JPH02293386A - Hetero-bonded material using inorganic material as base material - Google Patents

Abstract

PURPOSE:To enable the bonding of a metallized film having excellent bonding strength, gas-tightness and surface-smoothness to an inorganic material by plating a substrate made of an inorganic material with a metallized film using an alkali metal titanate as an interlayer. CONSTITUTION:An alkali metal titanate is applied to at least the surface of a substrate made of an inorganic material and a metallized film is formed on the titanate layer by plating. The material for the substrate is e. g. glass, cement, ceramics, refractory and new ceramics. The alkali metal titanate used in the present process is expressed by general formula AaBbTicOd.eH2O (A is one or more materials selected from alkali metal and H<+>; B is bivalent or trivalent metal; a and b are >=0 and <8; c is >=1 and <=9; d is >=2 and <=19; e is >=0 and <=10). The application of alkali metal titanate as an interlayer can be performed e.g. by mixing raw material powder for the inorganic material with an alkali metal titanate powder and solidifying the mixture after forming.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application 1] The present invention relates to a heterojunction, that is, a composite structure, in which a metalized film having excellent adhesion, airtightness, and surface smoothness is integrally formed on an inorganic material. .

Forming a metallized film on an inorganic material gives it various properties such as wear resistance, mechanical strength, conductivity, and chemical properties, in addition to a metallic appearance that cannot be achieved with an inorganic material alone. ．．
Furthermore, by combining it with different materials, it is possible to take advantage of the characteristics of devices and systems to expand the range of applications and improve functionality.

Therefore, it can be widely used in a wide range of fields such as ornaments, daily necessities, electronic board materials, and functional rice grains.

[Prior Art] There are various methods for meclizing (forming a metallized film) on inorganic materials. For example, solid-phase vapor phase systems such as vapor deposition, ion-blating, sputtering, and CVD require expensive equipment and equipment, and are therefore subject to restrictions on the dimensions of the substrate. Furthermore, as counterfeit metal, the thickness is often increased by plating. Therefore, the equipment and process costs are high, and it is difficult to metalize large products.

Furthermore, the organic adhesive method is simple and inexpensive, but has the disadvantages of poor heat resistance and accessibility. The inorganic adhesive method is simple, inexpensive, and heat resistant, but the drawback is that moisture escapes and hardens during the heating process during the bonding operation, and it is difficult to achieve complete airtightness due to the microscopic holes. be.

Other methods include high melting point metal method, pressure bonding method, DC voltage application method, reduction method, thick film method, etc.
Dimensional accuracy decreases, bonding strength decreases due to increased residual stress, and costs increase. This is because inorganic materials generally have a smaller coefficient of thermal expansion than metals, so especially when joining by heating, tensile stress remains on the inorganic material side and compressive stress remains on the metal side.

As is well known, inorganic materials are weak against tensile stress, so the addition of residual tensile stress makes the bonded body increasingly vulnerable to tensile stress. In any case, the relative relationship of thermal expansion between the inorganic material and the metal, wetting, and interfacial reaction are important, and it is not possible to meet the requirements such as low cost, bonding strength, airtightness, and heat resistance. Under these circumstances, the direct plating method on inorganic materials is a simple and low-cost process that can be performed at almost room temperature, can be wrapped around substrates with complex shapes, and can be used to form fine wiring. It is attracting attention as a method of applying

[Problem to be Solved by the Invention 1] However, it is difficult to make an inorganic material a plateable surface (roughened surface), and special techniques are required.

It is difficult to perform reasonable mechanical etching on hard inorganic materials by sandblasting, tumble polishing, etc., and in many cases, the surface smoothness of the substrate is impaired, and the metallized film is not uniformly etched on the substrate. It is difficult to form a In addition, inorganic materials are susceptible to stress concentration due to the influence of slight surface scratches, which reduces their reliability as structural materials. The present invention solves the above-mentioned conventional problems and provides highly reliable inorganic materials by forming a metallized film that has high bonding strength, airtightness, and excellent surface smoothness using a low-cost process. The object of the present invention is to provide a heterojunction having various properties such as wear resistance, electrical conductivity, and chemical properties.

