JP2018154862A - Method for manufacturing an aluminum composite having an aluminum porous sintered body - Google Patents

Abstract

The present invention provides a method for producing an aluminum composite having an aluminum porous sintered body that can increase the strength of the aluminum porous sintered body and suppress the occurrence of warpage even when rolled. . A powder that exhibits a eutectic reaction with aluminum is coated on the back surface of the aluminum foil in advance, and a sintering aid powder containing titanium and / or titanium hydride is mixed with the aluminum powder on the surface of the aluminum foil. A pre-sintered green body is formed by molding and foaming a viscous composition obtained by adding and mixing a water-soluble resin binder, water and a plasticizer to the mixed aluminum raw material powder. In the atmosphere, when the temperature at which the aluminum mixed raw material powder starts to melt is Tm (° C.), it is heated and fired at a heating and firing temperature T (° C.) that satisfies Tm−10 (° C.) ≦ T ≦ 685 (° C.). Thus, an aluminum composite in which an aluminum porous sintered body is integrated with the aluminum foil is obtained. [Selection] Figure 2

Description

  The present invention relates to a method for producing an aluminum composite in which an aluminum foil is integrated with an aluminum porous sintered body having a metal skeleton having a three-dimensional network structure and an Al-Ti compound dispersed in the metal skeleton. .

  The present inventors have previously developed a metal skeleton in which an Al-Ti compound having a three-dimensional network structure is dispersed from an aluminum mixed raw material powder obtained by previously mixing a sintering aid powder containing titanium or titanium hydride with aluminum powder. We have developed a method for producing an aluminum porous sintered body.

  According to this aluminum porous sintered body, a high porosity can be obtained, and therefore it can be suitably used for a current collector of a lithium ion secondary battery or an electric double layer capacitor, an LED heat sink heat sink, a radiator, etc. it can.

  FIG. 6 shows the conventional method for producing an aluminum porous sintered body. First, a water-soluble resin binder, water, a plasticizer, and a water-insoluble hydrocarbon organic solvent are added to the aluminum mixed raw material powder. After mixing to form a viscous composition 1, the viscous composition 1 is formed on a carrier sheet 3 by a doctor blade 2, then foamed in a foaming zone 4 and dried in a drying zone 5 to form before sintering After forming the body 6, the pre-sintered molded body 6 is cut into a molded sheet 8 having a predetermined shape with a cutting blade 7.

  Next, the molded sheet 8 is degreased and sent to the sintering step 9 where Tm-10 (° C.) when the temperature at which the aluminum mixed raw material powder starts melting is Tm (° C.) in a non-oxidizing atmosphere. The aluminum porous sintered body 10 is obtained by heating and baking at a heating and baking temperature T (° C.) satisfying ≦ T ≦ 685 (° C.).

  By the way, when manufacturing the aluminum porous sintered body, the aluminum powder as a raw material of the aluminum porous sintered body 10 is usually covered with an oxide on the surface, and usually has the desired strength in the conventional sintering. Difficult to get.

  For this reason, although the method of improving intensity | strength by adding a sintering auxiliary agent and taking out a part liquid phase was taken, sufficient intensity | strength was not able to be acquired by it. Further, when the strength is increased by increasing the amount of aluminum, there is a problem that the thickness dimension, the hole diameter, and the like change.

  Therefore, the inventors later formed the viscous composition 1 on an aluminum foil instead of the carrier sheet 3 in the following Patent Documents 1 and 2, and foamed and dried in the foaming zone 4 and the drying zone 5. After cutting together with the aluminum foil, the obtained molded sheet 8 was sent to a degreasing and sintering step 9 to integrate the aluminum porous sintered body 10 and the aluminum foil 11 as shown in FIG. A method for manufacturing the aluminum composite 12 has been proposed.

  According to the aluminum composite 12 obtained by the above manufacturing method, since the aluminum foil 11 is integrated with one surface of the aluminum porous sintered body 10, the overall strength can be increased.

  However, even in the aluminum composite 12, the strength can be increased as compared with the case where the aluminum porous sintered body 10 is used as a simple substance. When rolled to increase the packing density of the active material after filling, the aluminum porous sintered body 10 is obtained from the difference in strength between the aluminum foil 11 side at the time of rolling and the surface side of the aluminum porous sintered body 10 on the opposite side. The deformation on the surface side of the film becomes large, resulting in warping. For this reason, the problem that the process of adjusting curvature after that was needed has arisen.

