JP6573303B2 - Mixed particle, slurry containing mixed particle, composite, and joined body - Google Patents

Description

  The present invention relates to mixed particles that can be used, for example, in the manufacture of structural members mainly composed of ceramics.

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

  However, some porous ceramic members manufactured by conventional methods 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 countermeasures are being sought to reduce or suppress this problem.

Japanese Patent Application No. 2014-044124 “Method of joining ceramic member and aluminum member, and joined body” Japanese Patent Application No. 2014-180651 “Method of Joining Ceramic Member and Aluminum Member”

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

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

  In addition, it is possible to obtain a dense ceramic body by sandwiching metal particles that are easily deformed between the ceramic particles and then performing pressure molding, followed by heating in an oxidizing atmosphere. Applications 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 produce a structural member (porous member and dense body) having relatively good resistance to thermal stress. An object is to provide mixed particles.

In the present invention, mixed particles for structural members mainly composed of ceramics,
Including ceramic particles, metal particles, and organosilicon polymer,
The mixed particles are provided in which 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.

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

It is the figure which showed roughly the form of the mixed particle by one Embodiment of this invention. It is the figure which showed schematically another form of the mixed particle shown in FIG. It is the figure which showed schematically the form of another mixed particle by one Embodiment of this invention. It is the flowchart which showed roughly an example of the manufacturing method of the mixed particle of the form shown in FIG. It is the figure which showed schematically the form of another mixed particle by one Embodiment of this invention. FIG. 6 is a flowchart schematically showing an example of a method for producing mixed particles having the form shown in FIG. 5. It is the flowchart which showed roughly an example of the method of manufacturing a structural member using the mixed particle by this invention. It is the flowchart which showed roughly an example of the method of joining two members using the mixed particle by this invention, and obtaining a conjugate | zygote. It is the figure which showed the external appearance (photograph) of the composite_body | complex produced in Examples 1-5 (600-750 degreeC baking). 1 is an external view (photograph) of a composite (450 ° C.) produced in Example 1. FIG. 2 is a chart showing the results of X-ray diffraction analysis of the composite according to Example 1. FIG. 2 is a scanning electron microscope (SEM) photograph of the composite according to Example 1. FIG. 4 is a chart showing the results of X-ray diffraction analysis of the composite according to Example 2. 4 is a scanning electron microscope (SEM) photograph of the composite according to Example 2. FIG. 10 is a view showing an appearance (photo) of the composite produced in Example 6. It is the figure which showed the external appearance (photograph) of the conjugate | zygote produced in Example 8. FIG.

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

  In the following, the molded powder is molded as a “molded body”, the molded body is heated and integrated as a “composite”, the mixed powder for joining the members to be joined, slurry or / and slurry-like "Joint material" is a "joint material", a joint material is sandwiched between the members to be joined, and the pre-joint state by heat treatment is referred to as "assembly", and the assembly is heated and joined as "joint".

(Mixed particles according to the present invention)
As described above, some porous ceramic members have a characteristic of being weak against thermal stress. For this reason, a ceramic porous member having relatively good resistance to thermal stress is desired.

  Under these circumstances, the inventors of the present application have conducted intensive research and development on a method for producing a structural member made of ceramics having relatively good resistance to thermal stress. The inventors of the present application examined the presence of metal particles in the raw material for manufacturing the structural member as one proposal for coping with the above-described problems. In this case, the metal particles (i) function as an “adhesive” for bonding ceramic particles to each other during the production of the porous member, and (ii) the porous member was subjected to thermal stress when the porous member was used. In doing so, it exerts a function to relieve stress. Furthermore, as an application, (iii) it is expected that a dense body can be easily manufactured by filling gaps between ceramic particles by making use of the high deformability of metal.

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

  Therefore, the inventors of the present application have further conducted earnest research and development, and as a result, there are organic polymers that can exhibit a function of bonding ceramic particles and metal particles to each other, and structural members. When such an organic polymer is added to the raw material (hereinafter, the name of the porous member and the dense body is referred to as the structural member), the ceramic particles and the metal particles are properly used in the manufacturing process of the structural member. The present invention was found out that it can be bound to the present invention.

