JP5843665B2 - Ceramic metal bonded body and manufacturing method thereof - Google Patents

Description

  The present invention relates to a ceramic metal joined body in which a cylindrical metal tube is placed on the outside of a cylindrical ceramic and joined, and a method for manufacturing the same.

  When a certain level of heat resistance is required as a method for joining ceramics and metal, brazing is often used (for example, Patent Documents 1 and 2). It is placed in a vacuum furnace with a foil or paste brazing material sandwiched between ceramic and metal, and the brazing material is melted by heating to obtain a bond between the ceramic and the metal. However, it is difficult to join a cylindrical ceramic and a cylindrical metal tube. This is because even if a cylindrical ceramic is previously placed in a cylindrical metal tube and a brazing material is filled so as to fill the gap, the gap expands when the temperature is raised due to the difference in thermal expansion coefficient. For this reason, the brazing filler metal that has been filled becomes insufficient, and a large defect (void) occurs. It seems that brazing material with very good wettability to both ceramics and metal, or if there is surface treatment on ceramics and metal, brazing material can not enter by capillarity. Such a good combination has not been found. There is also a shrink fitting method, but for cylindrical ceramics and cylindrical metal tubes, the outer and inner diameter tolerances must be managed accurately, and the processing of ceramics is indispensable, resulting in a high cost. is there.

Japanese Patent No. 4210417 Japanese Patent No. 3813654

  As described above, there is a demand for a method for producing a joined body having good heat resistance and adhesion by integrating a cylindrical metal tube on the outside of the cylindrical ceramic.

  An object of the present invention is to provide a ceramic metal joined body having heat resistance and good adhesion, which is formed by covering a tubular ceramic tube with a tubular metal tube and joining the same, and a manufacturing method thereof.

  A ceramic metal joined body can be manufactured by covering the outer peripheral surface of the cylindrical ceramic body with a cylindrical metal tube with a gap between the outer peripheral surface and filling the molten metal into the gap. I found. That is, according to the present invention, there are provided a ceramic-metal bonded body in which a cylindrical metal tube is placed on the outside of a cylindrical ceramic and bonded, and a method for manufacturing the same.

[1] A cylindrical metal tube is placed on the outer peripheral surface of the cylindrical ceramic body with a gap of 0.5 to 5 mm between the outer peripheral surface and placed in a cavity formed by a mold. The molten metal having a melting point of 700 ° C. or lower is pressurized and supplied into the cavity, thereby filling the molten metal into the gap between the cylindrical ceramic body and the cylindrical metal tube, and solidifying it. A method for producing a ceramic metal joined body for producing a ceramic metal joined body obtained by joining the cylindrical ceramic body and the cylindrical metal pipe.

[2] With the sealing member disposed on the end surface of the cylindrical ceramic body, the cylindrical ceramic body and the cylindrical metal tube are disposed in the cavity, and the molten metal is supplied into the cavity. [1] A method for producing a ceramic-metal bonded body according to [1].

[3] The length of the cylindrical ceramic body is shorter than the length of the cylindrical metal tube, a spacer is disposed between the sealing member and the cylindrical ceramic body, and the molten metal is supplied into the cavity. The method for producing a ceramic-metal bonded body according to [2].

[4] The method for producing a ceramic-metal bonded body according to [3], wherein the spacer is provided with a concave portion that fits with the convex portion of the sealing member.

[5] The tubular ceramic body according to any one of the above [1] to [4], wherein the cylindrical ceramic body is a honeycomb structure in which a plurality of cells serving as fluid flow paths are partitioned by the partition walls. The manufacturing method of the ceramic metal joined body of description.

[ 6 ] The ceramic according to any one of [1] to [ 5 ], wherein the mold for supplying the molten metal is a temperature 15 to 500 ° C. lower than the melting point of the metal to be the molten metal. Manufacturing method of metal joined body.
[7] the cylindrical ceramic body covered with the tubular metal pipe, and disposed within the cavity, low-pressure casting, the filling of the molten metal in said gap by one of the high-pressure casting [1] to [6 ] The manufacturing method of the ceramic metal joined body in any one of.

[ 8 ] A cylindrical ceramic body and a cylindrical metal tube covered on the outer peripheral surface of the cylindrical ceramic body, and 0.5 to 5 mm between the cylindrical ceramic body and the cylindrical metal tube A ceramic metal joined body in which a metal having a melting point of 700 ° C. or lower is filled in a gap in a molten state and the metal is solidified to be joined.

[ 9 ] The length of the cylindrical ceramic body is shorter than the length of the cylindrical metal tube, and the axial end surface of the cylindrical ceramic body is accommodated in the cylindrical metal tube. The ceramic-metal bonded body according to [ 8 ], wherein a brim portion that does not contact the cylindrical ceramic body is formed.

[ 10 ] The ceramic according to [ 8 ] or [ 9 ], wherein the cylindrical ceramic body is a honeycomb structure having partition walls, and a plurality of cells serving as fluid flow paths are partitioned by the partition walls. Metal joint.

[ 11 ] The ceramic-metal bonded body according to [ 10 ], wherein the honeycomb structure includes silicon carbide as a component.

  According to the method for producing a ceramic-metal bonded body of the present invention, it is possible to manufacture a ceramic-metal bonded body in which the outer peripheral surface of the tubular ceramic body is covered and integrated with the tubular metal tube. Since the entire gap between the cylindrical ceramic body and the cylindrical metal tube is filled and solidified, it is possible to join them firmly. Moreover, since the ceramic metal joined body manufactured by this method has good adhesion between the cylindrical ceramic body and the cylindrical metal tube, the thermal conductivity between the cylindrical ceramic body and the cylindrical metal tube is also good.

