JP2019218260A - Mixed particles, slurry containing mixed particles, and composite - Google Patents

Abstract

To provide mixed particles that can produce a structural member with relatively good resistance to thermal stress.SOLUTION: Mixed particles for a structural member mainly composed of ceramics contain ceramic particles, metal particles, and organosilicon-based polymers. In the mixed particles, the metal particles are contained in the range of 1 vol% to 40 vol% with respect to total volume of the metal particle and the ceramic particles.SELECTED DRAWING: Figure 1

Description

  The present invention relates to mixed particles that can be used, for example, for manufacturing ceramics-based structural members.

  Ceramic porous members are used in various fields such as three-dimensional additive manufacturing, and are usually manufactured by sintering a raw material containing ceramic particles and an organic binder at a high temperature.

  However, some of the ceramic porous members manufactured by the conventional method have a characteristic of being weak against thermal stress. For example, some ceramic porous members are easily cracked or easily broken when subjected to thermal stress. Therefore, various measures have been sought to reduce or suppress this problem.

Japanese Patent Application No. 2014-0444124 "Method of bonding ceramic member and aluminum member, and bonded body" Japanese Patent Application No. 2014-180651 "Method of joining ceramic member and aluminum member"

  As described above, some of the porous members made of ceramics have a property of being weak against thermal stress, and various proposals have been made so far to reduce or suppress this problem.

  However, although various countermeasures have been proposed so far, it is difficult to say that the above-mentioned problem relating to thermal stress has been completely solved. Therefore, there is still a high need for a ceramic porous member having relatively good resistance to thermal stress.

  In addition, after compaction of metal particles that are easily deformed between ceramic particles, and after pressure molding, by heating in an oxidizing atmosphere, a dense ceramic body may be obtained. Application development such as simplification of dense body production can also be expected.

  The present invention has been made in view of such a background, and in the present invention, it is possible to manufacture a structural member (porous member and dense body) having relatively good resistance to thermal stress. It is intended to provide mixed particles.

In the present invention, a mixed particle for a structural member mainly composed of ceramics,
Including ceramic particles, metal particles, and an organosilicon-based polymer,
Mixed particles are provided, wherein the metal particles are contained in a range of 1 vol% to 40 vol% with respect to the total volume of the metal particles and the ceramic particles.

  According to the present invention, it is possible to provide a mixed particle capable of producing a structural member having relatively good resistance to thermal stress.

FIG. 2 is a view schematically illustrating a shape of a mixed particle according to an embodiment of the present invention. FIG. 2 is a diagram schematically illustrating another form of the mixed particles illustrated in FIG. 1. FIG. 5 is a view schematically illustrating another mixed particle according to an embodiment of the present invention. FIG. 4 is a flowchart schematically showing an example of a method for producing the mixed particles having the form shown in FIG. 3. FIG. 5 is a view schematically illustrating another form of mixed particles according to an embodiment of the present invention. FIG. 6 is a flowchart schematically showing an example of a method for producing the mixed particles having the form shown in FIG. 5. FIG. 4 is a flowchart schematically showing an example of a method for manufacturing a structural member using the mixed particles according to the present invention. FIG. 4 is a flowchart schematically showing an example of a method of joining two members to obtain a joined body using the mixed particles according to the present invention. It is the figure which showed the external appearance (photograph) of the composite body (fired at 600-750 degreeC) produced in Examples 1-5. FIG. 2 is a diagram showing an appearance (photograph) of a composite (450 ° C.) produced in Example 1. 4 is a chart showing the result of X-ray diffraction analysis of the composite according to Example 1. 3 is a scanning electron microscope (SEM) photograph of the composite according to Example 1. 9 is a chart showing the result of X-ray diffraction analysis of the composite according to Example 2. 6 is a scanning electron microscope (SEM) photograph of the composite according to Example 2. FIG. 14 is a diagram showing an appearance (photograph) of a composite produced in Example 6. FIG. 14 is a diagram showing an appearance (photograph) of a joined body produced in Example 8.

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

  In the following, a molded article of the mixed powder is referred to as a “compact”, a molded article obtained by heating and integrating the molded article is referred to as a “composite”, a mixed powder for joining the members to be joined, a slurry or / and a slurry. This is referred to as a “joining material”, the joining material is sandwiched between the members to be joined, the one before joining by heat treatment is referred to as an “assembly”, and the one obtained by heating and joining the assembly is referred to as a “joined body”.

(About the mixed particles according to the present invention)
As described above, some porous members made of ceramics have a property that they are weak against thermal stress. Therefore, a ceramic porous member having relatively good resistance to thermal stress has been demanded.

  Under such a background, the present inventors have intensively researched and developed a method for manufacturing a ceramic structural member having relatively good resistance to thermal stress. The inventors of the present application have studied the existence of metal particles in a raw material for producing a structural member, as a solution to the above-described problem. In this case, the metal particles function as an “adhesive” for bonding the ceramic particles during (i) production of the porous member, and (ii) the porous member was subjected to thermal stress when the porous member was used. At the time, it exerts a function of relieving stress. Further, as an application, it is expected that (iii) the gap between the ceramic particles is filled by utilizing the high deformability of the metal to easily produce a dense body.

