JPS60125375A - Metal-ceramic joined body and manufacture thereof - Google Patents

Abstract

PURPOSE:To manufacture a metal-ceramic joined body having superior heat resistance, wear resistance and a significant heat insulating effect by coating the surface of a metallic material with ceramics contg. Cr2O3 in the form of a slurry and by carrying out heat treatment to join firmly the ceramic layer to the metal. CONSTITUTION:The surface of an engine is roughened by sand blast, and it is coated with a slurry prepd. by adding at least one among SiO2, ZrO2, Al2O3, Fe2O3 and CaF to a concd. aqueous soln. of a soluble Cr compound such as CrO3 so that the expansion coefft. of the resulting ceramics is made close to that of the metal of the engine. The coated engine is heat treated to form a ceramic layer contg. Cr2O3 converted from CrO3. A mixed ceramic layer consisting of Cr2O3 and at least one among SiO2, ZrO2, Al2O3, Fe2O3, CaF, ZrSiO4, 2MgO.2Al2O3.5SiO2, SiC and Si3N4 is then laminated on the formed ceramic layer. Thus, the thermal efficiency of the engine is improved.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is characterized in that a metal member and ceramics are firmly bonded,
Heat resistance, insulation and! This invention relates to a metal-ceramic bonded body having excellent wear resistance and a method for manufacturing the same.

A lot of research is being conducted to reduce heat loss and increase thermal efficiency in mechanical devices that generate heat, such as diesel engines and gasoline engines. Composite structures of ceramics and gold particles have been frequently proposed. These are mainly made of ceramics and are joined to metal by shrink fitting or bolting, and there is a risk that the four pieces together may cause damage such as cracking or peeling due to looseness during engine operation.
Furthermore, the ceramics used for this purpose all require advanced manufacturing techniques, and have the disadvantage of significantly increasing manufacturing costs. In addition, a composite member in which ceramic spray coating is applied to one part of gold gauze surface is also being used.This method has the advantage of relatively low manufacturing cost and low thermal conductivity of the coating. Since there is no mechanical bond between the metal and the metal, the bonding strength is low, and when a coating is applied to the thickness necessary to obtain excellent heat insulation properties, the coating has the disadvantage that it easily peels off.

The Ministry of the Invention and others have carried out a lot of research in order to obtain a mechanically and thermally strong metal-ceramic bonded body that can firmly bond ceramics and gold members. The upper ceramic layer is made of a ceramic having a coefficient of thermal expansion approximating that of the gold kL member.
By forming the layer f, and by using a ceramic having a thermal expansion coefficient ρ smaller than the thermal expansion coefficient of the previous layer, the ceramic particles and the metal member can be mutually bonded. Cr produced by heat treatment, 0. The inventions of the present invention were made based on the recognition that the objects can be achieved by forming a ceramic coating by firmly bonding the ceramic coating. That is, the present invention provides S iow * Zr0t t Aft Os e F so that the thermal expansion coefficients of the core metal and the ceramic coating approximate to the surface of the metal member.
@* Os +Cr, 0. and CaF', a slurry prepared with a fine powder of at least 1 fl The present invention provides a metal-ceramic bonded body formed by forming a thick and strong ceramic coating on a gold IT member, and a method for manufacturing the same. Furthermore, on the @IM ceramic coating formed according to the invention.

F6 is slightly smaller than the coefficient of thermal expansion of this ceramic.
2 (J3, Crt (Ja + cap'l l
Zr 5104 H2Mg0' 2A11 (%
'5S 1t) 2 + S A slurry prepared with fine powder of at least one glaze compound selected from 1"C consisting of tC and 5lsNi and a soluble chromium compound is applied and heat treated. The metal-ceramic bonded body and its manufacturing method include preparing a slurry having a coefficient of thermal expansion slightly smaller than that of the ceramic layer, and sequentially applying and heat-treating the slurry to form a coating of a desired thickness. , after forming the first layer formation edge of ceramics and/or the final layer 1. Solubility U
The present invention provides a method for increasing the bonding strength between a metal member and a ceramic coating, or for further strengthening the structure of the obtained ceramic coating, by impregnating the metal member with a concentrated aqueous solution of muric acid and heat treating it. be.