That is, in the present invention, mixed particles for structural members mainly composed of ceramics,
Including ceramic particles, metal particles, and organosilicon polymer,
The mixed particles are provided in which 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” means 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.

  At about 430 ° C., the siloxane-based polymer has a property of being activated at 600 ° C. or higher. 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 affinity for both surfaces of the ceramic material and the metal material, it functions as an “adhesive” that bonds both of them (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, and the ceramic particles are passed through a glass phase containing silicon (Si) only by heat treatment. And metal particles can be appropriately bonded. Thereby, 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 exhibit 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 included 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 is difficult to sufficiently exhibit the above-described stress relaxation function. On the other hand, when the metal particles exceed 40 vol%, there is a problem that a large amount of metal remains in the manufactured structural member (that is, a structural member mainly composed of ceramics cannot be obtained).

(Regarding mixed particles according to an embodiment of the present invention)
Next, with reference to FIG. 1 and FIG. 2, the mixed particle by one Embodiment of this invention is demonstrated in detail.

  FIG. 1 schematically shows the 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 particle 100 includes 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 exist uniformly.

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

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

  Although there is no restriction | limiting in particular in the crystal form of the ceramic particle 110, As an alumina, alpha alumina, gamma alumina, etc. can be used conveniently.

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

  Further, the shape of the ceramic particles 110 may be spherical, plate-shaped, rod-shaped, fiber-shaped, or the like. The “average minimum dimension” means an average value of diameter when the ceramic particles 110 are spherical, and means an average value of the plate 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 limited to a range of 1 μm to 2000 μm. If the average minimum dimension of the metal particles 120 exceeds 2000 μm, the metal may remain excessively after the bonding process between the particles.

  Further, the shape of the metal particles 120 may be spherical, plate-like, rod-like, or fiber-like. 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-like. In the case of a fiber, it means the average value of the wire diameter.

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

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

  In the first mixed particle 100, the volume of the organosilicon 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 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 generated is reduced, and the ceramic particles 110 and the metal particles 120 are sufficiently bonded. It becomes difficult to do. In addition, 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, a decomposition gas such as carbon dioxide and silane discharged when the first mixed particles 100 are used. This causes an increase in the amount of solder and causes defective bonding (voids).

  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 bonding material for bonding 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. Thereby, it becomes possible to install the 1st mixed particle 100 in the predetermined location of a member to be joined comparatively easily.

  Here, in the example shown in FIG. 1, the organosilicon 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, in addition to such a solid polymer, a “liquid” polymer (including one having fluidity) can be used as the organosilicon polymer 130.

  In this case, the mixed particles may be in the form schematically shown in FIG. That is, in the mixed particle 101, the organosilicon polymer 130 is disposed so as to fill a gap between the ceramic particle 110 and the metal particle 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 particle 101 having the form shown in FIG. 2 is significant when used as a bonding material for bonding two members to each other.

  The first mixed particles 100 can be manufactured by sufficiently mixing the three of the ceramic particles 110, the metal particles 120, and the organosilicon polymer 130 with each other. In addition, this mixing process is normally implemented under air | atmosphere and room temperature.

  On the other hand, when the mixed particles 101 having the form as shown in FIG. 2 are manufactured, in order to reduce the viscosity of the organosilicon polymer 130, each material is mixed under a temperature condition higher than room temperature (45 ° C. to 400 ° C. ) Implemented below.

(Regarding 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 particle 200 includes ceramic particles 210, metal particles 220, and an organosilicon polymer 230. The entire ceramic particle 210 is coated with an 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.

  In addition, since the description regarding the said 1st mixed particle 100 is applicable to the other specification and characteristic of each component which comprise the 2nd mixed particle 200, detailed description is abbreviate | omitted here.