It is a schematic diagram which shows the end surface of one Embodiment of the ceramic metal joined body of this invention. It is a perspective view which shows one Embodiment of the ceramic metal joined body of this invention. It is a cross-sectional schematic diagram which shows the die-cast apparatus which manufactures the ceramic metal joined body of this invention. It is a schematic diagram which shows one Embodiment of the heat exchanger using the ceramic metal joined body of this invention. It is a perspective view which shows one Embodiment of the ceramic metal joined body which has a collar part. It is a perspective view which shows other embodiment of the ceramic metal joined body which has a collar part. It is sectional drawing which shows the sealing member for manufacturing the ceramic metal joined body which has a collar part. It is a top view which shows a spacer. It is AA sectional drawing of the spacer of FIG. 7A. It is a cross-sectional schematic diagram which shows the die-cast apparatus which manufactures the ceramic metal joined body which has a collar part. It is a schematic diagram for demonstrating the place which takes out a spacer using the jig for spacer taking out.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. The present invention is not limited to the following embodiments, and changes, modifications, and improvements can be added without departing from the scope of the invention.

(Embodiment 1)
FIG. 1 is a schematic view of a ceramic-metal bonded body (hereinafter also simply referred to as a bonded body) 10 according to the present invention viewed from one end face in the axial direction, and FIG. 2 is a perspective view of the bonded body 10. The joined body 10 includes a cylindrical ceramic body 11 and a cylindrical metal tube 12 that covers the outer peripheral surface 7 h of the cylindrical ceramic body 11. A metal having a melting point of 700 ° C. or less is filled in a molten state between the cylindrical ceramic body 11 and the cylindrical metal tube 12, which solidifies to become the metal bonding material layer 13 and the cylindrical ceramic body 11 and the cylinder. The metal pipe 12 is joined. The melted state in this specification is not only a completely melted state, but also a semi-molten state (a state in which solid and liquid coexist), and a semi-solid state (a state in which liquid is once solidified and liquid and solid coexist) Including semi-solids.

  The cylindrical ceramic body 11 is formed of ceramics in a cylindrical shape and has a fluid flow path penetrating from one end face 2 in the axial direction to the other end face 2. The cylindrical shape is not limited to a cylindrical shape (columnar shape), and may be a quadrangular prism shape or other shapes. An example of the cylindrical ceramic body 11 is a honeycomb structure 1 having a partition wall 4 in which a large number of cells serving as a fluid flow path are partitioned by the partition wall 4. The partition wall 4 may be a porous body. By having the partition wall 4, heat from the fluid flowing through the inside of the cylindrical ceramic body 11 can be efficiently collected and transmitted to the outside. 1 and 2 show an embodiment in which a honeycomb structure 1 in which a large number of cells 3 are formed is used as a cylindrical ceramic body 11. Note that a plurality of honeycomb structures 1 may be combined in series. At that time, in order to increase the flow resistance of the fluid passing through the cell 3, the phase of the cell 3 of each honeycomb structure 1 is rotated (for example, the relative angle of the two honeycomb structures 1). The cylindrical metal tube 12 may be covered with the honeycomb structure 1 (tubular ceramic body 11) in a state where the tube is rotated by 45 °.

  In the method for manufacturing a ceramic / metal bonded body according to the present invention, the cylindrical metal body 12 is covered with the outer peripheral surface of the cylindrical ceramic body 11 with a gap 49 between the outer peripheral surface and formed by the mold 41. Placed in the cavity 42 formed. Then, by supplying the molten metal into the cavity 42, the molten metal is filled into the gap 49 between the cylindrical ceramic body 11 and the cylindrical metal tube 12. This solidifies to become the metal bonding material layer 13, and becomes the ceramic metal bonded body 10 in which the cylindrical ceramic body 11 and the cylindrical metal tube 12 are bonded.

  As a method of forming the cavity 42 in the mold 41 and filling the molten metal into the gap 49 between the cylindrical ceramic body 11 and the cylindrical metal tube 12 disposed therein, gravity casting, low pressure casting, die Cast (high pressure casting) or the like can be used. Die-casting is excellent in cycle time (cost), and it is easy to fill molten metal in a narrow gap. In addition, the low pressure casting has a long cycle time but is excellent in quality, material yield and the like.

  FIG. 3 shows a die casting apparatus 40 as an embodiment that can be used in the method for producing a ceramic-metal bonded body according to the present invention. In addition, the manufacturing method of the ceramic metal joined body of this invention is not limited to die-casting. The die casting apparatus 40 includes a mold 41 and a sleeve 45. The mold 41 includes a movable mold 41a and a fixed mold 41b, and a cavity 42 is formed inside by clamping the movable mold 41a and the fixed mold 41b. The cavity 42 is formed so that the cylindrical ceramic body 11 and the cylindrical metal tube 12 can be accommodated. The cylindrical ceramic body 11 is disposed in the cavity 42 so that its axial direction is the vertical direction. Moreover, it is preferable that the cylindrical metal tube 12 and the cylindrical ceramic body 11 are configured so that the cylindrical metal tube 12 fits into the cavity 42 without a gap in a state having a gap 49. By doing in this way, the molten metal can be filled in the gap 49 between the cylindrical metal tube 12 and the cylindrical ceramic body 11. The gate 41 g serving as a supply port for supplying molten metal to the cavity 42 in which the cylindrical ceramic body 11 is arranged has a reduced diameter smaller than the diameter of the cylindrical ceramic body 11. Thereby, it can pressurize in the cavity 42 and can supply molten metal.

