JP2780304B2 - Sintered body of ceramic and plating film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a sintered body of a ceramic and a metal plating film.

<Prior Art> It is extremely easy to form a metal film on a ceramic surface by plating.

 Plating can inherently form a very precise film.

However, the disadvantage of this plating is that the bonding strength to the ceramic is low and the reliability is poor.

Generally, there are the following two methods for increasing the adhesion strength of the plating film.

One is an etching method, that is, a method in which the surface of the ceramic is roughened by etching to enhance the anchor effect and physically increase the adhesive strength.

According to this method, an adhesive strength of about 2 kg / mm ² may be obtained. That variation is also unavoidable.

Another method is a method according to the present inventor's invention, which involves co-depositing an active metal powder in a plating film as disclosed in Japanese Patent Application Laid-Open No. 62-105989. , Diffusion heat treatment.

According to this method, for alumina ceramics, 7
A tensile strength of 〜8 kg / mm ² is obtained, and the strength is satisfactory. However, the difficulty is that the active metal component diffuses into the plating film, so that it is difficult to obtain the plating film of the desired component.

Therefore, the present inventors have thought that in order to solve this problem, the plated layer on which the active metal powder is eutectoid is used as an intermediate layer for increasing the adhesive strength of the plated film.
This was implemented.

That is, a method in which an eutectoid plating layer of an active metal powder is provided on the surface of the ceramic in advance, and a target plating layer is provided thereon and subjected to diffusion heat treatment.

According to this method, the adverse effect due to the diffusion of the component into the plating film was almost prevented, and the intended purpose was achieved, but a new problem occurred.

This was the occurrence of blisters between the composite plating layer and the upper plating film.

<Problems Solved by the Invention> The present invention has been made in view of such problems, and an object of the present invention is to solve the above-mentioned problem of blisters.

<Means for Solving the Problems> As a result of intensive studies on the above problems, the present inventors have obtained the following knowledge.

That is, a composite plating layer in which a material powder diffusible in the ceramic is dispersed is formed between the ceramic and the plating film. In a sintered body of a ceramic and a plating film having a structure in which a plating layer and a plating film are mutually diffused and bonded, if the metal and ceramic powder particles are eutectoidally dispersed in the plating film, the above-mentioned problem of blisters may occur. We found that we could solve it.

 The present invention has been made based on the above findings.

<Operation> The plating film formed on the surface of the ceramic is easily blistered when heat-treated.

The purpose of co-depositing ceramic or metal powder particles on the plated metal film formed on the intermediate layer of the present invention is to prevent blisters during this heat treatment.

The particles to be eutectoid may be ceramic powders such as alumina, zirconia, silicon carbide and silicon nitride, and metal powders and oxide powders of the same kind or different from the plating metal of the intermediate layer (composite plating layer).

When a different kind of metal powder is used, the plating metal is alloyed with this metal powder by heat treatment.

When alloying is not preferred, the same type of metal powder may be used.

That is, for example, if Cu is used as the plating metal and Cu powder is used as the eutectoid powder, they are sintered together, but there is no contamination due to alloying.

The reason why blistering is prevented when these powders are co-deposited and heat-treated is unknown, but it is presumed that a kind of degassing or gas diffusion path is formed.

Observation of the eutectoid particles on the plating film with an electron microscope revealed that several particles were aggregated.

Microscopic gaps exist between the particles, which are presumed to form diffusion paths or gas vents.

If the eutectoid particles are metal particles, sintering proceeds between the particles and the plating metal by heat treatment, and the particles are integrated.

The gaps that contributed to gas release or gas diffusion in the initial stage of sintering are sintered and disappear with increasing temperature.

The size of eutectoid particles is most preferably from several microns to submicron.

Any kind of particles can be used as long as they do not dissolve or deteriorate in the plating bath.

The most typical example of the ceramic diffusible material in the composite plating layer of the intermediate layer is an active metal or a material which is thermally decomposed to change into an active metal during heat treatment.

The material which is thermally decomposed into an active metal is a hydride of the active metal.

Active metals include, for example, Ti, Zr, V, Nb, Ta, Mn, Cr, Ca, Mg, Y,
Rare earth metals and their alloys.

These metals and alloys may be used alone or in admixture with other inert metals, if necessary, or
It is used in a form coated with an inert metal.

The plating metal of the composite plating layer that forms the intermediate layer is Cu,
All commonly used electroplated or electroless plated metals such as Ni, Co, Ag, Au, Cr, Sn, Zn, Ni-P, Ni-B, Co-P, Co-B or their alloys are used it can.

The amount of diffusible metal powder in the interlayer is
In the case of, a tentative standard is approximately 0.5 g / or more in the bath.