  In the second mixed particle 200 having such a configuration, the amount of the organosilicon polymer 230 contained in the mixed particle can be reduced as compared with the first mixed particle 100 described above. For this reason, when the second mixed particles 200 are used, the amount of decomposition gas such as carbon dioxide and silane that causes poor bonding (void) is reduced, and in addition, the amount of 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 particle 210 when the ceramic particle 210 having an average diameter of 2 mm is covered with a thickness of 0.1 μm. In the same way 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 particle 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 described above. % Is preferable.

  In the example shown in FIG. 3, the organosilicon polymer 230 is disposed so as to cover the surface of each ceramic particle 210. However, this is merely an example, and the organosilicon polymer 230 may be disposed so as to cover the surface of the “aggregated ceramic particle cluster” composed of the 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 diagram of an example of a method for manufacturing the second mixed particle 200 (hereinafter referred to as “first manufacturing method”). The first manufacturing method is
Preparing metal particles and ceramic particles (step S110);
Coating the surface of the ceramic particles with an organosilicon polymer (step S120);
Mixing the metal particles and ceramic particles coated with the organosilicon polymer (step S130);
Have

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

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

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

  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 particle 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.

  Among 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 are allowed to stand, and then volatilizing the organic solvent by heating or the like. When spraying, the ceramic particles 210 may be in a dynamic state with a rotary kiln or the like.

  In the lyophilization 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 the treatment liquid. Then, after freezing the treatment liquid in which the ceramic particles 210 are immersed, the organic solvent is agglomerated in a low-temperature region by standing in a vacuum line having a low-temperature region with liquid nitrogen or the like. Ceramic particles 210 coated with polymer 230 can be obtained. For the purpose of increasing the volatilization of the organic solvent, the ceramic particles 210 may be in a dynamic state with a rotary kiln or the like.

  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 the treatment liquid. Thereafter, 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. For mixing, a rotary mill, an evaporator, a magnetic stirrer or the like may be used.

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

  Through the above steps, the third mixed particles 200 having the form 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 other methods. In the first manufacturing method shown in FIG. 4, the metal particles 220 and the ceramic particles 210 are prepared in Step S <b> 110, and then the ceramic particles 210 are coated with the organosilicon polymer 230 in Step S <b> 120. However, the metal particles 220 are prepared after the ceramic particles 210 coated with the organosilicon polymer 230 are prepared. Various other changes are possible.

(About further mixed particles 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. 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 particle 300 includes 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 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.

  In addition, since the description regarding the said 1st mixed particle 100 is applicable to the other specification and characteristic of each component which comprise the 3rd mixed particle 300, detailed description is abbreviate | omitted here.

  In the 3rd mixed particle 300 of such a form, compared with the above-mentioned 1st mixed particle 100, the quantity of the organosilicon polymer 330 contained in a mixed particle can be reduced. For this reason, when the third mixed particles 300 are used, the amount of decomposition gas such as carbon dioxide and silane that causes poor bonding (void) is reduced, and additionally, 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 organosilicon 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 μm. In the same way as the maximum value in the case of the first mixed particle 100, the total volume of the metal particles 320 can be 1.75 times the range.

  On the other hand, the content of the ceramic particles 310 in the third mixed particles 300 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 polymer 330 is disposed so as to cover the surface of each metal particle 320. However, this is merely an example, and the organosilicon polymer 330 is disposed so as to cover the surface of an “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 particles 300 can be further reduced.

FIG. 6 shows a schematic flow diagram of an example of a method for manufacturing the third mixed particles 300 (hereinafter referred to as “second manufacturing method”). The second manufacturing method is
Preparing metal particles and ceramic particles (step S210);
Coating the surface of the metal particles with an organosilicon polymer (step S220);
Mixing the ceramic particles and 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 clarity, the reference numerals used in FIG. 5 are used to represent each item.

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

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

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

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

  The method for coating the organosilicon polymer 330 is not particularly limited. As the coating method, the spray drying method, the freeze drying method, the solvent impregnation method, or 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. For mixing, a stirrer or the like may be used.