  The sleeve 45 communicates with the mold 41 and includes a plunger 46 and a pouring port 47. The sleeve 45 can temporarily hold the molten metal injected from the pouring port 47. Then, the molten metal injected into the sleeve 45 is supplied into the cavity 42 of the mold 41 by the plunger 46. In addition, when supplying a molten metal in the metal mold | die 41, it is preferable to set metal mold temperature to the temperature below melting | fusing point. Specifically, the mold temperature when supplying the molten metal is preferably 15 to 500 ° C. lower than the melting point of the molten metal, more preferably 30 to 400 ° C., more preferably 30 to 300 ° C. Particularly preferred is a low temperature. If the mold temperature is too low, it becomes difficult to fill the gap 49 between the cylindrical ceramic body 11 and the cylindrical metal tube 12 with the molten metal, and if it is too high, the energy cost is increased and the lead time is increased, Mold life is also shortened.

  By pressurizing the molten metal in the sleeve 45 with the plunger 46, the molten metal can be injected into the mold, and the molten metal can be filled in the gap 49 between the cylindrical ceramic body 11 and the cylindrical metal tube 12. Since the molten metal is pressurized and supplied into the cavity 42, the molten metal can be filled in the gap 49 between the cylindrical ceramic body 11 and the cylindrical metal tube 12. And the joined body 10 can be obtained because it is cooled. Although the metal used as a molten metal is not specifically limited, It is preferable that it is a metal with melting | fusing point of 700 degrees C or less, and it is more preferable that it is melting | fusing point of 78 degrees C or more. If it is 700 degrees C or less melting | fusing point, cost can be held down. A melting point of 78 ° C. or higher is excellent in heat resistance during use. As the molten metal, for example, a metal containing at least one of Al, Mg, Sn, Cu, Ag, Zn, Cd, In, and Bi can be used. The thermal conductivity of the metal is preferably 20 W / m · K or more, more preferably 90 W / m · K or more, and particularly preferably 150 W / m · K or more. By setting it to 20 W / m · K or more, a product having good heat transfer characteristics can be obtained. The proof stress of the metal is preferably 150 MPa or less, more preferably 130 MPa or less, and particularly preferably 70 MPa or less. By setting the pressure to 150 MPa or less, the ceramic can be prevented from cracking and the durability of the product can be improved.

  When integrating the cylindrical ceramic body 11 and the cylindrical metal tube 12 by shrink fitting, it is necessary to accurately produce the outer diameter of the cylindrical ceramic body 11 and the inner diameter of the cylindrical metal tube 12. However, the method of filling the molten metal by high-pressure casting like the manufacturing method of the present invention has an advantage that it is possible to reduce the cost because high-precision processing of ceramics is unnecessary. The size of the gap 49 is preferably 0.05 to 5 mm, more preferably about 0.1 to 3 mm, and particularly preferably about 0.5 to 2 mm. If the size of the gap 49 is too large, heat transfer characteristics may deteriorate and heat exchange performance may deteriorate, and if it is too small, the gap 49 between the cylindrical ceramic body 11 and the cylindrical metal tube 12 is filled with molten metal. It becomes difficult to let you. By performing high pressure casting with the die casting apparatus 40, the entire gap 49 between the cylindrical ceramic body 11 and the cylindrical metal tube 12 can be filled. Since the entire gap 49 is filled with the molten metal and solidified, the cylindrical ceramic body 11 and the cylindrical metal tube 12 are firmly joined. Moreover, since these adhesiveness is good, the heat conductivity of the cylindrical ceramic body 11 and the cylindrical metal tube 12 is also good.

  Shrink fit does not have good chemical transfer due to lack of chemical bonds. On the other hand, in the case of brazing or molten metal joining according to the present invention, a chemical bond is obtained, so heat conduction is achieved instead of heat transfer, and heat transfer characteristics are improved. Chemical bonding is the same for brazing and molten metal joining, but in the case of brazing, since the time during which the ceramic or metal and brazing material are in contact with each other at a high temperature is long, the reaction proceeds too much, and between hard and brittle metals. Often a compound is made. On the other hand, in the case of molten metal joining, which is a method for producing a ceramic metal joined body according to the present invention, since the work is performed in units of seconds from filling to solidification, chemical bonding is obtained in a very small range, and the reaction proceeds too much. Therefore, it is preferable that an intermetallic compound having poor mechanical properties is not easily formed.

  When a hollow ceramic body 11 or the like is used as the tubular ceramic body 11, the honeycomb structure 1 and the tubular metal tube 12 are disposed in the cavity 42 with the sealing member 50 disposed on the end surface 2. Then, the molten metal is supplied into the cavity 42. The sealing member 50 prevents the molten metal from entering the inside of the cylindrical ceramic body 11 and has a shape that covers the end surface of the cylindrical ceramic body 11. Further, in order to guide the flow of the molten metal to the gap between the cylindrical ceramic body 11 and the cylindrical metal tube 12, a cone such as a cone or a pyramid may be used. By disposing such a sealing member 50, the molten metal can be filled in the gap between the cylindrical ceramic body 11 and the cylindrical metal tube 12. Furthermore, it is preferable to sandwich the soft packing between the cylindrical ceramic body 11 and the sealing member 50 in order to make the sealing more complete. An example of the soft packing is a graphite sheet. The thickness of the soft packing is preferably 0.025 to 1.5 mm.

