JP6810438B2 - Mixed particles, slurries containing mixed particles, composites, and conjugates - Google Patents

Description

The present invention relates to mixed particles containing ceramic particles and metal particles, which can be used for producing a metal-ceramic composite (MMC) or the like.

Mixed particles containing ceramic particles and metal particles have many uses. For example, the metal-ceramic composite (MMC), which has features such as light weight, high rigidity, high thermal conductivity, and low thermal expansion and is expected as an alternative to steel materials, is a ceramic particle and a metal particle contained in a mixed particle. It can be manufactured by combining with each other.

Japanese Unexamined Patent Publication No. 07-188803 Japanese Patent Application No. 2014-044124 "Method of joining ceramic member and aluminum member, and joint body" Japanese Patent Application No. 2014-180651 "Method of joining a ceramic member and an aluminum member"

It is known that ceramic particles do not have very good bondability with metal particles. Therefore, when the ceramic particles and the metal particles are bonded to each other, a process of modifying the surface of the ceramic particles in advance to improve the bondability with the metal particles is required.

Conventionally, in order to modify the surface of such ceramic particles, it is necessary to heat-treat the ceramic particles at a high temperature (more than 1200 ° C.) and a high pressure (more than 1 MPa) (Patent Document 1).

However, such a process including heat treatment under high temperature and high pressure is not very realistic as a method for preparing mixed particles. Therefore, there is a demand for mixed particles capable of bonding ceramic particles and metal particles to each other by a more realistic method.

The present invention has been made in view of such a background, and an object of the present invention is to provide mixed particles capable of bonding ceramic particles and metal particles to each other by a simpler method.

The present invention provides mixed particles characterized by containing ceramic particles, metal particles, and organosilicon-based polymers.

In the present invention, it is possible to provide mixed particles capable of bonding ceramic particles and metal particles to each other by a simpler method.

It is a figure which showed schematic form of the mixed particle by one Embodiment of this invention. It is a figure which showed roughly another form of the mixed particle shown in FIG. It is a figure which showed schematic the form of another mixed particle by one Embodiment of this invention. It is a flow chart which showed typically an example of the manufacturing method of the mixed particle of the form shown in FIG. It is a figure which showed the morphology of yet another mixed particle according to one Embodiment of this invention schematically. It is a flow chart which showed typically an example of the manufacturing method of the mixed particle of the form shown in FIG. FIG. 5 is a flow chart schematically showing an example of a method for producing a metal-ceramic composite (MMC) using the mixed particles according to the present invention. It is a flow chart which showed typically an example of the method of joining two members to obtain a bonded body using the mixed particles according to the present invention. It is a chart which showed the result of the X-ray diffraction analysis of the complex which concerns on Example 1. It is a scanning electron microscope (SEM) photograph of the complex which concerns on Example 1. FIG. It is a chart which showed the result of the X-ray diffraction analysis of the complex which concerns on Example 2. It is a scanning electron microscope (SEM) photograph of the complex which concerns on Example 2. FIG. It is a figure which showed the appearance (photograph) of the complex produced in Example 3.

Hereinafter, an embodiment of the present invention will be described.

In the following, a molded mixed powder is a "molded body", a molded body is heated and integrated into a "composite", and a mixed powder, slurry or / or slurry for joining members to be joined to each other. A material is referred to as a "joining material", a material in which a joining material is sandwiched between members to be joined and before joining by heat treatment is referred to as an "assembly", and a material obtained by heating and joining the assembly is referred to as a "joint".

(About mixed particles according to the present invention)
As described above, when the ceramic particles and the metal particles are bonded to each other, a process of modifying the surface of the ceramic particles in advance to improve the bondability with the metal particles is required. In order to modify the surface of the ceramic particles, it is necessary to heat-treat the ceramic particles at a high temperature (more than 1200 ° C.) and a high pressure (more than 1 MPa). However, such a process including heat treatment under high temperature and high pressure is not very realistic as a method for preparing mixed particles.

On the other hand, the present invention provides mixed particles characterized by using ceramic particles, metal particles, and an organosilicon polymer.

Here, the "organic silicon-based polymer" is a general term for organic polymers having a two-dimensional or three-dimensional structure and having a Si—C—Si group or a Si—O—Si group in the main chain. That is, a siloxane-based polymer, a polycarbosilane-based polymer, and the like are included.

This siloxane-based polymer has a property of being activated at about 430 ° C., and the polycarbosilane-based polymer has a property of being activated at 600 ° C. or higher. Further, the organosilicon polymer has a property of forming a glass phase containing silicon (Si) at the contact interface between the ceramic material and the metal material when activated. Since this glass phase has an affinity for both the surfaces of ceramic materials and metal materials, it functions as an "adhesive" that binds the two (Patent Documents 2 and 3).

In the present invention, the ceramic material and the metal material are used as ceramic particles and metal particles to form mixed particles with an organic silicon-based polymer, so that the ceramic particles can be passed through a glass phase containing silicon (Si) only by heat treatment. And metal particles can be properly bonded.