As the metal member in the present invention, iron and iron-based alloys such as cast iron, carbon steel, stainless steel, aluminum and aluminum alloys, nickel and nickel-based alloys, etc. are used. Metal showa is + U9 Tsukumura h#L
Before going to the palace, the surface is washed with acid or alkali so that the slurry is evenly distributed, and then sandblasting is used, for example, to increase the bonding surface with the ceramics. It is preferable to perform a surface roughening treatment, and it is preferable to use fused alumina or silicon carbide with a particle size of 297 to 350 μm.Also, when the metal member is made of dung iron, after the surface roughening treatment, the specific gravity is 1. .3 to 1.6 le C
It is preferable to perform a treatment (Japanese Patent Application No. 58-61661) in which the material is immersed in a heated aqueous solution of RY4 and treated at 70 to 100 DEG C. to remove graphite that appears on the surface of the material. In addition, in the case of metal or aluminum alloy, it is preferable to perform hard alumite treatment after the above-mentioned surface roughening treatment and to perform pue 5 or nickel plating.

Next, the ceramic in contact with the metal member is SiOt
y Zr0t + At, os, Fe2osl
CrOm HcaF', , Zr5iO, *2Mg0
・2Alt On' 5 S 10! -S Ic
and 5lsN4, etc., and Cr, Us. For Sl, use silica (α-type quartz crystal) with a Si ox purity of 99.5% or more. For r, ZrO! A cubic Zr Offi solid solution obtained by stabilizing ZrO with a purity of 99.51 or higher at 1550°C with CaO3,
As l1 Os, g-A1. with a purity of 99.5% or more is used.
Q, as Z r S i O4, Z r S
l'04 Zircon sand with a purity of 99% or more, StC, α-5tC with a purity of 99% or more, Si,
As N4, Si, α-81 with a purity of 98.5 or higher
To convert mN4 to 2Mg0・2A1101・581, use synthetic copierite with a synthesis rate of 98% as F @! 0@
Commercially available products such as gCaFt + Crl O@ can be used.

These have a particle size of 44 μm or less and an average particle size of 10 to 5 μm.
It is preferable that the powder be adjusted to a fine powder.

In addition, 1 part of CrtO is prepared by dissolving Cry in water)I
It can be supplemented in the form of a concentrated aqueous solution of ICr04.

A soluble chromium compound is a concentrated aqueous solution containing hexavalent chromium ions, such as H in which CrO3 is dissolved in water,
CrO, concentrated aqueous solution or ZnO or MgO as HsC
rQ, 0.1 to 0.2 mol for 1 mol/l/&C
Examples include those dissolved in an aqueous rO4 chain solution, and the degree of neck is adjusted to a ratio of 1165 to 1.7.

Therefore, the ceramic is coated with a ceramic whose coefficient of thermal expansion is close to that of the metal member, or whose coefficient of thermal expansion is smaller than that of the ceramic layer immediately below between each layer of the laminated ceramic layer, and therefore, It is convenient to suitably combine the above compounds and measure their thermal expansion coefficients in advance. That is, the mixed powder was wetted with an aqueous solution of H*Cr0411 with a specific gravity of 1.7, and
Pressure molded at 0 kg7am”, dried and then heated at 4°C/m
The temperature was raised to 700° C. at a rate of i n , and the material was fired at 700° C. for about 60 minutes to obtain a hardened product.The material was then impregnated with the &CrO4 concentrated aqueous solution and heat-treated in the same manner as above. Impregnation with
A ceramic sample was prepared by repeating the heat treatment three times,
Thermal expansion characteristics at room temperature to 600°C were measured. A part of this result is illustrated in the first world.

