JPS59156976A - Metal member-ceramic member bonded body and method therefor - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention The present invention provides heat resistance, heat insulation, and wear resistance to metal members used in high-temperature gas flow passages of gas turbines, magnetohydrodynamic power generation, diesel engines, Kallin engines, gas burner cans, etc. The present invention relates to a bonded body with a ceramic member for imparting properties, etc., and a method for bonding the same.

Hitherto, high-temperature sintered ZrO2 ceramics and plasma coatings have been used as cylinder liners for diesel engines, but manufacturing costs are extremely high.On the other hand, it is difficult to fit, caulk, and bolt the FC and ceramics at the top of the piston. has been proposed, but it suffers from damage such as cracking and peeling during operation, and has problems in terms of reliability and cost, so it has not yet been put into practical use.

In order to eliminate these conventional problems, the present invention has been developed to create a bond between a ceramic member that has excellent heat resistance, heat insulation, and abrasion resistance, and a metal member that has a relatively large difference in thermal expansion. The fibers are reinforced with a chromium compound, an intermediate layer consisting of a fiber structure with elasticity and flexibility is interposed, and each member is bonded to each other (with a bonding agent made of a concentrated solution of a soluble chromium compound), and the The joint is bonded by heat treatment at a low temperature, and the purpose is to provide a joined body of a ceramic member and a metal member at a low cost, which allows a very wide range of materials to be selected. An embodiment of the present invention will be described in detail below with reference to the drawings.

FIG. 1 is a sectional view showing an embodiment of the joined body of the present invention.

As shown in the figure, a felt member 3 made of a fiber structure having elasticity and flexibility strengthened by treatment with a chromium compound is interposed between a ceramic member 1 and a metal member 2. A chromium compound solution or a chromium compound solution containing a small amount of metal oxide is applied as a bonding agent 4 to each bonding surface of the metal members 2, and the members are stacked together, and then heat treated preferably at a temperature of 460° C. or higher. , by converting a chromium compound into Cr203, the ceramic member 1 and the metal member 2 are bonded via the fibrous structure felt 3, or when the fibrous structure felt 3' is metallic as shown in FIG. As shown in Fig. 1, the felt 3' and the metal member 2 were joined by metal brazing, spot welding, or cast joining 5, and the felt 3' and the ceramic member 1 were joined using a chromium compound-based bonding agent 4 as shown in Fig. 1. It is something.

The material of the ceramic member 1 used in the present invention should be selected depending on particularly important properties such as heat resistance, heat insulation, abrasion resistance, thermal shock resistance, and toughness. (mullite), 2J0・2A120a・5SiO2 (cordierite) + Mgk1204 (spinel), 0-31 to 2M
02 (holsterite), ZrO2, ZrO2・5
iOz (zircon), C'a (Sr) Zr031
One or more composite systems such as oxides such as MgO-ZrO2, JO, and glass ceramics, and SiC and Si3N4 are used, and the coefficient of thermal expansion is not particularly limited.

These ceramic members 1 are made by converting a molded body of raw material powder or a calcined body thereof into a concentrated aqueous solution of a soluble chromium compound, for example, H2Cr.
Ceramics strengthened by bonding and hardening O4, ZnCrO4+H2CrO4, MgCrO4+H2CrO4, etc. by impregnation and heat treatment and high-temperature sintered bodies are used. In addition, in order to improve thermal shock resistance and heat resistance, the porosity should generally be 10 to 18%, although it depends on the material, and the bonding surface with the felt member 3.3' as an intermediate layer should be coated with a bonding agent.
It is preferable that the surface be roughened so that the contact area with the surface is large.

Next, the metal member 2 is made of ferrous alloys and non-ferrous alloys commonly used as structural members of equipment and equipment, such as carbon steel, stainless steel, nickel steel, etc.

ROM steel, nickel-chromium alloy, Inconel, Hastelloy, aluminum alloy, copper-based alloy, etc. are used, and the materials are determined by the surface temperature of the ceramic member 1 of the joined product, the temperature of the metal member 2, the heat flow rate at the point of use, and each member. The selection should be made depending on the thermal conditions such as the thermal conductivity of the structure, the structure of the structure, etc., and it is not fixed. However, when the metal member 2 is made of carbon steel, aluminum alloy, copper alloy, etc., and a chromium compound-based bonding agent 4 is used when bonding these to the fiber structure felt 3, it is difficult to obtain a good bond. It is preferable to apply nickel or chromium plating to the joining surface of the member 2 in advance, and good results can also be achieved by applying an anodic oxide coating instead of this plating in the case of aluminum alloys. can get.

