JPS586712B2 - Method for manufacturing heat-resistant high-strength joined body - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a bonded body formed by bonding two or more of at least one material selected from metal materials, ceramic materials, and carbon materials using a bonding agent. This relates to a manufacturing method.

In particular, the present invention relates to a method for producing a heat-resistant, high-strength bonded body, which is characterized by using an organosilicon polymer compound whose main skeleton components are carbon and silicon as a bonding agent.

Light bulbs, discharge lights, mechanical parts, communication equipment, electron tubes, semiconductor envelopes, IC boards, various packages, etc. contain metal. Bonded bodies made by bonding ceramics, carbon, etc. are used, and their use in many fields has been expanding in recent years.

However, according to the conventionally known method of manufacturing a bonded body, it is difficult to obtain a bonded body with excellent heat resistance and strong bonding strength, and the manufacturing process is complicated, resulting in high manufacturing costs. Its uses were limited.

As shown in Table 1, typical conventional bonding methods include the Telefunken method, the solder glass method, the active metal method, and the Mo vapor deposition method.

Bonding strength using the Telefunken method or Mo vapor deposition method is high, but these methods require that a material other than metal, such as ceramics, is heated in a humidified gas and then metallized with a metal such as Mo (metallization treatment of the surface layer). In addition, it is necessary to go through a complicated process of brazing to the target metal using a brazing filler metal, which has the drawback of extremely high manufacturing costs.

In addition, the solder glass method is a method in which a solder containing PbOAl203, CaO, etc. as a main component is placed between, for example, a ceramic and a metal, and then heat-treated and bonded, but the optimum joining temperature range of these solders is relatively low. Since the solder paste is narrow, it is necessary to accurately control the processing temperature to match the solder's surface condition, and the quality of the solder paste is difficult to control because the joining performance changes sensitively depending on the surface condition of the solder. There is.

In addition, the active metal method uses active metals such as Ti and Zr to form a low melting point alloy with Ni. Cu. This is a relatively simple method in which Ag or the like is interposed between a ceramic and a ceramic or a ceramic and a metal so that it has a eutectic composition, and then heated in a vacuum or in an inert gas to form a bonded body. As shown in Table 1, the bonded body obtained by this method has a weak bonding strength and extremely poor heat resistance, so the range of use of the obtained bonded body is inevitably limited.

The object of the present invention is to provide a manufacturing method that eliminates the various drawbacks seen in the conventional methods and can inexpensively manufacture a heat-resistant and high-strength joined body. The present invention relates to a method for manufacturing a bonded body, in which two or more bodies to be bonded, interposed with a bonding agent whose main component is an organosilicon polymer compound as a skeleton component, are heated to a high temperature in a non-acidic atmosphere.

Next, the manufacturing method of the present invention will be explained in detail.

The objects to be joined that can be used in the present invention are composed of at least one material selected from metal materials, ceramic materials, and carbon materials having a melting point of 800° C. or higher.

Namely, the above materials such as metal-metal, metal-ceramics, ceramic-ceramics, ceramic-carbon, carbon-metal, carbon-carbon, etc. can be used as a main component of organosilicon polymer compounds whose main skeleton components are carbon and silicon. A bonded body can be obtained by freely bonding with a bonding agent.

As mentioned above, the bonding agent used in the present invention is mainly composed of an organosilicon polymer compound whose main skeleton components are carbon and silicon, and this organosilicon polymer compound was already invented by the present inventors. The following patent applications have been filed since 1980:
No. 50223, Japanese Patent Application No. 50-50529, Japanese Patent Application No. 1983
~52471, patent application No. 50-52472, patent application No. 52472
0-58033, Japanese Patent Application No. 50-58034, Japanese Patent Application No. 50-70302, Japanese Patent Application No. 50-70303, Japanese Patent Application No. 77219, Japanese Patent Application No. 50-79972, Japanese Patent Application No. 1987- No. 107371, patent application 1973-132718
No. 50-132719, patent application No. 1987-146
No. 267 and Japanese Patent Application Nos. 50-149468, the method for producing this compound will be described below.

Organosilicon compounds that can be used as starting materials for the organosilicon polymer compound whose main skeleton components are silicon and carbon used in the present invention are those classified into the following types (1) to (10). It consists of any four or two or more selected from.

