JP4659812B2 - Method of manufacturing ceramic member for bonding, ceramic member for bonding, vacuum switch, and vacuum vessel - Google Patents

Description

  The present invention relates to a member that requires bonding strength, airtightness, and the like, for example, when a metal and ceramic are bonded, a method for manufacturing a bonding ceramic member, a bonding ceramic member, a bonded body, a vacuum switch, and the like It relates to a vacuum vessel.

  Conventionally, a molybdenum-manganese method (Mo-Mn method; Telefunken method) is known as a method for metallizing the surface of a ceramic substrate.

This Mo-Mn method is a metallized paste in which a bonding aid such as Mn powder, Ti powder, glass component (SiO ₂ ), etc. is added to a powder of a high melting point metal such as W or Mo and mixed with an organic binder. This is a method (firing method) in which ink is applied onto a ceramic substrate and baked.

In the prior art described above, the baking temperature of the metallization is a high temperature of 1300 to 1500 ° C., and there is a problem that the firing cost is high, such as the furnace structure, the utility cost, and the heat-resistant consumable material.
Further, there is a problem that the ceramic itself is deformed by baking at a high temperature, resulting in a product that does not satisfy the dimensional accuracy.

  As a countermeasure against this, it is conceivable to bake a metallized ink having a conventional composition at a low temperature of less than 1300 ° C. However, in this case, there is a problem that sufficient bonding strength cannot be obtained, and improvement thereof has been demanded.

  The present invention has been made in order to solve the above-mentioned problems, and its purpose is to provide a method for manufacturing a ceramic member for bonding, which can provide sufficient metallized bonding strength even when fired at a low temperature, a ceramic member for bonding, a bonded body, To provide a vacuum switch and a vacuum vessel.

In the conventional metallization method, the metal is joined to the ceramic mainly by two actions. That is, sintering of refractory metal particles and diffusion and penetration of the glass component into the gaps between the particles.
In this conventional method, when the metallization firing temperature is sufficiently high, the sintering of the high melting point metal proceeds, the strength of the metallization layer itself is improved, and the vitreous material (SiO ₂ etc.) in the ceramic or ink component is high. It penetrates between the melting point metal particles and mechanically improves the bonding strength as an anchoring effect. However, a temperature of 1300 ° C. or higher is necessary for a sufficient reaction to obtain these effects.

On the other hand, in the present invention, Ni can be sintered at a low temperature by reacting with a refractory metal to promote sintering .

The present invention has been obtained based on the above-described findings. Each claim will be described below.
(1) The invention of claim 1 for achieving the above object is to produce a metallized ink as a paste by mixing a mixture containing a refractory metal powder of W and / or Mo and Ni powder with an organic binder. The metallized ink is applied to a ceramic substrate which is a ceramic fired body and baked to form a metallized layer , which is a method for producing a ceramic member for joining , wherein the mixture is a refractory metal of W and / or Mo. A mixture containing 70 to 97% by weight of powder and 1 to 10% by weight of the Ni powder is used, and the ceramic substrate containing SiO ₂ is used. The firing temperature during the baking is 1150 ° C. or higher and 1250 ° C. It is characterized by being made to permeate between the refractory metal particles of the metallized layer with the SiO ₂ in the ceramic substrate at the time of firing. The gist of the manufacturing method of the joining ceramic member is as follows.

In the present invention, since the metallized ink contains Ni, as described above, Ni reacts with the refractory metal and promotes sintering in the metallized layer. Thereby, it is possible to sufficiently sinter even at a low temperature of 1150 to 1250 ° C.

  As a result, it is possible to reduce the firing cost related to the furnace structure, the utility cost, the heat-resistant consumables, and the like as compared with the conventional case. In addition, by baking at a low temperature, the ceramic itself is hardly deformed, and there is a remarkable effect that high dimensional accuracy can be obtained. Furthermore, since sintering can be performed sufficiently even at a low temperature, there is an advantage that high bonding strength can be secured.