  However, in general, it may be difficult to bond the ceramic particles and the metal particles to each other. For example, it is well known to those skilled in the art that it is difficult to bond alumina particles and aluminum particles.

  Therefore, the inventors of the present application have conducted further research and development, and as a result, some organic polymers can exhibit a function of mutually bonding ceramic particles and metal particles. When such an organic polymer is added to the raw material of the raw material (hereinafter, the name combining the porous member and the dense body is referred to as a structural member), the ceramic particles and the metal particles are properly adjusted in the manufacturing process of the structural member. And found that the present invention can be combined.

That is, in the present invention, the mixed particles for structural members mainly composed of ceramics,
Including ceramic particles, metal particles, and an organosilicon-based polymer,
Mixed particles are provided, wherein the metal particles are contained in a range of 1 vol% to 40 vol% with respect to the total volume of the metal particles and the ceramic particles.

  Here, "organosilicon-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, siloxane-based polymers, polycarbosilane-based polymers, and the like are included.

  The polycarbosilane-based polymer has a property of being activated at about 600 ° C. or more at about 430 ° C. of the siloxane-based polymer. The organic silicon-based polymer has a property of forming a glass phase containing silicon (Si) at a contact interface between a ceramic material and a metal material when activated. This glass phase has an affinity for both the surface of the ceramic material and the surface of the metal material, and thus functions as an "adhesive" for bonding the two (Patent Documents 1 and 2).

  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 organosilicon polymer, so that the ceramic particles can be formed only by heat treatment via a glass phase containing silicon (Si). And metal particles can be appropriately bonded. In addition, a structural member mainly composed of ceramics can be obtained after the heat treatment.

  Furthermore, as described above, the metal particles contained in the manufactured structural member can exert a function of relieving stress when the structural member receives thermal stress. For this reason, when a structural member is manufactured using the mixed particles according to the present invention, it is possible to provide a structural member having relatively good resistance to thermal stress.

  In the mixed particles according to the present invention, the metal particles are contained in the range of 1 vol% to 40 vol% with respect to the total volume of the metal particles and the ceramic particles. This is because if the amount of the metal particles is less than 1 vol%, it becomes difficult to sufficiently exert the above-described stress relaxation function. On the other hand, if the content of the metal particles exceeds 40 vol%, there is a problem that a large amount of metal remains in the structural member after production (that is, a structural member mainly composed of ceramics cannot be obtained).

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

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

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

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

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

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

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

  The shape of the ceramic particles 110 may be spherical, plate-like, rod-like, fibrous, or the like. The “average minimum dimension” means the average value of the diameter when the ceramic particles 110 are spherical, and the average value of the thickness of the ceramic particles 110 when the ceramic particles 110 are plate-like. When 110 is rod-like or fibrous, it means the average value of the wire diameter.

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

  The average minimum dimension of the metal particles 120 is narrowed to a range of 1 μm to 2000 μm. If the average minimum dimension of the metal particles 120 exceeds 2000 μm, an excessive amount of metal may remain after the bonding process between the particles.

  The shape of the metal particles 120 may be a sphere, a plate, a bar, a fiber, or the like. In addition, the said "average minimum dimension" means the average value of the diameter when the metal particles 120 are spherical, and the average value of the plate thickness when the metal particles 120 are plate-shaped, and the metal particles 120 are rod-shaped or In the case of fibrous, it means the average value of the wire diameter.

  As the organosilicon-based polymer 130, a siloxane-based polymer or a polycarbosilane-based polymer can be suitably used.

  The siloxane-based polymer may be a polymer having a linear Si-O-Si group as a main chain, for example, polymethylhydrosiloxane (PMHS) and polymethylphenylsiloxane (PMPhS). The siloxane-based polymer also includes a silsesquioxane-based polymer having a three-dimensional Si—O—Si group as a 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, such as polycarbosilane (PCS) and allyl hydride polycarbosilane (AHPCS).

  In the first mixed particles 100, the volume of the organosilicon-based polymer 130 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. When the volume of the organosilicon-based 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 generated glass phase decreases, and the ceramic particles 110 and the metal particles 120 are sufficiently bonded. It becomes difficult to do. When the volume of the organosilicon-based polymer 130 exceeds 1.75 times the total volume of the ceramic particles 110 and the metal particles 120, the decomposition gas such as carbon dioxide and silane discharged when the first mixed particles 100 are used. Increases, and causes defective bonding (void) and the like.

  Such first mixed particles 100 can be used for manufacturing a structural member mainly composed of ceramics. However, the first mixed particles 100 can also be used as a joining material for joining two members to each other.