Based on this bag, a ceramic is selected depending on the type of metal member or has a coefficient of thermal expansion smaller than that of the ceramic of the previous layer. That is, for example, S 10t of the first layer
-Alt Os and Cr! 0. Ceramics consisting of Sin, 54 Toryobe,
15 parts by weight of AItos and 16 parts by weight of Cr, O, both in powder form with an average particle size of 10 μm, were mixed with Cr.
, 0.20 parts by weight dissolved in 14 parts of water has a specific gravity of approximately 1.
70H2CrQ46≧In addition to 32 parts by weight of the aqueous solution, 20 parts by weight of water was added, and 2 parts by weight were added using an alumina ball mill.
Mix for 0 hours and make the slurry! IN.

In addition, ceramics consisting of S [02, Zr (Jt and crow) are made of the same material and have a content of 5iOtts parts by weight, zro
, 68.5 parts by weight of each fine powder of Cr, 0.51 parts by weight, 24 parts by volume of an aqueous solution of Cr4 Affl having a specific gravity of 1.7, and 14 parts by weight of water are mixed well to prepare. Also, Zr
Ceramics consisting of O, Cr, and O were similarly prepared by adding 39 parts by weight to ZR, 0.50 parts by weight of each fine powder, 22 parts by weight of a concentrated aqueous solution of HsCr04 with a specific gravity of 1.7, and 15 parts by weight of water. Mix well [5]. Also, Zr5(O
4eAI, 0. and CrtOA, Zr5iO, 45 parts, AI! 0.18 parts by weight and 0.22 parts by weight of each fine powder, Cr with a specific gravity of 1.7
0432 and 14 parts by weight of water are mixed well at the same mKt as above to prepare. SaraK-Z r S 104
e 2Mg 0・2A1,0.・5SiO, and Cr
Similarly, ceramics consisting of O□ are Zr510a
451 Keibu, 2Mg0・2Alt On・5SiO
t 35 parts by weight, and Cr! 10 parts by weight of each fine powder of Ox, 26 parts by weight of a concentrated aqueous solution of CrO4 with a specific gravity of 1.7, and 13 parts by weight of water are thoroughly mixed to prepare.

In the first and third aspects of the present invention, for example, SiOt*AltOs and Cr,0. Ceramic slurry, degreasing and cleaning,
It is applied to the surface of roughened and decarbonized gray cast iron (thermal tensile coefficient 12 x 10"/'Cat room temperature to 600°C). Application can be done by brushing, spraying, dipping, etc. In order to form a uniform system, a dipping method is preferred in which the entire area of the member is immersed in a slurry.The coated metal member is dried at 70-80°C and then heat-treated at 450-600°C. The temperature rate varies depending on the shape and size of the metal member, but is usually 3 to 6°C/min, and the atmosphere is not particularly limited.Lamination of the ceramic coating is performed by applying the same treatment as above to the metal member that has undergone the above treatment. The slurry is applied onto the first layer and dried and heat treated as described above.

Then, a metal-ceramic bonded body is obtained by repeating the coating-drying-heat treatment process until the thickness of the ceramic coating reaches a predetermined thickness.

Moreover, the second aspect of the present invention. In the fourth invention, for example,
In the case of the above-mentioned gray cast iron, 5i01. AI, O, and Cr, 0. The first layer was formed by processing the slurry under the same concave-spherical conditions as the first layer forming conditions of the first invention.

The second layer is SiOS adjusted by 5K as described above.

The first step was carried out using a slurry consisting of zrO and Cr@us.
It is formed in the same manner as the layer. Then, in the third layer, Z
A slurry consisting of r01 and Cr, O, was used for the fourth layer, a slurry consisting of ZrS 104-Alt On and crtos was used for the fifth layer, and ZrS i04, 2M was used for the fifth layer.
g0・2A1tOs '5H! Each layer is formed in the same manner as the first layer using ceramic slurries having a smaller coefficient of thermal expansion than the previous layer, such as 0, Or, O, and so on.