  In order to maintain a uniform space between the cylindrical ceramic body 11 and the cylindrical metal tube 12, it is preferable to insert a spacer between the cylindrical ceramic body 11 and the cylindrical metal tube 12. As the spacer, for example, a plate material having the same thickness as the gap 49 between the cylindrical ceramic body 11 and the cylindrical metal tube 12 and made of the same kind of material as the metal to be melted can be used. By arranging a plurality of such spacers in the gap 49, the molten metal can be filled with the gap 49 as a uniform interval.

  The cylindrical ceramic body 11 preferably has a thermal conductivity of 100 W / m · K or more. More preferably, it is 120-300 W / m * K, More preferably, it is 150-300 W / m * K. By setting it as this range, heat conductivity becomes favorable and the heat | fever in the cylindrical ceramic body 11 can be efficiently discharged | emitted to the outer side of the metal tube 12. FIG.

  The cylindrical ceramic body 11 is preferably made of ceramics having excellent heat resistance, and considering heat conductivity in particular, it is preferable that SiC (silicon carbide) having high thermal conductivity is the main component. The main component means that 50% by mass or more of the cylindrical ceramic body 11 is silicon carbide.

  However, the entire cylindrical ceramic body 11 does not necessarily need to be composed of SiC (silicon carbide), and SiC (silicon carbide) may be included in the main body. That is, the cylindrical ceramic body 11 is preferably made of a ceramic containing SiC (silicon carbide).

  However, even if it is SiC (silicon carbide), in the case of a porous body, high thermal conductivity cannot be obtained. Therefore, it is preferable to impregnate silicon in the process of manufacturing the cylindrical ceramic body 11 to obtain a dense structure. High heat conductivity can be obtained by using a dense structure. For example, in the case of a porous body of SiC (silicon carbide), it is about 20 W / m · K, but by making it a dense body, it can be about 150 W / m · K.

As the cylindrical ceramic body 11, Si-impregnated SiC, (Si + Al) -impregnated SiC, metal composite SiC, recrystallized SiC, Si ₃ N ₄ , SiC, or the like can be adopted. Si-impregnated SiC and (Si + Al) -impregnated SiC can be employed to obtain a body structure. Si-impregnated SiC has a structure in which the SiC particle surface is surrounded by solidified metal-silicon melt and SiC is integrally bonded via metal silicon, so that silicon carbide is shielded from an oxygen-containing atmosphere and prevented from oxidation. Is done. Furthermore, SiC has the characteristics of high thermal conductivity and easy heat dissipation, but SiC impregnated with Si is densely formed while exhibiting high thermal conductivity and heat resistance, and has sufficient strength as a heat transfer member. Indicates. That is, the cylindrical ceramic body 11 made of a Si—SiC-based (Si-impregnated SiC, (Si + Al) -impregnated SiC) material has excellent heat resistance, thermal shock resistance, oxidation resistance, and corrosion resistance against acids and alkalis. In addition to showing properties, it exhibits high thermal conductivity.

  The cylindrical ceramic body 11 can be formed as a honeycomb structure 1 in which a plurality of cells 3 serving as fluid flow paths penetrating from one end face 2 to the other end face 2 are partitioned by partition walls 4. In this case, the shape of the cross section perpendicular to the axial direction of the cell 3 may be appropriately selected from a circular shape, an elliptical shape, a triangular shape, a quadrangular shape, and other polygonal shapes.

The cell density of the honeycomb structure 1 (that is, the number of cells per unit cross-sectional area) is not particularly limited, and may be appropriately designed according to the purpose, but is 25 to 2000 cells / in 2 (4 to 320 cells / cm ² ) is preferable. By setting the cell density in this range, the pressure loss when the heat medium flows through the cells 3 while preventing the strength of the partition walls 4 and, consequently, the strength of the honeycomb structure 1 itself and the lack of effective GSA (geometric surface area). Can be prevented from becoming large.

  The number of cells per honeycomb structure 1 is preferably 1 to 10,000, and particularly preferably 200 to 2,000. By making the number of cells within this range, it is possible to prevent the honeycomb itself from becoming larger, thereby increasing the heat conduction distance from the first fluid side to the second fluid side and increasing the heat conduction loss. it can. In addition, the heat transfer area on the first fluid side becomes small, the heat resistance on the first fluid side cannot be lowered, and the heat flux can be prevented from becoming small.

  The thickness (wall thickness) of the partition walls 4 of the cells 3 of the honeycomb structure 1 may be appropriately designed according to the purpose, and is not particularly limited. The wall thickness is preferably 50 μm to 2 mm, and more preferably 60 to 500 μm. By setting the wall thickness within this range, it is possible to increase the mechanical strength and prevent breakage due to impact or thermal stress. Further, the proportion of the cell volume in the honeycomb structure side can be increased, and the pressure loss of the fluid can be reduced. Furthermore, the heat exchange rate can be improved.

The density of the partition walls 4 of the cells 3 of the honeycomb structure 1 is preferably 0.5 to ⁵ g / cm ³ . By setting it as this range, the intensity | strength of the partition 4 can be made sufficient. Further, it is possible to reduce the weight while making the partition wall 4 sufficiently strong. Furthermore, the effect of improving thermal conductivity is also obtained.