(1) R4S, a compound containing only Si-C bonds, called siIahydrocarbon
This includes t+R3St(R'StR2)nR'SiR3 and its carbon monofunctional derivatives.

Examples (CH3)4Si, (CH2=CH)4St. (CH
3) 38iC2CSi(CH3)a, (CH2)58i
(CH2)4, (C2H5)38icH2CH2C4(
C6H5)3sicO2H. (2) Compounds containing Si-H bonds in addition to Si-C bonds, such as mono-, di-, and triorganosilanes, belong to this category.

Example (C2H5)2Si, (CH2)5SiH2, (CH
3) 3SicH2Si(CH3)2H. CICH2Si
Ha, (3) an arsenic compound organohalogensilane having a Si-Ha13 bond.

Example CH22CHSsFs, C2H5SiHC12, (C
H3)2(C6CH2)SiSi(CH3)2C6. (
C6H5)3SsB2. (4) Arsenic compound having Si-N bond This includes silylamine and the like.

(5) Si-OR organoalkoxy (or alloxy) silane.

Example (CHs)2si(CH2H5)2. C2H5SiC
62 (QC2H5), P-C606H4OSi (CH3
)3, (6) Compounds with Si-OH bond Organosilanol examples (C2Hs)3SiOH, (CH3)2si(OH)
2, C6HsSi(OH)s, (HO)(CH,)2s
iCH2si(CH3)2(OH). (7) Examples of compounds containing Si-Si bonds (CH3)3Stsi(CH3)2CJ, (CH3)
38iSi(CH3)3,(C6H5)38iSi(C
6H5)2si(c6H5)2cg, (8)Si-0-
Organosiloxane is a compound containing Si bonds.

Example (CH3)3siOsi(CH3)3,HO(CHs
)2SiOSt(CH3)20H. Ce2(CH3)S
tOS+(CH3)CIOSi(CH3)CI2,((
CaH5)2SiO)4, CH2=C(CH3)C02CH2St'(CH3)2
CH202C(CH3)(9) Organosilicon compound ester; ester thought to be formed from silanol and acid, including (CHs)2Si(OCOCHs)2 and the like.

(10) Organosilicon compound peroxide: (CHs)3Si
00c・(CH3)3,(CH3)3si00si(C
H3)3 etc.

In the molecular structures of (1) to (10) above, R represents an alkyl group or an aryl group.

In the present invention, an organosilicon polymer compound having silicon and carbon as main skeleton components, for example, a compound having the following molecular structure, is produced from the raw materials.

d) A substance containing the skeletal structure described in (a) to (c) above as at least one partial structure among a chain structure and a three-dimensional structure, or a mixture of (a), (b), and (c).

Examples of compounds having the above molecular structure include the following.

n21, poly(silmethylenesiloxane) n2, poly(silethylenesiloxane) n=6, poly(silphenylenesiloxane) n21, poly(methyleneoxysiloxane) n-2, poly(ethyleneoxysiloxane) )n=
5. Poly(phenyleneoxysiloxane) n=12, poly(diphenyleneoxysiloxane) n21, polysilmethylene n-2, polysilethylene n-3, polysiltrimethylene r26. polysilphenylene n212, polysildiphenylene (d) containing the skeleton components described in (a) to (c) above as at least one partial structure among chain, cyclic, and three-dimensional structures, or (i) ) (b) (c) mixture.

Moreover, the following (e) to (e) can be mentioned as organosilicon polymer compounds containing different elements other than silicon, carbon, hydrogen, and oxygen that can be used in the present invention.

(g) Polymer having a carborane nucleus The organosilicon polymer compound containing the above-mentioned foreign element can be synthesized by a known method.

In addition to the organosilicon compound containing a different element synthesized by the above-mentioned known method, there is
It can also be manufactured by the manufacturing method described in the specifications of Nos. 1 to 149468.

That is, at least one organometallic compound selected from the organometallic compounds listed below (11) to (19) is added to the organosilicon compounds (1) to (10) above, and the mixture is heated for 200 min in a non-oxidizing atmosphere. An organosilicon polymer compound containing different elements other than silicon, carbon, hydrogen, and oxygen can be synthesized by heating to a temperature range of ~1500°C.