Japanese Patent No. 5407663 Japanese Patent No. 5509786

  The present invention has been made in view of the above circumstances, and can enhance the strength of an aluminum porous sintered body and can suppress the occurrence of warpage even when rolled. An object of the present invention is to provide a method for producing an aluminum composite having a body.

  In order to solve the above-mentioned problems, the invention described in claim 1 is to mix an aluminum powder with a sintering aid powder containing titanium and / or titanium hydride to obtain an aluminum mixed raw material powder, and then to the aluminum mixed raw material powder. A water-soluble resin binder, water, a plasticizer, and an organic solvent are added and mixed to form a viscous composition, and this viscous composition is molded on the surface of an aluminum foil and foamed to obtain a pre-sintered molded body. Later, Tm-10 (° C.) ≦ T ≦ 685 (° C.), where Tm (° C.) is the temperature at which the aluminum mixed raw material powder starts melting in a non-oxidizing atmosphere. In the method for producing an aluminum composite having an aluminum porous sintered body in which the aluminum foil is integrated by heating and firing at a heating and firing temperature T (° C.) of By fixing the powder showing the aluminum and eutectic reaction on the back surface of the iodonium foil, it is characterized in that foaming and molding the viscous composition on the surface of the aluminum foil.

  The invention of claim 2 is the invention of claim 1, wherein the powder is silicon (Si), magnesium (Mg), nickel (Ni), copper (Cu), zinc (Zn) or iron. It is a powder of (Fe).

  Furthermore, the invention according to claim 3 is the invention according to claim 1, wherein the powder is silicon (Si), and the amount in the range of 2 to 8% by mass with respect to the aluminum foil is in the range of 2 to 8% by mass. It is characterized by being fixed to the back surface of aluminum.

  According to the invention according to any one of claims 1 to 3, when the pre-sintered molded body is heated and fired together with the aluminum foil, a liquid phase is generated by the eutectic reaction between the aluminum foil and the powder applied to the back surface thereof. Thus, the amount of dissolution of the aluminum foil can be increased.

  As a result, the aluminum porous sintered body and the aluminum foil can be integrated to improve the strength, and the aluminum foil side and the surface side of the aluminum porous sintered body in the obtained aluminum composite can be further improved. The difference in strength can be reduced, and thus the occurrence of warpage can be suppressed even when a rolling process is performed.

In one Embodiment of this invention, (a) is a schematic diagram which shows the state which apply | coats powder to aluminum foil, (b) is a schematic diagram which shows the state fixed after drying of the said powder. It is a schematic block diagram of the principal part in the apparatus for implementing said one Embodiment. It is a graph which shows the result of the Example of this invention. The scanning electron micrograph by the side of the aluminum porous sintered compact of the aluminum composite obtained by the said Example is shown, (a) is 50 times of imaging magnification, (b) is 500 times, (c) is 1000. Is double. It is a scanning electron micrograph of the aluminum foil side of the aluminum composite of FIG. It is a schematic block diagram which shows the apparatus which enforces the manufacturing method of the conventional aluminum porous sintered compact. It is a perspective view which shows the conventional aluminum complex.

  FIG. 1 and FIG. 2 are views for explaining an embodiment of a method for producing an aluminum composite having an aluminum porous sintered body according to the present invention, and are attached to the same components as those shown in FIG. Are simplified by using the same reference numerals.

  In this production method, an aluminum powder is mixed with a sintering aid powder containing titanium and / or titanium hydride to obtain an aluminum mixed raw material powder, and then the aluminum mixed raw material powder is mixed with a water-soluble resin binder, water and a plasticizer. And a water-insoluble hydrocarbon-based organic solvent are added and mixed to obtain a viscous composition 1, which is formed on the surface of the aluminum foil 11 by the doctor blade 2, foamed in the foaming zone 4 and dried. After forming into a pre-sintered molded body 6 by drying in zone 5, the aluminum mixed raw material powder starts to melt in a non-oxidizing atmosphere in the pre-sintered molded body 6 as shown in FIG. When the temperature to be heated is Tm (° C.), it is roughly constituted by heating and baking at a heating and baking temperature T (° C.) that satisfies Tm−10 (° C.) ≦ T ≦ 685 (° C.).