Furthermore, when the present invention is applied to parts that are subject to strong mechanical vibrations, the bonding strength between the metal member and the ceramic coating is further increased as in the fifth invention, and the entire ceramic layer of each laminated layer is Can be strengthened. That is, in the fifth aspect of the present invention, after applying the first layer of ceramic VI to the metal member as described above, an acid aqueous solution of the bath-compatible chromium compound, which has been reduced to 1 as described above, is applied, for example. After impregnating the first FfJ with a dipping method and drying, a heat treatment is performed at 450 to 600°C. This treatment increases the bonding strength between the metal member and the ceramic, but as shown in 8111e, the number of pores is reduced, and increasing the amount of this treatment reduces the layer thickness of the ceramic layered on the mold. Therefore, 1 to 3
It is preferable to carry out this treatment twice.

Second coating: After laminating the ceramic coating until it reaches the desired thickness to strengthen the bond, proceed as above.
The process involves impregnating, drying, and heat-treating the ceramic coating with a seasonally soluble chromium compound, and it is preferable to repeat this process several times.As the number of treatments increases, the pore size and amount of pores in the ceramic coating decrease, and the structure becomes denser. This increases the strength.

By forming the ceramic coating in this way, the radius of the ceramic covering obtained by the first and third aspects of the present invention is, for example, 100 to 100 in the first scrap.
150μm, second layer 600-700μm, third layer 1
100-1200/jrn.

4th layer is 1300~1600μm, 5th layer is 2500~
Layers having a thickness such as 3500 .mu.m are formed one on top of the other to form a ceramic coating having a total thickness of 5.5 to 7 Il. Therefore, the thickness of this ceramic coating depends on the shape, size and distribution of solid particles contained in the ceramic slurry.
It depends on the slurry concentration and coating conditions, etc.
When these are constant, the thickness of the layer formed on the ceramic coating Φ is determined by the amount of pores in the underlying layer,
As mentioned above, the thickness of the upper layer increases rapidly. The ceramic coating formed as described above has an apparent porosity of 20 to 30 cm, and an apparent thermal conductivity of 0.001 to 30 cm.
0.003 ca'/cWL1! It is possible to obtain a bonded body with extremely excellent heat insulation properties, which are on the order of lec'lc.

Further, in the ceramic coating obtained by the second and third inventions, when 5r@ is formed as described above, the coefficient of thermal expansion of each layer is 12.0 x 10yC for the first layer.

2nd layer is 10.4 x 101/'C, 3rd layer is 8.3
x10''/6c.

The fourth layer is 6. OX 1 o-e/'C, 5th layer is 3.
6 x 10-'/'C, the total layer thickness is 5.7 cm, the average porosity is 24.3 cm, and the apparent thermal conductivity is 0.0021 ca. '/cm・
see・”c. In this case, 40X40X thickness 6
A sample of No. 111 cast iron plate coated with ceramic to a thickness of about 6 dew was prepared in the same manner and heated to 500°C for 30 minutes in an electric furnace.
As a result of 50 cycles of rapid heating and cooling, in which the sample was held in the air at room temperature for 30 minutes, then rapidly heated again, no abnormalities such as cracks or peeling were observed in the sample, indicating good heat resistance. It has been recognized that it has impact resistance and is suitable for parts used in areas where temperature changes are severe. A ceramic coating was formed to obtain a coating with a thickness of 3.2 mm, an average porosity of 20.9 mm, and an apparent thermal conductivity of 0.0028 ca'/cWL・8.
ee'c, and the tensile strength was 337 kg/(,''.

Furthermore, when the H, CrO, a aqueous solution treatment was repeated five times after forming the final layer, the apparent porosity of the ceramic coating was 14%, and the apparent thermal conductivity was 0.003.
A coating with a tensile strength of 370 kg/ryn'' or more was obtained.