Specifically, in the present invention, since 1 to 10% by weight of Ni is contained in the metallized ink, as described above, Ni reacts with the refractory metal and promotes sintering in the metallized layer. This allows a sufficiently sintered even at a low temperature of 1150 to 1250 ° C..

Further, the Si component functions as vitreous SiO ₂ , and when this SiO ₂ penetrates between the high melting point metal particles, the joint strength is mechanically improved as an anchoring effect. In particular, high bonding strength can be obtained even at low temperatures.

(2) The invention according to claim 2 is a bonding ceramic member manufactured by the method for manufacturing a bonding ceramic member according to claim 1.
( 3 ) The invention of claim 3 is a joined body characterized in that a metal member is joined to the joining ceramic member according to claim 2 via the metallized layer.

In the present invention, a joining ceramic member and a metal member are joined by the metallized layer containing Ni or the like described above.
Therefore, as described above, when manufacturing a bonded body in which the ceramic member for bonding and the metal member are bonded, the manufacturing cost is reduced, and the bonded body has high bonding strength and dimensional accuracy. It is done.

( 4 ) The gist of the invention of claim 4 is characterized in that the joining ceramic member according to claim 2 is joined to another joining ceramic member via the metallized layer.

  In the present invention, a joining ceramic member and another joining ceramic member are joined by the above-described metallized layer containing Ni or the like. In joining, it is preferable to apply plating to the joining surface on the metallized layer. Moreover, brazing joining is suitable as a joining method.

  Therefore, as described above, when manufacturing a bonded body in which the ceramic members for bonding are bonded, the manufacturing cost is reduced, and the bonded body can have high bonding strength and dimensional accuracy.

( 5 ) The invention of claim 5 is summarized in a vacuum switch comprising the joined body of claim 3 or 4 .
The present invention is a vacuum switch using the above-described joined body. The vacuum switch is an electric circuit switch using an insulating valve made of ceramic, for example, and is particularly suitable for high voltage and large current switching.

( 6 ) The invention of claim 6 is summarized in a vacuum vessel comprising the joined body of claim 3 or 4 .
The present invention is a vacuum vessel (for example, an insulating valve) used for the above-described vacuum switch, and a vacuum switch (electric circuit switch) can be formed by disposing an electrode or the like in the vacuum vessel.

  As described above in detail, the method for manufacturing a ceramic member for bonding according to the first aspect of the invention allows sufficient sintering of the metallization at a low temperature, so that the furnace structure, utility cost, The firing cost for consumables and the like can be reduced. Moreover, high dimensional accuracy and high bonding strength can be realized.

In addition, since the ceramic member for bonding according to the second aspect of the present invention has a metallized layer that has been sufficiently sintered even at a low temperature, as in the case of the first aspect, the firing cost can be reduced, and high dimensional accuracy and high bonding strength. Have

Furthermore, since the joined body of claim 3 and claim 4 has the joining ceramic member described above, there are advantages such as cost reduction, high joining strength, and high dimensional accuracy, as described above.
In addition, since the vacuum switch of the invention of claim 5 and the vacuum container of the invention of claim 6 have the joined body provided with the above-described joining ceramic member, the cost reduction, high joining strength and There is an advantage of high dimensional accuracy.

Hereinafter, an example (example) of an embodiment of a manufacturing method of a joining ceramic member, a joining ceramic member, a joined object, a vacuum switch, and a vacuum vessel of the present invention is explained with reference to drawings.
Example 1
Here, a joined body of a joining ceramic member and a metal member is taken as an example.

a) As schematically shown in FIG. 1, in this embodiment, a joining ceramic member 1 and a metal member 3 are joined together by a brazing material 5 to form a joined body 7.
Specifically, the bonding ceramic member 1 is obtained by forming a metallized layer 11 on a ceramic base material 9, a plated layer 13 is formed on the metallized layer 11, and the plated layer 13 and the metal member 3 are low-coated. The ceramic member 1 for joining and the metal member 3 are joined and integrated by the material 5.

b) Next, a method for producing a circular test piece as an example of the joined body will be described together with a method for producing a joining ceramic member.
1) First, a powder (for example, 87% by weight) of a metallized ink component shown in Table 1 below was pulverized and mixed and mixed with an organic binder (for example, 13% by weight) such as etose to obtain a metallized ink.