  As said aluminum powder, a thing with an average particle diameter of 2-200 micrometers is used. Here, when the average particle diameter is smaller than 2 μm, in order that the viscous composition 1 is viscous enough to be molded into a desired shape and the pre-sintered molded body 6 has handling strength, aluminum is used. A large amount of water-soluble resin binder must be added to the powder. However, when a large amount of the water-soluble resin binder is added, the amount of carbon remaining in the foamed aluminum increases when the pre-sintered shaped body 6 is heated and fired, and the sintering reaction is hindered.

  On the other hand, when the particle diameter of the aluminum powder exceeds 200 μm, the strength of the aluminum porous sintered body 10 is lowered. Therefore, as the aluminum powder, those having an average particle diameter in the range of 2 to 200 μm, more preferably 4 to 40 μm, and still more preferably 7 to 40 μm are used as described above. Here, the average particle diameter is measured by a laser diffraction method.

  This aluminum powder is mixed with a sintering aid containing titanium, specifically, titanium and / or titanium hydride. As a result, when titanium is mixed with aluminum powder and the pre-sintered molded body 6 (molded sheet 8) is heated and fired at Tm-10 (° C.) ≦ heating and firing temperature T ≦ 685 (° C.), It is possible to perform non-pressure sintering of aluminum without generating lumps.

Further, titanium hydride (TiH ₂ ) has a titanium content of 47.88 (molecular weight of titanium) / (47.88 + 1 (molecular weight of hydrogen) × 2) and is 95% by mass or more, and is 470 to 530 ° C. Therefore, it is thermally decomposed into titanium when heated and fired as described above. Thereby, even when titanium hydride is mixed, non-pressure sintering of aluminum is possible without generating a lump of droplets. As the sintering aid, a sintering aid powder other than titanium or titanium hydride may be used, or a sintering aid powder containing titanium may be used.

  The sintering aid containing titanium preferably contains 0.1 to 20% by mass of titanium with respect to 100% by mass of aluminum and titanium in total.

  Here, when the average particle diameter of titanium and / or titanium hydride is r (μm) and the blending ratio of titanium and / or titanium hydride is W (mass%), 1 (μm) ≦ r ≦ 30 ( μm), 0.1 (mass%) ≦ W ≦ 20 (mass%), and preferably 0.1 ≦ W / r ≦ 2.

  That is, in the case of titanium hydride powder having an average particle diameter of 4 μm, since 0.1 ≦ W / 4 ≦ 2, the compounding ratio W is preferably 0.4 to 8% by mass. In the case of titanium powder having an average particle diameter of 20 μm, the compounding ratio W is 2 to 40% by mass from the condition of 0.1 ≦ W / 20 ≦ 2, but 0.1 (% by mass) ≦ It is preferable to add the condition of W ≦ 20 (mass%) to 2 to 20 mass%.

  The average particle diameter of titanium hydride is preferably 0.1 (μm) ≦ r ≦ 30 (μm), more preferably 4 (μm) ≦ r ≦ 20 (μm). If the average particle size of titanium hydride is smaller than 0.1 μm, it may spontaneously ignite, and if it exceeds 30 μm, the Al—Ti compound phase is formed from the titanium particles coated with the Al—Ti compound produced by sintering. This is because peeling tends to occur and a desired strength cannot be obtained in the sintered body.

  Furthermore, the blending ratio W is preferably 0.1 (mass%) ≦ W ≦ 20 (mass%). When the blending ratio W of the sintering aid powder exceeds 20 mass%, the aluminum mixed raw material powder This is because the sintering aid powder has contact points, and the reaction heat between aluminum and titanium cannot be controlled, and a desired porous sintered body cannot be obtained.

  However, when the test was conducted under various conditions, the reaction heat between aluminum and titanium was large depending on the particle size of the sintering aid powder even within the range of 0.1 (% by mass) ≦ W ≦ 20 (% by mass). In some cases, the temperature of the aluminum melted by the reaction heat rises further, the viscosity decreases, and droplets may be generated.