  As will be described later, the joined body 10 can be used for the heat exchanger 30 (see FIG. 4). When the first fluid (high temperature side) to be circulated through the heat exchanger 30 is exhaust gas, a catalyst is supported on the wall surface inside the cell 3 of the honeycomb structure 1 through which the first fluid (high temperature side) passes. It is preferable. This is because in addition to the role of exhaust gas purification, reaction heat (exothermic reaction) generated during exhaust gas purification can also be exchanged. Noble metals (platinum, rhodium, palladium, ruthenium, indium, silver, and gold), aluminum, nickel, zirconium, titanium, cerium, cobalt, manganese, zinc, copper, zinc, tin, iron, niobium, magnesium, lanthanum, samarium, It is preferable to contain at least one element selected from the group consisting of bismuth and barium. These may be metals, oxides, and other compounds.

  The supported amount of the catalyst (catalyst metal + support) supported on the partition walls 4 of the cells 3 of the first fluid circulation part 5 of the honeycomb structure 1 through which the first fluid (high temperature side) passes is 10 to 400 g / It is preferable that it is L, and if it is a noble metal, it is still more preferable that it is 0.1-5 g / L. When the loading amount of the catalyst (catalyst metal + support) is within this range, the catalytic action is sufficiently exhibited. In addition, an increase in pressure loss and an increase in manufacturing cost can be prevented.

  The tubular metal tube 12 is preferably one having heat resistance and corrosion resistance, for example, a steel tube such as a SUS tube or a Cr—Mo alloy steel tube, a copper alloy tube such as a copper tube or a brass tube, an aluminum tube, an aluminum alloy, or the like. Non-ferrous pipes can be used. In the case of special applications such as nuclear power, a titanium tube, a nickel alloy tube, a cobalt alloy tube, or the like can be used. The inner diameter of the cylindrical metal tube 12 is larger than the outer diameter of the cylindrical ceramic body 11. When the inner diameter of the cylindrical metal body 12 is dm and the outer diameter of the cylindrical ceramic body 11 is dc, dm = dc + 0.1 mm. It is preferably ˜dc + 4.0 mm, more preferably dm = dc + 0.2 mm to dc + 2.0 mm, and particularly preferably dm = dc + 0.5 mm to dc + 1.5 mm. It is preferable to be within this range in order to fill the gap 49 between the cylindrical metal tube 12 and the cylindrical ceramic body 11 with the molten metal to obtain a strong ceramic-metal bonded body 11. Moreover, it is also preferable that the inner surface of the cylindrical metal tube 12 or the outer surface of the cylindrical ceramic body 11 is subjected to a surface treatment by plating or the like. The wettability with the molten metal is improved and the product quality is improved. Alternatively, for the same reason, it is also preferable to apply a flux to the same surface.

  Next, the manufacturing method of the joined body 10 of this invention is demonstrated. First, a clay containing ceramic powder is extruded into a desired shape to produce a honeycomb formed body. As the material of the honeycomb structure 1, the above-described ceramics can be used. For example, when manufacturing the honeycomb structure 1 mainly composed of a Si-impregnated SiC composite material, a predetermined amount of C powder, SiC powder, binder Then, water or an organic solvent is kneaded to form a clay and molded to obtain a honeycomb molded body having a desired shape.

  The honeycomb formed body is dried and fired by impregnation with Si, whereby the honeycomb structure 1 in which a plurality of cells 3 serving as gas flow paths are partitioned by the partition walls 4 can be obtained.

  Next, as shown in FIG. 3, the outer peripheral surface 7 h of the honeycomb structure 1 is covered with a cylindrical metal tube 12 with a gap 49 between the outer peripheral surface 7 h and formed by a mold 41. In the cavity 42. Then, by supplying the molten metal into the cavity 42, the molten metal is filled into the gap 49 between the cylindrical ceramic body 11 and the cylindrical metal tube 12. The filled molten metal is solidified to become the metal bonding material layer 13, and the ceramic metal bonded body 10 in which the cylindrical ceramic body 11 and the cylindrical metal tube 12 are bonded can be obtained.

  Next, the heat exchanger 30 is demonstrated as one Embodiment using the ceramic metal joined body 10. FIG. FIG. 4 shows a perspective view of the heat exchanger 30 including the joined body 10 of the present invention. By flowing a first fluid inside the cylindrical ceramic body 11 and a second fluid having a temperature lower than that of the first fluid on the outer peripheral surface 12h side of the cylindrical metal tube 12, the first fluid and the second fluid Heat exchange with the fluid can be performed. As shown in FIG. 4, the heat exchanger 30 is formed by a joined body 10 (honeycomb structure 1 + metal joining material layer 13 + tubular metal tube 12) and a casing 21 including the joined body 10 therein. The cells 3 of the honeycomb structure 1 of the cylindrical ceramic body 11 serve as the first fluid circulation part 5 through which the first fluid flows. The heat exchanger 30 is configured such that a first fluid having a temperature higher than that of the second fluid flows in the cells 3 of the honeycomb structure 1. In addition, an inlet 22 and an outlet 23 for the second fluid are formed in the casing 21, and the second fluid circulates on the outer peripheral surface 12 h of the cylindrical metal tube 12 of the joined body 10.