As described above, in the mixed particles according to the present invention, when the ceramic particles and the metal particles are bonded to each other, it is not necessary to carry out the surface modification treatment of the ceramic particles under high temperature and high pressure as in the conventional case, which is more convenient. And quickly, both particles can be bonded to each other.

(About mixed particles according to one embodiment of the present invention)
Next, the mixed particles according to one embodiment of the present invention will be described in detail with reference to FIGS. 1 and 2.

FIG. 1 schematically shows a form of mixed particles (hereinafter, referred to as “first mixed particles”) according to an embodiment of the present invention. Further, FIG. 2 shows another form of the first mixed particles.

As shown in FIG. 1, the first mixed particle 100 has ceramic particles 110, metal particles 120, and an organosilicon polymer 130. It is preferable that the ceramic particles 110, the metal particles 120, and the organosilicon polymer 130 are sufficiently mixed in the first mixed particles 100 and are present uniformly.

The ceramic particles 110 are composed of alumina, mullite, calcia, zirconia, silicon nitride, and / or silicon carbide and the like.

As the alumina, high-purity alumina containing 90 wt% or more of alumina can be preferably used. As the aluminum nitride, high-purity alumina nitride containing 90 wt% or more of aluminum nitride can be preferably used. As the silicon nitride, high-purity silicon nitride containing 90 wt% or more of silicon nitride can be preferably used.

The crystal form of the ceramic particles 110 is not particularly limited, but α-alumina, γ-alumina, or the like can be preferably used as the alumina.

The average minimum size of the ceramic particles 110 is not particularly limited, but is in the range of 0.01 μm to 2000 μm.

Further, as the shape of the ceramic particles 110, a spherical shape, a plate shape, a rod shape, a fibrous shape, or the like can be considered. The "average minimum dimension" means the average value of the diameters when the ceramic particles 110 are spherical, and means the average value of the plate thicknesses of the ceramic particles 110 when the ceramic particles 110 are plate-shaped. When 110 is rod-shaped or fibrous, it means the average value of wire diameters.

The metal particles 120 are made of aluminum, an aluminum alloy, silicon, and / or a silicon alloy or the like.

The average minimum size of the metal particles 120 is narrowed down to the range of 1 μm to 2000 μm. If the average minimum size of the metal particles 120 exceeds 2000 μm, excess metal may remain after the bonding treatment between the particles.

Further, as the shape of the metal particles 120, a spherical shape, a plate shape, a rod shape, a fibrous shape, or the like can be considered. The "average minimum dimension" means the average value of the diameter when the metal particles 120 are spherical, and means the average value of the plate thickness when the metal particles 120 are plate-shaped, and the metal particles 120 are rod-shaped or rod-shaped. In the case of fibrous, it means the average value of the wire diameter.

As the organosilicon polymer 130, a siloxane polymer or a polycarbosilane polymer can be preferably used.

The siloxane-based polymer may be a polymer having a linear Si—O—Si group as a main chain, for example, polymethylhydrosiloxane (PMHS) or polymethylphenylsiloxane (PMPhS). The siloxane-based polymer also includes silsesquioxane-based polymers having a three-dimensional structure Si—O—Si group as the main skeleton, such as polymethylsilsesquioxane (PMSQ) and polyphenylsiloxane (PPSQ).

The polycarbosilane-based polymer may be a polymer having a linear Si—C—Si group as a main chain, for example, polycarbosilane (PCS), allylhydride polycarbosilane (AHPCS), or the like.

In the first mixed particle 100, the volume of the organosilicon polymer 130 is preferably in the range of 0.0003 to 1.75 times the total volume of the ceramic particles 110 and the metal particles 120. When the volume of the organosilicon polymer 130 is less than 0.0003 times the total volume of the ceramic particles 110 and the metal particles 120, the amount of the glass phase produced decreases, and the ceramic particles 110 and the metal particles 120 are sufficiently bonded. It becomes difficult to do. Further, when the volume of the organosilicon polymer 130 exceeds 1.75 times the total volume of the ceramic particles 110 and the metal particles 120, decomposition gas such as carbon dioxide and silane emitted when the first mixed particle 100 is used. The amount of carbon dioxide increases, which causes poor bonding (voids) and the like.

Such a first mixed particle 100 can be used for producing a metal-ceramic composite (MMC).

In particular, when used in the production of a metal-ceramic composite (MMC), the content of the metal particles 120 in the first mixed particles 100 is 40 vol% or more with respect to the total volume of the ceramic particles 110 and the metal particles 120. It is preferably in the range of 80 vol%. If the amount of the metal particles 120 is less than 40 vol%, the amount of the metal particles 120 bonded to the ceramic particles 110 becomes excessively small, which may make it difficult to produce a metal-ceramic composite (MMC). is there. Further, when the content of the metal particles 120 exceeds 80 vol%, the amount of the ceramic particles 110 bonded to the metal particles 120 becomes excessively small, and in this case as well, it is difficult to obtain a metal-ceramic composite (MMC). Become.

Further, the first mixed particle 100 can also be used as a bonding material for bonding two members to each other. The form of joining means that two ceramics, metals, or metal and ceramic plates, rods, wires, linear ceramics, or metals are joined together in an arbitrary area.