  Therefore, from the results of observing the test pieces prepared under various conditions with an electron microscope, within a range in which the calorific value can be controlled by the blending amount of titanium and the particle diameter, the thickness of the titanium particles is almost constant from the exposed surface side. Only the surface layer was found to react with aluminum. Thus, it was experimentally found that in order to prevent the generation of droplets, it is desirable that 1 (μm) ≦ r ≦ 30 (μm) and 0.1 ≦ W / r ≦ 2.

  Next, at least one selected from the group consisting of polyvinyl alcohol, methylcellulose and ethylcellulose as the water-soluble resin binder, and polyethylene glycol, glycerin and phthalate di- At least one selected from the group consisting of n-butyl is added, and distilled water and alkylbetaine as a surfactant are added.

  Thus, when polyvinyl alcohol, methylcellulose, or ethylcellulose is used as the water-soluble resin binder, a relatively small amount is sufficient. Therefore, the addition amount of the water-soluble resin binder is 0.5 to 7% by mass with respect to 100% by mass of the aluminum mixed raw material powder. If the amount is more than 7% by mass with respect to 100% by mass of the aluminum mixed raw material powder, the sintering reaction is hindered due to an increase in the amount of carbon remaining in the pre-sintered green body 6 before heating and firing, and 0.5% by mass. It is because the handling intensity | strength of the molded object 6 before sintering is not ensured that it is less than%.

  Moreover, 0.02-3 mass% of alkylbetaines as surfactants are added to 100 mass% of the mass of the aluminum mixed raw material powder. When the content is 0.02% by mass or more with respect to 100% by mass of the aluminum mixed raw material powder, bubbles are effectively generated when the water-insoluble hydrocarbon organic solvent described later is mixed, and the mass is 3% by mass or less. If so, inhibition of the sintering reaction due to an increase in the amount of carbon remaining in the pre-sintered molded body 6 is prevented.

  And after knead | mixing these, it is made to foam by mixing a C5-C8 water-insoluble hydrocarbon type organic solvent, and the viscous composition 1 with which the bubble was mixed is adjusted. As the water-insoluble hydrocarbon organic solvent having 5 to 8 carbon atoms, at least one selected from the group consisting of pentane, hexane, heptane and octane can be used.

  Next, a doctor blade method, a slurry extrusion method, a screen printing method, or the like is performed on the strip-shaped aluminum foil 11 so that the viscous composition has a thickness of 0.05 mm to 5 mm (in this embodiment, the doctor blade 2). After coating, the ambient temperature and humidity are controlled for a certain period of time, the air bubbles are sized in the foaming zone 4, and then dried in the drying zone 5 at a temperature of 70 ° C. in an air dryer.

  And in this embodiment, as shown in FIG.1 (a), eutectic powder is ethanol on the back surface (surface opposite to the viscous composition application surface) of the aluminum foil 11 used at this time as pretreatment. Apply an organic solvent such as a urethane resin emulsion sprayed and dispersed in an organic solvent such as the above, and dry it at 70 ° C. in an air dryer as shown in FIG. Use a fixed system powder.

  Incidentally, Si, Fe, Ni, Cu, Zn, Co, Mn, etc. can be used as the eutectic powder. And when using Si, a thing with an average particle diameter of 0.1-20 micrometers is used. Further, the Si amount is preferably 2 to 8% by mass with respect to the aluminum foil. If the amount is less than 2% by mass, the amount of aluminum foil dissolved is small and the warping during rolling cannot be suppressed. If the amount is 8% by mass or more, the amount of dissolution increases, the sintering of the porous body proceeds, the dimensional change becomes too large, and cracks occur. It will occur.

  Moreover, it is preferable that the aluminum foil 11 to be used is a weight ratio of 0.25 to 1.4 with respect to the basis weight of the viscous composition 1 coated on the aluminum foil 11, and the basis weight is 100 g / weight. In the case of m2, it is preferable that the weight per unit weight of the aluminum foil is 25 to 140 g / m2, and the thickness of the aluminum foil is 10 to 50 μm.