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

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

  In this case, the mixed particles may have a form as schematically shown in FIG. That is, in the mixed particles 101, the organosilicon-based 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 exist in a form dispersed in the liquid organosilicon polymer 130.

  In particular, the mixed particles 101 having the form shown in FIG. 2 are significant when used as a joining material for joining two members to each other.

  The first mixed particles 100 can be manufactured by sufficiently mixing the ceramic particles 110, the metal particles 120, and the organosilicon-based polymer 130 with each other. This mixing process is usually performed at room temperature in the atmosphere.

  On the other hand, when producing the mixed particles 101 having the form as shown in FIG. 2, in order to lower the viscosity of the organosilicon-based polymer 130, the mixing of each material is performed under a temperature condition higher than room temperature (45 ° C. to 400 ° C.). ).

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

  FIG. 3 schematically shows the form of another mixed particle (hereinafter, referred to as “second mixed particle”) according to an embodiment of the present invention. The second mixed particles 200 include ceramic particles 210, metal particles 220, and an organosilicon-based polymer 230. The entirety of the ceramic particles 210 is 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.

  The other specifications and characteristics of each component constituting the second mixed particles 200 can be the same as those described above for the first mixed particles 100, and thus detailed description thereof is omitted here.

  In the second mixed particles 200 having such a configuration, the amount of the organosilicon-based polymer 230 contained in the mixed particles can be reduced as compared with the first mixed particles 100 described above. For this reason, when the second mixed particles 200 are used, the amount of decomposition gas such as carbon dioxide or silane which causes a bonding failure (void) or the like is reduced, and in addition, the amount of the organosilicon-based polymer used is reduced. That is, the cost can be suppressed.

  In the second mixed particles 200, the content of the organosilicon-based 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. In the same concept as the maximum value in the case of the first mixed particles 100, the range can be 1.75 times that of the ceramic particles 210.

  On the other hand, in the second mixed particles 200, the content of the metal particles 220 is 1 vol% to 40 vol with respect to the total volume of the ceramic particles 210 and the metal particles 220 as in the case of the first mixed particles 100. % Is preferable.

  In the example shown in FIG. 3, the organic silicon-based polymer 230 is disposed so as to cover the surface of each ceramic particle 210. However, this is only an example, and the organosilicon-based polymer 230 may be arranged so as to cover the surface of the “agglomerated ceramic particle cluster” including the plurality of ceramic particles 210.

  In such a mode, the amount of the organosilicon-based polymer 230 contained in the second mixed particles 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 a “first production method”). The first manufacturing method is
Preparing metal particles and ceramic particles (step S110);
Coating the surface of the ceramic particles with an organosilicon-based polymer (step S120);
Mixing the metal particles and ceramic particles coated with the organosilicon-based polymer (step S130);
Having.

  Hereinafter, each step will be described in detail. In the following description, for the sake of clarity, the 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 described above, as the ceramic particles 210, alumina, mullite, calcia, zirconia, silicon nitride, and / or silicon carbide can be used.

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

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

  The method of coating the organosilicon-based 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.

  Among them, in the spray drying method, an organic silicon-based polymer 230 is added to an appropriate organic solvent (toluene, ethanol, or the like) to prepare a treatment liquid. This treatment liquid is sprayed on the surface of the ceramic particles 210 that have been allowed to stand, and then the organic solvent is volatilized by heating or the like, whereby the ceramic particles 210 coated with the organosilicon polymer 230 can be obtained. At the time of spraying, the ceramic particles 210 may be brought into a dynamic state by a rotary kiln or the like.

  In the lyophilization method, an organic silicon-based 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 the treatment liquid. Then, after the treatment liquid in which the ceramic particles 210 are immersed is frozen, the organic solvent is aggregated in the region where the temperature has been lowered by leaving it in a vacuum line having a region where the temperature has been lowered with liquid nitrogen or the like. The ceramic particles 210 coated with the polymer 230 can be obtained. For the purpose of increasing the volatilization of the organic solvent, the ceramic particles 210 may be made dynamic by a rotary kiln or the like.

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

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

  This mixing step is usually performed at room temperature under air.

  Through the above steps, third mixed particles 200 having the form as shown in FIG. 3 can be manufactured.

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

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

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

  As shown in FIG. 5, the third mixed particles 300 include ceramic particles 310, metal particles 320, and organosilicon-based polymer 330.

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

  The other specifications and features of each component constituting the third mixed particles 300 can be the same as those described above for the first mixed particles 100, and thus detailed description is omitted here.

  In the third mixed particles 300 having such a configuration, the amount of the organosilicon-based polymer 330 contained in the mixed particles can be reduced as compared with the first mixed particles 100 described above. For this reason, when the third mixed particles 300 are used, the amount of decomposition gas such as carbon dioxide or silane that causes a bonding failure (void) or the like is reduced, and in addition, the amount of the organosilicon-based polymer used is reduced. That is, the cost can be suppressed.