In the case of this application example, it is preferable that the first mixed particles 100 are provided in the form of a slurry having fluidity, not as a powder. This makes it possible to relatively easily install the first mixed particle 100 at a predetermined position on the member to be joined.

Here, in the example shown in FIG. 1, the organosilicon polymer 130 is in the form of a solid powder and is homogeneously mixed together with the ceramic particles 110 and the metal particles 120. However, as the organosilicon polymer 130, in addition to such a solid polymer, a "liquid" polymer (including a fluid polymer) can also be used.

In this case, the mixed particles may be in the form generally shown in FIG. That is, in the mixed particles 101, the organosilicon polymer 130 is arranged so as to fill the gap between the ceramic particles 110 and the metal particles 120. In other words, the ceramic particles 110 and the metal particles 120 may be present in a form dispersed in the liquid organosilicon polymer 130.

In particular, the mixed particle 101 having a form as shown in FIG. 2 is significant when it is used as a bonding material for bonding two members to each other.

The first mixed particle 100 can be produced by sufficiently mixing the ceramic particles 110, the metal particles 120, and the organosilicon polymer 130 with each other. The mixing process is usually carried out in the air and at room temperature.

On the other hand, mixing of each material in producing the mixed particles 101 having the form shown in FIG. 2 lowers the viscosity of the organosilicon polymer 130, so that the temperature conditions are higher than room temperature (45 ° C. to 400 ° C.). Implemented below.

(About another mixed particle according to one embodiment of the present invention)
Next, another mixed particle according to one embodiment of the present invention will be described with reference to FIG.

FIG. 3 schematically shows a form of another mixed particle (hereinafter, referred to as “second mixed particle”) according to one embodiment of the present invention. The second mixed particle 200 has ceramic particles 210, metal particles 220, and an organosilicon polymer 230. The entire ceramic particles 210 are coated with the organosilicon polymer 230. In other words, the second mixed particle 200 has a form in which the metal particle 220 and the ceramic particle 210 whose surface is coated with the organosilicon polymer 230 are mixed.

Since the above-mentioned description regarding the first mixed particle 100 can be applied to other specifications and features of each component constituting the second mixed particle 200, detailed description thereof will be omitted here.

In the second mixed particle 200 having such a form, the amount of the organosilicon polymer 230 contained in the mixed particle can be reduced as compared with the above-mentioned first mixed particle 100. Therefore, when the second mixed particle 200 is used, the amount of decomposition gas such as carbon dioxide and silane that causes bonding failure (void) and the like is reduced, and in addition, the amount of the organosilicon polymer used is reduced. That is, the cost can be suppressed.

In the second mixed particle 200, the content of the organosilicon polymer 230 is from 0.0003 times the total volume of the ceramic particles 210 when the ceramic particles 210 having an average diameter of 2 mm are covered with a thickness of 0.1 μm. , The range can be 1.75 times that of the ceramic particles 210 in the same way as the maximum value in the case of the first mixed particles 100.

On the other hand, in the second mixed particle 200, the content of the metal particle 220 is 40 vol% to 80 vol with respect to the total volume of the ceramic particle 210 and the metal particle 220, as in the case of the first mixed particle 100 described above. It is preferably in the range of%.

In the example shown in FIG. 3, the organosilicon polymer 230 is arranged so as to cover the surface of each of the ceramic particles 210. However, this is only an example, and the organosilicon polymer 230 may be arranged so as to cover the surface of the "aggregated ceramic particle cluster" composed of a plurality of ceramic particles 210.

In such a form, the amount of the organosilicon polymer 230 contained in the second mixed particle 200 can be further reduced.

FIG. 4 shows a schematic flow chart of an example of a method for producing the second mixed particles 200 (hereinafter, referred to as “first production method”). The first manufacturing method is
The step of preparing metal particles and ceramic particles (step S110) and
The step of coating the surface of the ceramic particles with an organosilicon polymer (step S120),
A step of mixing the metal particles and the ceramic particles coated with the organosilicon polymer (step S130).
Have.

Hereinafter, each step will be described in detail. In the following description, for the sake of clarification, the reference reference numerals used in FIG. 3 will be used to represent each element.

(Step S110)
First, ceramic particles 210 and metal particles 220 are prepared.

As the ceramic particles 210, as described above, alumina, mullite, calcia, zirconia, silicon nitride, and / or silicon carbide and the like can be used.

Further, as the metal particles 220, aluminum, an aluminum alloy, silicon, and / or a silicon alloy or the like can be used as described above.

(Step S120)
Next, the surface of the ceramic particles 210 is coated with the organosilicon polymer 230.

The coating method of the organosilicon polymer 230 is not particularly limited. As a coating method, a spray-drying method, a freeze-drying method, a solvent impregnation method, or the like may be used.

