JPH075407B2 - Ceramics metallized composition, metallized method and metallized product - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel composition for metallizing (metallizing) the surface of various ceramics such as oxides, nitrides, borides, silicides or carbides. The present invention relates to a metallization method using the same and a metallized product using them.

Conventionally, M is limited only when it contains a few% or more of SiO ₂ component like Al ₂ O ₃ ceramics which is an oxide ceramic.
Mix O, Mn and frit components in wet hydrogen at 1300-15
The method of metallizing the surface of the baking ceramics in the temperature range of 00 ° C, that is, the Mo-Mn method has been adopted. However, high-purity Al ₂ O ₃ , partially stabilized ZrO ₂ , MgO, BeO, etc.
Oxide ceramics not containing _two components, Si ₃ N ₄ , AlN, TiN
Nitrides etc. ceramics, TiB _2, ZrB _2, BN borides such as _{ceramics, MoSi 2, WSi 2, TaSi} 2 Tang silicide ceramics or SiC, SiC-Si, strongly directed to the carbide ceramics or the like of TiC etc. The metallization technology with strong bond strength has not been established. Therefore, as a pre-treatment at the time of brazing when joining these ceramics and metal, or as a pattern baking treatment of the conductive circuit, Si-containing
Development of a metallization method such as Mo-Mn method for O ₂ Al ₂ O ₃ ceramics has been required.

The present invention has been made in view of such a situation,
A metallized composition comprising a component represented by the following composition formula and inevitable impurities: a · Ag + b · Cu + c · Sn + d · Ti + e · Nb + f · V + g
・ Zr ＋ h ・ F ＋ i ・ Mn ＋ j ・ Be where F is high melting point metal such as W, Ta, Re, Os or high melting point inorganic graphite, diamond, TiN, ZrN, VN, TaN, Ti
Any one of B ₂ and ZrB ₂ or two or more kinds of filling materials, and a, b, c, d, e, f, g, h, i, j are each weight% within the range of the following numerical values. And

13.0 ≦ a ≦ 72.4, 13.6 ≦ b ≦ 44.0, 1.2 ≦ c ≦ 9.0, 3.6 ≦ d ≦ 18.0, 1.6 ≦ e ≦ 11.0, 0.2 ≦ f ≦ 4.5, 0.8 ≦ g ≦ 5.0, h ≦ 40.0, i ≦ 10.0, j ≦ 5.0 where a + b + c + d + e + f + g + h + i + j = 100
Is.

The ceramics to be metallized in the present invention is Al ₂ O
₃ , stabilized and partially stabilized ZrB ₂ , MgO, BeO, mica ceramics, glass ceramics, oxide ceramics such as barium titanate, sialon, nitride ceramics such as Si ₃ N ₄ , AlN, TiN, TiB ₂ , ZrB Examples thereof include boride ceramics such as ₂ and BN, silicide ceramics such as MoSi ₂ , WSi ₂ and TaSi _2, and carbide ceramics such as SiC, SiC-Si and TiC.

Ti in the metallized composition of the present invention is an active element,
When the metallized composition melts or semi-melts on the surface of the target ceramics, it diffuses into the ceramics and Ti
It is effective in forming a strong bond by forming oxides, nitrides, borides, silicides or carbides of the above, and it is necessary to contain 3.6 to 18.0% by weight in order to lower the melting point.

Zr is more active than Ti and is effective in achieving strong bonds even in small amounts. However, if it is contained in too large an amount, it will be melted or semi-melted, and when welding the metallized layer, the phenomenon that the welded area becomes smaller than the applied area, that is, the phenomenon of shrinkage occurs, which causes a problem. .
A range of 8 to 5.0% by weight is effective.

Nb participates in a partial reaction that is less active than Ti and forms a matrix with the above oxides, nitrides, borides, silicides or carbides that Ti and Zr are formed at the interface between the ceramic and the metal layer. Since it has a function of strengthening and promoting the bond with certain Cu, Ag, Sn, etc., it is effective for forming a metallized layer having excellent mechanical strength. However, if a too large amount is blended, the problem of shrinkage tends to occur similarly to Zr, so the range is 1.6 to 11.0% by weight.