  Next, the pre-sintered molded body 6 obtained by drying in the drying zone 5 is cut into a desired shape in the same manner as shown in FIG. 6 together with the aluminum foil 11 to form a molded sheet 8, which is shown in FIG. In the degreasing and sintering step shown, the sample is placed on an alumina setter coated with a zirconia powder or the like, and calcined by heating and holding at 520 ° C. for 1 hour in an argon atmosphere with a dew point of −20 ° C. or lower. .

  As a result, debinding that volatilizes and / or decomposes the binder solution of the water-soluble resin binder component, plasticizer component, distilled water and alkylbetaine in the molded sheet 8 is performed, and titanium hydride is used as a sintering aid powder. When is used, dehydrogenation is performed.

  Then, the aluminum foil 11 is integrated with the aluminum porous sintered body 10 by heating and firing the molded sheet 8 after temporary firing at Tm-10 (° C.) ≦ heating and firing temperature (T) ≦ 685 (° C.). Thus obtained aluminum composite 12 is obtained.

  At this time, when the molded sheet 8 is heated to Tm (° C.): 660 ° C., which is the melting temperature of aluminum, it is considered that the reaction between aluminum and titanium starts. The melting point is lowered by eutectic alloy elements such as Fe and Si, and in fact, the reaction between aluminum and titanium starts by heating at Tm-10 (° C.), and the porous aluminum sintered body 10 is formed. Is done.

  Specifically, while the melting point of aluminum is 660 ° C., the melting start temperature is around 650 ° C. for atomized powder having a purity of about 98% to 99.7% distributed as pure aluminum powder. On the other hand, if the heating and firing temperature is maintained at a temperature higher than 685 ° C., aluminum droplet-like lumps are generated in the sintered body.

  The aluminum porous sintered body 10 thus obtained has pores derived from bubbles at the time of foaming of the viscous composition and pores formed in the metal skeleton itself derived from being a sintered body. And two different types of holes.

  Furthermore, in this manufacturing method, a liquid phase is generated by a eutectic reaction with the eutectic powder fixed to the back surface side of the aluminum foil 11, and starts to melt below the sintering temperature during the temperature rise, and the temperature rises. At the same time, the melting area expands, and when the sintering temperature is reached, 20 to 70% of the aluminum foil 11 is melted, and a part of the molten aluminum foil 11 is absorbed by the skeleton of the aluminum porous sintered body 10.

  As a result, the strength is improved by integrating the aluminum porous sintered body 10 and the aluminum foil 11, and the amount of melting of the aluminum foil 11 is further increased, so that the aluminum foil 11 side and the aluminum in the aluminum composite 12 are increased. Since the difference in strength from the surface side of the porous sintered body 10 is reduced, the occurrence of warpage is suppressed even when a rolling process is performed.

  In addition, in order to suppress the growth of the oxide film of the aluminum particle surface and the titanium particle surface, it is necessary to perform the heat baking in the sintering process 9 in a non-oxidizing atmosphere. However, if the heating temperature is 400 ° C. or lower and maintained for about 30 minutes, the oxide film on the aluminum particle surface and the titanium particle surface does not grow so much even when heated in air. After debinding by heating and holding at 300 ° C. to 400 ° C. for about 10 minutes in air, it may be fired at a predetermined temperature in an argon atmosphere.

  Here, the non-oxidizing atmosphere means an atmosphere that includes an inert atmosphere or a reducing atmosphere and does not oxidize the aluminum mixed raw material powder. Moreover, the above-mentioned heating and firing temperature is not the temperature of the aluminum mixed raw material powder, that is, the reaction temperature of the aluminum mixed raw material powder or the like, but means the holding temperature around the aluminum mixed raw material powder.

  In order to verify the effect of the method for producing an aluminum composite having an aluminum porous sintered body according to the present invention, the aluminum composites of Examples 1 to 4 and Comparative Examples 1 to 4 were prepared by the following production methods.

[Pretreatment of aluminum foil]
First, as a pretreatment for aluminum foil, 0.05 g of urethane resin emulsion (resin amount 30 mass%) as a binder is added to 50 ml of ethanol, and 2.5 g of silicon powder having an average particle diameter of 1 μm is suspended and suspended. In this state, a predetermined amount was applied to an aluminum foil having a thickness of 20 μm, and then dried at 70 ° C. for 10 minutes with an air drier, thereby fixing Si to the aluminum foil.

