deformation is high as described above, so that the movement of atoms is likely to occur and diffusion is facilitated. Can be obtained.

In this way, in the metal glass, a phenomenon of being in a supercooled state occurs at a temperature extremely lower than its melting point. Therefore, by using the metal glass as an intermediate material and utilizing this phenomenon, bonding at a lower temperature can be achieved. It becomes possible.
Therefore, there are no thermal effects on the materials to be joined or thermal modification effects, and it is possible to secure strong joint strength, and because of restrictions on the manufacturing process, such as parts with complicated shapes that cause thermal stress and thermal shock. The method of the present invention can also be applied to a joint structure in which an upper limit of the joining process temperature exists.

  Further, in the method of the present invention, no flux is used for removing the oxide film, so that it remains at the joining interface and the soundness of the joining interface is not impaired, and corrosion due to the remaining flux does not occur. And the cleaning process after joining becomes unnecessary, it leads to cost reduction by reduction of production man-hours and omission of a cleaning device, and the expandability of industrial applications is great.

In the present invention, examples of the element whose standard free energy for formation of oxidation is smaller than that of Al include La, Ce, and Pr.
That is, regarding the standard free energy of formation of oxidation of each metal, Al ₂ O ₃ is −497 kJ / mol-O ₂ at 2823 K, whereas La ₂ O ₃ , CeO ₂ , Ce ₂ O ₃ , Pr _2. It is known that that of O ₃ is −928 kJ / mol-O ₂ , −775 kJ / mol-O ₂ , −900 kJ / mol-O ₂ , and −989 kJ / mol-O ₂ , respectively.

Therefore, it is desirable to use a metallic glass containing at least one of these elements as a main component as the intermediate material. In this case, the “main component” means a component that is contained most in the material.
In addition, it is needless to say that the “standard generation free energy of oxidation” is the standard generation free energy at the bonding process temperature, that is, the temperature at which the metal glass as the intermediate material becomes a supercooled liquid state.

FIGS. 1A to 1E are explanatory views showing a joining process of an aluminum-based material according to the method of the present invention.
As shown in FIG. 1A, first, as an intermediate material 3 between materials to be joined 1 and 2 made of an aluminum alloy, in this example, a La-based metal glass La ₅₅ Al ₂₅ Ni ₂₀ (glass transition temperature Tg). = 480K, crystallization temperature Tx = 551K, supercooled liquid region temperature: 480 to 551K). At this time, an oxide film F made of Al ₂ O ₃ is formed on the surfaces of the materials 1 and 2 to be bonded.

When heating is started and the intermediate material 3 made of La-based metallic glass reaches its glass transition temperature Tg (480 K), the intermediate material 3 enters a supercooled liquid state.
As a result, the reactivity of La contained in the intermediate material 3 is increased, and as shown in FIG. 1 (b), La efficiently reduces the oxide film F on the surfaces of the materials to be bonded 1 and 2, and the reduction reaction proceeds. As a result, Al ₂ O ₃ is decomposed, and the new surfaces of the materials 1 and 2 are exposed as shown in FIG.

When the new surfaces of the materials to be bonded 1 and 2 are exposed and directly contact the molten intermediate material 3, a diffusion reaction occurs between them as shown in FIG. 1 (d).
At this time, since the intermediate material 3 is in a supercooled liquid state, the degree of freedom of deformation is greater than that in the normal solid phase state, so that the adhesion increases even with light pressure and the interatomic distance decreases. Then, the movement of the atoms becomes easy to occur and the diffusion easily proceeds, and the bonding is completed as shown in FIG.

  Thereby, the joining structure by which the new surfaces of the to-be-joined materials 1 and 2 made from an aluminum alloy were joined via the intermediate material 3 which consists of metallic glass which contains La as a main component is obtained.

About the intermediate material in the aluminum alloy joint obtained by the method of the present invention, amorphous metal glass may be used depending on the application site.
However, since the deformation resistance (strength) is reduced in the supercooled liquid region between the glass transition temperature Tg and the crystallization temperature Tx, the metallic glass has a base composed of an aluminum-based material at a crystallization temperature Tx or higher as necessary. The intermediate material can be crystallized by heating to a temperature below the annealing temperature of the material. Once crystallized, the crystalline state is maintained regardless of the temperature, thereby improving the joint strength.

  Hereinafter, the present invention will be described more specifically based on examples. The present invention is not limited to these examples.