Further, the fiber structure felt members 3, 3' interposed between the ceramic member 1 and the metal member 2 are intermediate layers laid to alleviate thermal distortion caused by the difference in thermal expansion between the two members 1. It is a felt made of a fiber structure of a non-metallic or non-metallic inorganic material and a composite system thereof, such as stainless steel fiber, nickel-chromium fiber, Inconel fiber, Hastelloy fiber, alumina fiber, silicon carbide fiber, silicon nitride fiber, glass fiber, copper nickel. Felts, mats, and webs made from coated carbon fibers, glass-coated metal fibers, etc., with filament diameters of 5 to 200 μm, and have elasticity,
The bulk density of felt varies depending on its flexibility and wire diameter, but it usually has a bulk density of 20 to 70%, which is immersed in a concentrated aqueous solution of a soluble chromium compound to coat the fibers, and excess saliva is centrifuged. After removal using a machine, heat treatment is performed at a temperature of 460° C. or higher. By repeating immersion in this solution and heat treatment 2 to 4 times, the multi-fibers cross and
The contact points are hardened by chemical bonding as the solution adhering to these points is heated and converted to C r2 owl, thereby reinforcing the fibers.

Furthermore, the concentrated solution of soluble chromium compound as bonding agent 4 is ZnO or Mgo and both are H2CrO.

The amount of ZnO or Mgo and Mgo+ZnO dissolved in a concentrated aqueous solution is 12CrO.

It is appropriate that the ratio is 0.15 to 0.5 mol per 1 mol of Cr in the aqueous solution, and the specific gravity of the aqueous solution is 1.2 to 1.5.

However, as shown in FIG. 2, when the felt member 3' serving as the intermediate layer is made of metal fibers, and ordinary brazing or spot welding 5 is used to join the felt member 3' to the metal member 2,
If Cr2O5 is bonded to the joint surface of the felt member 3' due to the above-described fiber reinforcement treatment, brazing and welding will be difficult. Therefore, it is necessary to take measures to prevent the Cr203 film from binding.

For this reason, the fibers on the bonding surface are coated with an organic substance in advance before the fiber reinforcement treatment. This coating film decomposes and disappears during the heat treatment for reinforcing the felt, and the Cr2O3 deposits peel off. Nitrocellulose and polystyrene are suitable as organic substances. In addition, when using the Kurome compound bonding agent 4 described later and as a bonding process procedure, the metal member 2
In the case where the first step is to join the metal felt member 3' to the metal felt member 3', and then the fiber reinforcement treatment is performed after that, the coating with the organic substance described above is not necessary.

In addition, to prepare the bonding agent 4 for each member, a concentrated aqueous solution of a soluble chromium compound or Z r 02 *TiO2,
SiO+, Al120s, Cr2O5, Fe2O
3. Adding a small amount of one or more fine powders of metal oxides such as M<Alzoa with a size of 4 μm or less, preferably 1 μm or less, preferably 4 to 10% by weight in total to the concentrated liquid,
Grind and mix using a ball mill to prepare a water slurry. As a concentrated aqueous solution of soluble chromium compound, ZnO or M
A small amount of gO and a mixture thereof, for example, 0.15 to 0.5 mol of oxide per 31 mol of Cr in a chromic acid solution is dissolved to give a specific gravity of 1.65 to 1.7.

Next, the manufacturing process of the joined body will be described.

In the process of manufacturing a bonded body using a chromium compound adhesive 4 to bond each member shown in FIG. A bonding agent consisting of a concentrated aqueous solution of a soluble chromium compound or a slurry of a chromium compound containing a small amount of oxide powder is then applied to at least one of the surfaces to be bonded, preferably to the opposing surfaces. 3. Overlap each member, preferably at 460°C or higher.
Heat treatment is performed by raising the temperature at a rate of 5°C/min. The heat treatment temperature and atmosphere vary depending on the material of each member, but
For example, when the fiber structure felt is nickel-coated carbon fiber or when the copper alloy base is used, 4oo6c, IJ
The above temperature is suitable in an inert or reducing atmosphere, and when the substrate is an aluminum alloy, the maximum processing temperature is 450 to 500°C.