(11) Examples of organosilicon compounds containing nitrogen (C2H5
)3SiNH2, (CH3)3SiNHSi(CH3)
3. (CHs)3si(CN), (CHs)3StNc
O, (CH3)3SiNCS (12) Organometallic compound containing Group I metal (coordination-containing compound) Example CH3Li. C2H5Na. C6H5Li. Na [(
CH3)2Li), KCH3+AgCH3. AuC3H
g (13) Organometallic compound containing Group Ⅰ metal (coordination compound) Examples: BeC2H6, MgCH2. CaC2H6, BaC2
H6. ZnC4H10. CdC2T6. HgCH3Br
, SrC2H6 (14) Organometallic compound containing Group Ⅰ metal (coordination compound) Example BCH502. BC3H9, AlC2H7. GaCH
30. InC2H8N, InC3H9, TIC3H9.
SC(CH3COCHCOH3)3, La(CH3CO
CHCOCH3)3,Ce(CH3COCHCOCH3
)4, Pr(CH3COCHCOCH3)3. Nd(C
H3COCHCOOCH3)3, Sm(CH3COCH
COCH3)3. Eu(CH3COCHCOCH3)3
．． Gd(CH3COCHCOCH3)3, Tb(CH3
COCHCOCH3)3,Py(CH3COCHCOC
H3)3. Ho(CH3COCHCOCH3)3. Er
(CH3COCH3)3,Tm(CH3COCHCOC
H3)3,Yb(CH3COCHCOCH3)3,Ln
(CH3COCHCOCH3)3 (15) Organometallic compound containing Group ■ metal (coordination-containing compound) Example HfC1oH10Cl2, CaC2H8, SnC2H
8, PbC2H8 (16) Organometallic compound containing Group V metal (containing compound) Example VC606, NbC606. Tac606, C4H4
N, PC2H505. PC2H7. ASCH3S. As
C2H7, SbC2H7, B+C3Hg (17) Organometallic compound containing Group Ⅰ metal (coordination compound) Example WC4H6C3. C2H5SH, SeCH2. TeC
2H6, PoC2H6 (18) Organometallic compound containing Group ■ metal (coordination-containing compound) Example MnC12H10, TCCIOHIO+ReC6H3
05(19) Organometallic compound containing Group Ⅰ metal (coordination compound) Example FeC10H1o*CoC6H503, NtC6H1
0, RuC1oH1o, RhCgH13, PdCgH1
o, Pdc5H5cl. OsC1oH10. IrC30
3, PtC+H12 Organosilicon polymer compounds whose main skeleton components are mainly silicon and carbon as shown in (a) to (d) above synthesized in this way, and the above (e) to (g), (1)～
(19) At least one or more organosilicon polymer compounds selected from organosilicon polymer compounds containing a different element other than silicon, carbon, hydrogen, and oxygen, which are produced from two or more compounds shown in (19) above. , can be used as a bonding agent in the present invention.

The organosilicon polymer compound described above, which has carbon and silicon as its main skeleton components and optionally contains a metal element in its skeleton, can be obtained by a relatively simple and inexpensive manufacturing method, and is solid or solid at room temperature. Since it is a viscous liquid and a solid becomes liquid when heated above 300°C, both liquid and solid can be used as the bonding agent of the present invention.

In addition, it is advantageous and necessary to clean the surface of the objects to be joined in advance by sandblasting, pickling, high-frequency cleaning, etc., or to add a certain degree of roughness in order to obtain a good joined object. Accordingly, one or more types of powder particles selected from metals, ceramics, and carbon can be appropriately selected and added to the organosilicon compound depending on the type of materials to be joined.

When using a bonding agent in which such powder or granules are added to the organosilicon polymer compound, when the bonding agent is heated, SiC and liberate are released during the thermal decomposition process of the organosilicon polymer compound in the bonding agent. Carbon and free silicon are produced, and if there is a metal element in the powder or granule, it combines with this metal element to produce metal carbon or metal silicide, and if there is carbon in the powder or granule, This carbon and free silicon combine to further produce SiC.

Therefore, by adding the powder or granules, the coefficient of thermal expansion of the pyrolysis product of the binder can be made larger or smaller than the coefficient of thermal expansion of the pyrolysis product of the binder consisting only of an organosilicon polymer compound, that is, mainly SiC. Since the coefficient of thermal expansion can be freely adjusted as necessary, for example, when two types of objects are to be joined by the method of the present invention, the coefficient of thermal expansion can be adjusted to be between the coefficients of thermal expansion of the two types of objects. By adjusting the type and amount of powder and granules added to the bonding agent, it is possible to produce a bonded body that is less prone to peeling even after repeated heating and cooling and has high adhesive strength even at high temperatures. can do.