  In the third mixed particles 300, the content of the organosilicon-based polymer 330 is from 0.0003 times the total volume of the metal particles 320 when the metal particles 320 having an average diameter of 2 mm are covered with a thickness of 0.1 μm. In the same manner as the maximum value of the first mixed particles 100, the total volume of the metal particles 320 can be set to 1.75 times.

  On the other hand, in the third mixed particles 300, the content of the ceramic particles 310 is 1 vol% to 40 vol with respect to the total volume of the ceramic particles 310 and the metal particles 320 as in the case of the first mixed particles 100 described above. % Is preferable.

  In the example shown in FIG. 5, the organosilicon-based polymer 330 is disposed so as to cover the surface of each metal particle 320. However, this is only an example, and the organosilicon-based polymer 330 is disposed so as to cover the surface of the “agglomerated metal particle cluster” including the plurality of metal particles 320.

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

FIG. 6 shows a schematic flow chart of an example of a method for producing the third mixed particles 300 (hereinafter, referred to as a “second production method”). The second manufacturing method is
Preparing metal particles and ceramic particles (step S210);
Coating the surface of the metal particles with an organosilicon-based polymer (step S220);
Mixing the ceramic particles and the metal particles coated with the organosilicon-based polymer (step S230);
Having.

  Hereinafter, each step will be described in detail. In the following description, for the sake of clarity, the 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 described above, as the ceramic particles 310, alumina, mullite, calcia, zirconia, silicon nitride, and / or silicon carbide can be used.

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

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

  The method of coating the organosilicon-based polymer 330 is not particularly limited. As the coating method, the spray drying method, the freeze drying method, the solvent impregnation method, and the like as described above 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 mixer may be used for mixing.

  This mixing step is usually performed at room temperature under air.

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

  The above description of the manufacturing method is merely an example, and the third mixed particles 300 may be manufactured by another method.

(Example of use of 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 of the first mixed particles 100 will be described. However, it is obvious to those skilled in the art that the following description can be similarly applied to other mixed particles of the present invention such as the mixed particles 101, 200, and 300.

(Manufacture of structural members mainly composed of ceramics)
The mixed particles according to the present invention can be used for producing structural members mainly composed of ceramics.

  FIG. 7 schematically shows an example of a flow of a method of manufacturing a structural member mainly composed of ceramics using the mixed particles according to the present invention (hereinafter, referred to as a “method of manufacturing a structural member”).

As shown in FIG. 7, the manufacturing method of this structural member is as follows.
Preparing a first mixed particle (step S710);
Forming the first mixed particles to form a formed body (step S720);
Heat treating the molded body (step S730);
Having.

  Hereinafter, each step will be described in detail.

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

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

  In addition, as described above, the content of the metal particles 120 in the first mixed particles 100 is in a range of 1 vol% to 40 vol% with respect to the total volume of the ceramic particles 110 and the metal particles 120.

  The volume of the organosilicon polymer 130 in the first mixed particles 100 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 content of the organosilicon-based polymer 130 is less than 0.0003 times, in the next step S710, there is a possibility that the bonding between the ceramic particles 110 and the metal particles 120 may not be sufficiently generated. When the volume of the organosilicon-based polymer 130 exceeds 1.75 times the total volume of the ceramic particles 110 and the metal particles 120, in the next step S710, the amount of the decomposition gas such as silane discharged increases.

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

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

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

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

  By performing the heat treatment, the organosilicon-based polymer 130 in the first mixed particles 100 is activated. Thereby, 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 mutually bonded via the glass phase.

  Here, the glass phase generated by the heat treatment changes depending on the type of the metal particles 120 used. For example, when the metal particles 120 include aluminum, aluminosilicate is formed as a glass phase. When the metal particles 120 contain silicon, silica is formed as a glass phase.

  The conditions of the heat treatment are not particularly limited as long as a desired structural member can be obtained. However, since the activation temperature (the temperature at which a glass phase starts to form) of the organosilicon-based polymer 130 in the first mixed particles 100 is about 430 ° C. or more, the heat treatment is performed in a temperature range of 450 ° C. or more. Need to be

  The heat treatment temperature during the production of the present composite is preferably in the range of 450 ° C to 1500 ° C. When the temperature exceeds 1500 ° C., the polymer and the glass phase generated from the polymer may be vaporized.

  When a siloxane-based polymer is used as 130, the siloxane-based polymer is most active at about 550 to 650 ° C, and is preferably carried out at about 600 ° C. When the polycarbosilane-based polymer is used as 130, the highest activity of the polycarbosilane-based polymer is from 600 ° C to 1200 ° C, and it is particularly preferable to carry out the reaction at a temperature in the range of 800 ° C to 1000 ° C.