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

  Through the above steps, the third mixed particle 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 other methods.

(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, the application example will be described using the first mixed particle 100 described above as an example. However, it will be apparent to those skilled in the art that the following description can be similarly applied to other mixed particles of the present invention, such as 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 manufacturing a structural member mainly composed of ceramics.

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

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

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

  As described above, the content of the metal particles 120 in the first mixed particles 100 is in the 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 particle 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, there is a possibility that bonding is not sufficiently generated 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 decomposition gas such as silane discharged increases in the next step S710.

(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 compacting method or an extrusion molding method. Moreover, you may further pressurize with respect to the molded object after shaping | molding, and may arrange a shape.

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

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

  By performing the heat treatment, the organosilicon 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 bonded to each other through the glass phase.

  Here, the glass phase produced | generated by heat processing changes with the kind of metal particle 120 used. For example, when the metal particle 120 contains aluminum, an aluminosilicate is formed as a glass phase. Moreover, when the metal particle 120 contains silicon, silica is formed as a glass phase.

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

  The heat treatment temperature during the production of the composite is preferably in the range of 450 ° C to 1500 ° C. When it 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., particularly preferably at about 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 preferable that the temperature is in the range of 800 ° C. to 1000 ° C.

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

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

  A structural member obtained by such a method has better resistance to thermal stress than a structural member manufactured by a conventional method.

(Join two members)
The mixed particles according to the present invention can also be used as a bonding material when the first and second members to be bonded are bonded to obtain a bonded body.

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

As shown in FIG. 8, the manufacturing method of this joined body is:
Preparing the first mixed particles and the first and second members to be joined (step S810);
Installing a layer containing the first mixed particles in a joining portion of at least one member to be joined (step S820);
Combining the first and second members to be joined together with the layer interposed therebetween (step S830);
Heat-treating the assembly to join the first and second members to be joined (step S840);
Have

  Hereinafter, each step will be described in detail.

(Step S810)
First, the 1st and 2nd to-be-joined member joined mutually is prepared. In addition, 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, an aluminum alloy, silicon, and a silicon alloy.

  The shape of the first member to be bonded is not particularly limited, and the first member to be bonded may be a bar 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.

  As the first mixed particles 100, the same particles as those described with respect to the above-described MMC manufacturing method 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 this method for manufacturing a joined body, the first mixed particles 100 may have any composition as long as the two members to be joined 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 a member to be bonded. In this case, the first mixed particles 100 are used in a state where they are dispersed in a solvent such as water, alcohol, toluene, cyclohexane, or benzene.

  Moreover, when providing the 1st mixed particle 100 as a paste, such a paste can be prepared with an evaporator, a magnetic stirrer, etc.

  Alternatively, the “liquid” mixed particles 101 as described above may be used as the mixed particles. In the mixed particle 101, when a highly viscous liquid polymer is used as the organosilicon polymer 130, the mixed particle 101 itself has fluidity, and is easily installed on the member to be joined.

(Step S820)
Next, the 1st mixed particle 100 is installed in a layer form with respect to at least one joined surface among the 1st and 2nd members to be joined.

  The installation method is not particularly limited. The 1st mixed particle 100 may be installed in the joined surface of a to-be-joined member by the apply | coating method, the spray method, a spin coat, the sheet sticking method, dipping etc.

(Step S830)
Next, the first member to be bonded and the second member to be bonded are overlapped with each other via the layer including the first mixed particles 100. Thereby, an assembly is constituted.

  In addition, when the 1st mixed particle 100 is provided with the form of a slurry etc., after comprising an assembly, preliminary heat processing may be implemented before step S840 of the next process, and a solvent may be vaporized.

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

  By performing the heat treatment, the organosilicon 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 bonded to each other through the glass phase, and bonded to the interface between the first bonded member and the second bonded member. A layer is formed.

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

  Here, the glass phase produced | generated by heat processing changes with the kind of metal particle 120 used. When the metal particle 120 contains aluminum, an aluminosilicate is formed as a glass phase. Moreover, when the metal particle 120 contains silicon, silica is formed as a glass phase.