Further, as shown in FIG. 2, when the fiber structure felt member 3' is made of metal fibers and the metal member 2 is to be joined by brazing, spot welding, or by casting all 114 members 2, first the felt member 3' is made of metal fibers. The joint surface of the member 3' is coated with an organic substance, and then treated with a chromium compound to be fiber reinforced. After that, 11 marks were placed on the metal member 2,
They are joined by welding or casting, and in the final step, the joined body and the ceramic member 1 are coated with a chromium compound bonding agent 4 and heat treated to complete the manufacture of the joined body.

However, since this manufacturing process requires many man-hours and is relatively complicated, the metal felt member 3' and the metal member 2 are brazed, welded, or cast together in the first step, and the fibers are reinforced in the second step. In the third step, it is preferable that this joined body and the ceramic member 1 are made into a joined body of the ceramic member 1 and the metal member 2 using a chromium compound bonding agent 4.

Since the bonded body manufactured in this way has a fiber structure felt having elasticity and flexibility as an intermediate layer, there is no difference in thermal expansion between the ceramic member and the metal member, and each material can be used over a wide range. Insulation of high-temperature gas passage walls, liners, pistons, etc. of gas turbines, magnetohydrodynamic power generation, diesel engines, Kallin engines, U-high-m gas burners, etc.
It can be used to great effect in heat-resistant and wear-resistant structural members.

Example-1 (1) A compound as a ceramic member was ground and mixed using an alumina ball mill, and H2CrO with a specific gravity of 1.65 was added to the dried product.

Add about 13% by weight of a concentrated aqueous solution to the powder and mix well.
This wet powder is packed into a mold and 300 to 9/rs
Pressure molding was performed at t2. 3. Place this molded product in an electric furnace.
It was heated at a rate of 5°C/min and held at a maximum of 700°C for 40ml1nN. This cured product was further treated with the above H2CT.
04 solution, impregnated with the liquid, and 700 ml in the same manner as above.
The impregnation and heat treatment were repeated 8 times to prepare a cylindrical ceramic having an outer diameter of 50 cm, a length of 50 x m, and a wall thickness of 5 nm. The thus obtained member had an apparent porosity of 9.3 and a Rockwell hardness of 15-N93.5.

(2) Fiber structural member (intermediate layer) Nickel-coated carbon fiber (filament diameter 10 μm
, 3,000 filaments) and high silicate glass fibers (filament diameter: 10 μm, bundle of 1,000 filaments) with a volume ratio of approximately 50,750, cylindrical shape with an inner diameter of 50 mW, a length of 50 mrn, and a wall thickness of 3.5 mm. CrO felt
7. Into a concentrated aqueous solution of H2CrO4 prepared by dissolving 3100g. No. 17 g was dissolved to prepare an aqueous solution with a specific gravity of 1.4, felt was immersed in this solution and printed, and the felt was applied to a centrifuge to remove excess liquid adhering between the fibers. This treated material is placed in an electric furnace at 5°C/m
The degree of convexity is increased by in, and above 400℃, heat treatment is performed for 40ml at a maximum temperature of 500'C in an N2 gas atmosphere.
Further, immersion in this liquid and heat treatment were repeated three times. Through this treatment, the contact points where each fiber intersects with each other form a felt with a significantly strengthened non-metallic inorganic fiber structure due to the conversion and bonding of the adhering solution to Cr2O3, and the bulk density is approximately 50%, which is a considerable amount. It had elasticity.

(3) A metal member aluminum alloy casting (JISAC-4C equivalent product) is processed into a cylinder with an inner diameter of 57.3 mm, a length of 50 mrn, and a wall thickness of 8 mm.
Then, a solution was used to apply anodic oxidation coating to a film thickness of 45 μm.

(4) Preparation of bonding agent First, dissolve CrO3, 200Fr in water, and
Make a concentrated aqueous solution of O4 and add Zn017g and Mg to it.
08g was dissolved, water was added to make the specific gravity 1.65, and further, approximately 3.5% by weight of powder of A7203 and 5i02 with a size of 10μm or larger was added to the solution, and the mixture was ground for 24 hours using an alumina ball mill.・Adhesive was prepared by mixing.

(5) Bonding procedure After applying the bonding agent in (4) well to the surfaces to be bonded of each member described in (1) to (3), stack them one on top of the other.
The temperature was raised at a rate of 5° C./min and maintained at a maximum of 500° C. for 40 min to produce a joined body of the ceramic member and the metal member.