  The atmosphere for the heat treatment is an atmosphere having a low oxygen partial pressure, for example, an atmosphere of an inert gas such as argon, helium, or nitrogen, or a vacuum atmosphere. For example, when the heat treatment is performed in the air or in an oxidizing atmosphere, the organic silicon-based polymer 130 is oxidized and decomposed by oxygen in the air, and the organic silicon-based polymer 130 is bonded to the ceramic particles 110 and the metal particles 120. , It is difficult to use it effectively.

  Through the above steps, a structural member mainly composed of ceramics can be manufactured.

  Structural members obtained by such a method have better resistance to thermal stress than structural members manufactured by conventional methods.

(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 obtain a joined body.

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

As shown in FIG. 8, the manufacturing method of this joined body is as follows.
Preparing a first mixed particle and first and second members to be joined (step S810);
Placing a layer containing the first mixed particles on a joint portion of at least one member to be joined (step S820);
Configuring the assembly by combining the first and second members to be joined with the layer interposed (step S830);
Heat treating the assembly to join the first and second members to be joined (step S840);
Having.

  Hereinafter, each step will be described in detail.

(Step S810)
First, first and second members to be joined to each other are prepared. Further, first mixed particles 100 are prepared.

  Each of the first and second members to be joined is a ceramic member or a metal member.

  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 be a bar, a plate, a disk, a block, 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 mutually different shapes.

  As the first mixed particles 100, the same particles as those described in regard to the above-described method for manufacturing the MMC can be used. However, the composition of the first mixed particles 100 used in the method for manufacturing the joined body is not particularly limited. That is, in the method for manufacturing a joined body, the first mixed particles 100 may have any composition as long as the two joined members can be appropriately joined.

  Note that the first mixed particles 100 are preferably provided as a liquid (including an object having fluidity) or a paste in order to facilitate installation on the member to be joined. In this case, the first mixed particles 100 are used in a state of being dispersed in a solvent such as water, alcohol, toluene, cyclohexane, and benzene.

  When the first mixed particles 100 are provided as a paste, such a paste can be prepared by an evaporator, a magnetic stirrer, or the like.

  Alternatively, the “liquid” mixed particles 101 as described above may be used as the mixed particles. When a highly viscous liquid polymer is used as the organosilicon-based polymer 130 in the mixed particles 101, the mixed particles 101 themselves have fluidity, which facilitates installation on a member to be joined.

(Step S820)
Next, the first mixed particles 100 are disposed in a layered manner on at least one of the first and second members to be joined.

  The method of installation is not particularly limited. The first mixed particles 100 may be provided on the joining surface of the members 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 overlapped with each other via a layer containing the first mixed particles 100. Thus, an assembly is formed.

  In the case where the first mixed particles 100 are provided in the form of a slurry or the like, after forming the assembly, a preliminary heat treatment may be performed before step S840 of the next process to evaporate the solvent.

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

  By performing the heat treatment, the organosilicon-based polymer 130 in the first mixed particles 100 is activated. Thereby, 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 particles 100 are mutually bonded via the glass phase, and are bonded to the interface between the first member and the second member. A layer is formed.

  Furthermore, the first member to be joined and the second member to be joined are joined to each other by the glass phase contained in the joining layer.

  Here, the glass phase generated by the heat treatment changes depending on the type of the metal particles 120 used. When the metal particles 120 include aluminum, aluminosilicate is formed as a glass phase. When the metal particles 120 contain silicon, silica is formed as a glass phase.

  The condition of the heat treatment is not particularly limited as long as the first and second members can be properly joined.

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

  The heat treatment temperature during the production of the present composite is preferably in the range of 450 ° C to 1500 ° C. When the temperature exceeds 1500 ° C., the polymer and the glass phase generated from the polymer may be vaporized.

  When a siloxane-based polymer is used as 130, the siloxane-based polymer is most active at about 550 to 650 ° C, and is preferably carried out at about 600 ° C. When the polycarbosilane-based polymer is used as 130, the highest activity of the polycarbosilane-based polymer is from 600 ° C to 1200 ° C, and it is particularly preferable to carry out the reaction at a temperature in the range of 800 ° C to 1000 ° C.

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

  Through the above steps, a joined body in which two members to be joined are joined via the joining layer can be manufactured.

  Hereinafter, examples of the present invention will be described.

(Example 1)
15.8 g of alumina powder having an average particle diameter of 12 μm (AS-40: manufactured by Showa Denko KK), 3.4 g of aluminum powder having an average particle diameter of 3 μm (# 800F: manufactured by Minarco), and polymethylphenylsiloxane (KF -54: manufactured by Shin-Etsu Chemical Co., Ltd.) in a toluene solvent and thoroughly mixed. At this mixing ratio, 20 vol% of the aluminum powder is contained in the calculation based on the total volume of the aluminum powder and the alumina powder, and the content of polymethylphenylsiloxane is about 0.1% of the total volume of the aluminum powder and the alumina powder. 01 times.

  The obtained mixed liquid was heated to evaporate the solvent to obtain mixed particles. Next, the mixed particles were pressed into a pellet having a diameter of 15 mm to prepare a molded body. Further, this molded body was heat-treated at 600 ° C. for 1 hour in an argon atmosphere.