  The heat treatment conditions are not particularly limited as long as the first and second members to be joined can be appropriately 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 performed in a temperature range of 450 ° C. or higher.

  The heat treatment temperature during the production of the composite is preferably in the range of 450 ° C to 1500 ° C. When it 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., particularly preferably at about 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 preferable that the temperature is 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 atmosphere or in 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.

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

  Examples of the present invention will be described below.

Example 1
15.8 g of alumina powder (AS-40: Showa Denko) with an average particle size of 12 μm, 3.4 g of aluminum powder (# 800F: manufactured by Minalco) with an average particle size of 3 μm, and polymethylphenylsiloxane (KF) -54: manufactured by Shin-Etsu Chemical Co., Ltd.) was added to a toluene solvent and mixed well. In this blending ratio, the aluminum powder is contained in an amount of 20 vol% with respect to the total volume of the aluminum powder and the alumina powder, and the polymethylphenylsiloxane is about 0.00% of the total volume of the aluminum powder and the alumina powder. 01 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 compact. Furthermore, this molded body was heat-treated at 600 ° C. for 1 hour in an argon atmosphere.

  As a result, 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.

  In addition, the temperature of the heat processing of a molded object was changed in the range of 450 to 750 degreeC, and the same experiment was implemented. 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 manufactured by firing at 450 ° C.

  In FIG. 11, the result of the X-ray diffraction analysis of the composite_body | complex which concerns on Example 1 is shown. As apparent from FIG. 11, as a result of X-ray diffraction analysis, diffraction peaks of aluminum, alumina, and aluminosilicate were observed.

  In FIG. 12, the scanning electron microscope (SEM) photograph of the composite_body | complex which concerns on Example 1 is shown. 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.

  Further, a plurality of molded bodies or / and assemblies can be combined to make further large composites and / or joined bodies.

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

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

(Example 2)
Add 3.4 g of aluminum powder (# 800F: manufactured by Minalco) having an average particle diameter of 3 μm and 0.25 g of polymethylphenylsiloxane (KF-54: manufactured by Shin-Etsu Chemical Co., Ltd.) in a toluene solvent. Mixed. The obtained mixed solution was heated to evaporate the solvent, thereby obtaining aluminum powder coated with polymethylphenylsiloxane.

  Next, this aluminum powder and 15.8 g of alumina powder (AS-40: Showa Denko KK) having an average particle diameter of 12 μm were mixed to prepare a mixed powder.

  In Example 2, 20% by volume of aluminum powder is included in the total volume of the aluminum powder and alumina powder, and polymethylphenylsiloxane is about 0% of the total volume of aluminum powder and alumina powder. .01 times included.

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

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

  In addition, the temperature of the heat processing of a molded object was changed in the range of 600 to 750 degreeC, and the same experiment was implemented. 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 produced by firing at 600, 650, 700, and 750 ° C.

  In FIG. 13, the result of the X-ray diffraction analysis of the composite_body | complex which concerns on Example 2 is shown. As is clear from FIG. 13, as a result of X-ray diffraction analysis, diffraction peaks of aluminum, alumina, and aluminosilicate were observed.

  In FIG. 14, the scanning electron microscope (SEM) photograph of the composite_body | complex which concerns on Example 2 is shown. FIG. 14 shows 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 results of X-ray diffraction analysis, this silicon is expected to be an aluminosilicate.

  Further, a plurality of molded bodies or / and assemblies can be combined to make further large composites and / or joined bodies.

(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) were added to a toluene solvent. , Well mixed. The obtained mixed solution was heated to evaporate the solvent, thereby obtaining alumina powder coated with polymethylphenylsiloxane.

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

  In Example 3, 20% by volume of aluminum powder is included in the total volume of the aluminum powder and alumina powder, and polymethylphenylsiloxane is approximately 0% of the total volume of aluminum powder and alumina powder. .01 times included.

