JPS60200871A - Metal and ceramic bonding method - 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 relates to a method for solid-phase bonding metals and ceramics using a hot isostatic press device.

<Industrial Application Fields> In recent years, there has been a noticeable trend toward higher efficiency and larger sizes of various high-temperature equipment, and in order to develop high-performance high-temperature materials required to cope with these trends, the combination of metal materials and ceramics has become more prominent. Bonding technology has come to occupy an extremely important position.

<Prior art> Conventionally, methods for joining metals and ceramics include: ■ Joining with adhesives, ■ Joining by brazing such as soldering or play song, and ■ Mechanical means such as shrink fitting and cold tight fitting. Bonding, etc. are known and have been put into practical use, but all of these methods have problems such as weak bonding strength and a tendency to peel when heated to high temperatures. When using mechanical means, it is impossible to avoid the disadvantage that the shapes of the metal members or ceramics to be joined are inevitably restricted.

For this reason, in recent years, solid-phase bonding methods have been attracting attention, in which ceramics and metals are directly bonded at high temperature while applying high pressure using a hot isostatic press device.

However, with the exception of specific cases such as bonding between Nb-based metals and M2O3-based ceramics, sufficient bonding cannot be achieved even if the metal and ceramics are directly pressure-welded using solid phase bonding. This is clear from numerous research results. The following reasons a) and b) have been pointed out as reasons for this. That is, a) Si, C, B, etc., which are the constituent elements of ceramics,
It diffuses into the metal at high temperatures, forming a brittle layer on the metal side of the interface or causing deterioration of the ceramic, making it easier to peel in that area.

For example, a sintered body of iron-based metal and ceramics (TiN).

T IC+ T I B 2 + AQ 203 +
Z r O2r Al! N + SIC, SI
3N, 4, etc.) directly using a hot isostatic press machine, it may not be bonded at all, or the reaction may be intense and a brittle layer may be formed in the middle, making it difficult to form the desired bonded product. It is not possible to obtain.

b) Because the thermal expansion coefficients of metals and ceramics are different, stress concentrates on the bonding interface during cooling after pressure welding, resulting in peeling.

However, as mentioned above, Nb-based metals and All! 203
In the case of ceramics, there is almost no difference in thermal expansion between the two, and an appropriate reaction layer (N
bOx ) is formed, resulting in an exceptionally good bond.

Therefore, in order to avoid such inconvenience, recently Ae
A method has also been proposed in which an "intermediate layer made of a mixed powder of rFe and AC203 is sandwiched between the two to alleviate the thermal expansion difference between the two when in-phase bonding of 203 ceramics and Fe is carried out." Ceramics Association's ``1981 Pension Performance'' held from May 16th to 18th, 1988).

In addition, a method has been proposed in which nitride-based ceramics and MO are bonded together after sandwiching an "intermediate layer made of a mixed powder of rMo and the ceramic powder to be bonded" ( Journal of America
n Ceramic 5ociek'7 Cll'l'
page).

However, according to this method, it is true that Ag2O3 and Fe
Although it was possible to obtain a good bonded body of Mo and nitride ceramics, the target was rAQ.
In addition to being limited to ``bonding of 203 ceramics and Fe'' and ``bonding of nitride ceramics and Mo,'' it also had disadvantageous problems such as the necessity of mixing an intermediate layer prior to bonding. be.

<Purpose of the Invention> In view of the above-mentioned problems, the inventors of the present invention have developed a method to reduce the thermal expansion difference between metal and ceramics and to reduce the reaction between them during solid-phase bonding. The most promising means of achieving a strong joint with appropriate control is to interpose an appropriate intermediate layer between the two materials. The result of repeated research was to find a method for bonding metal components and sintered ceramic components with sufficient bonding strength without the need for complicated auxiliary work such as the process of mixing intermediate layers. , we have come to the following findings as shown in (a) to (e) below.

<Knowledge> (a) TiN, which is known as a relatively stable compound even at high temperatures, is a compound that is highly stable even at high temperatures.
, Co, Ni, Nb, Mo, Cr, etc. do not react with most metals, but for example, TiC
Ceramics such as Ti (C, N) form a solid solution at high temperatures.

(b) Therefore, if a layer of TiN powder is interposed between a metal member and a ceramic sintered member, and then these are heated to a high temperature and both members are pressed together under high pressure, the constituent parts of the metal member are will be diffused into the TiN powder layer, and the TiN powder will be bonded to each other without reacting with the TiN powder.

In other words, the TiN powder intermediate layer turns into a cermet-like layer in which TiN powder particles are bonded to each other using metal as a binder, and is firmly bonded to the metal member without forming a brittle diffusion layer on the metal member side. .

Furthermore, since the intermediate layer of TiN powder is strongly bonded to the ceramic member directly or partially through the diffusion metal,
As a result, a strong joined body of the metal member and the ceramic sintered member can be obtained.