  Thus, a composite of alumina containing aluminum (composite according to Example 1) was obtained.

  FIG. 9 shows the appearance (photograph) of the composite according to Example 1 manufactured by firing at 600, 650, 700, and 750 ° C.

  The same experiment was performed by changing the temperature of the heat treatment of the molded body in the range of 450 ° C. to 750 ° C. As a result, almost the same composite could be produced at any heat treatment temperature.

  FIG. 10 shows the appearance (photograph) of the composite according to Example 1 produced by firing at 450 ° C.

  FIG. 11 shows the result of X-ray diffraction analysis of the composite according to Example 1. As is clear from FIG. 11, as a result of the X-ray diffraction analysis, diffraction peaks of aluminum, alumina, and aluminosilicate were respectively observed.

  FIG. 12 shows a scanning electron microscope (SEM) photograph of the composite according to Example 1. From FIG. 12, 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.

  In addition, multiple compacts or / and assemblies can be combined to make larger composites / and / or joints.

  Table 1 below shows the results of elemental analysis at the interface between the alumina particles and the aluminum particles.

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

(Example 2)
3.4 g of aluminum powder having an average particle diameter of 3 μm (# 800F: manufactured by Minarco) and 0.25 g of polymethylphenylsiloxane (KF-54: manufactured by Shin-Etsu Chemical Co., Ltd.) were added to a toluene solvent, and then sufficiently added. Was mixed. The resulting mixture was heated to evaporate the solvent to obtain an aluminum powder coated with polymethylphenylsiloxane.

  Next, this aluminum powder was mixed with 15.8 g of an alumina powder having an average particle size of 12 μm (AS-40: manufactured by Showa Denko KK) to prepare a mixed powder.

  In this Example 2, 20 vol% of the aluminum powder was included in the calculation based on the total volume of the aluminum powder and the alumina powder, and the polymethylphenylsiloxane was contained in about 0% of the total volume of the aluminum powder and the alumina powder. .01 times.

  The obtained mixed powder was compacted into a pellet having a diameter of 15 mm to prepare a molded body. Further, this molded body was heat-treated at 600 ° C. for 1 hour in an argon atmosphere.

  Thus, a composite of alumina containing aluminum (composite according to Example 2) was obtained.

  In addition, the same experiment was performed by changing the temperature of the heat treatment of the molded body in the range of 600 ° C to 750 ° C. As a result, almost the same composite could be produced at any heat treatment temperature.

  FIG. 9 shows the appearance (photograph) of the composite according to Example 2 manufactured by firing at 600, 650, 700, and 750 ° C.

  FIG. 13 shows the result of X-ray diffraction analysis of the composite according to Example 2. As apparent from FIG. 13, as a result of the X-ray diffraction analysis, diffraction peaks of aluminum, alumina, and aluminosilicate were respectively observed.

  FIG. 14 shows a scanning electron microscope (SEM) photograph of the composite according to Example 2. From FIG. 14, 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.

  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 result of the X-ray diffraction analysis, this silicon is expected to be an aluminosilicate.

  In addition, multiple compacts or / and assemblies can be combined to make larger composites / and / or joints.

(Example 3)
15.8 g of alumina powder having an average particle size of 12 μm (AS-40: manufactured by Showa Denko KK) and 1.05 g of polymethylphenylsiloxane (KF-54: manufactured by Shin-Etsu Chemical Co., Ltd.) were added to a toluene solvent. , Mixed well. The resulting mixture was heated to evaporate the solvent to obtain an alumina powder coated with polymethylphenylsiloxane.

  Next, 3.4 g of this alumina powder and 3.4 g of aluminum powder having an average particle diameter of 3 μm (# 800F: manufactured by Minarco) were mixed to prepare a mixed powder.

  Note that, in Example 3, 20 vol% of the aluminum powder was included in the calculation based on the total volume of the aluminum powder and the alumina powder, and polymethylphenylsiloxane was contained in about 0% of the total volume of the aluminum powder and the alumina powder. .01 times.

  The obtained mixed powder was compacted into a pellet having a diameter of 15 mm to prepare a molded body. Further, this molded body was heat-treated at 700 ° C. for 1 hour in an argon atmosphere.

  Thereby, a composite of alumina containing aluminum (composite according to Example 3) was obtained.

  In addition, the same experiment was performed by changing the temperature of the heat treatment of the molded body in the range of 600 ° C to 750 ° C. As a result, almost the same composite could be produced at any heat treatment temperature.

  FIG. 9 shows the appearance (photograph) of the composite according to Example 3 produced by firing at 600, 650, 700, and 750 ° C.

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

  In addition, as a result of observation with a scanning electron microscope (SEM), it was found that in the composite, the alumina particles and the aluminum particles were well bonded to each other. Further, 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 result of the X-ray diffraction analysis, this silicon is expected to be an aluminosilicate.