  2) Next, the metallized ink is made of an alumina ceramic substrate 9 (for example, 92% by weight of alumina) (for example, a cylindrical test piece having a thickness of 5 mm, an outer diameter of 30 mm, and an inner diameter of 8.5 mm). About 10-20 micrometers in thickness was apply | coated to the surface.

3) Next, the ceramic base material 9 coated with the metallized ink was placed in a furnace, and 1150 shown in Table 2 below in a forming gas atmosphere of H ₂ / N ₂ (1: 1) with a wetter temperature of 50 ° C. Baked (metallized) at a temperature in the temperature range of 1350 ° C. Thereby, the joining ceramic member 1 provided with the metallized layer 11 on the surface of the ceramic base material 9 was obtained.

4) Next, Ni plating was applied to the surface (metallized surface) of the metallized layer 11 by electrolytic plating to form a plated layer 13. Thereafter, the plating layer 13 was baked (sintered) at a temperature of 830 ° C. in an H ₂ atmosphere.

  5) Next, the ceramic member 1 for bonding and the metal member 3 made of Kovar (Fe—Ni—Co) were brazed.

  Specifically, a silver brazing material (BAg-8) 5 foil is disposed between the plating layer 13 and the metal member 3 (for example, a Kovar disk having a thickness of 1 mm and an outer diameter of φ16 mm), and predetermined brazing. By heating and cooling at a temperature, the joining ceramic member 1 and the metal member 3 were brazed and joined to complete the joined body 7.

That is, as shown in FIG. 2, the manufacturing process of (1) to (5) described above differs in the components of the metallized ink, and as shown in FIG. Seventeen round test pieces (samples) were prepared. Here, sample No. 15 is a sample within the scope of the present invention, and sample Nos . ₂ to 14, 16, and 17 are reference examples including SiO ₂ in the metallized ink . A sample No. 1 of a comparative example in which the composition of the metallized ink was different (that is, Ni was not included) was also prepared.

  Moreover, the quantitative analysis of the component of the metallized layer 11 of the manufactured ceramic member 1 for joining was performed in the case of the manufacturing process mentioned above. Specifically, quantitative analysis was performed using an electron probe microanalyzer (acceleration voltage: 20 kV, spot diameter: 5 μm). The results are shown in Table 2 below.

  In addition, in order to reduce the influence of segregation, the analysis was performed at five locations for each sample, and the average value was obtained. Moreover, the weight% of Si, Al, Ca, Mg is a value in terms of oxide.

However, sample No. 10 uses W instead of Mo.
c) Next, the bonding strength of each sample of the bonded body manufactured by the above manufacturing method was examined.
Specifically, as shown in FIG. 3, the joined body 7 is arranged with the metal member 3 facing downward, and the lower end of the outer periphery of the ceramic base 9 is supported by a cylindrical iron cradle 21. In this state, a cylindrical stainless steel punching rod 25 is disposed in the central through hole 23 of the ceramic base 9 from above, and the punching rod 25 is moved downward in the figure at a load speed of 0.5 mm / min.

  Then, the strength (breaking strength) when the metal member 3 peeled at this time was measured by a load meter (not shown) arranged above the punching rod 25, and this was used as brazing strength. The brazing strength is shown in Table 3 below according to the firing temperature of each sample.

  In the evaluation of Table 3, at 1150 to 1250 ° C., ◯ indicates that there is a peak of 17 MPa or more, Δ indicates that there is a peak of 11 to 17 MPa, and × indicates that there is no peak of 10 MPa or more.

As is apparent from Table 3, the sample No. 15 within the scope of the present invention is suitable because the metallized layer is sufficiently sintered despite the firing at a low temperature, so that a high brazing strength is obtained. . For example, the firing at 1150 ° C. has a strength of 6.9 MPa or more. Further, since sintering at a low temperature is possible, there is an advantage that the cost for sintering can be reduced. Furthermore, since sufficient sintering at a low temperature is possible, there is an effect that the dimensional accuracy of the ceramic member for bonding is higher than that at high temperature.