V is also one of the active elements, but it is less active than Ti, Zr or Nb. However, since it is easy to form a liquid phase oxide having a low melting point by combining with oxygen, it reacts with O ₂ which is adsorbed and stored in the atmosphere or in the powder before the whole is melted to form a glassy oxide having a low melting point, Since it has a function of protecting the surface of each particle, it helps maintain the activity of Ti, ZR, Nb and the like at high temperatures, and has a function of smoothing the metallized surface. However, if it is contained in too much amount, similarly, shrinkage easily occurs, so the content is made 0.2 to 4.5% by weight.

Sn has a function of dissolving the matrix element relatively early,
Active elements such as Ti, ZR, Nb directly contact the residual O ₂ ,
In order to prevent the particles from being oxidized, they play a role of protecting and coating the surface of the particles at an early stage during temperature rising. 1.
2 to 9.0% by weight is suitable, and if the amount is further increased, the unevenness of the surface of the metallized layer tends to increase, which is not preferable.

Ag is an element having an oxidation resistance, and is an essential element for preventing the oxidation of Ti, ZR, Nb, etc. Further, at the welding temperature of the composition of the present invention of about 900 ° C., Ag is Ti or Since it is difficult to form a hard and brittle intermetallic compound with Zr, it tends to make the metallized layer more flexible.In the case of metallizing ceramics with low thermal expansion coefficient and low strength, the amount of Ag should be increased. Adjust within the range of 13.0 to 72.4% by weight. Increasing the blending amount more than this lowers the bonding strength of the metallized layer to the ceramics, which is disadvantageous.

Cu is a main element that constitutes the mother phase together with Ag, and is an element effective in forming a eutectic with Ti and Zr to lower the melting point. However, if added in a too large amount, the unevenness of the surface of the metallized layer will be increased, and the amount of the phase of the intermetallic compound with fragile Ti and Zr will be increased, which will have an adverse effect.
It is necessary to blend in the range of up to 44.0% by weight.

Be is an element effective for strengthening the bond of the metallized phase to SiC of normal pressure sintering and carbide-based ceramics such as SiC-Si ceramics produced by impregnating Si by reaction sintering. Originally, it is stable and difficult to react with SiC, Ti, Zr, etc. in the temperature range of about 900 ° C, but Be easily forms a eutectic at the same temperature as Si, which is a component of SiC, and has good wettability with SiC. In addition, it is a very effective element because it does not form brittle Be silicide or free carbon. It can be blended in an arbitrary range of 5% by weight or less, but if it is blended more than this, unevenness on the surface of the metallized layer increases, which is not preferable.

The F component is W, Ta, Re, Os of refractory metals, graphite, diamond, TiN, ZrN, TaN, VN, TiB ₂ , ZrB _{2 of} refractory inorganic substances. All of these components have a melting temperature of about 900 ° C. of the composition of the present invention, and Ag, Cu, Sn, Ti, Nb, V, Zr
Or it will not dissolve in alloys such as Be,
It is a filling material having only wettability. For that reason,
An arbitrary range up to 40% by weight for adjusting or imparting various properties of the lower component, such as thermal expansion coefficient, electric conductivity, thermoelectric conductivity, hardness, heat resistance, and oxidation resistance. Can be blended with.

Finally, Mn is an element effective for improving the wettability between the above-mentioned various filling material components and the melting component and improving the strength of the metallized layer itself. If added in a too large amount, the oxidation resistance will be impaired, so an arbitrary amount of 10.0% by weight or less is set.

The method of the present invention of depositing the metallized composition of the present invention on various ceramics is 150 mesh or less of the composition as described above, preferably 325 mesh or less, and 500 mesh or less of the alloy or each metal for depositing a finer pattern. In order to impart appropriate fluidity and adhesion to the surface of the ceramics to the mixed fine powder of (1), a vehicle such as ethyl cellulose or acrylic is mixed as a binder to form a paste. To apply the paste to the surface of the ceramics, screen printing, spatula coating, brush coating, etc. are carried out, and after drying, it is dried in a non-oxidizing atmosphere such as Ar, H ₂ , N ₂ or vacuum 880 ~ In this method, the temperature is kept at 940 ° C. for 5 to 20 minutes to melt or semi-melt it to react the surface of the ceramic with the metal layer to weld the metallized layer.