When a suitable amount of suitable powder or granules is added to the bonding agent, the intense thermal decomposition reaction caused by heating is appropriately controlled by the presence of the powder or granules. Since the solid solution, metal carbide, and metal silicide are formed relatively gradually compared to when the heating temperature is simply controlled, the generation of the SiC, intermediate solid solution, metal carbide, and metal silicide occurs more concurrently. , these compounds form a bonding layer that is tightly bonded, and the bonding strength between the objects to be bonded and the bonding layer is high.

The ratio of such additive powder to the organosilicon polymer compound varies depending on the degree of wettability and reactivity between the materials to be joined and SiC, and it is recommended to add a large amount if the wettability is poor or the reactivity is severe. is advantageous.

A suitable example of such additive powder is Ae203-
Cr203 for Cr system, M for TIC-Co system
o, Si for SiC-Si3N4 system. BN-SiC
Examples include BN for the system.

According to the present invention, such suitable additive powders can be added as necessary.

According to the present invention, after the bonding agent is interposed between the objects to be bonded, an atmosphere consisting of one or more selected from vacuum, inert gas, CO gas, hydrogen gas, and organic compound gas is provided. Inside, it is heated in a temperature range of 800 to 1800°C under any one of reduced pressure, normal pressure, and increased pressure.

As the heating method, for example, a commonly used sintering heating method under normal pressure or a hot pressing method can be used.

The chemical reactions and changes that occur when the objects to be bonded with the bonding agent interposed therein are heated will be described below.

The organosilicon polymer compound used in the present invention is gradually converted into SiC, a small amount of free carbon, and free silicon by heating at 700°C or higher, and this conversion is completed at 800°C or higher, so the heating temperature in the present invention is 800°C. The above is preferable.

Next, constituent molecules such as organic groups, free carbon, and free silicon that are liberated or volatilized during this heating process are used for effective bonding of both objects to be bonded, such as increasing wettability. Has a function.

In particular, free carbon and free silicon are extremely effective when one or both of the objects to be joined are metals, since they form carbides and silicides on the surfaces of the metals to improve adhesion.

At the bonding interface of the bonded body of the present invention, in addition to SiC, metal carbide, metal silicide, the intermediate solid solution, etc. are mainly present, and are strongly bonded to each other and to the objects to be bonded, Further, the inclusions have high mechanical strength even at high temperatures and are also excellent in oxidation resistance and corrosion resistance, so the joined body of the present invention can be advantageously used even at high temperatures.

Next, the present invention will be described with reference to examples.

Example 1 For the purpose of joining 18-8 stainless steel of 15φ x 2OLmm3 and a SiC self-sintered body of the same size, both were sandblasted, and then polysilane powder, which is a type of organosilicon polymer compound, and the stainless steel A mixture of steel powder and steel powder at a volume ratio of 1:1 is placed between the upper stainless steel and the lower SiC to a thickness of about 1 mm, and then 2 kg is placed on top of the upper stainless steel as a pressure source. of the same type of stainless steel and heated at 1300℃ in Ar 1 atm.
Heating was performed for an hour.

Table 2 shows the temperature change in the bonding strength of this bonded body.

Table 2 Bonding Strength of Stainless Steel-SiC Bonded Body As is clear from the above table, the bonded body of this example has excellent temperature characteristics with almost no change in bonding strength from room temperature to high temperature.

The bonding interface of this bonded body was analyzed using an X-ray microanalyzer to examine the distribution state of each atom, and the results are shown in the figure.

As is clear from the figure, Cr mainly in 18-8 stainless steel reacts with Si and C liberated from polysilane, intervening at the bonding interface as chromium carbide and chromium silicide, and forming a strong bond with the base metal. It has been found.

It is presumed that the presence of these inclusions brings about extremely advantageous effects such as improving the strength of the joint and alleviating the difference in coefficient of thermal expansion between the objects to be joined.

Thus, it is expected that this joined body will be widely used as a heat-resistant material such as high-temperature mechanical parts and high-temperature wear-resistant materials.