Example 1
As shown in FIG. 2, the diameter 15mm made of pure aluminum material (A1050-H24), between the disc-shaped members to be joined 2 of the thickness of 2 mm, made of La-based metallic glass _La 55 _Al 25 _{Ni 20} The intermediate material 3 having a thickness of 30 to 40 μm was sandwiched, and the pedestals S and S were joined.
The metal glass has a glass transition temperature Tg of 480K, a crystallization temperature Tx of 551K, and a supercooled liquid region temperature of 480 to 551K.

As the bonding apparatus, as shown in FIG. 3, a high-frequency heating apparatus provided with a test piece installation section and a pressurizing section in a vacuum chamber and capable of detecting and controlling the temperature in the chamber with a thermocouple was used.
As joining conditions, the joining temperature was 540 K, the strain rate was 10 ⁻³ / s (distance between gauge points: 4 mm), and the true strain rate was constant and the displacement was pushed to 0.7 mm.

After the joining was completed, a test piece was cut out from the joined joint, and the joining cross section was observed by SEM, and energy dispersive X-ray analysis (EDX) was performed on Al, La, Ni, and O.
As a result, as shown in FIG. 4, no contamination due to oxides or other components was detected at the bonding interface. Moreover, in the joining interface, the void which is an unjoined area | region was not confirmed but the favorable joining interface was obtained.

  In addition, after joining the said to-be-joined materials 1 and 2 via the intermediate material 3, the intermediate material 3 is hold | maintained for 10 minutes at the temperature more than 480K which is the glass transition temperature Tg of the said metal glass. It was confirmed that can be crystallized.

(Example 2)
When joining the same materials 1 and 2 to be joined, La ₅₅ Al ₂₀ Cu ₂₅ which is La-based metallic glass (glass transition temperature Tg = 423K, crystallization temperature Tx = 487K, supercooled liquid region) The same operation as in Example 1 was repeated except that the bonding temperature was set to 473 K using the temperature: 423 to 487 K) to obtain a bonded joint of this example.

As a result of conducting SEM observation and energy dispersive X-ray analysis (Al, La, Cu, O) of the bonded cross section, the base material was similarly broken, and no oxide or contamination was detected at the bonded interface. An SEM observation image and an EDX mapping image of the above elements are shown in FIG.
At the bonding interface, voids that were unbonded regions were not confirmed, and a good bonding interface was obtained.

(Example 3)
When joining the materials 1 and 2 to be joined, the intermediate material 3 is Ce ₇₀ Al ₁₀ Cu ₂₀ which is a Ce-based metallic glass (glass transition temperature Tg = 341K, crystallization temperature Tx = 408K, supercooled liquid region temperature: 341 to 408K), and the same operation as in Example 1 was repeated except that the bonding temperature was 380K, to obtain a bonded joint of this example.
As a result, also in this example, the presence of oxide or contamination at the bonding interface was not detected.

Example 4
Similarly, when joining the materials 1 and 2 to be joined, as the intermediate material 3, Pr-based metallic glass Pr ₆₈ Cu ₂₅ Al ₇ (glass transition temperature Tg = 382 K, crystallization temperature Tx = 402 K, supercooled liquid region temperature) : 382-402K) and the joining temperature was set to 392K, the same operation as in Example 1 was repeated to obtain a joint joint of this example.
As a result, also in this example, the presence of oxide or contamination was not detected at the bonding interface.

  As described above, by interposing a metallic glass containing La, Ce, and Pr as main components between the joining surfaces of the materials to be joined made of an aluminum-based material, a flux for removing the oxide film is provided. It has been found that aluminum materials can be joined with high strength at a temperature significantly lower than the melting point of aluminum materials without using them.

DESCRIPTION OF SYMBOLS 1 To-be-joined material 2 To-be-joined material 3 Intermediate material F Oxide film

Claims (6)

The supercooled liquid region temperature of the above-mentioned metallic glass with an intermediate material made of metallic glass containing an element whose standard free energy of oxidation is smaller than that of Al interposed between the materials to be joined made of aluminum or an aluminum alloy A method for joining aluminum materials characterized by heating and pressurizing and joining.   The joining method according to claim 1, wherein the intermediate material is crystallized after joining. The joining method according to claim 1 , wherein the intermediate material contains La, Ce, or Pr as a main component.   An aluminum-based material characterized in that new surfaces of materials to be joined made of aluminum or an aluminum alloy are joined to each other via an intermediate material made of metallic glass containing an element whose standard free energy of oxidation is smaller than that of Al. Junction structure.   The junction structure according to claim 4, wherein the intermediate material is crystallized. The junction structure according to claim 4 or 5, wherein the intermediate material contains La, Ce, and Pr as main components.

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