WO1986001446A1

WO1986001446A1 - Ceramic adherent alloy

Info

Publication number: WO1986001446A1
Application number: PCT/JP1985/000443
Authority: WO
Inventors: Seiichiro Miyata
Original assignee: Miyata Giken Co., Ltd.
Priority date: 1984-08-31
Filing date: 1985-08-07
Publication date: 1986-03-13

Abstract

Ceramic-adherent alloy capable of melt adhering to ceramic of an oxide, carbide, nitride, boride or a mixture thereof at a contact angle of 0o, which fundamentally comprises Si and one or more elements selected from among Ti group elements, V group elements, Y, and Ca. The ratio of Si to total of Ti group and V group elements, Y, and Ca (by weight) is (5-95): (100 - amount of Si), with the sum of Si and Ti group and V group elements, Y, and Ca being at least 60% by weight based on the total weight of the alloy. This alloy can be utilized for metallizing ceramics, cementing metal and ceramics or cementing ceramics to each other, or as metal for binding phase of cermet.

Description

Description Ceramic fusion alloy

Technical field

The present invention relates to a composition of an alloy which is completely wetted and fused to ceramics, for example, oxides, carbides, nitrides, and borides at a contact angle of zero degree.

Background Technology ·

In order for ceramic materials to become widely used in the future, it will be necessary to mix them well with metallic materials and other ceramics. In particular, joining with metals is an important theme in terms of eliminating the brittleness of ceramics. For these reasons, research on composites of ceramics and metals has been very active, and several methods have already been published.

The basic method for joining is to first metallize the ceramic and then use appropriate brazing material to join it.

Therefore, metallization of ceramics is an essential and important issue for this theme. The method underlying the prior art of metallizing ceramics is the active metal method. In this method, an alloy of an active metal such as Ti, Zr, V, Nb, Ta, Cr, or Mn is melted in an atmosphere furnace and fused to the ceramic. Is added for the purpose of lowering the melting point of this alloy, and Fe, Ni, Co, Cu, Ag, AI, Sn, In, and Pb are used as this element.

However, this conventional alloy has the disadvantage that the combination of Fe, Ni, Co, Cu. Ag, and AI has a contact angle of approximately 20-70 degrees when fused in a ceramic and does not wet completely. . In addition, in combination with low melting elements such as Sn, In, and Pb, this alloy certainly wets completely and fuses, but because of its low melting point and high quality, its fusion strength is extremely low. There is a disadvantage that it cannot be applied to practical strength members at all.

If the fused metal is not completely wetted by the ceramic, the droplet will fuse in a raised state In addition, it cannot be completely adhered to the metal on the other side during the subsequent brazing.

Therefore, the surface must be polished smoothly. Alternatively, it is necessary to perform an operation of fusing under pressure.

In addition, if the wetting is not complete, a problem occurs in the fusion strength.

Therefore, the present invention has been made in view of such problems, and an object of the present invention is comparable to a conventional active metal and an alloy of a combination of Fe, Ni, Co, Cu and Ag. The purpose of the present invention is to provide an alloy having a high melting point and a high strength, which is completely wetted by ceramics (each contact is zero degree).

Disclosure of the invention

That is, the alloy of the present invention has the following composition.

1. A ceramic fused alloy comprising one or more elements selected from the group consisting of Ti group element, group V element, Y and Ca, and Si as an essential component.

2. The composition ratio (weight ratio) of Ti group element, V group element, Y and Ca and Si is

S i: (sum of T i group, V group elements, Y and C a)

(5 to 95): (100—Si amount)

2. The ceramic melt according to claim 1, wherein the sum of Si and Ti group, group V elements, Y and Ca is at least 60% (% by weight) or more of the whole. Wear alloy. With the above composition, the alloy of the present invention is completely wetted and fused to an oxide ceramic, a carbide ceramic, a nitride ceramic, a boron ceramic, or a mixed ceramic thereof at a contact angle of zero.