(C) Possibly, the cermet-like intermediate layer in which TiN particles are dispersed in the metal base has a thermal expansion between that of metal and ceramics, so the metal member and ceramic sintered part are joined at high temperature. The coating shall not peel off even after cooling.

(d) In other words, when solid-phase joining a metal member and a sintered ceramic member, if the joining operation is performed with an intermediate layer of TiN powder sandwiched between the two, during the HIP process (hot isostatic pressing) During the treatment, a TiN powder layer or a cermet-like mixed layer of F metal and TiN forms, which not only forms a strong bond with the metal component, but also alleviates the difference in thermal expansion coefficient between the metal and the ceramic. 2. Since TiN and ceramics are bonded well while the reaction between the metal and ceramics is moderately suppressed, a composite member of metal and ceramics with excellent bonding strength can be obtained.

(e) If a mixed powder layer containing TiN powder mixed with powder of a metal that is the same as that of the metal member or does not have an adverse effect on the metal member is applied as an intermediate layer between the metal member and the ceramic member prior to the bonding operation, a comparison result will be obtained. <Structure of the Invention> This invention was made based on the above knowledge, and it is possible to bond a metal material and a ceramic sintered body using a hot isostatic pressing device. When joining under high temperature and high pressure, by interposing a TiN powder layer or a mixed powder layer of TiN powder and metal powder as the joining intermediate layer, peeling does not occur even under heat cycle conditions. The present invention is characterized in that a composite member having excellent bonding properties can be manufactured at a low cost.

The above-mentioned "metal material" is not limited to a specific type, but Fe is particularly difficult to react with TiN.

Co, Ni, Nb, Mo, Cr, or an alloy thereof is preferable. However, the above-mentioned "ceramics" are not limited to a specific type, and include TiC.

TiN, TiB2, ZrO2, or Ac2o
This also applies to sintered compacts such as No. 3.

The heating temperature during bonding may be selected within a range where the metal used does not melt and the reaction with TiN does not become large, and at which sufficient diffusion occurs. In addition, in the case of ordinary steel or stainless steel, the heating temperature should be set to 1100 to 140.
It is best to keep it at around 0'C.

The pressing force during joining should be selected appropriately considering the degree of adhesion, deformation, capacity of the equipment, etc. of the joining members, and is 500-15.
A wide range of about 00 kg/ffl can be selected.

Further, the TiN powder or metal powder used as the intermediate layer preferably has a particle size of about -300 mesh, and it is also possible to use fine particles with a diameter of about 2 to 6 μm.

In addition, the thickness of the intermediate layer made of powder is 100 μm to 1 μm.
You can choose about vatt level, but special K T i
If only N powder is used, the brittleness of the intermediate layer itself becomes a problem, so the thinner the layer, the better, and the thickness is preferably about 200 to 4C) Om.

Now, FIG. 1 is a schematic illustration of a method of assembling a joining member when a metal member 1 and a ceramic sintered body 2 are to be joined by the method of the present invention.
A TiN powder layer 3 is interposed between the ceramic sintered body 2 and the ceramic sintered body 2.

Now, when this assembly is treated at high temperature and high pressure using a hot isostatic pressing device, a part of the metal constituting the metal member 1 will be diffused into the TiN powder layer as shown in FIG. It penetrates and reaches the 2nd surface of the ceramic sintered body, turning the TiN powder layer into a cermet-like one in which TiN particles 4 are dispersed in the metal, thereby firmly bonding the metal member 1 and the TiN powder layer. Become.

On the other hand, the ceramic sintered body 2 and the TiN particles 4 are firmly bonded to each other due to the formation of a solid solution by each component due to the high temperature, or by the diffusion metal acting as an intermediary.

Furthermore, the cermet-like intermediate layer formed by metal diffusion has a thermal expansion intermediate between that of the metal member 1 and the ceramic sintered body 2, so it has the effect of alleviating the difference in thermal expansion between the two. Even if the metal member 1 and the ceramic sintered body 2 are cooled after the bonding operation, the metal member 1 and the ceramic sintered body 2 will not separate.

Next, the present invention will be specifically explained using Examples and Comparative Examples.

<Example> Comparative Example 1 Under pressure of 1000 atm using a hydrostatic pressure device, 1700
A TiN sintered body (dimensions: 7φ x 1.5t, relative density: 98%), which was sintered under the conditions of holding at ℃ for 2 hours, and iron (dimensions: 7φ x 5t,) were prepared, and the surfaces of both were polished with No. 600 emery paper. did.

These samples were piled up and treated using the glass capsule method by holding at 1300°C for 1 hour under a pressure of 1000 atm in a hot isostatic pressurizer, and then cooled to room temperature at a cooling rate of 300°C/hr. A sample was taken from.

When the sample was examined, it was confirmed that the TiN sintered body and the iron were not bonded to each other at all, and were separated at the interface between the two.