  That is, the second fluid circulation portion 6 is formed by the inner surface 24 of the casing 21 and the outer peripheral surface 12 h of the cylindrical metal tube 12. The second fluid circulation part 6 is a second fluid circulation part formed by the casing 21 and the outer peripheral surface 12 h of the cylindrical metal tube 12, and the first fluid circulation part 5 and the partition walls 4 of the honeycomb structure 1, Heat conduction of the first fluid flowing through the first fluid circulation portion 5 is separated by the metal bonding material layer 13 and the cylindrical metal tube 12, and the heat of the first fluid flowing through the first fluid circulation portion 5 is supplied to the partition wall 4, the metal bonding material layer 13, and the cylindrical metal. Heat is transferred to the heated body, which is the second fluid that is received and circulated through the pipe 12. The first fluid and the second fluid are completely separated, and these fluids are configured not to mix.

  The first fluid circulation portion 5 is formed as a honeycomb structure, and in the case of the honeycomb structure, when the fluid passes through the cell 3, the fluid cannot flow into another cell 3 by the partition wall 4, and the honeycomb structure The fluid travels linearly from one inlet to the outlet. Moreover, the honeycomb structure 1 in the heat exchanger 30 of the present invention is not plugged, so that the heat transfer area of the fluid is increased and the size of the heat exchanger 30 can be reduced. Thereby, the amount of heat transfer per unit volume of the heat exchanger 30 can be increased. Furthermore, since it is not necessary to process the honeycomb structure 1 such as forming plugged portions or forming slits, the heat exchanger 30 can reduce the manufacturing cost.

  It is preferable that the heat exchanger 30 circulates the first fluid having a temperature higher than that of the second fluid and conducts heat from the first fluid to the second fluid. When gas is circulated as the first fluid and liquid is circulated as the second fluid, heat exchange between the first fluid and the second fluid can be performed efficiently. That is, the heat exchanger 30 of the present invention can be applied as a gas / liquid heat exchanger.

  The heating element that is the first fluid to be circulated through the heat exchanger 30 of the present invention having the above configuration is not particularly limited as long as it is a medium having heat. For example, if it is gas, the exhaust gas of a motor vehicle etc. are mentioned. In addition, the medium to be heated, which is the second fluid that takes heat from the heating body (exchanges heat), is not particularly limited as a medium, as long as the temperature is lower than that of the heating body.

(Embodiment 2)
5A and 5B show an embodiment of a ceramic metal joined body 10 having a brim portion. FIG. 5A shows an embodiment in which a hollow ceramic tube is used as the cylindrical ceramic body 11. FIG. 5B shows an embodiment in which the honeycomb structure 1 is used as the cylindrical ceramic body 11.

  As shown in FIGS. 5A and 5B, the joined body 10 of the present invention has a cylindrical ceramic body 11 shorter than the length of the cylindrical metal tube 12, and the end face 11s of the cylindrical ceramic body 11 in the axial direction. Is contained in the cylindrical metal tube 12. A flange portion 12 a that does not contact the cylindrical ceramic body 11 is formed on the cylindrical metal tube 12. When the end surface 11s of the cylindrical ceramic body 11 is accommodated in the cylindrical metal tube 12 and the flange portion 12a is formed, the joined body 10 is easily processed and easily connected to a pipe or the like.

  A method for manufacturing the joined body 10 having the flange 12a will be described with reference to FIGS. FIG. 6 shows a sealing member 51 for manufacturing the ceramic-metal bonded body 10 having the brim portion 12a. The sealing member 51 is composed of two parts. A main body 51a which is a cone such as a cone, and a convex 51b which protrudes from the main body 51a.

  FIG. 7A is a plan view of the spacer 52 for manufacturing the ceramic metal joined body 10 having the brim portion 12a, and FIG. 7B is a cross-sectional view taken along line AA of FIG. 7A. The spacer 52 has a concave portion 52b formed at the center of one surface of the disk-shaped main body 52a, and a female screw portion 52c formed at the center of the concave portion 52b. The outer diameter side surface 52t of the main body portion 52a and the inner diameter side surface 52s of the main body portion 52a (the boundary surface between the main body portion 52a and the concave portion 52b) forming the concave portion 52b are attached and detached when a taper of 2 to 3 degrees is provided. Easy and desirable.

  The spacer 52 is provided with a concave portion 52 b that fits with the convex portion 51 b of the sealing member 51. By fitting the convex portion 51 b of the sealing member 51 and the concave portion 52 b of the spacer 52, the sealing member 51 and the spacer 52 can be centered. Moreover, it can prevent that a molten metal flows in into the internal thread part 52c.

  FIG. 8 is a schematic cross-sectional view showing a die-casting device 40 that manufactures the ceramic metal joined body 10 having the brim portion 12a. The length of the cylindrical ceramic body 11 is shorter than the length of the cylindrical metal tube 12. For this reason, the spacer 52 is disposed between the sealing member 51 and the cylindrical ceramic body 11, and the molten metal is supplied into the cavity 42. After filling the gap 49 with the molten metal and solidifying the molten metal, the sealing member 51 is removed as shown in FIG. Then, the spacer 52 is taken out using the spacer taking-out jig 53. Specifically, the spacer 52 can be taken out by inserting the male screw portion 53 c of the spacer taking-out jig 53 into the female screw portion 52 c of the spacer 52. As described above, the ceramic-metal bonded body 10 having the brim portion 12a can be manufactured.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these Examples.