This treatment with a 5 kb cro, pore water solution is not only carried out after the formation of the first N coating or after the formation of the final layer, but can also be carried out in the same way both after the formation of the first N coating and after the formation of the final layer. possible, and the advantages of each can be obtained in combination.

The first ceramic coating is made by chemically bonding ultrafine crystals of CR, O, produced by heating chromic acid between particles of raw material powder, and the results of X-ray diffraction indicate that the ceramic coating When the raw material mixture was fired at 700°C, the presence of reaction products between Cr, O, and the above various powders and powders was not observed, and the measurement results of thermal expansion properties indicated that the raw materials were made of the above raw materials. The coefficient of thermal expansion of ceramics shows additivity. For this reason, it is possible to select a ceramic material having thermal expansion characteristics similar to those of a metal member.

Therefore, the metal-ceramic bonded body obtained here has excellent heat resistance, heat insulation, and abrasion resistance, so it can be used in cylinder liners, piston tops, exhaust boats, and other high-temperature, high-pressure gas and liquids in adiabatic internal combustion engines. It is suitable as a component for the inner wall of transport pipes, etc.

The present invention provides p? The first Ji is formed of a ceramic having a coefficient of thermal expansion close to the coefficient of expansion L, and thereafter, the same ceramic as described above is coated with M layers, or ceramics having a coefficient of thermal expansion smaller than that of the previous layer are sequentially laminated, and , after forming the first layer or after forming the final layer, or after forming the first layer and after forming the final layer K H
t cro4 Since the treatment was carried out with a concentrated aqueous solution, a coating of the desired thickness could be formed, and the resulting forest had good heat insulating properties,
It has excellent heat resistance and abrasion resistance, and can also achieve thermal shock resistance, increase the bonding strength between metal parts and ceramic nuclides, and increase the strength and densification of ceramics, depending on the location of use. Excellent effects have been recognized, such as ease of application regardless of the shape of the metal member.

Next, examples of the present invention will be described.

Example 1 (1st. 8th invention) 1) Adjustment of gold parting Gray cast iron CJIS FC-25 equivalent, thermal expansion coefficient 1
2.3 x 10-@/'C (room temperature to 600℃))
After roughening the surface of a specimen measuring 40 x 6 m with molten alumina of 295 to 350 μm, it was cleaned with 51HC1 solution, and then HCl with a specific gravity of 135 was used. The metal part was immersed in a cro4 aqueous solution and heat-treated at 80°C for 15 minutes to remove graphite on the surface of the part, and then masked to prevent the slurry from adhering to the surface that was not coated with ceramic to prepare the metal part. .

2) Preparation of ceramic plug forming agent 1) Preparation of concentrated aqueous solution of soluble chromium compound Cr, 0.10
0 parts by weight was dissolved in 55 parts of water, and water was added thereto to prepare a concentrated aqueous solution with a specific gravity of 1.7.

11) Adjustment of slurry From Table 1, 810t-A 11 is a ceramic having a thermal expansion coefficient close to that of gray steel.
0S -Crtos ceramics were selected and the thermal expansion coefficient was approximately 12.3 x 10"7℃.
iQ, 54.5 parts by weight of 99.5% or more silica, α-type A
0.15 parts by weight of Cr, ol, and 15.5 parts by weight of Cr, ol were all made into fine powders of 44 μm or less and an average particle size of 10 μm, and Ht G ”0 with a specific gravity of 1.7 adjusted in 1) was prepared.
The mixture was mixed with 32 parts by weight of a 4U aqueous solution and 20 parts by weight of water for 20 hours using an alumina ball mill.

3) Manufacture of ceramic coating By immersing the steel stock prepared in step 1) in the slurry prepared in step 2) and pulling it out after a few seconds, a uniform coating can be applied to the surface of the member. After drying this at 70°C for 60 minutes, the temperature was raised to 560°C at a heating rate of 4°C/min, held for 20 minutes, and then lowered at a rate of 5°C/1 m1 to about 200°C. Ceramic id+a of snoring LNtl was formed by sometimes taking it out of the furnace. Next, the nuclide member was subjected to υ soaking-drying-heat treatment under the same conditions using the same slurry as above to form a second layer coating, and thereafter a fourth layer up to the branch shape was formed under the same conditions.