Example 2 In order to join BeO of 15φ×20Lmm3 and St3N4 of the same size, 30% by weight of S was added to polysilane powder.
i A mixture of metal powder was placed between the two to a thickness of about 1 mm.

This was placed in a graphite mold and hot pressed at 1500° C. for 30 minutes while applying a pressure of 200 kg/cm 2 in a vacuum of 10 −4 mmHg.

Table 3 shows the temperature change in the bonding strength of this bonded body.

Table 3 Bonding strength of BeO-SisN4 bonded body As is clear from the above table, at temperatures above 1000°C, the BeO main body rather than the bonded portion breaks.

This is because the Si powder added to polycarbosilane is BeO
This is thought to be because it has an extremely good wettability and has the effect of strengthening the bonding force between SiC and BeO mainly generated from polysilane.

Furthermore, since Si3N4 and SiC are strongly bonded by the same Si bond, the bonded body is excellent overall.

As in this example, Si3N4 is easily oxidized compared to BeO.
By covering Si3N4 with an oxide such as BeO, the excellent properties of Si3N4 can be exhibited even in an oxidizing atmosphere, and it is expected that the range of applications of such a bonded body by the method of the present invention will be extremely wide. Ru.

Example 3 In order to join graphite of 15φ x 20L and TiO2 of the same size, a polycarbosilane containing about 15% by weight of Ti elements as its skeleton component was placed between them to a thickness of about 1.5mm, Using a graphite mold in an atmosphere of Arl atmospheric pressure,
Hot pressing was performed at 1200°C for 30 minutes.

Table 4 shows the temperature variations in the bonding strength of the obtained bonded bodies.

As is clear from the above table, in this bonded body, no fracture is observed at the joint, but rather fracture occurs in graphite or TiO2.

This is because graphite and Ti have good wettability, and there is mutual diffusion between Ti02 and Ti, resulting in a strong bond between the two materials to be bonded through SiC and TiC.

A graphite bonded body like this example is promising as a structural material for a nuclear reactor core, for example, and has a wide range of applications.

In addition, although the above-mentioned examples show only a few representative examples by the manufacturing method of the present invention, the manufacturing of joined bodies using combinations of various other metals, ceramics, and graphite is equally excellent. I was able to see some results.

In addition, the combination of objects to be joined is not limited to simple A-B, but also A-B-A-B, A-B-C. A-B-A
-C etc., conjugated bodies with various combinations can be manufactured in the same way.

As described above, according to the present invention, joined bodies made of various combinations of metals, ceramics, and graphite can be easily and inexpensively manufactured, and these joined bodies have favorable properties such as excellent heat resistance and bonding strength. It is expected that it will be extremely advantageously and widely used in various fields such as the aerospace industry, the automobile and ship industry, the nuclear industry, the metal metallurgy industry, the ceramics industry, the petrochemical industry, the electrical and electronic industry, and others.

[Brief explanation of the drawing]

The figure shows the element distribution at the joint interface of a joined body of SiC and 18-8 stainless steel, analyzed by an X-ray microanalyzer.

Claims (1)

[Scope of Claims] 1. A method for manufacturing a bonded body in which two or more of at least one material selected from metal materials, ceramic materials, and carbon materials are bonded together using a bonding agent. Using an organosilicon polymer arsenide whose main skeleton components are carbon and silicon, and with the bonding agent interposed in the gap between the opposing surfaces of two or more materials to be bonded, it was heated for 800 minutes in a non-oxidizing atmosphere. The organosilicon polymer compound is thermally decomposed into mainly S by heating within a temperature range of ~1800°C.
A method for producing a heat-resistant, high-strength bonded body, characterized in that the two or more materials to be bonded are firmly bonded by generating iC and using the SiC. 2 Claim 1 in which an organosilicon compound containing silicon and a metal element other than silicon as a skeletal component and whose main skeletal components are carbon and silicon is used as a bonding agent.
A method for producing the heat-resistant high-strength joined body described above. 3. Claim 1 or 3, in which an organosilicon polymer compound whose main skeleton components are carbon and silicon, which is mixed with one or more of the materials to be joined and the same type of powder or granules as a bonding agent, or 2. The method for producing a heat-resistant, high-strength joined body according to 2.