This cylindrical joined body was subjected to a rapid heating and cooling test of 10 cycles at 500° C., 1 hr heating (electric furnace), 42 room temperature 1 hr (air cooling).

After the test, this sample was cut and cracks in the ceramic member were detected.
As a result of inspection for peeling, no abnormalities were found.

Example 2 (1) Uhr wet pulverization and mixing of a ceramic component composition using an alumina ball mill, and after drying, a small amount of 2-inch PVA solution was added to moisten the powder well, and the powder was mixed with a powder of 800 to 9/2. crn2 pressure molded. This was sintered for 1hr at 1470° C. using an electric furnace to prepare a disk-shaped sintered body with a diameter of 47 mu and a thickness of 51 nN. The apparent porosity of this alumina sintered body is 10.4
%Met.

(2) Fiber structural member (intermediate layer) Cr 18%-Ni with filament diameter 100 μm
Commercially available felt made from B-chi stainless steel costs 50
x 50yam", thickness 5mm, and bulk density 33q6. To braze the metal parts to one side of the felt, first apply a solution of nitrocellulose in ethyl acetate to one side of the felt to coat the fibers of the parts to be joined. After coating, the fibers were strengthened by repeating dipping, centrifugation, and heat treatment three times using a concentrated aqueous chromium compound solution in the same manner as described in (2) of Example 1. However, the atmosphere of the heat treatment was controlled. No bonding of Or2bs to the coated portion was observed because the coating of the 2FZ solution on the nitro was carried out before immersion in the chromium compound solution.

(3) Metal member A square block of acid-free copper 50 x 50 m x 10 mm thick was used.

A method similar to that described in (3) of Example-1 is carried out.

However, when bonding to stainless steel felt using a chromium compound bonding agent, it is necessary to plate the copper bonding surface with Ni.

(4) Preparation of bonding agent Dissolve CrCrO31O0, dissolve Zn018gr in a concentrated H2Cr04 aqueous solution, add fine powder of Cr2O3 with a particle size of 10 μm or less to this, about 5 weight of the liquid, and grind for 24 hours using an alumina ball mill. Mix and prepare slurry.

(5) Joining procedure First, apply soldering flux to the copper substrate described in (3) and lay a thin plate of silver solder BAg-1, and then (2)
Predetermined surfaces of the described stainless steel felts were overlapped, set in an electric furnace, and brazed at 750° C. in a reducing atmosphere.

Next, the bonding agent described in (4) was thoroughly applied to the felt outer surface of this bonded product and the bonding surface of the ceramic member, and both surfaces were stacked with the ceramic member facing down, and heated at 3.5°C/mi.
Increase the temperature at a rate of n, and above 350℃ in a reducing atmosphere,
A bonded body of a ceramic member and a metal member was manufactured by maintaining the temperature at 570° C. for 40 ml.

This product was heated at 500°C and lh in the same manner as in Example-1.
A rapid heating/quenching test of 10 cycles of r heating and room temperature Ihr cooling was conducted. As a result, no abnormalities such as cracks or peeling of the ceramic members were observed.

In addition, the tensile bonding strength was measured by bonding using an epoxy bonding agent and showed a value of 380 kg 7 cm2 or more (peeling at the bonded surface of the epoxy resin).

As described above, the present invention can provide a member that is extremely useful for imparting heat resistance, heat insulation, and wear resistance to metal structural members exposed to high temperatures, and the manufacturing cost is low, so it is suitable as an industrial manufacturing method.

[Brief explanation of the drawing]