In addition, tests were similarly conducted on TiC sintered bodies and iron, AQzOs sintered bodies and iron, and ZrCh sintered bodies and iron, but all of them peeled off at the interface between the ceramic and iron and were not bonded. I understand.

Comparative Example 2 A TiBz sintered body was made using the same method as in Comparative Example 1, and an attempt was made to bond it to iron using the same method as in Comparative Example 1.

However, in this case, TiB2 and iron reacted violently during the treatment, and a weak reaction layer was formed on the iron side between iron and Ti82, so that both of them peeled off during cooling.

Example l TiN and TiC produced by the same method as Comparative Example 1.

TiB2. Sintered bodies made of AQ203 and ZrO2 were prepared.

On the other hand, an iron material similar to that shown in Comparative Example 1 was also prepared.

Next, TiN powder (300 mesh or less) was interposed between the sintered body and the iron as shown in FIG. 1, and the two were overlapped. The thickness of the 'I' i N powder layer at this time was 100 to 500 μm.

This stacked body was heated to 1300°C under a pressure of 1000 atm using a hot isostatic pressurizing device using a glass capsule method.
The sample was then subjected to a holding process, cooled to room temperature at a cooling rate of 300°C/hr, and then taken out from the apparatus.

When the samples were examined, it was confirmed that the iron and ceramic sintered bodies were well bonded in all cases.

These samples were then cut directly at the joint interface and examined under a microscope, but no cracks were observed in the samples. In addition, Figure 3 is A+! FIG. 2 is a micrograph of a bonded part of a bonded body of 203 sintered body and iron.

Example 2 Ceramic sintered body and 5US similar to those in Example 1
304 stainless steel was prepared, and the two were joined using the same method as in Example 1.

As a result, despite the fact that 5US304 stainless steel has a considerably larger coefficient of thermal expansion than iron, it was found that the 5US304 stainless steel intermediate layer in which TiN was dispersed formed a good bond with any ceramic sintered body. It was confirmed that this was occurring.

Example 3 The same test as in Example 2 was conducted except that SUS 410 stainless steel was used instead of SUS 304 stainless steel, but in this case as well, the test results were as good as when iron or SUS 304 stainless steel was used. It was confirmed that a bond could be obtained.

Example 4 A ceramic sintered body and an iron material similar to those in Example 1 were prepared, and a bonding test was conducted on each under the same conditions as in Example 1, except that the pressing force was 500 atm.
In both cases, good bonding similar to that obtained in Example 1 was obtained. I was able to do that.

Example 5 A ceramic sintered body and iron material similar to those in Example 1 were prepared. As the intermediate layer, TiN powder (300 mesh or less) is used with SO weight cracking and 1? e Powder (average particle size 8 μm,)z
o% by weight of the mixture was used. The thickness of the intermediate layer is approximately 300μ
A sample was assembled in the same manner as in Example 1 as m, and subjected to i (IP treatment) using the glass capsule method.The processing conditions were 1100
°C, 11 hours.

The test was carried out at 1000 atm. It was confirmed that good bonding could be obtained in this case as well, as in the case where only T i N powder was used.

<Overall Effects> As mentioned above, this invention makes it possible to stably, reliably, and relatively easily perform solid-phase bonding between metal materials and ceramic sintered bodies, which was almost impossible. It is possible to implement this method, and it brings about industrially useful effects such as being able to provide a metal-ceramic composite material with good bonding strength at a low cost.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram showing an example of a member assembly method when joining metal and ceramics by the method of the present invention, FIG. 2 is a schematic diagram showing the state of the joint after the joining is completed, and FIG. FIG. 3 is a microscopic photograph of a joint of a Fe-AA203 sintered composite member obtained by the method. In the drawings, 1. Metal member, 2. Ceramic sintered body, 3. TiN powder layer, 4. TiN particles. Applicant: Sumitomo Metal Industries, Ltd. and one other agent: Tomi
1) Kazuo and 1 other person Figure 1 Darkness 2 Figure 100μ July 5, 1980 Director General of the Patent Office Manabu Hoga 1 Indication of the case Patent application No. 1983-59141 2 Name of the invention Method for joining metals and ceramics 3. The 4th person making the amendment, Mr. Ri, June 6, 1980 (Shipping date: June 26, 1982)
In the Statement of Contents of the Amendment, page 16, lines 6 to 7, the words "microscopic photograph" are corrected to "microscopic tissue photograph."that's all

Claims (2)

[Claims] (1) When a metal material and a ceramic sintered body are bonded under high temperature and high pressure using a hot isostatic pressing device, a TiN powder layer is interposed as a bonding intermediate layer.
A method for joining metals and ceramics. (2) When joining a metal material and a ceramic sintered body under high temperature and high pressure using a hot isostatic pressing device, a mixed powder layer of TiN powder and metal powder is interposed as a joining intermediate layer. A method for joining metals and ceramics.