  At this time, the aluminum foil was adjusted so that the amount of Si was 2% by mass (Example 1), and was adjusted to be 3% by mass (Example 2), 5% by mass. (Example 3) prepared so that it might become, and (Example 4) adjusted so that it might become 8 mass% were prepared.

[Production of aluminum composite]
An aluminum composite having an aluminum porous sintered body was manufactured according to the manufacturing method shown in the embodiment described above.
First, an aluminum powder having an average particle diameter of 24 μm (including impurities: Fe: 0.15 mass%, Si: 0.05 mass%, and Ni: 0.01 mass%), and an average particle diameter of 9.1 μm The titanium hydride powder was mixed in a total of 500 g so that the mass ratio of the aluminum powder and the titanium hydride powder was 99: 1 to prepare an aluminum mixed raw material powder.

  Binder solution: 100% by mass of binder solution: 0.1% by mass of methyl cellulose, 2.9% by mass of ethyl cellulose, 3% by mass of glycerin, 3% by mass of polyethylene glycol, 0.5% of alkyl betaine %, The ratio of the remaining water, and a total of 500 g.

  Next, the aluminum mixed raw material powder: 50% by mass, the binder solution: 49% by mass, and heptane: 1% by mass were mixed in a total of 500 g to prepare a viscous composition.

  Next, this viscous composition was applied by stretching to the surface of the aluminum foil prepared for each of Examples 1 to 4 that had not been fixed by the doctor blade method, and the temperature and humidity were maintained for a certain period of time. Then, after air bubbles were sized, they were dried at a temperature of 70 ° C. with an air dryer. The amount of the viscous composition applied was 100 g / m @ 2, the temperature was 35 DEG C., the humidity was 90%, and the holding time was 20 minutes. Subsequent drying was performed at 70 ° C. for 50 minutes. And the sintered body before sintering after drying was cut out into a square with a side of 150 mm together with an aluminum foil to obtain a plurality of molded sheets.

  This molded sheet was placed on an alumina setter coated with zirconia bed powder, pre-baked (debindered) in an argon stream atmosphere, and then heated and fired to obtain an aluminum composite. This debinding was performed at 520 ° C. for 30 minutes. Moreover, the said heat baking was performed for 30 minutes at 660 degreeC in argon atmosphere, and the aluminum complex 1 was obtained. Here, the aluminum foil was melted by 40% in area ratio. Moreover, the thickness of the obtained aluminum composite was 0.5 mm.

[Production of Comparative Examples 1 to 4]
This was carried out except that the viscous composition was applied on a polyethylene sheet coated with a release agent instead of an aluminum foil, and after drying, the viscous composition was peeled off from the polyethylene sheet to prepare a pre-sintered molded body. A plurality of porous aluminum sintered bodies of Comparative Example 1 were prepared in the same manner as the aluminum composites of Examples 1 to 4.

  Moreover, the porous aluminum sintered body of Comparative Example 2 was prepared in the same manner as the aluminum joined body, except that the above viscous composition was applied onto an aluminum foil not sprayed with silicon (Si) to prepare a pre-sintered molded body. Created multiple bodies.

  Further, 0.05 g of urethane resin emulsion (resin amount 30% by mass) as a binder in 50 ml of ethanol was added, and 2.5 g of silicon powder having an average particle diameter of 1 μm was suspended, and the thickness was kept suspended. : A predetermined amount was applied to a 20 μm aluminum foil, and then dried at 70 ° C. for 10 minutes in an air dryer to fix Si to the aluminum foil. At this time, the coating amount was adjusted so that the silicon amount was 1% by mass (Comparative Example 3) and 10% by mass (Comparative Example 4) with respect to the aluminum foil.

  And the viscous composition was apply | coated to the surface of the said aluminum foil, and the aluminum composite of the comparative example 3 and the comparative example 4 was produced in multiple numbers by baking, respectively, similarly to Examples 1-4.

  Next, the aluminum composites prepared as Examples 1 to 4 and Comparative Examples 1 to 4 were each subjected to roll rolling with a rolling reduction of 40%, and the amount of warpage was measured. In the measurement of the amount of warpage, the side of one side of a 150 mm square material on the surface plate was suppressed, and the distance between the opposite side and the surface plate was taken as the amount of warpage.