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

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

  In addition, the temperature of the heat processing of a molded object was changed in the range of 600 to 750 degreeC, and the same experiment was implemented. 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.

  Further, as a result of observation with a scanning electron microscope (SEM), it was found that the alumina particles and the aluminum particles were well bonded to each other in the composite. 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 an aluminosilicate.

  Further, a plurality of molded bodies or / and assemblies can be combined to make further large composites and / or joined bodies.

Example 4
15.8 g of alumina powder (AS-40: Showa Denko) having an average particle size of 12 μm, 3.4 g of aluminum powder (# 800F: manufactured by Minalco) having an average particle size of 3 μm, and polymethylsilsesquioxane (YR3370: manufactured by Momentive Performance Japan) 1.3 g was added to a toluene solvent and mixed well. In this blending ratio, for calculation purposes, the aluminum powder is contained in an amount of 20 vol% with respect to the total volume of the aluminum powder and the alumina powder, and the polymethylsilsesquioxane is about the total volume of the aluminum powder and the alumina powder. 0.0003 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 compact. Furthermore, this molded body was heat-treated at 600 ° C. for 1 hour in an argon atmosphere.

  As a result, an alumina composite containing aluminum (composite according to Example 4) was obtained.

  In addition, the temperature of the heat processing of a molded object was changed in the range of 600 to 750 degreeC, and the same experiment was implemented. 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 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.

  Further, as a result of observation with a scanning electron microscope (SEM), it was found that the alumina particles and the aluminum particles were well bonded to each other in the composite. 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 an aluminosilicate.

  Further, a plurality of molded bodies or / and assemblies can be combined to make further large composites and / or joined bodies.

(Example 5)
15.8 g of alumina powder having an average particle diameter of 12 μm (AS-40: Showa Denko), 3.4 g of aluminum powder having an average particle diameter of 3 μm (# 800F: manufactured by Minalco), and polymethylphenylsilsesquioxy 1.3 g of Sun (SR-21, manufactured by Konishi Chemical Co., Ltd.) was sufficiently mixed to obtain a mixed powder. In Example 5, no solvent was used during mixing.

  In this mixing ratio, the aluminum powder is included in the calculation in an amount of 20 vol% with respect to the total volume of the aluminum powder and the alumina powder, and the polymethylphenylsilsesquioxane is about 0% of the total volume of the aluminum powder and the alumina powder. .01 times included.

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

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

  In addition, the temperature of the heat processing of a molded object was changed in the range of 600 to 750 degreeC, and the same experiment was implemented. 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 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.

  Further, as a result of observation with a scanning electron microscope (SEM), it was found that the alumina particles and the aluminum particles were well bonded to each other in the composite. 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 an aluminosilicate.

  Further, a plurality of molded bodies or / and assemblies can be combined to make further large composites and / or joined bodies.

(Example 6)
11.85 g of alumina powder (AS-40: Showa Denko) having an average particle diameter of 12 μm, 5.4 g of aluminum powder (# 800F: manufactured by Minalco) having an average particle diameter of 3 μm, and polymethylphenylsiloxane (KF) -54: manufactured by Shin-Etsu Chemical Co., Ltd.) was added to a toluene solvent and mixed well. In this blending ratio, the aluminum powder is included 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 0.00% of the total volume of the aluminum powder and the alumina powder. 01 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 compact. Furthermore, this molded body was heat-treated at 600 ° C. for 1 hour in an argon atmosphere.

  As a result, an alumina composite containing aluminum (composite according to Example 6) was obtained.

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

  In addition, the temperature of the heat processing of a molded object was changed in the range of 600 to 750 degreeC, and the same experiment was implemented. 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.

  Further, as a result of observation with a scanning electron microscope (SEM), it was found that the alumina particles and the aluminum particles were well bonded to each other in the composite. 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 an aluminosilicate.

  Further, a plurality of molded bodies or / and assemblies can be combined to make further large composites and / or joined bodies.