On the other hand, when the No. 1 sample of the comparative example is fired at a low temperature, the metallized layer does not sinter sufficiently, so that the brazing strength is low, which is not preferable.
(Example 2)
Next, the second embodiment will be described, but the description of the same parts as the first embodiment will be omitted.

Here, a bonded body obtained by bonding ceramic members for bonding to each other will be described as an example.
a) As schematically shown in FIG. 4, in this embodiment, the first bonding ceramic member 31 made of alumina and the second bonding ceramic member 33 made of alumina are bonded by a brazing material 35. Thus, a joined body 37 is formed.

  Specifically, the first bonding ceramic member 31 is obtained by forming a first metallized layer 41 on a first ceramic substrate 39, and the first metallized layer 41 is plated with Ni by first plating. 1 plating layer 43 is formed. On the other hand, the second bonding ceramic member 33 is obtained by forming a second metallized layer 47 on a second ceramic substrate 45, and the second metallized layer 47 is second plated by Ni plating. The plating layer 49 is formed. Then, the first plating layer 43 and the second plating layer 49 are joined together by the brazing material 35, whereby the first joining ceramic member 31 and the second joining ceramic member 33 are joined together. It has become.

b) Next, a method for producing a circular test piece as an example of the joined body will be described together with a method for producing a joining ceramic member.
1) As explained in Example 1 (the contents omitted below are the same as in Example 1), the metallized ink component powders shown in Table 1 above were used to produce metallized ink for each sample. did.

  2) Next, the metallized ink was applied to the surfaces of the first ceramic substrate 39 and the second ceramic substrate 45.

  3) Next, the first and second ceramic base materials 39 and 45 coated with the metallized ink are placed in a furnace and fired at a temperature of 1150 to 1350 ° C. 31 and 33 were obtained.

  4) Next, Ni plating was applied to the surfaces of the first and second metallized layers 41 and 47 to form first and second plated layers 43 and 49.

  5) Next, a silver brazing material 35 was placed between the plated layers 43 and 49 and brazed and joined, and the joined ceramic members 31 and 33 were joined and integrated to complete a joined body 37.

c) Next, the bonding strength of each sample of the bonded body manufactured by the above manufacturing method (test pieces of sample Nos. 1 to 17) was examined by the same method as in Example 1.
The results are shown in Table 4 below.

  In the evaluation of Table 4, at 1150 to 1250 ° C., ◯ indicates that there is a peak of 60 MPa or more, Δ indicates that there is a peak of 40 to 60 MPa, and × indicates that there is no peak of 40 MPa or more.

As is apparent from Table 4, the No. 15 sample within the scope of the present invention is suitable because the metallized layer is sufficiently sintered despite high-temperature firing, and high brazing strength is obtained. is there. Further, since sintering at a low temperature is possible, there is an advantage that the cost for sintering can be reduced. Furthermore, since sintering at a low temperature is possible, there is an effect that the dimensional accuracy of the bonding ceramic member is higher than that at high temperature.

On the other hand, when the No. 1 sample of the comparative example was fired at a low temperature, the metallized layer was not sufficiently sintered, and the brazing strength was low, which is not preferable.
(Example 3)
Next, the third embodiment will be described, but the description of the same parts as the first and second embodiments will be omitted.

The present embodiment is an example in which a joined body made of a joining ceramic member and a metal member as in the first embodiment is used for a vacuum switch.
That is, the vacuum switch according to the present embodiment is a high load switch that incorporates an electrode or the like in a vacuum vessel and is suitable for switching a high voltage and a large current.

  Specifically, as shown in FIG. 5, the vacuum load switch 100 includes an insulating valve 101, first and second end covers 102 and 103 attached by closing the end of the insulating valve 101, A fixed electrode 104 attached to the end lid 102 and projecting into the insulating valve 101 and a movable electrode 105 slidably disposed on the second end lid 103 are provided. A contact 106 is formed by the fixed electrode 104 and the movable electrode 105. Is configured.