The ceramic product whose surface is metallized by the above-mentioned method of the present invention can be directly brazed as it is, or, further, on its metallized surface, Co, Ag, Ni
By using a product in which the metal is laminated, Ti, Zr, Nb, V, etc. in the metallized layer are not oxidized on the surface due to a trace amount of residual O ₂ gas component in the brazing air flow during brazing. Can be formed to prevent the flowability of a brazing material such as silver brazing from being impeded. Therefore, Kovar, 42% Ni-Fe alloy, W,
Mo, Cu, Cu alloy, Ag, Al, Al alloy, carbon steel, special steel, cast iron,
It can be brazed to various practical alloys such as stainless steel, Inconel and Incoloy. At this time, when the coefficient of thermal expansion of the ceramic and the metal to be joined is remarkably different, a relatively soft metal such as copper or silver is brazed between the two to braze it. It is also possible to achieve stable and firm brazing by absorbing the difference in shrinkage strain generated in the cooling process.

By applying the metallizing composition and the metallizing method of the present invention, it has become possible to produce a ceramics product having a strong metallizing surface with a strong bonding force of the present invention, as a result, conventionally composed of a ceramic alone, or simply For various products that were mechanically combined, it was possible to combine the most rational materials from the viewpoint of special production and economical viewpoint. Also, as a single metallized ceramic product, it can be used for a new application utilizing the characteristics such as thermal conductivity and electrical conductivity. Therefore, it has become possible to expand the use of ceramics to various uses such as automobile parts, electronic parts, other industrial machines, and wear-resistant plates.

Examples of the present invention will be described below.

Example 1. As the metallized composition of the present invention, the composition shown in Table 1 as the composition shown in Table 1 was compounded with fine powder of each metal element of 325 mesh or less, and an ethylcellulose-based vehicle was prepared. While adjusting, after mixing in an appropriate amount, to form a paste, after the paste is screen-printed on the ceramics described in the table and dried, in the atmosphere described in the table,
After holding for 10 minutes in the temperature range of 910 ~ 930 ℃ to weld,
Co, Ag, and Ni are laminated in this order and plated, and if necessary, a copper plate with a thickness of 0.3 mm is used as an intermediate cushioning material with a diameter of 8 mm.
The end face of each of the cylindrical Kovar pieces of No. 2 was brazed with 72% eutectic silver brazing in an H ₂ stream at 840 ° C. for 5 minutes to prepare a shear strength test piece. The test results showed good practical values as shown in the table.

Example 2. As a metallized composition of the present invention, Ag 19.9 wt%, Cu24.
7wt%, Sn5.9wt%, Ti12.8wt%, Nb6.7wt%, V2.5
% Of Zr, 3.4% by weight of Zr, 30.0% by weight of W, 5.0% by weight of Mn was added as a fine powder of 500 mesh or less in the above-mentioned Example.
Using the same method as in 1, make a paste and screen 99.5% high-purity Al ₂ O ₃ , AlN, Si ₃ N _{4 with} a thickness of about 0.64 mm and a line with a width of 0.1 mm with a gap of 0.2 mm. It can be printed and welded at 905 to 915 ° C for 7 minutes to form a fine metallized pattern with a width of 0.1 mm and a thickness of 0.020 mm. In addition, a metallization pattern of 2 mm opening was formed by the same method, Ni plating was applied, and then a Cu wire with a thickness of 0.3 mm was soldered, and the pull-out strength was measured. The value that can be endured is shown.

Example 3. As a metallized composition of the present invention, Ag 21.4 wt%, Cu26.
6wt%, Sn4.1wt%, Ti9.0wt%, Nb4.7wt%, V1.8wt%, Zr2.4wt%, Mn5.0wt%, and diamond,
25 various filler materials such as graphite, TiN, ZrN, TaN, VN, TiB ₂ and ZrB ₂
% By weight, blended with a fine powder of 325 mesh or less, and made into a paste by the same method as in Example 1 or 2 above,
SiO ₂ containing 94% Al ₂ O ₃ ceramics and AlN ceramics 0.
A pattern with a line width of 2 mm and a length of 25 mm is printed on a plate with a thickness of 64 mm, kept at 930 ° C for 10 minutes in an H ₂ stream to form a metallized layer with a thickness of 0.035 mm, and then polished with a diamond grindstone. It was confirmed that the metallized layer did not easily fall off during polishing.