(Example 1)
After extruding the clay containing ceramic powder into a desired shape, drying and Si impregnation firing, the material is silicon carbide, the body size is 43mm in diameter (outer diameter), and the columnar shape (cylinder shape) is 100mm in length. The honeycomb structure 1 was manufactured. That is, the honeycomb structure 1 was used as the cylindrical ceramic body 11. The honeycomb structure 1 had a cell density of 23.3 cells / cm ² , the partition walls 4 had a thickness (wall thickness) of 0.3 mm, and the honeycomb structure 1 had a thermal conductivity of 150 W / m · K.

  A SUS tube having a diameter of 45 mm and a thickness of 0.5 mm was produced as the cylindrical metal tube 12. The cylindrical ceramic body 11 is covered with the cylindrical metal tube 12 with a gap 49 (0.5 mm) between the outer peripheral surface and the outer peripheral surface of the cylindrical ceramic body 11, and both end faces 2, 2, a soft graphite sheet 0.25 mm is pasted so as to cover 2, and then a conical sealing member 50 made of the same material as that of the mold 41 is stacked, and the cavity 42 formed by the S45C mold 41 is placed inside. It arrange | positioned so that the flow of a molten metal may not be impaired, and the metal mold | die 41 was heated up at 510-610 degreeC (refer FIG. 3). Then, a 99.5% aluminum melt (melting point 657 ° C.) having a thermal conductivity of approximately 200 W / m · K and a proof stress of approximately 34 MPa is pressurized and supplied into the cavity 42 in a state of being heated above the melting point, thereby forming a cylindrical shape. The gap 49 between the ceramic body 11 and the cylindrical metal tube 12 was filled with molten metal. By solidifying the molten metal, a ceramic metal joined body 10 in which the tubular ceramic body 11 and the tubular metal tube 12 were joined was obtained.

(Example 2)
A SUS tube having a diameter of 45 mm and a thickness of 0.5 mm was produced as the cylindrical metal tube 12. The cylindrical ceramic body 11 is covered with the cylindrical metal tube 12 with a gap 49 (1.0 mm) between the outer peripheral surface and the outer peripheral surface of the cylindrical ceramic body 11, and both end faces 2, 2, a soft graphite sheet 0.25 mm is pasted so as to cover 2, and then a conical sealing member 50 made of the same material as that of the mold 41 is stacked, and the cavity 42 formed by the S45C mold 41 is placed inside. It arrange | positioned so that the flow of a molten metal might not be impaired, and the metal mold | die 41 was heated up at 450-550 degreeC (refer FIG. 3). Then, pressurizing and supplying an Al—Si—Fe alloy (melting point 584 ° C.) having a resistance of about 170 W / m · K and a proof stress of about 69 MPa into the cavity 42 in a state of being heated to the melting point or higher, The molten metal was filled in the gap 49 between the tubular metal tube 12. By solidifying the molten metal, a ceramic metal joined body 10 in which the tubular ceramic body 11 and the tubular metal tube 12 were joined was obtained.

(Comparative Example 1)
A SUS tube having a diameter of 45 mm and a thickness of 0.5 mm was used as the cylindrical metal tube 12. Fill the gap 49 between the cylindrical ceramic body 11 and the cylindrical metal tube 12 with the Ni brazing material BNi-2 having a melting point of about 1000 ° C. as much as the thickness of the gap 49 (if it does not enter at room temperature) Only the cylindrical metal tube 12 was warmed), the temperature was raised in vacuum, and the brazing treatment was performed at a temperature higher by +30 to 50 ° C. than the melting point.

(Comparative Example 2)
A low expansion Kovar tube having a diameter of 45 mm and a thickness of 0.5 mm was used as the cylindrical metal tube 12. An active silver brazing material (sheet-like) having a melting point of about 780 ° C. is filled into the gap 49 between the cylindrical ceramic body 11 and the cylindrical metal tube 12 as much as the thickness of the gap 49 ( Only the metal tube 12 was warmed), the temperature was raised in vacuum, and brazing was carried out at a temperature higher by 30 to 50 ° C. than the melting point.

(Comparative Example 3)
A low expansion Kovar tube having a diameter of 45 mm and a thickness of 0.5 mm was used as the cylindrical metal tube 12. An amorphous copper alloy (sheet-like) having a melting point of about 660 ° C. is filled into the gap 49 between the cylindrical ceramic body 11 and the cylindrical metal tube 12 as much as the thickness of the gap 49 (if it does not enter at room temperature, it is cylindrical Only the metal tube 12 was warmed), the temperature was raised in vacuum, and a brazing treatment was performed at a temperature higher by +30 to 50 ° C. than the melting point.

(result)
In brazing of Comparative Examples 1 to 3, the filling rate of the brazing material was 50% or less, and cracking of the cylindrical ceramic body 11 was also observed. In the molten metal joining of Examples 1 and 2, filling of the molten metal of 90% or more was obtained, and cracks of the cylindrical ceramic body 11 were not seen, and the thermal conductivity was good.

(Example 3 )
The ceramic metal joined body 10 having the brim portion 12a was manufactured as follows. First, in the same manner as in Example 1, a cylindrical (tubular) honeycomb structure 1 having a material of silicon carbide, a main body size of 42 mm in diameter (outer diameter), and a length of 80 mm was manufactured. The honeycomb structure 1 had a cell density of 23.3 cells / cm ² , the partition walls 4 had a thickness (wall thickness) of 0.3 mm, and the honeycomb structure 1 had a thermal conductivity of 150 W / m · K.