Of these, in the spray-drying method, the organosilicon polymer 230 is added to an appropriate organic solvent (toluene, ethanol, etc.) to prepare a treatment liquid. The ceramic particles 210 coated with the organosilicon polymer 230 can be obtained by spraying the treatment liquid on the surface of the ceramic particles 210 that have been allowed to stand and then volatilizing the organic solvent by heating or the like. When spraying, the ceramic particles 210 may be brought into a dynamic state by a rotary kiln or the like.

Further, in the freeze-drying method, the organosilicon polymer 230 is added to an appropriate organic solvent (benzene, cyclohexane, etc.) to prepare a treatment liquid. Next, the ceramic particles 210 are immersed in this treatment liquid. Then, after freezing the treatment liquid in which the ceramic particles 210 are immersed, the organic solvent is allowed to stand in a vacuum line having a region cooled by liquid nitrogen or the like to aggregate the organic solvent in the region cooled to an organic silicon system. Ceramic particles 210 coated with the polymer 230 can be obtained. The ceramic particles 210 may be brought into a dynamic state by a rotary kiln or the like for the purpose of increasing the volatilization of the organic solvent.

Further, in the solvent impregnation method, the organosilicon polymer 230 is added to an appropriate organic solvent (benzene, cyclohexane, etc.) to prepare a treatment liquid. Next, the ceramic particles 210 are immersed in this treatment liquid. After that, the ceramic particles 210 coated with the organosilicon polymer 230 can be obtained by volatilizing the organic solvent by heating or the like.

(Step S130)
Next, the metal particles 220 and the ceramic particles 210 coated with the organosilicon polymer 230 are sufficiently mixed. A rotary mill, an evaporator, a magnetic stirrer, or the like may be used for mixing.

This mixing step is usually carried out in the air at room temperature.

By the above steps, the second mixed particle 200 having the form shown in FIG. 3 can be produced.

The above description of the production method is merely an example, and the second mixed particle 200 can be produced by another method. In the first manufacturing method shown in FIG. 4, the metal particles 220 and the ceramic particles 210 are prepared in step S110, and then the ceramic particles 210 are coated with the organosilicon polymer 230 in step S120. However, the ceramic particles 210 coated with the organosilicon polymer 230 are prepared, and then the metal particles 220 are prepared. In addition, various changes are possible.

(For yet another mixed particle according to one embodiment of the present invention)
Next, still another mixed particle according to one embodiment of the present invention will be described with reference to FIG.

FIG. 5 schematically shows a form of yet another mixed particle (hereinafter, referred to as “third mixed particle”) according to one embodiment of the present invention.

As shown in FIG. 5, the third mixed particle 300 has ceramic particles 310, metal particles 320, and an organosilicon polymer 330.

In the third mixed particle 300, the entire metal particle 320 is coated with the organosilicon polymer 330. In other words, the third mixed particle 300 has a form in which the ceramic particles 310 and the metal particles 320 whose surface is coated with the organosilicon polymer 330 are mixed.

Since the above-mentioned description regarding the first mixed particle 100 can be applied to other specifications and features of each component constituting the third mixed particle 300, detailed description thereof will be omitted here.

In the third mixed particle 300 having such a form, the amount of the organosilicon polymer 330 contained in the mixed particle can be reduced as compared with the above-mentioned first mixed particle 100. Therefore, when the third mixed particle 300 is used, the amount of decomposition gas such as carbon dioxide and silane that causes bonding failure (void) and the like is reduced, and in addition, the amount of organosilicon polymer used is reduced. That is, the cost can be suppressed.

In the third mixed particle 300, the content of the organic silicon-based polymer 330 is 0.0003 times the total volume of the metal particle 320 when the metal particle 320 having an average diameter of 2 mm is covered with a thickness of 0.1 micron. The range can be set to 1.75 times the total volume of the metal particles 320 in the same way as the maximum value in the case of the first mixed particles 100.

On the other hand, in the third mixed particle 300, the content of the ceramic particle 310 is 40 vol% to 80 vol with respect to the total volume of the ceramic particle 310 and the metal particle 320, as in the case of the first mixed particle 100 described above. It is preferably in the range of%.

In the example shown in FIG. 5, the organosilicon polymer 330 is arranged so as to cover the surface of each metal particle 320. However, this is only an example, and the organosilicon polymer 330 can be arranged so as to cover the surface of a "aggregated metal particle cluster" composed of a plurality of metal particles 320.

In such a form, the amount of the organosilicon polymer 330 contained in the third mixed particle 300 can be further reduced.

FIG. 6 shows a schematic flow chart of an example of a method for producing the third mixed particle 300 (hereinafter, referred to as “second production method”). The second manufacturing method is
The step of preparing metal particles and ceramic particles (step S210) and
The step of coating the surface of the metal particles with an organosilicon polymer (step S220),
A step of mixing the ceramic particles and the metal particles coated with the organosilicon polymer (step S230).
Have.

Hereinafter, each step will be described in detail. In the following description, for the sake of clarification, the reference reference numerals used in FIG. 5 will be used to represent each object.

(Step S210)
First, ceramic particles 310 and metal particles 320 are prepared.

As the ceramic particles 310, as described above, alumina, mullite, calcia, zirconia, silicon nitride, and / or silicon carbide and the like can be used.