4) Test results The thickness of each layer of the ceramic coating, starting from the first layer, was 13.
9,617. LIOo was 1,490 μm, and the total thickness of the prayer was 3.35 m. The bonding strength between the cast iron member and the ceramic was tested by a peel test using an epoxy resin adhesive to adhere a spread test jig to the ceramic optical surface and cast iron interface of the specimen. Peeling occurred, and its strength was 275' to 9Xcm'', and the apparent porosity of the nuclide was determined by the water displacement method (a common method for measuring the porosity of ceramics). 28.1%, and the result of measuring the apparent thermal conductivity by the hot wire method is 0.0022 cal.
℃, and it was recognized that the material had excellent heat insulation properties.

Example 2 (Invention of No. 2.m4) 1) The metal plate member was made of carbon steel (JIS S-45C compatible product, #expansion coefficient 14,
5 x 10″Ll/℃ (room temperature to 600℃))
X40 1) Preparation of soluble chromium compound concentrated aqueous solution Example 1-2)
- Adjustment was made in the same manner as in 1).

11) Adjustment of slurry (a) Slurry for forming the first layer From the first layer, ZrO, -CaF, -C are used as ceramics having a thermal expansion coefficient approximating that of carbon steel.
R, OS ceramics are selected, and the coefficient of thermal expansion is 1.
Y14. I
Stabilized zr0,5 obtained by stabilizing at 1550°C with Ft 994 or higher fluorite 30 twill part, CaO3 weight J
7 parts by weight and 4 parts by weight of Cr, OB 13
As a clear ship length of 4 μm or more 1-4W Senchobo 111zzm, CrO with a specific gravity of 1.7 adjusted in the previous section was mixed with 18 parts by weight of a concentrated aqueous solution and 15 parts by weight of water using an alumina nine-ball mill for 20 hours. Prepared.

(b) Slurry for forming the second layer S l (%
-Aft Ox -Fs, o, -crl ol
We selected ceramics with a thermal expansion coefficient of approximately I L 5.
X 10” s i 0ffi9 as indicating 7℃
39 parts by weight of sand stone of 9.5 inches or more, α-type A 1 t 0
s20in part, Fe, 9316 parts by weight and Cr*0s1
0 parts by weight, all with an average particle size of 44 μm or less and 10 μm
as a fine powder with a specific gravity of 1.7 adjusted according to 1) above.
It was prepared in the same manner as in (a) above with 32 parts by weight of the 11ICr04a aqueous solution and 10 parts by weight of water.

(c) Third layer forming slurry A 110B -Z r 02 in the same manner as in (b) above
- C%03 thread ceramics (coefficient of thermal expansion s, 5X
10-'/'C), α-type Al, 0.37 parts by weight, and stabilized zrO obtained in the same manner as in (a) above. 30 parts by weight, 0.18 parts by weight of Cr, both as the same fine powder as above, and H with a specific gravity of 1.7 adjusted according to l) above.
It was prepared in the same manner as B) above with 32 parts by weight of CrO4 fresh water solution and 10 parts by weight of water.

B) Fourth M forming slurry A120m-ZrS from Table 1 in the same manner as in (B) above
104-Cr, Os-based ceramics (thermal expansion! 6
．． OX 10-8 layers ℃) ft selection, a - yj,
II Al, 0818 parts by weight, purity 99% or more Zr
510.45 parts by weight and 0.22 parts by weight of Cr, both as the same fine powder as above, were mixed with 32 parts by weight of the aqueous solution of kcro4a (with a specific gravity of 1.7 prepared by I) above and 9 parts by weight of water. ) was adjusted in the same manner.