[Means for Solving the Problem] In order to achieve the above object, the present inventors have conducted intensive research and found that a metal with excellent adhesion strength, airtightness, and surface smoothness can be obtained by using alkali titanate as an inclusion. We obtained the knowledge that suppuration can be bonded to inorganic materials and arrived at the present invention. That is, the present invention is a heterojunction characterized in that an inorganic material is used as a base material, an alkali titanate is solidified on at least the surface, and a metallized film is formed through this by plating. The base materials used in the present invention include inorganic materials that have been used for a long time such as glass, cement, ceramics, and refractories, new ceramics that are attracting attention as new industrial materials, and composite materials whose matrix is an inorganic material. I can list the following. Further, the alkali titanate used as an inclusion in the present invention is represented by the general formula of AaBbT1cOa'aHxO.

Here, A is one or more of alkali metals and H9, and B is:
It is a divalent or trivalent metal.

C is a number from 1 to 9. a. b is a number from 0 to 8, d is a number from 2 to 19, and e is a number from 0 to 10. In other words, alkali titanate is basically TiOz
complex oxide and hydrate with T106 octahedron, (Ti
．． It is characterized by a crystal structure consisting of a BlOs octahedron or a Ties triangular bipyramidal chain structure.

The shape of powdered alkali titanate is fibrous, plate-like,
It is not subject to any shape restrictions such as spherical or irregular shapes. Powders such as calcium carbonate, alumina, magnesia, zinc oxide, kaolinite, curcum, wollastonite, glass, etc., as well as alkali titanate, may be used to improve the adhesion and other properties of the metallized film within the scope of its intended use. You may add more than one type of body. Another method for reducing the amount of alkali titanate, which is an inclusion, is to adhere alkali titanate powder to the surface of the formed or consolidated inorganic material by coating, etc., and if necessary, consolidate it. It will be done.

In addition, in order to improve the properties of the base material and provide alkano titanate to the surface of the base material by using fibrous alkali titanate, it is necessary to mix the raw material of the inorganic material of the base material and the alkali titanate. , a method of solidifying after forming is selected. When the above-mentioned consolidation method is by firing, as long as the temperature range is such that alkali titanate is produced, a mixed powder of alkali titanate raw materials containing a titanium source and an alkali source may be used. In order to further enhance the adhesion strength of the metal film to be formed later, it is preferable to fuse or sinter the alkali titanate to the base material. The temperature at that time is fI of alkali titanate.
By selecting the same type, it is possible to operate in a wide temperature range of about 800 to 1600℃, without damaging the properties of the base material.
This allows for fixation or simultaneous sintering that suits the base material.

At least, the method of forming a metallized pattern on a base material with alkali titanate solidified on its surface using alkali titanate as an inclusion can be carried out without changing the conventional plating equipment at all. The plating method is a well-known method such as etching,
After degreasing, cleaning, sensitizing, and activating, electroless plating is performed. If necessary, further electrolytic plating or brazing can be employed. For example, if you want to deposit electroless Ni, SnCl
2 aqueous solution, and then PdC1. Activates in water. This is the origin of the precipitation of metallic Ni from the electroless Ni plating solution. Activators include not only PB but also gold,
Noble metals such as platinum group metals are also used. [Operations and Effects] According to the present invention, a metallized film with excellent adhesion strength can be bonded to an inorganic material by using an alkali titanate as an inclusion. This high adhesion strength and airtightness are due to the Ties octahedron of alkali titanate, fTi. Bl
Due to the above-mentioned crystal structure consisting of a chain of os octahedrons or Ties triangular bodies, the tunnels formed, the layer sides, or the zigzag-shaped connecting parts created by sharing the edges play an important role, and the microscopic The concave portion provides a strong anchor effect. Further, in the present invention, it is preferable to perform etching as a pretreatment for the purpose of increasing the amount of alkali titanate exposed on the surface of the base material. In the case of chemical etching, the inorganic material that is connected to the substrate is etched (using a liquid solution).