  In addition, multiple compacts or / and assemblies can be combined to make larger composites / and / or joints.

(Example 4)
15.8 g of alumina powder having an average particle diameter of 12 μm (AS-40: manufactured by Showa Denko KK), 3.4 g of aluminum powder having an average particle diameter of 3 μm (# 800F: manufactured by Minarco), and polymethylsilsesquioxane (YR3370: manufactured by Momentive Performance Japan) was added to a toluene solvent and mixed well. In this mixing ratio, 20 vol% of the aluminum powder is included in the calculation based on the total volume of the aluminum powder and the alumina powder, and polymethylsilsesquioxane accounts for about the total volume of the aluminum powder and the alumina powder. 0.0003 times.

  The obtained mixed liquid was heated to evaporate the solvent to obtain mixed particles. Next, the mixed particles were pressed into a pellet having a diameter of 15 mm to prepare a molded body. Further, this molded body was heat-treated at 600 ° C. for 1 hour in an argon atmosphere.

  Thus, a composite of alumina containing aluminum (composite according to Example 4) was obtained.

  In addition, the same experiment was performed by changing the temperature of the heat treatment of the molded body in the range of 600 ° C to 750 ° C. As a result, almost the same composite could be produced at any heat treatment temperature.

  FIG. 9 shows the appearance (photograph) of the composite according to Example 4 manufactured by firing at 600, 650, 700, and 750 ° C.

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

  In addition, as a result of observation with a scanning electron microscope (SEM), it was found that in the composite, the alumina particles and the aluminum particles were well bonded to each other. Further, 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 result of X-ray diffraction analysis, this silicon is expected to be an aluminosilicate.

  In addition, multiple compacts or / and assemblies can be combined to make larger composites / and / or joints.

(Example 5)
15.8 g of alumina powder having an average particle diameter of 12 μm (AS-40: manufactured by Showa Denko KK), 3.4 g of aluminum powder having an average particle diameter of 3 μm (# 800F: manufactured by Minarco), and polymethylphenylsilsesquioki 1.3 g of Sun (SR-21, manufactured by Konishi Chemical Co., Ltd.) was sufficiently mixed to obtain a mixed powder. Note that, in Example 5, no solvent was used at the time of mixing.

  At this mixing ratio, 20 vol% of the aluminum powder is contained in the calculation based on the total volume of the aluminum powder and the alumina powder, and polymethylphenylsilsesquioxane is about 0% of the total volume of the aluminum powder and the alumina powder. .01 times.

  Next, the mixed powder was pressed into a pellet having a diameter of 15 mm to prepare a molded body. Further, this molded body was heat-treated at 600 ° C. for 1 hour in an argon atmosphere.

  Thus, a composite of alumina containing aluminum (composite according to Example 5) was obtained.

  In addition, the same experiment was performed by changing the temperature of the heat treatment of the molded body in the range of 600 ° C to 750 ° C. As a result, almost the same composite could be produced at any heat treatment temperature.

  FIG. 9 shows the appearance (photograph) of the composite according to Example 5 manufactured by firing at 600, 650, 700, and 750 ° C.

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

  In addition, as a result of observation with a scanning electron microscope (SEM), it was found that in the composite, the alumina particles and the aluminum particles were well bonded to each other. Further, 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 result of the X-ray diffraction analysis, this silicon is expected to be an aluminosilicate.

  In addition, multiple compacts or / and assemblies can be combined to make larger composites / and / or joints.

(Example 6)
11.85 g of an alumina powder having an average particle diameter of 12 μm (AS-40: manufactured by Showa Denko KK), 5.4 g of an aluminum powder having an average particle diameter of 3 μm (# 800F: manufactured by Minarco), and polymethylphenylsiloxane (KF -54: Shin-Etsu Chemical Co., Ltd.) in a toluene solvent, and mixed well. In this mixing ratio, 40 vol% of the aluminum powder is included in the calculation based on the total volume of the aluminum powder and the alumina powder, and the content of polymethylphenylsiloxane is about 0.1% of the total volume of the aluminum powder and the alumina powder. 01 times.

  The obtained mixed liquid was heated to evaporate the solvent to obtain mixed particles. Next, the mixed particles were pressed into a pellet having a diameter of 15 mm to prepare a molded body. Further, this molded body was heat-treated at 600 ° C. for 1 hour in an argon atmosphere.

  Thus, a composite of alumina containing aluminum (composite according to Example 6) was obtained.

  FIG. 15 shows a photograph of the composite according to Example 6.

  In addition, the same experiment was performed by changing the temperature of the heat treatment of the molded body in the range of 600 ° C to 750 ° C. As a result, almost the same composite could be produced at any heat treatment temperature.

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

  In addition, as a result of observation with a scanning electron microscope (SEM), it was found that in the composite, the alumina particles and the aluminum particles were well bonded to each other. Further, 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 result of X-ray diffraction analysis, this silicon is expected to be an aluminosilicate.