(e) Slurry for forming the fifth layer Z r Si 0 from Table 1 in the same manner as in (b) above
4-2Mg0・2A1t Os・531 Q, select ceramics (thermal expansion coefficient 3.6 x 10@/'C), same as above) Zr810+ 50 parts by weight, synthetic 2M
g0-2AltOn-5SiO, (content 98%) 31
Parts of kf and parts by weight of Cr1019 were both made into the same fine powders as above, and the specific gravity L was adjusted according to the above :).
It was prepared in the same manner as in (a) above with 26 parts by weight of Hs cro4 concentrated aqueous solution of No. 7 and 12 parts by weight of water.

3) Production of ceramic coating The carbon steel member prepared in 1) was coated, dried, and heat treated in the same manner as in Example 1-3) using the slurry for forming the first layer prepared in 2)-+1)-(a). to form a first layer coating, and then coating, drying, and heat treatment were sequentially performed on each layer using the slurries prepared in (B), (C), (C), and (E) above. to form the second to fifth layer encapsulations.

4) Test results The thickness of each layer of the ceramic coating thus obtained was 124, 186, 1020°L370.
a900. c+m, and the total thickness of the coating was 6, On. Further, as a result of testing in the same manner as in Example 1, the apparent porosity was 26.3 cm, and the thermal conductivity was 0.0025 cal/
crIL・SeC・℃, the bonding strength between the metal member and the ceramics, and the tensile strength of the ceramics are 305 to 9 layers cm
“That’s it for ivy.

Example 3 (Application example of the fifth invention to the first and third invention-1) After forming the first layer coating in the same manner as in Example 1, 2)-
1) by it! I Adjusted specific gravity 1.7 1 (tcr
O4 concentrated aqueous solution is impregnated with the solution, dried and heat treated under the same conditions as for forming the first layer coating, and further coated with another layer.
A double impregnation-drying-heat treatment was performed. Subsequently, coatings up to the fourth layer were formed in the same manner as in Example 1.

The thickness of each layer of the obtained ceramic coating, starting from the first layer, was 137,573,970. L was 380 μm, and the total thickness of the coating was 3.06 m. Also, the bonding strength between the metal part side and the ceramics is 304 kg/crn"
The apparent porosity is 24.3% and the apparent thermal conductivity is α
0027 ``l/an-see'C.

Application example-2) After forming a four-layer ceramic coating in the same manner as in Example 1, bcro with a specific gravity of 1.7 obtained in 2)-1) was
The sample was immersed in i9 aqueous solution to be impregnated with the solution, dried and heat treated under the same conditions as for forming the first layer, and the impregnation-drying-heat treatment was repeated four times.

The thickness of each layer of the resulting ceramic coating was 140,615 mm thicker than the first layer. LO90, 1490μm,
The total thickness of the coating was 3.3 mm. As a result of testing in the same manner as in Example 1, the bonding strength between the cast iron member and the ceramic was 290 kg/cm', and the apparent porosity was 2α.
2-1 Apparent thermal conductivity was α0030e town price/SeC/°C.

Example 5 (Example where the fifth invention is applied to the second and fourth invention) After forming the first layer branch root in the same manner as in Example 2, 2)-
1) kb cro4' with a specific gravity of 1.7 adjusted by
The first layer coating was impregnated with the solution by immersion in 1 m water, and dried and heat treated under the same conditions as for forming the first layer. The impregnation-drying-heat treatment was repeated one more time. Next, the second to fifth layers were formed in the same manner as in Example 2, and after forming the fifth layer, the specific gravity was 1.
7) Impregnation-drying-heat treatment of bcr04 concentrated aqueous solution first
The treatment was repeated 8 times in the same manner as on N α.