Further, as the metal particles 320, aluminum, an aluminum alloy, silicon, and / or a silicon alloy or the like can be used as described above.

(Step S220)
Next, the surface of the metal particles 320 is coated with the organosilicon polymer 330.

The coating method of the organosilicon polymer 330 is not particularly limited. As the coating method, the above-mentioned spray-drying method, freeze-drying method, solvent impregnation method and the like may be used.

(Step S230)
Next, the ceramic particles 310 and the metal particles 320 coated with the organosilicon polymer 330 are sufficiently mixed. A stirrer or the like may be used for mixing.

This mixing step is usually carried out in the air at room temperature.

Through the above steps, the third mixed particle 300 having the form shown in FIG. 5 can be produced.

The above description of the production method is merely an example, and the third mixed particle 300 may be produced by another method.

(About the use example of the mixed particles according to the present invention)
Next, an example of using the mixed particles according to the present invention having the above-described configuration will be described. Here, as an example, an application example thereof will be described by taking the above-mentioned first mixed particle 100 as an example. However, it will be apparent to those skilled in the art that the following description can be applied to other mixed particles of the present invention as well, such as mixed particles 101, 200 and 300.

(Manufacturing of metal-ceramic composite (MMC))
The mixed particles according to the present invention can be used for producing a metal-ceramic composite (MMC).

FIG. 7 schematically shows an example of a flow of a method for producing a metal-ceramic composite (MMC) using the mixed particles according to the present invention (hereinafter, referred to as “method for producing MMC”).

As shown in FIG. 7, the method for manufacturing MMC is as follows.
The step of preparing the first mixed particles (step S710) and
In the step of molding the first mixed particles to form a molded product (step S720),
The step of heat-treating the molded product (step S730) and
Have.

Hereinafter, each step will be described in detail.

(Step S710)
First, the first mixed particle 100 having the above-described configuration is prepared.

As described above, as the material of the ceramic particles 110, alumina, mullite, calcia, zirconia, silicon nitride, and / or silicon carbide and the like can be used. As the material of the metal particles 120, aluminum, aluminum alloy, silicon, and / or silicon alloy and the like can be used. Further, as the organosilicon polymer 130, a siloxane polymer, a polycarbosilane polymer, or the like can be used.

When producing a metal-ceramic composite (MMC), the content of the metal particles 120 in the first mixed particles 100 is 40 vol% to 80 vol% with respect to the total volume of the ceramic particles 110 and the metal particles 120. It is preferably in the range of. When the content of the metal particles 120 is less than 40 vol%, the amount of the metal particles 120 bonded to the ceramic particles 110 becomes excessively small, and it becomes difficult to obtain a metal-ceramic composite (MMC). Further, when the content of the metal particles 120 exceeds 80 vol%, the amount of the ceramic particles 110 bonded to the metal particles 120 becomes excessively small, and it becomes difficult to obtain a metal-ceramic composite (MMC).

The volume of the organosilicon polymer 130 in the first mixed particles 100 is preferably in the range of 0.0003 times to 1.75 times the total volume of the ceramic particles 110 and the metal particles 120. If the content of the organosilicon polymer 130 is less than 0.0003 times, a sufficient bond may not be formed between the ceramic particles 110 and the metal particles 120 in the next step S710. When the volume of the organosilicon polymer 130 exceeds 1.75 times the total volume of the ceramic particles 110 and the metal particles 120, the amount of decomposed gas such as carbon dioxide and silane emitted in the next step S710 increases. It increases and causes poor bonding (voids).

(Step S720)
Next, a molded product is formed using the first mixed particles 100 prepared in step S710.

The method for forming the molded product is not particularly limited. The molded body can be formed by a powder compacting method, an extrusion molding method, or the like. Further, the molded body after molding may be further pressurized to adjust the shape.

If necessary, the obtained molded product may be subjected to a drying treatment and / or a preheat treatment. As a result, the volatile components (excluding the organosilicon polymer 130) contained in the molded product are decomposed and removed.

(Step S730)
Next, the molded product obtained in step S720 is heat-treated.

By performing the heat treatment, the organosilicon polymer 130 in the first mixed particle 100 is activated. As a result, a glass phase containing silicon (Si) is formed at the contact interface between the ceramic particles 110 and the metal particles 120. As a result, the ceramic particles 110 and the metal particles 120 are bonded to each other via the glass phase.

Here, the glass phase produced by the heat treatment changes depending on the type of the metal particles 120 used. When the metal particles 120 contain aluminum, aluminosilicates are formed as the glass phase. When the metal particles 120 contain silicon, silica is formed as the glass phase.

The conditions of the heat treatment are not particularly limited as long as the desired metal-ceramic composite (MMC) can be obtained. However, since the activation temperature (the temperature at which the glass phase begins to form) of the organosilicon polymer 130 in the first mixed particles 100 is about 430 ° C. or higher, the heat treatment is carried out in a temperature range of 450 ° C. or higher. Need to be.

The heat treatment temperature at the time of producing the present composite is preferably in the range of 450 ° C. to 1500 ° C. If the temperature exceeds 1500 ° C., the polymer and the glass phase formed from the polymer may vaporize.