  A SUS tube having a diameter of 45 mm and a thickness of 0.5 mm was produced as the cylindrical metal tube 12. The cylindrical ceramic body 11 is covered with the cylindrical metal tube 12 with a gap 49 (1.0 mm) between the outer peripheral surface and the outer peripheral surface of the cylindrical ceramic body 11, and both end faces 2, Cavity formed with S45C mold 41 by stacking a conical sealing member 51 made of the same material as spacer 52 and mold 41 after pasting a soft graphite sheet 0.25 mm so as to cover 2 It arrange | positioned so that the flow of a molten metal may not be impaired in 42, and the metal mold | die 41 was heated up at 520 degreeC (refer FIG. 8). Then, in the cavity 42, a 99.5% aluminum melt (melting point 657 ° C.) (die casting alloy ADC12 / HT-1) having a thermal conductivity of approximately 200 W / m · K and a proof stress of approximately 34 MPa is heated to the melting point or higher. The molten metal was filled in the gap 49 between the cylindrical ceramic body 11 and the cylindrical metal tube 12 by pressurizing and supplying to the tube. By solidifying the molten metal, a ceramic metal bonded body 10 was obtained.

(result)
In the molten metal joining in Example 3 , 90% or more of the molten metal could be filled, and the honeycomb structure 1 (cylindrical ceramic body 11) was not cracked, and the heat conductivity was good.

  The production method of the present invention can be used for joining a cylindrical ceramic body and a cylindrical metal tube. In the ceramic-metal bonded body of the present invention, the cylindrical ceramic body is protected by a cylindrical metal tube, and can be used as a heat exchanger or the like.

1: honeycomb structure, 2: end face (in axial direction), 3: cell, 4: partition, 5: first fluid circulation part, 6: second fluid circulation part, 7: outer peripheral wall, 7h: (honeycomb structure) ), Outer peripheral surface, 10: bonded body, 11: cylindrical ceramic body, 11s: end surface, 12: cylindrical metal tube, 12a: brim portion, 12h: outer peripheral surface (of metal tube), 13: metal bonding material layer, 21: casing, 22: inlet of (second fluid), 23: outlet of (second fluid), 24: inner surface of (casing), 30: heat exchanger, 40: die cast device, 41: gold 41a: movable mold, 41b: fixed mold, 41g: gate, 42: cavity, 45: sleeve, 46: plunger, 47: pouring gate, 49: gap, 50, 51: sealing member, 51a: body part, 51b: convex part, 52: spacer, 52a: body part, 52 : Recess, 52c: female screw portion, 52s: inner diameter side, 52t: outer diameter surface, 53: spacer extraction jig, 53c: male thread portion.

Claims (11)

Cover the outer peripheral surface of the cylindrical ceramic body with a cylindrical metal tube with a gap of 0.5 to 5 mm between the outer peripheral surface and place it in the cavity formed by the mold,
By supplying pressurized molten metal having a melting point of 700 ° C. or less into the cavity, the molten metal is filled in the gap between the cylindrical ceramic body and the cylindrical metal tube, and is solidified. A method for producing a ceramic-metal joined body for producing a ceramic-metal joined body obtained by joining the tubular ceramic body and the tubular metal tube.   The state which has arrange | positioned the cylindrical ceramic body and the said cylindrical metal pipe in the state which has arrange | positioned the sealing member in the end surface of the said cylindrical ceramic body, and supplies a molten metal in the said cavity. Manufacturing method of ceramic metal bonded body.   The length of the cylindrical ceramic body is shorter than the length of the cylindrical metal tube, a spacer is disposed between the sealing member and the cylindrical ceramic body, and molten metal is supplied into the cavity. The manufacturing method of the ceramic metal joined body as described in any one of.   The method for producing a ceramic-metal bonded body according to claim 3, wherein the spacer is provided with a concave portion that fits with the convex portion of the sealing member.   The ceramic metal according to any one of claims 1 to 4, wherein the cylindrical ceramic body is a honeycomb structure having partition walls, and a plurality of cells serving as fluid flow paths defined by the partition walls. Manufacturing method of joined body. The method for producing a ceramic-metal bonded body according to any one of claims 1 to 5 , wherein the mold for supplying the molten metal is at a temperature lower by 15 to 500 ° C than the melting point of the metal to be the molten metal. . The cylindrical ceramic body covered with the tubular metal pipe, and disposed within the cavity, low-pressure casting, any one of claims 1 to 6, filling the molten metal into the gap by one of the high-pressure casting The manufacturing method of the ceramic metal joined body as described in any one of. A cylindrical ceramic body;
A cylindrical metal tube covered on the outer peripheral surface of the cylindrical ceramic body,
A ceramic having a melting point of 700 ° C. or less filled in a molten state in a gap of 0.5 to 5 mm between the cylindrical ceramic body and the cylindrical metal tube, and the metal is solidified to be joined. Metal joint. The length of the cylindrical ceramic body is shorter than the length of the cylindrical metal tube, and the axial end surface of the cylindrical ceramic body is accommodated in the cylindrical metal tube, and the cylindrical metal tube has the cylindrical shape. The ceramic metal joined body according to claim 8 , wherein a brim portion that does not contact the ceramic body is formed. The ceramic-metal bonded body according to claim 8 or 9 , wherein the cylindrical ceramic body is a honeycomb structure having partition walls, and a plurality of cells serving as fluid flow paths are defined by the partition walls. The ceramic-metal bonded body according to claim 10 , wherein the honeycomb structure includes silicon carbide as a component.

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