The thickness of each layer of the obtained ceramic nuclide is 1
@, 135,340,610,965°L350μm
The total thickness of the coating was 3.13. or,
As a result of conducting the same test as in Example 1, the apparent porosity was '
1.3 cm, and the apparent thermal conductivity is 0.00358a'/
crIL・8eC・℃, and the bonding strength between the metal member and the ceramic and the tensile strength of the ceramic are 438 kl.
l/ca" or more.Furthermore, as a result of 50 rapid heating and cooling tests held at 500℃ and room temperature for 30 minutes, no abnormalities such as cracks or peeling were observed, and the product has excellent thermal shock resistance and heat insulation properties. was recognized as having the following.

Patent applicant Yoshihisa Oshida, agent for Usui Kokusai Sangyo Co., Ltd. Voluntary procedure, amendment dated 1st 1980, 26th Kazuo Wakasugi, Commissioner of the Japan Patent Office, Indication of the case 1988 Patent Application No. 230925 2, Invention Name: Metal-ceramic bonded body and its manufacturing method 4, Agent Ikumasa Sho Special pf1 1982-230925 1, Details: $7, line 17, WF, line 11, WF, line 12, and 1200, line 6 re ros J? rCroom=1
2 Correct.

2 Ibid No. 1600, line 19, amend “3rd” and “4th” 3゜1rii, page 20, line 18 r Cr s OsJ
Correct to "x r C'r On" 〇 Patent applicant Usui Kokusai Sangyo Co., Ltd.

Claims (1)

[Claims] 1) Sin! so that the thermal tensile coefficient of the obtained ceramic approximates the thermal Tg coefficient of the metal member. . Zr0t e Alt Us + Fe201 and C,
A metal-ceramic bonded body, characterized in that a metal member is laminated and coated with a ceramic prepared by using CRTO and at least one compound selected from the group consisting of F. 2) In a metal-ceramic bonded body in which ceramics are laminated and coated, the first layer of ceramics has a coefficient of thermal expansion that approximates the thermal tensile coefficient of the Kinwa 6 member, and the coefficient of thermal expansion of the ceramics in the upper layer gradually increases. b 102 g zro, so that the coefficient of thermal expansion is smaller than that of the ceramic of the previous layer.
@Alt On * Fe @ 0B g cmF
, lZr5104.2Mg0 "2A50m"
At least one compound selected from the group consisting of 58 to, *SIC and 5isN4, Cr, 0. What is claimed is: 1. A gold maple-ceramic bonded body, characterized in that a metal member is sequentially laminated and coated with a ceramic prepared by using the following ingredients: 3) Add zrO1+A 11 to Sl so that the coefficient of thermal expansion of the obtained ceramic approximates the coefficient of thermal expansion of the metal member.
0n + F @! Osg Crl 0m and CaF
! A ceramic private layer is formed by coating a metal member with a ceramic slurry prepared from a small amount of fine powder of one type of compound and a concentrated aqueous solution of a soluble chromium compound selected from the group consisting of A method for manufacturing a metal-ceramic bonded body, characterized by: 4) In manufacturing a metal-ceramic bonded body coated with a ceramic ttfAffj, the first layer of ceramic has a thermal expansion coefficient close to that of a metal-ceramic bond. has expansion retention i,
Sequentially, the thermal expansion coefficient of the upper layer ceramic is smaller than the thermal expansion coefficient of the previous layer ceramic.
e Zr0m e Alv O@, Few Os
tCrl Os + CILP't e ZrS 1
04 w 2Mg0 ” 2A110.' 58101
+Ceramic slurry prepared with a fine powder of at least one M compound selected from the group consisting of SiC, Si, and N4 and a concentrated aqueous solution of a soluble chromium compound.A ceramic coffin is produced by sequentially subjecting a metal member to a grinding process and heat treatment. A method for manufacturing a metal-ceramic bonded body, comprising forming an M coating. 5) A ceramic coating is applied to the metal layer to form a koji layer,
A method for producing a metal-ceramic bonded body, characterized in that after forming the first M ceramic coating and/or after forming the final ceramic coating, impregnation with an aqueous solution of a soluble chromium compound and heat treatment are performed one or more times.