(Example 7)
15.8 g of alumina powder having an average particle size of 12 μm (AS-40: Showa Denko), 0.1 g of aluminum powder having an average particle size of 3 μm (# 800F: manufactured by Minalco), and polymethylphenylsiloxane (KF) -54: manufactured by Shin-Etsu Chemical Co., Ltd.) was added to a toluene solvent and mixed well. In this blending ratio, the aluminum powder is included in an amount of 1 vol% with respect to the total volume of the aluminum powder and the alumina powder, and the polymethylphenylsiloxane is about 0.00% 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 compact. Furthermore, this molded body was heat-treated at 600 ° C. for 1 hour in an argon atmosphere.

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

  In addition, the temperature of the heat processing of a molded object was changed in the range of 600 to 750 degreeC, and the same experiment was implemented. 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.

  Further, as a result of observation with a scanning electron microscope (SEM), it was found that the alumina particles and the aluminum particles were well bonded to each other in the composite. 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 an aluminosilicate.

Further, a plurality of molded bodies or / and assemblies can be combined to make further large composites and / or joined bodies.
(Example 8)
Two 30 × 40 × 5 mm aluminum plates (manufactured by Niraco, purity 99% or more) were prepared. Next, the mixed powder produced by the same material and the same conditions as Example 2 was apply | coated to the arbitrary surface of 40x5 mm of an aluminum plate, the application surface was faced | matched and heat processing was performed at 630 degreeC for 10 minutes.

  Thereby, a joined body of aluminum plates (a joined body according to Example 8) was obtained.

  In FIG. 16, the external appearance (photograph) of the joined body which concerns on Example 8 is shown.

  Further, as a result of observation with a scanning electron microscope (SEM), it was found that the alumina particles and the aluminum particles were well bonded to each other in the joined body. From the results of 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 is used, a structural member mainly composed of ceramics can be manufactured relatively easily. Since the structural member mainly composed of ceramics obtained by this method contains metal particles, it is expected to exhibit relatively good resistance to thermal stress.

  Further, a plurality of molded bodies or / and assemblies can be combined to make further large composites and / or joined bodies.

  The present invention can be used for manufacturing a structural member mainly composed of ceramics.

100 1st mixed particle 101 1st mixed particle (modification)
110 Ceramic Particles 120 Metal Particles 130 Organosilicon Polymer 200 Second Mixed Particle 210 Ceramic Particle 220 Metal Particle 230 Organosilicon Polymer 300 Third Mixed Particle 310 Ceramic Particle 320 Metal Particle 330 Organosilicon Polymer

Claims (11)

Mixed particles for structural members mainly composed of ceramics,
Including ceramic particles, metal particles, and a siloxane polymer,
The metal particles are included in a range of 1 vol% to 40 vol% with respect to the total volume of the metal particles and the ceramic particles ,
The mixed particles are used as a bonding material for two members .   2. The mixed particle according to claim 1, wherein the siloxane-based 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. .   The siloxane polymer is a mixed polymer containing at least one of polymethylhydrosiloxane, polymethylphenylsiloxane, polymethylsilsesquioxane, and polyphenylsiloxane. Mixed particles as described in 1.   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.   5. The mixed particle according to claim 1, wherein the metal particle includes a material selected from the group consisting of aluminum, an aluminum alloy, silicon, and a silicon alloy.   The mixed particles according to claim 1, wherein the metal particles have an average diameter in a range of 1 μm to 2000 μm.   The mixed particles according to claim 1, 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 siloxane polymer.   The mixed particles according to any one of claims 1 to 8, wherein the metal particles are coated with the siloxane-based polymer. A slurry containing the mixed particles according to any one of claims 1 to 9 . A joined body composed of ceramic members, metal members, or a ceramic member and a metal member,
The ceramic member is selected from the group consisting of alumina, mullite, 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, respectively.
The mixed particles according to any one of claims 1 to 9 or the slurry according to claim 10 are interposed and heated in a bonding portion of each member constituting the bonded body, and the bonded body is characterized in that A joined body having a glass phase containing silicon between the joints of the members constituting the structure.