When the siloxane-based polymer is used as 130, the siloxane-based polymer is most active at about 550 to 650 ° C., and is particularly preferably carried out at around 600 ° C. When the polycarbosilane-based polymer is used as 130, the polycarbosilane-based polymer is most active at 600 ° C to 1200 ° C, and it is particularly desirable that the polycarbosilane-based polymer is carried out in the range of 800 ° C to 1000 ° C.

The atmosphere of the heat treatment is an atmosphere of an inert gas such as argon, helium, and nitrogen, or a vacuum atmosphere. When the heat treatment is carried out in the atmosphere or an oxidizing atmosphere, the organosilicon polymer 130 is oxidized and decomposed by oxygen in the atmosphere, and the organosilicon polymer 130 is effective for bonding the ceramic particles 110 and the metal particles 120. It becomes difficult to use it.

By the above steps, a metal-ceramic composite (MMC) can be produced.

In such a method, it is not necessary to carry out the surface modification treatment of the ceramic particles under high temperature and high pressure as in the conventional method, so that the ceramic particles 110 and the metal particles 120 can be bonded to each other by a simpler process. Can be done.

(Joining of two members)
The mixed particles according to the present invention can also be used as a joining material when joining the first and second members to be joined to obtain a joined body.

FIG. 8 shows an example of a flow of a method of obtaining a bonded body by joining the first and second members to be joined using the mixed particles according to the present invention (hereinafter, referred to as “method for manufacturing a bonded body”). Is shown schematically.

As shown in FIG. 8, the method for producing this bonded body is as follows.
In the step of preparing the first mixed particles and the first and second members to be joined (step S810),
A step of installing a layer containing the first mixed particles at the joint portion of at least one member to be joined (step S820).
A step (step S830) of forming an assembly by combining the first and second members to be joined with the layer interposed therebetween.
A step (step S840) of heat-treating the assembly to join the first and second members to be joined.
Have.

Hereinafter, each step will be described in detail.

(Step S810)
First, first and second members to be joined to each other are prepared. In addition, the first mixed particle 100 is prepared.

Each or both of the first and second members to be joined are ceramic members or metal members.

Examples of the ceramic member include alumina, mullite, calcia, zirconia, silicon nitride, and / or silicon carbide. Examples of the metal member include aluminum, aluminum alloy, silicon, and silicon alloy.

The shape of the first member to be joined is not particularly limited, and the first member to be joined may have a rod shape, a plate shape, a disk shape, a block shape, or a more complicated shape. The same applies to the shape of the second member to be joined. The first member to be joined and the second member to be joined may have different shapes from each other.

As the first mixed particle 100, the same particles as described above for the method for producing MMC can be used. However, the composition of the first mixed particles 100 used in the method for producing the bonded body is not particularly limited. That is, in this method for producing a bonded body, the first mixed particle 100 may have any composition as long as the two members to be bonded can be properly bonded.

The first mixed particles 100 are preferably provided as a slurry or paste having fluidity in order to facilitate installation on the member to be joined. In this case, the first mixed particle 100 is used in a state of being dispersed in a solvent such as water, alcohol, toluene, cyclohexane, and benzene.

Further, when the first mixed particle 100 is provided as a paste, such a paste is used.
It can be prepared by an evaporator, a magnetic stirrer, or the like.

Alternatively, as the mixed particles, the “liquid” mixed particles 101 as described above may be used. When a highly viscous liquid polymer is used as the organosilicon polymer 130 in the mixed particles 101, the mixed particles 101 themselves become fluid and can be easily installed on the member to be joined.

(Step S820)
Next, the first mixed particles 100 are installed in layers on at least one of the joint surfaces of the first and second members to be joined.

The installation method is not particularly limited. The first mixed particle 100 may be installed on the joint surface of the member to be joined by a coating method, a spray method, a spin coating method, a sheet sticking method, dipping or the like.

(Step S830)
Next, the first member to be joined and the second member to be joined are superposed on each other via a layer containing the first mixed particles 100. As a result, the assembly is constructed.

When the first mixed particles 100 are provided in the form of a slurry or the like, the solvent may be vaporized by performing a preliminary heat treatment after forming the assembly and before step S840 of the next step.

(Step S840)
Next, the assembly constructed in step S830 is heat-treated.

By performing the heat treatment, the organosilicon polymer 130 in the first mixed particle 100 is activated. As a result, a glass phase containing silicon (Si) is formed at the contact interface between the ceramic particles 110 and the metal particles 120. As a result, the ceramic particles 110 and the metal particles 120 in the first mixed particle 100 are bonded to each other via the glass phase, and are bonded to the interface between the first member to be bonded and the second member to be bonded. Layers are formed.

Further, the glass phase contained in the bonding layer allows the first member to be bonded and the second member to be bonded to be bonded to each other.

Here, the glass phase produced by the heat treatment changes depending on the type of the metal particles 120 used. When the metal particles 120 contain aluminum, aluminosilicates are formed as the glass phase. When the metal particles 120 contain silicon, silica is formed as the glass phase.