Incidentally, the contact angle of conventional active metal brazing material is 20-70 degrees, and the contact angle of Si alone is about 30 degrees (for silicon nitride, silicon carbide, and zirconia).

Combination of Si and the above-mentioned elements makes complete wetting possible.

When the alloy of the present invention deviates from the above composition, complete wetting cannot be obtained.

However, at least within this range, complete wetting is obtained. Therefore, the whole

Elements up to less than 40% can be replaced by elements other than the above. For example, Fe. Ni, Co. Mn, Cr., For the purpose of lowering the melting point or changing physical, chemical, mechanical properties, etc.

Cu, Ag. AI, Sn, etc. can be added. The most preferred element in the T i and V groups is “S.V.Nb.T a, especially T i .V.

Thus, according to the alloy of the present invention, the coating fused to the ceramic becomes a smooth coating having a uniform thickness, and can be closely adhered to the brazing surface of the counterpart metal without forming a gap.

In addition, it can sufficiently penetrate into very narrow gaps and pores, and can be applied to the production of sacrifices by the infiltration method.

In addition, when used for joining ceramics and ceramics, joining can be achieved simply by sandwiching and melting this alloy at the joint. There is no need to apply pressure from above.

The alloy of the present invention also has the following advantages.

Generally, a brittle intermediate layer is formed at the boundary between the ceramic and the fusion alloy. However, in the conventional base metal, this layer is deep, and there are some bases which reach 100 degrees.

In the alloy of the present invention, the generation of the diffusion layer is small and is at most several microns to several tens microns. This favors the strength and toughness of the joint.

BEST MODE FOR CARRYING OUT THE INVENTION

In order to explain the present invention in more detail, the present invention will be described below with reference to examples.

Example 1 (Wetability test 1)

Oxide (zirconia), carbide (silicon carbide), nitride (silicon nitride, sialon), borides, and alloys of the following various compositions are placed on these mixed ceramics, and heated and melted under reduced pressure ( After cooling, the contact angles were measured.

Table 1 shows the measurement results for oxides (zirconia), Table 2 shows the results for carbides (silicon carbide), and Table 3 shows the results for nitrides (silicon nitride, sialon). , And the results for these mixed ceramics are shown in Table 4.

ro ro

J J1 CO>-'<> ro O CD CO an / (J) Οϊ n 0) (/ (I) ω ω CD ω CD I. I. I. I. I. I. I. I.

1 1 1 1 1 1 1 1 1 1 1 1 1 1O GO CO CO C ro ro IV) CT)

〇〇〇〇〇〇〇

1

1 1 I H H CH

〇〇〇〇〇

1 1 1 1 1 π 1 1 <J J H

O) Z N 1 -i ~ i-}

O 〇〇〇〇 O "~ i 1 1 1 1

1 1 〇 0J c GO P cr <<2 O 〇〇 o

X cr σ <<<

One

1 1

_i u ro ro 'CD

00 00 0D 00 CP n exposure cn cn CJi O

O 〇〇 O 〇〇〇 5

J®

o 〇 ο oo O o 〇〇 O o 〇〇〇 '〇 t

9 S i -10 V 1480 0 0 S i -30V 1480 0 1 S i -40 (Fe-50V) 1480 0.2 S i -60 (Fe-50V) 1480.03 S i -1 OT i 1450 4 S i -30T i 1450 "0 5 S i -50 T i 1450 0 6 S i -95 T i 1550 0 7 S i -3 OZ r 1480 0 8 S i -45 Y 1480 0 Table 3 , Sialon)

Table 4 (Z “B ₂ , mixed composition”) Ceramic composition, gold composition Heating temperature () Contact angle (degree)

Z r B ₂ S-13T i 1500 0

s -20T i 1500 0 s -50T i. 1500 0 s -95T i 1350 0 s -20V 1480 0 s -30V 1480 0 s 12Y 1480 0 s — 20Z r 1480-0 s -30N b 1450 0 s-30 T a 1450 0,

A l ₂ 〇 ₃ s -20T i 1500 '0

s -50T i 1500 0

30% Ζ “s -20V 148 Ο. '0

-s -20Z r 1480 '0

s -12 Y 1480 0

AI h 0 ₃ s-20 T i 1500 0

+ s -'SOT i 1500 0

T i B ₂ s -3 ON b 1450 0

As can be seen from the results of Tables I to 4, the alloys of the present invention are completely fused only by keeping them at a temperature lower than the firing temperature of each ceramic for several minutes.