In the case of mechanical etching for the same purpose, the low hardness of alkali titanate allows for reasonable cutting and processing, and the surface on which the metal film is formed can be made extremely smooth. Taking advantage of its workability, it is also easy to obtain metallic films with specular luster. As explained above, the present invention makes it possible to form a metal film on an inorganic material at a low cost by using a plating method, which has both high adhesion strength and airtightness, which were difficult to achieve in the past, and surface smoothness, which was difficult to achieve in the past. It can be used in a wide range of fields, and its effects are extremely large. [Example] Next, an example of the present invention will be explained. The present invention is not limited to the following examples.

[Example 11 Pottery stone 24.3%, feldspar 4.1%, silica stone 4.9%, frog's eye clay 10.7%, Honbushi clay 6.0%, and (K+.3
110. 11 14Mgo. What is the chemical composition of 7T1710111? 50% alkali titanate was mixed in a ball mill and press-molded to a thickness of 1 Omm and a length of 15 mm.
0mm. A rectangular specimen with a width of 50 mnn was formed and fired at 1200°C for 5 hours to obtain a sintered body as a base material. The surface of the sintered body was polished using gamma alumina abrasive with a particle size of 0.05 μm. After finishing with puff polishing and degreasing with medieval detergent,
A nickel plating layer was obtained by electroless plating and electrolytic plating according to conventional methods. The surface roughness of the obtained nickel film was measured using a surface roughness meter and heated at 250°C for 10 seconds → 20°C 3
A 0 second heating/cooling thermal cycle test was conducted for up to 5 cycles. We also conducted an adhesion test. The results are shown in Table 1. [Example 2] SiOz 80%, s,oxt 3%, Na20 5%.
Borosilicate glass powder with a composition of AlzO*2%, Na
20% alkali titanate with a chemical composition of 2o・3TiO■
% added and mixed, thickness 5mm, length 150mm, width 50m
A rectangular test piece with a size of m was formed. At 1000℃,
The sintered body that is fired for 3 hours and becomes the base is called λ. ? The surface of the compact was finished by puff polishing using a gamma alumina abrasive with a particle size of 0.05 μm, and after degreasing with a medieval detergent, electroless copper plating was performed, followed by electrolytic nickel plating. Table 1 shows the results of a test similar to Example 1. [Example 3] κzO. After applying alkali titanate with a chemical composition of 6Txo■ and drying it, heat it at 1300℃.
The alkali titanate was baked for 1 hour to fix the alkali titanate. The surface was polished using gamma alumina abrasive with a particle size of 0.05 μm.
After finishing with puff polishing and degreasing, a copper plating layer was obtained by electroless plating and electrolytic plating according to conventional methods. Table 1 shows the results of a test similar to Example 1. [Example 4] ZrCh9 4. 7%, YzOm5. KaO・15Ti is applied to the surface of a partially stabilized zirconia substrate consisting of 2%
O■・0.5H. After drying, the alkali titanate having a chemical composition of 0 was applied and baked at 1,500°C for 1 hour to fix the alkali titanate. Thereafter, without polishing, after degreasing with a 3% caustic soda solution, a copper plated layer was obtained by electroless plating and electrolytic plating. Table 1 shows the results of a test similar to Example 1.
It is shown in [Comparative Example 1] Surface center line average roughness Ra used in Example 3 = 0.2μ
The surface of the alumina substrate of m was finished by emery polishing and adjusted to have a centerline average roughness Ra of 0.6 μm. Ra=0.2u
Copper plating layers of two types, m and 0.6 μm, were obtained in the same manner as in Example 3. Table 1 shows the results of a test similar to Example 1. Table 1 As seen in Table 1, the bonded product according to the present invention has high adhesion strength and excellent surface smoothness.

Claims (1)

[Claims] 1. A heterojunction comprising an inorganic material as a base material, an alkali titanate solidified on at least the surface thereof, and a metallized film formed thereon by a plating method.