The conditions of the heat treatment are not particularly limited as long as the first and second members to be joined can be properly joined.

However, since the activation temperature of the organosilicon polymer 130 in the first mixed particles 100 is about 430 ° C. or higher, the heat treatment needs to be carried out in a temperature range of 450 ° C. or higher.

The heat treatment temperature at the time of producing the present composite is preferably in the range of 450 ° C. to 1500 ° C. If the temperature exceeds 1500 ° C., the polymer and the glass phase formed from the polymer may vaporize.

When the siloxane-based polymer is used as 130, the siloxane-based polymer is most active at about 550 to 650 ° C., and is particularly preferably carried out at around 600 ° C. When the polycarbosilane-based polymer is used as 130, the polycarbosilane-based polymer is most active at 600 ° C to 1200 ° C, and it is particularly desirable that the polycarbosilane-based polymer is carried out in the range of 800 ° C to 1000 ° C.

The atmosphere of the heat treatment is an atmosphere of an inert gas such as argon, helium, and nitrogen, or a vacuum atmosphere. When the heat treatment is carried out in the atmosphere or an oxidizing atmosphere, the organosilicon polymer 130 is oxidized and decomposed by oxygen in the atmosphere, and the organosilicon polymer 130 is effective for bonding the ceramic particles 110 and the metal particles 120. It becomes difficult to use it.

By the above steps, it is possible to manufacture a bonded body in which two members to be bonded are joined via a bonding layer.

Hereinafter, examples of the present invention will be described.

(Example 1)
Alumina powder with an average particle size of 12 μm (AS-40: manufactured by Showa Denko) 3.95 g, aluminum powder with an average particle size of 3 μm (# 800F: manufactured by Minaruko) 10.96 g, and polymethylphenylsiloxane (KF) -54: manufactured by Shin-Etsu Chemical Co., Ltd.) was added to a toluene solvent and mixed thoroughly. In this blending ratio, the aluminum powder is calculated to be contained in an amount of 80 vol% with respect to the total volume of the aluminum powder and the alumina powder, and the polymethylphenylsiloxane is about 0. 01 times included.

The obtained mixed solution was heated to evaporate the solvent to obtain mixed particles. Next, the mixed particles were compacted into pellets having a diameter of 10 mm to prepare a molded product. Further, this molded product was heat-treated at 600 ° C. for 1 hour under an argon atmosphere.

As a result, a composite of aluminum and alumina (composite according to Example 1) was obtained.

The heat treatment temperature of the molded product was changed in the range of 450 ° C. to 600 ° C., and the same experiment was carried out. As a result, almost the same composite could be produced at any heat treatment temperature.

FIG. 9 shows the results of X-ray diffraction analysis of the complex according to Example 1. As is clear from FIG. 9, as a result of X-ray diffraction analysis, diffraction peaks of aluminum, alumina, and aluminosilicate were observed, respectively.

FIG. 10 shows a scanning electron microscope (SEM) photograph of the complex according to Example 1. From FIG. 10, it can be seen that in the composite according to Example 1, the alumina particles and the aluminum particles are well bonded to each other. Moreover, as a result of elemental analysis at the interface between the alumina particles and the aluminum particles, it was confirmed that silicon was present at this location. From the results of X-ray diffraction analysis, this silicon is expected to be aluminosilicate.

In addition, multiple compacts and / and assemblies can be combined to form larger composites and / and conjugates.

(Example 2)
Sufficiently, 10.96 g of aluminum powder (# 800F: manufactured by Minarco) and 7.5 g of polymethylphenylsiloxane (KF-54: manufactured by Shinetsu Chemical Co., Ltd.) having an average particle size of 3 μm are added to a toluene solvent. Was mixed with. The obtained mixture was heated to evaporate the solvent to obtain an aluminum powder coated with polymethylphenylsiloxane.

Next, this aluminum powder and 3.95 g of an alumina powder (AS-40: manufactured by Showa Denko KK) having an average particle size of 12 μm were mixed to prepare a mixed powder.

In Example 2, the aluminum powder was calculated to be contained in an amount of 80 vol% based on the total volume of the aluminum powder and the alumina powder, and the polymethylphenylsiloxane was contained in about 1 of the total volume of the aluminum powder and the alumina powder. .75 times included.

The obtained mixed powder was compacted into pellets having a diameter of 10 mm to prepare a molded product. Further, this molded product was heat-treated at 600 ° C. for 1 hour under an argon atmosphere.

As a result, a composite of aluminum and alumina (composite according to Example 2) was obtained.

The heat treatment temperature of the molded product was changed in the range of 450 ° C. to 600 ° C., and the same experiment was carried out. As a result, almost the same composite could be produced at any heat treatment temperature.

FIG. 11 shows the results of X-ray diffraction analysis of the complex according to Example 2. As is clear from FIG. 11, as a result of X-ray diffraction analysis, diffraction peaks of aluminum, alumina, and aluminosilicate were observed, respectively.