As described above, according to the present invention, it is possible to perform metallization having excellent bonding strength with respect to various ceramics, and the product of the present invention can be used in various fields.

Claims (3)

[Claims] 1. A ceramic metallized composition comprising a component represented by the following composition formula and unavoidable impurities: a.Ag + b.Cu + c.Sn + d.Ti + e.Nb + f.V + g.Zr + h.F + i.Mn + j・ Be where F is a refractory metal such as W, Ta, Re, Os or refractory inorganic graphite, diamond, TiN, ZrN, V
N, TaN, TiB ₂ or ZrB _{2 which} is one or more filler materials, and is a, b, c, d, e, f, g, h, i, j.
Is the weight% within the range of the following numerical values. 13.0 ≦ a ≦ 72.4, 13.6 ≦ b ≦ 44.0, 1.2 ≦ c ≦ 9.0, 3.6 ≦ d ≦ 18.0, 1.6 ≦ e ≦ 11.0, 0.2 ≦ f ≦ 4.5, 0.8 ≦ g ≦ 5.0, h ≦ 40.0, i ≦ 10.0, j ≦ 5.0, where a + b + c + d + e + f + g + h + i + j = 100. 2. A powder of an alloy or a mixed powder of a component of a metallizing composition for ceramics, which is composed of a component represented by the following composition formula and unavoidable impurities, is applied to the surface of the ceramic to obtain a non-oxidizing property. A metallizing method characterized by metallizing the surface of ceramics by melting or semi-melting in an atmosphere. a ・ Ag + b ・ Cu + c ・ Sn + d ・ Ti + e ・ Nb + f ・ V + g ・ Zr + h ・ F + i ・ Mn + j ・ Be where F is a refractory metal such as W, Ta, Re, Os or refractory inorganic graphite, diamond, TiN , ZrN, V
N, TaN, TiB ₂ or ZrB _{2 which} is one or more filler materials, and is a, b, c, d, e, f, g, h, i, j.
Is the weight% within the range of the following numerical values. 13.0 ≦ a ≦ 72.4, 13.6 ≦ b ≦ 44.0, 1.2 ≦ c ≦ 9.0, 3.6 ≦ d ≦ 18.0, 1.6 ≦ e ≦ 11.0, 0.2 ≦ f ≦ 4.5, 0.8 ≦ g ≦ 5.0, h ≦ 40.0, i ≦ 10.0, j ≦ 5.0, where a + b + c + d + e + f + g + h + i + j = 100. 3. A powder of an alloy or a mixed powder of a component of a metallizing composition for ceramics, which is composed of a component represented by the following composition formula and unavoidable impurities, is applied to the surface of the ceramic to make it non-oxidizing. A metallized product characterized by being melted or semi-melted in an atmosphere to have its surface metallized, or further, Co, Ag, and Ni are laminated and plated. a ・ Ag + b ・ Cu + c ・ Sn + d ・ Ti + e ・ Nb + f ・ V + g ・ Zr + h ・ F + i ・ Mn + j ・ Be where F is a refractory metal such as W, Ta, Re, Os or refractory inorganic graphite, diamond, TiN , ZrN, V
N, TaN, TiB ₂ or ZrB _{2 which} is one or more filler materials, and is a, b, c, d, e, f, g, h, i, j.
Is the weight% within the range of the following numerical values. 13.0 ≦ a ≦ 72.4, 13.6 ≦ b ≦ 44.0, 1.2 ≦ c ≦ 9.0, 3.6 ≦ d ≦ 18.0, 1.6 ≦ e ≦ 11.0, 0.2 ≦ f ≦ 4.5, 0.8 ≦ g ≦ 5.0, h ≦ 40.0, i ≦ 10.0, j ≦ 5.0, where a + b + c + d + e + f + g + h + i + j = 100.