FIG. 1 is a cross-sectional view showing one embodiment of the joined body of the present invention, and FIG. 2 is a cross-sectional view showing another embodiment of the present invention. l... Ceramic member, 2... Metal member, 3, 3'
... Fiber structure felt member (middle layer), 4... Bonding agent, 5... Metal brazing, spot welding or contact joining. Patent Applicant: Usui Kokusai Sangyo Co., Ltd. Agent 1) Yoshihisa 9 Figure 1 Figure 2 Voluntary Procedure Auxiliary Device April 5, 1981 1. Indication of the Case 1988 Patent Application No. 30514 2. Invention Title: Combined body of metal and ceramic members and method of joining the same 4. Agent 8. Contents of the amendment: Amended as shown in the attached document Patent Application No. 58-30514 1. Percentage The scope of the claims is amended as follows. (1) A felt member made of a fiber structure of a metallic or nonmetallic inorganic material or a composite thereof, which has been strengthened with a chromium compound and has elasticity and flexibility, is interposed between the metal member and the ceramic member. , and the joint surface of each of these? A combination of a metal member and a ceramic member, characterized in that they are integrally bonded to each other by a chromium compound. (2) A felt member made of a metallic fiber structure having elasticity and flexibility reinforced with a chromium compound is laid between the metal member and the ceramic member, and the felt member is interposed between the metal member and the felt member. A metal member and a ceramic member characterized in that their joint surfaces are joined by metal brazing, spot blast welding, or cast fusion, and the joint surfaces of the ceramic member and the felt member are integrally joined to each other by a chromium compound. A combination with. (3) A felt member made of a fiber structure of an elastic and flexible metallic or non-metallic inorganic material, or a composite thereof, which has been immersed in a concentrated solution of a soluble chromium compound and has a coating layer of the concentrated solution on its surface. is heat-treated to strengthen the fibers, and then, when bonding on both sides, a single solution of iA% FA solution of soluble chromium compound or metal is applied to the joint surfaces of the metal member side and the ceramic member side. A type of oxide stone is coated with a soluble chromium compound ζ. By heat-treating the concentrated solution in
Hardening layer due to conversion to rρ8? 1. A method of joining a metal member and a ceramic part, characterized in that the mutual joining surfaces are joined together through a metal member and a ceramic part. (4) A felt member consisting of a metallic fiber structure having elasticity and flexibility, which has a covering layer of the concentrated solution, is soaked in a concentrated solution of a soluble chromium compound in advance, and then heat-treated to form a fiber. After that, the bonding surface between one side and the metal member is bonded by metal brazing, spot explosion welding, or cast fusion, and the bonding surface between the other side and the ceramic member is A concentrated solution of a soluble chromium compound or one type of metal oxide is applied to at least one surface of these stones, or a concentrated solution of a soluble chromium compound containing one or more of these is applied, and then heat treatment is applied. A method for joining a metal member and a ceramic member, characterized in that they are integrally joined to each other via a hardened layer formed by converting a concentrated solution into Cr=Og. 4

Claims (1)

[Scope of Claims] (1,1 Between the metal member and the ceramic member, a fiber structure made of a metallic or nonmetallic inorganic material or a composite thereof, which has elasticity and flexibility and has been reinforced in advance with a chromium compound) A combination of a metal member and a ceramic member characterized by interposing a felt member and integrally bonding their joint surfaces to each other with a chromium compound. (2) Between the metal member and the ceramic member. , a felt member made of a metallic fiber structure having elasticity and flexibility reinforced with a chromium compound is laid and interposed;
And metal brazing the joint surface of the metal member and the felt member,
Alternatively, a combined body of a metal member and a ceramic member, characterized in that they are joined by spot blast welding or cast fusion, and the joining surfaces of the ceramic member and the felt member are integrally joined to each other by a chromium compound. (3) A felt member made of a fiber structure of an elastic and flexible metallic or non-metallic inorganic material, or a composite thereof, which has been immersed in a concentrated solution of a soluble chromium compound and has a coating layer of the concentrated solution on its surface. is heat-treated at 460°C or higher to strengthen the fibers, and then a concentrated solution of a soluble chromium compound is applied to the bonding surfaces on both sides, or to the bonding surfaces on the metal member side and the ceramic member side. To add one or more metal oxides, a concentrated solution of a soluble chromium compound containing one or more of these compounds is applied, a felt member is interposed between the metal member and the ceramic member, and the felt member is further heat-treated in this state. In particular, Cr2 of said concentrated solution
A method for joining a metal member and a ceramic member, characterized in that their mutual joint surfaces are integrally joined through a hardened layer formed by conversion to O3. (4) A felt member made of a metallic fiber structure having elasticity and flexibility is immersed in 88 liquid of a soluble chromium compound in advance and has a coating layer of the concentrated solution on the surface.
The fibers are strengthened by heat treatment at temperatures above °C, and then the bonding surface of the fiber and the metal member is bonded by metal brazing, spot welding, or cast fusion, and the other side is The joint surface between and the ceramic member,
A single layer of a concentrated solution of a soluble chromium compound or a type of metal oxide applied to at least one side of these is one of these.
By applying i′^ solutions of soluble chromium compounds containing Cr or
A method for joining a metal member and a ceramic member, characterized in that they are integrally joined to each other via a hardened layer formed by conversion to 2O.