FIG. 12 shows a scanning electron microscope (SEM) photograph of the complex according to Example 2. From FIG. 12, it can be seen that in the composite according to Example 2, the alumina particles and the aluminum particles are well bonded to each other.

Table 1 below shows the results of elemental analysis at the interface between the alumina particles and the aluminum particles (marked positions in FIG. 12).

From Table 1, it was confirmed that silicon was present at this interface.

In addition, multiple compacts and / and assemblies can be combined to form larger composites and / and conjugates.

(Example 3)
11.85 g of alumina powder with an average particle size of 12 μm (AS-40: manufactured by Showa Denko), 5.4 g of aluminum powder with an average particle size of 3 μm (# 800F: manufactured by Minaruko), and polymethylphenylsiloxane (KF). -54: manufactured by Shin-Etsu Chemical Co., Ltd.) 0.8 g was added to a toluene solvent and mixed thoroughly. In this blending ratio, the aluminum powder is calculated to be contained in an amount of 40 vol% with respect to the total volume of the aluminum powder and the alumina powder, and the polymethylphenylsiloxane is about 0. It is included 03 times.

The obtained mixed solution was heated to evaporate the solvent to obtain mixed particles. Next, the mixed particles were compacted into pellets having a diameter of 15 mm to prepare a molded product. Further, this molded product was heat-treated at 600 ° C. for 1 hour under an argon atmosphere.

As a result, a composite of aluminum and alumina (composite according to Example 3) was obtained.

FIG. 13 shows a photograph of the complex according to Example 3.

The heat treatment temperature of the molded product was changed in the range of 450 ° C. to 600 ° C., and the same experiment was carried out. As a result, almost the same composite could be produced at any heat treatment temperature.

As a result of the X-ray diffraction analysis of the composite according to Example 3, diffraction peaks of aluminum, alumina, and aluminosilicate were observed, respectively.

Further, as a result of observation with a scanning electron microscope (SEM), it was found that in the composite according to Example 3, the alumina particles and the aluminum particles were well bonded to each other. Moreover, as a result of elemental analysis at the interface between the alumina particles and the aluminum particles, it was confirmed that silicon was present at this location. From the results of X-ray diffraction analysis, this silicon is expected to be aluminosilicate.

In addition, multiple compacts and / and assemblies can be combined to form larger composites and / and conjugates.

As described above, it was confirmed that the metal-ceramic composite (MMC) can be produced by a relatively simple process when the mixed powder according to the embodiment of the present invention is used.

The present invention can be used for manufacturing a metal-ceramic composite (MMC), joining two members, and the like.

100 First mixed particles 101 First mixed particles (modification example)
110 Ceramic particles 120 Metal particles 130 Organosilicon-based polymer 200 Second mixed particles 210 Ceramic particles 220 Metal particles 230 Organosilicon-based polymer 300 Third mixed particles 310 Ceramic particles 320 Metal particles 330 Organosilicon-based polymer

Claims (13)

Ceramic particles containing 90 wt% or more of alumina (excluding particles containing silicon carbide), metal particles containing aluminum, and mixed particles containing an organosilicon polymer (excluding cases containing phenol resin). ,
The organosilicon polymer is a mixed particle selected from the group consisting of polymethylhydrosiloxane, polymethylphenylsiloxane, polymethylsilsesquioxane, and polyphenylsiloxane. The mixed particles according to claim 1, wherein the metal particles are contained in a range of 40 to 80 vol% with respect to the total volume of the metal particles and the ceramic particles. The first or second claim, wherein the organosilicon polymer is contained in a volume range of 0.0003 times to 1.75 times the total volume of the metal particles and the ceramic particles. Mixed particles. The mixed particles according to any one of claims 1 to 3, wherein the metal particles have an average minimum dimension in the range of 1 μm to 2000 μm. The mixed particles according to any one of claims 1 to 4, wherein the ceramic particles have an average minimum dimension in the range of 0.01 μm to 2000 μm. The mixed particles according to any one of claims 1 to 5, wherein the ceramic particles are coated with the organosilicon polymer. The mixed particles according to any one of claims 1 to 6, wherein the metal particles are coated with the organosilicon polymer. The mixed particles according to any one of claims 1 to 7, wherein the mixed particles are used as a raw material for producing a metal-ceramic composite. The mixed particles according to any one of claims 1 to 8, wherein the mixed particles are used as a bonding material for two members. A slurry containing the mixed particles according to any one of claims 1 to 9. A metal-ceramic composite, which comprises heating and bonding the mixed particles according to any one of claims 1 to 9. A metal-ceramic composite, which comprises heating and bonding the slurry according to claim 10. A joint made of ceramic members, metal members, or ceramic members and metal members.
The ceramic member is selected from the group consisting of alumina, mulite, calcia, zirconia, silicon nitride, and silicon carbide, and the metal member is selected from the group consisting of aluminum, aluminum alloy, silicon, and silicon alloy.
The bonded body is characterized in that the mixed particles according to any one of claims 1 to 9 or the slurry according to claim 10 are interposed in the bonded portion of each member constituting the bonded body and heated to bond. A bonded body having a glass phase containing silicon between the bonded members of each member.