Therefore, there is no adverse effect on the ceramic material.

Example 2 (Wettability test 2)

Using the same oxide, carbide, and nitride ceramic as the test of Example 1, the wettability of the multi-component composition was tested.

The base alloy used had a composition of 50T i -50S i, and the contact angles of the alloys containing 20% and 40% of AI, Cu. Ag, Fe, Ni, Fe—Mn, respectively, were added. It was measured.

With the addition of 20%, all compositions exhibited complete wetting.

Those with 40% addition did not necessarily lead to complete wetting.

Example 3 (joining with metal)

Place a small grain of Si-50Ti alloy on a partially stabilized zirconia plate of 10X10X10, heat it to 1450 for 5 minutes under reduced pressure, and complete A fused metallizing layer was formed.

Next, an attempt was made to join a SUS304 austenitic stainless steel chip (10X10x5m) to the metallized surface prepared as described above.

An Ni-B-Si-based amorphous brazing foil was sandwiched between the stainless steel tip and the metallized surface, and heated and fused at 1000 ^ for 1 minute in a vacuum atmosphere to observe the state of fusion. In the case of using the alloy of the present invention, the stainless steel and the zirconia ceramic were firmly joined, and no fine defects were observed.

On the other hand, for comparison, a conventional alloy (Ti-50Cu) metallized and subjected to the same treatment had cracks at the boundary between ceramic and metallized.

. It was confirmed that the welding power of the alloy of the present invention was much higher than that of the conventional alloy. Example 4 (Application to Metallizing) ''

10x1 Ox A mixture of small particles and massive Fe-Nb is placed on a silicon carbide plate at a pressure of 3 pressure to form Si-30 (FeN). r And heated to 1480¾ for 5 minutes to fuse.

The fusion layer spread evenly and evenly over the entire surface at a contact angle of zero degree, and partially wet the side surfaces.

Example 5 (joining of ceramics)

100% S! C and 50% S i C, 50% S i ₃ between two types of sintered compact chips, a slurry mixed powder of S i -50 (Fe-N b) composition to about 1 mm thickness The coating was performed, and heating was performed under reduced pressure (5x1 O '^ xTorr) for 1480 for 5 minutes to perform joining.

The two ceramic pieces were completely wetted and strongly bonded by the Si-50 (Fe-Nb) alloy.

Example 6 (Cermet bonding layer)

Si-30 (Ni-Nb) alloy on porous SiC sintered body and porous zirconia sintered body (each 10X1Ox2) prepared by reaction sintering method And heated to 1480ΐ for 5 minutes under reduced pressure of 5x Ί T * T or “, and the pores of each ceramic were completely impregnated.

Industrial applicability

As described above, the ceramic fusion alloy according to the present invention can be used as an alloy for metallizing ceramics, as an alloy for a binder when forming a cermet of ceramic and metal, or by bonding ceramic and ceramic. It is useful as a brazing filler metal when welding, especially as a metallizing or mouthpiece when joining ceramic and metal.

Claims

The scope of the claims

1. A ceramic fusion alloy comprising one or more elements selected from the group consisting of Ti group elements, group V elements, 丫, and Ca, and S I as essential components.

2. The component ratio (weight ratio) of Ti and V elements, Y and Ca and Si is

S i: (Ti group, V element, Y and C a)

(5 to 95): (100-S i amount)

2. The ceramic melt according to claim 1, wherein the sum total of Si, Ti and Group V elements, Y and Ca is at least 60% (by weight 96) or more. Arrival