The particle size of the powder is preferably under 325 mesh, especially under 10 microns.

The intermediate layer may be formed on the ceramic by plating directly on the ceramic. However, after the ceramic surface is mainly coated with a thin metal film, a composite plating is performed on the thin film.

For forming a thin film, all existing film forming techniques such as plating, vapor deposition, and sputtering can be used.

As the atmosphere for the diffusion heat treatment, a non-oxidizing atmosphere such as a vacuum, a reducing gas, or an inert gas is preferable.

The effect is sufficiently exhibited at least in a temperature range of 700 to 900 ° C. in which the plated metal exists in a solid phase.

After chemical plating of about 0.5 micron copper 96% alumina plate <Example> Example 1 50 × 50 × 1mm, and the composite plating of CU-TiH ₂ thereon.

The particle size of TiH ₂ is under 10 microns. Quantity is 5g in plating bath
/ Dispersed.

 The thickness of the composite plating layer is about 3 microns.

Next, a copper powder-copper eutectoid plating was performed on the composite plating layer using a copper pyrophosphate plating bath in which 0.04 micron pure copper powder was dispersed at a rate of 10 g /. Plating thickness is about
12 microns.

<Diffusion Heat Treatment> Heat treatment was performed at 850 ° C. for 30 minutes in a vacuum of 4 × 10 ⁻⁵ Torr.

<Evaluation> There was no blistering.

By the way, if the copper powder is not eutectoid, the diameter is 1-20mm
Numerous blisters with large φ occurred.

Further, the tensile strength of the plating film was 7.8 kg / mm ² .

Example 2 Approximately 0.25 mm was formed on a 50 mm × 50 mm × 0.5 mm aluminum nitride plate.
After chemically plating micron copper, TiH ₂ -Ni
Composite plating was performed.

<Composite plating> Ni plating bath bottom is deposited TiH ₂ powder of particle size 10 microns under the, extra - powder of TiH ₂ by electroplating embedding ceramic plated with copper into this was fixed on the copper plated surface.

 The thickness of the plating layer is about 5 microns.

After removing the ceramic from the plating layer and washing away excess powder, the next copper plating was performed.

<Copper plating> Pure copper powder under 0.37 micron in copper pyrophosphate bath
Using a bath of 15 g / dispersion, Cu powder-Cu eutectoid plating was performed. The plating thickness is about 15 microns.

<Heat treatment> Performed in a hydrogen atmosphere at 900 ° C for 20 minutes.

<Evaluation> No blisters occurred.

Example 3 After depositing 0.5 μm of copper on the surface of a 50 × 50 × 1 mm silicon carbide plate, a composite plating of Ti powder and Cu was performed.

Ti particle size is under 10 microns, amount is 5g / in plating bath
Dispersed.

 The thickness of the composite plating is about 5 microns.

Next, eutectoid plating of alumina copper was performed on the composite plating layer using a copper pyrophosphate bath in which alumina powder of 1 micron under was dispersed at a rate of 3 g /.

 The plating thickness is about 12 microns.

<Diffusion treatment> The diffusion treatment was performed at 800 ° C for 40 minutes in a hydrogen atmosphere.

<Evaluation> There was no blistering.

The tensile strength of the plating film was 4.5 kg / mm ² .

<Effects of the Invention> (1) No blistering occurs.

(2) High adhesive strength.

(3) Inexpensive.

Claims (6)

(57) [Claims] A composite plating layer in which a material powder diffusible in the ceramic is dispersed is formed between the ceramic and the plating film, and a diffusible material component in the composite plating layer is diffused into the ceramic. A sintered body of a ceramic and a plating film having a structure in which the plating film, the composite plating layer, and the ceramic are diffusion-bonded to each other, wherein ceramic or metal powder particles are co-folded and dispersed in the plating film. A sintered body of a ceramic and a plating film. 2. The ceramic according to claim 1, wherein said diffusible material is an active metal or a thermally decomposable compound of an active metal. 3. The sintered body according to claim 2, wherein the thermally decomposable compound is a hydride. 4. The plating metal of the plating film is Cu, Ni, Co, Ag,
The sintered body according to claim 1, wherein the sintered body is Au, Cr, Ni-P, Ni-B, Co-P, Co-B, or an alloy containing these as one component. 5. The plating metal of the composite plating is Cu, Ni, Co, A
The sintered body according to claim 1, wherein the sintered body is g, Au, Cr, Sn, Zn, Ni-P, Ni-B, Co-P, Co-B, or an alloy containing these as one component. 6. The eutectoid powder in the plating film is Fe, Ni, Co, C
The sintered body according to claim 1, wherein the sintered body is powder of u, Ag, Au, Cr, Mo, W, or an alloy containing these as one component.