  In addition, from another aluminum composite prepared as Examples 1 to 4 and Comparative Examples 1 to 4, a length of 100 mm and a width of 10 mm were cut out into a rectangular shape to obtain a tensile test piece. Tensile strength was measured.

FIG. 3 shows this result.
From the figure, it can be seen that the aluminum composites of Examples 1 to 4 all have high tensile strength and suppress warpage during rolling.

  On the other hand, Comparative Example 1 in which the aluminum foil is not integrated (only the aluminum porous sintered body) has no warp during rolling, but the strength is low, and the aluminum porous sintered body is made of aluminum foil. It can be seen that Comparative Example 2 which is a conventional aluminum composite simply integrated has a large warp during rolling, although the tensile strength is large.

  Further, in both Comparative Example 3 and Comparative Example 4, Si was applied to the back surface of the aluminum foil in advance, but in Comparative Example 3, the amount of Si was small, so the dissolved amount of the aluminum foil was small, and the tensile strength was low. Although it is strong, warping during rolling has increased. On the other hand, in Comparative Example 4, since the amount of Si is excessive, the dissolution amount of the aluminum foil is increased, and the liquid phase is increased, so that the dimensional change during the sintering of the porous body becomes too large and the porous body is formed. It can be seen that cracking has occurred and the tensile strength is reduced.

  Next, FIG. 4 is a scanning electron microscope (SEM) photograph obtained by photographing the aluminum porous sintered body side of the aluminum composite of Example 2, and the photographing magnification is 50 times in FIG. 4A and FIG. b) is 500 times, and FIG. 4C is 1000 times. These photographs show the structure of the porous aluminum sintered body in which pores are dispersed in the framework of the three-dimensional network structure in the aluminum composite according to the present invention. It shows that the structure is the same as that.

On the other hand, FIG. 5 is a scanning electron micrograph of the aluminum foil side of the aluminum composite of FIG.
From this photograph, on the aluminum foil side, when the pre-sintered molded body is heated and fired together with the aluminum foil, the powder applied to the back surface of the aluminum foil is compared with the conventional one shown in Patent Document 1 above. It can be seen that the liquid phase is generated by the eutectic reaction and the area ratio of the holes formed by increasing the amount of dissolution of the aluminum foil is large.

  Thereby, according to the aluminum composite of this example, the difference in strength between the aluminum foil side and the surface side of the porous aluminum sintered body is reduced by reducing the area of the aluminum foil due to melting of the aluminum foil. As a result, as shown in FIG. 3, it is presumed that the occurrence of warpage can be suppressed even when the rolling process is performed.

DESCRIPTION OF SYMBOLS 1 Viscosity composition 8 Forming body before sintering 10 Aluminum porous sintered body 11 Aluminum foil 12 Aluminum composite

Claims (3)

Mixing sintering powder containing titanium and / or titanium hydride into aluminum powder to make aluminum mixed raw material powder, then add water-soluble resin binder, water, plasticizer and organic solvent to this aluminum mixed raw material powder -Mixing into a viscous composition, forming this viscous composition on the surface of the aluminum foil and foaming it into a pre-sintered molded body, and then pre-sintering the molded body in a non-oxidizing atmosphere, When the temperature at which the aluminum mixed raw material powder starts melting is Tm (° C.), the above-mentioned temperature is obtained by heating and firing at a heating firing temperature T (° C.) that satisfies Tm−10 (° C.) ≦ T ≦ 685 (° C.). In the method for producing an aluminum composite having an aluminum porous sintered body in which an aluminum foil is integrated,
A porous aluminum sintered body characterized in that a powder showing a eutectic reaction with aluminum is fixed to the back surface of the aluminum foil in advance, and the viscous composition is molded and foamed on the surface of the aluminum foil. A method for producing an aluminum composite.   2. The porous aluminum according to claim 1, wherein the powder is a powder of silicon (Si), magnesium (Mg), nickel (Ni), copper (Cu), zinc (Zn) or iron (Fe). For producing an aluminum composite having a sintered material.   The said powder is silicon (Si), and has fixed the quantity of the range of 2-8 mass% in the mass% with respect to the said aluminum foil to the said back surface of the said aluminum. A method for producing an aluminum composite having an aluminum porous sintered body.