  In addition, multiple compacts or / and assemblies can be combined to make larger composites / and / or joints.

(Example 7)
15.8 g of alumina powder having an average particle diameter of 12 μm (AS-40: manufactured by Showa Denko KK), 0.1 g of aluminum powder having an average particle diameter of 3 μm (# 800F: manufactured by Minarco), and polymethylphenylsiloxane (KF -54: Shin-Etsu Chemical Co., Ltd.) in a toluene solvent and mixed well. In addition, at this mixing ratio, 1 vol% of the aluminum powder is included in the calculation based on the total volume of the aluminum powder and the alumina powder, and polymethylphenylsiloxane is contained in an amount of about 0.1% of the total volume of the aluminum powder and the alumina powder. 03 times included.

  The obtained mixed liquid was heated to evaporate the solvent to obtain mixed particles. Next, the mixed particles were pressed into a pellet having a diameter of 15 mm to prepare a molded body. Further, this molded body was heat-treated at 600 ° C. for 1 hour in an argon atmosphere.

  Thereby, a composite of alumina containing aluminum (composite according to Example 7) was obtained.

  In addition, the same experiment was performed by changing the temperature of the heat treatment of the molded body in the range of 600 ° C to 750 ° C. As a result, almost the same composite could be produced at any heat treatment temperature.

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

  In addition, as a result of observation with a scanning electron microscope (SEM), it was found that in the composite, the alumina particles and the aluminum particles were well bonded to each other. Further, 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 result of the X-ray diffraction analysis, this silicon is expected to be an aluminosilicate.

In addition, multiple compacts or / and assemblies can be combined to make larger composites / and / or joints.
(Example 8)
Two 30 × 40 × 5 mm aluminum plates (manufactured by Nilaco, purity 99% or more) were prepared. Next, the mixed powder prepared under the same materials and under the same conditions as in Example 2 was applied to an arbitrary surface of an aluminum plate having a size of 40 × 5 mm, and the applied surfaces were abutted and heat-treated at 630 ° C. for 10 minutes.

  Thus, a joined body of the aluminum plate (joined body according to Example 8) was obtained.

  FIG. 16 shows the appearance (photograph) of the joined body according to Example 8.

  In addition, as a result of observation by a scanning electron microscope (SEM), it was found that in the joined body, the alumina particles and the aluminum particles were well bonded to each other. From the result of the X-ray diffraction analysis, this silicon is expected to be an aluminosilicate.

  Thus, it was confirmed that when the mixed powder according to one embodiment of the present invention was used, a structural member mainly composed of ceramics could be manufactured relatively easily. Since the structural member mainly composed of ceramics obtained by this method contains metal particles, it is expected that the structural member has relatively good resistance to thermal stress.

  In addition, multiple compacts or / and assemblies can be combined to make larger composites / and / or joints.

  INDUSTRIAL APPLICATION This invention can be utilized for manufacture of the structural member mainly made of ceramics.

100 First Mixed Particle 101 First Mixed Particle (Modification)
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)

Mixed particles for structural members mainly composed of ceramics,
Including ceramic particles, metal particles, and organosilicon-based polymer (but excluding phenolic resin),
The mixed particles are characterized in that the metal particles are contained in a range of 1 vol% to 40 vol% with respect to the total volume of the metal particles and the ceramic particles.   The mixing according to claim 1, wherein the organosilicon-based polymer is contained in a volume range of 0.0003 to 1.75 times the total volume of the metal particles and the ceramic particles. particle.   3. The organic silicon-based polymer is a siloxane-based polymer, a polycarbosilane-based polymer, or a mixed polymer containing one or more siloxane-based polymers or polycarbosilane-based polymers. Mixed particles.   The mixed particles according to any one of claims 1 to 3, wherein the ceramic particles include a material selected from the group consisting of alumina, mullite, calcia, zirconia, silicon nitride, and silicon carbide.   The mixed particles according to any one of claims 1 to 4, wherein the metal particles include a material selected from the group consisting of aluminum, an aluminum alloy, silicon, and a silicon alloy.   The mixed particle according to claim 1, wherein the metal particle has an average diameter in a range of 1 μm to 2000 μm.   The mixed particles according to any one of claims 1 to 6, wherein the ceramic particles have an average diameter in a range of 0.01 µm to 2000 µm.   The mixed particles according to claim 1, wherein the ceramic particles are coated with the organosilicon-based polymer.   The mixed particle according to claim 1, wherein the metal particle is coated with the organosilicon-based polymer.   The mixed particles according to any one of claims 1 to 9, wherein the mixed particles are used as a raw material for manufacturing a metal-ceramic composite.   A slurry comprising the mixed particles according to any one of claims 1 to 10.   A metal-ceramic composite, wherein the mixed particles according to claim 1 are heated and bonded.   A metal-ceramic composite, wherein the slurry according to claim 11 is heated and bonded.