  The insulating valve 101 is made of a ceramic fired body of 92% by weight of alumina and has a substantially cylindrical shape with an inner diameter of 80 mm, a thickness of about 5 mm, and a length of 100 mm. Further, the insulating valve 101 has a straight body portion 110 having a constant inner diameter and a convex portion 112 that protrudes inwardly in the middle of the inner peripheral wall 111. Further, a glaze layer 115 is provided on the outer peripheral surface of the insulating valve 101.

  The first and second end lids 102 and 103 are formed of a disk-shaped Kovar (Fe—Ni—Co) plate, and holes 121 and 132 for fixing the fixed electrode 104 and the guide 131 are provided in the respective central portions. It has been. The guide 131 is provided so that the movable shaft 151 of the movable electrode 105 can easily slide.

The fixed electrode 104 is a fixed shaft 141 whose tip is fixed to the hole 121, and an annular electrode 142 whose tip is projected into the insulating valve 101.
The movable electrode 105 has a movable shaft 151 that slides in the guide 131 at the rear end, and an electrode 152 that contacts the electrode 142 on the fixed electrode 104 side. The movable electrode 105 can be opened and closed in a vacuum state by a bellows-shaped metal bellows 153 provided between the movable shaft 151 near the electrode 152 and the second end cover 103.

  The metal bellows 153 is surrounded by a bellows cover 154 to prevent direct contact with metal vapor generated from the electrodes 142 and 152 (that is, the contacts 143 and 155 at the tips) when the current is opened and closed.

  The contact 106 has a structure in which a high melting point tungsten-based sintered metal is used for the contacts 143 and 155 with which the electrodes 142 and 152 are contacted, and is difficult to be welded by a generated vacuum arc.

  An arc shield 161 is disposed around the contact 106. This arc shield 161 is joined to the convex portion 112 of the insulating valve 101 by brazing in order to prevent the above-described metal vapor from adhering to the inner peripheral wall 111 of the insulating valve 101 and lowering the insulation.

  That is, in the high load switch 100 of the present embodiment, the arc shield 161 that is a metal member is provided on the convex portion 112 of the insulating valve 101 that is a ceramic member for bonding, as in the joined body of the first embodiment. Joined by brazing with 162.

  Specifically, as schematically shown in FIG. 6, a metallized layer 171 is formed at the tip of the convex portion 112 of the insulating valve 101 by metallization at a low temperature as shown in the first embodiment. A plated layer 173 is formed on the metallized layer 171 by Ni plating, and the plated layer 173 and the arc shield 161 are joined by brazing with a brazing material 162.

Thereby, the insulation valve 101 (hence, high load switch 100) provided with the arc shield 161 can be manufactured at low cost, and high dimensional accuracy and high joint strength can be realized.
Example 4
Next, Example 4 will be described, but the description of the same parts as Example 3 will be omitted.

The present embodiment is an example in which a joined body made of a joining ceramic member and a metal member is used for a vacuum switch as in the third embodiment, but the structures of the arc shield and the insulating valve are different.
As schematically shown in FIG. 7, the vacuum switch (high load switch) 200 of this embodiment is made of a metal made of oxygen-free copper between the upper insulating valve 201 and the lower insulating valve 203. The connecting member 205 is brazed, and the arc shield 207 is brazed and joined to the distal end side of the connecting member 205.

  In particular, metallized layers 211 and 213 are respectively formed in portions (fixed portions 209) where the upper insulating valve 201 and the lower insulating valve 203 and the connection member 205 are fixed in the same manner as in the first embodiment. Plated layers 215 and 217 are formed on the metallized layers 211 and 213 by Ni plating, respectively.

  The plated layers 215 and 217 and the connecting member 205 are joined by the brazing materials 219 and 221, respectively, so that both the insulating valves 201 and 203 and the connecting member 205 are joined and integrated.

Note that glaze layers 223 and 225 similar to those of the third embodiment are formed on the outer peripheral surfaces of the both insulating valves 201 and 203, respectively.
Also according to this embodiment, the same effects as those of the third embodiment can be obtained.

  In addition, this invention is not limited to the said Example at all, and it cannot be overemphasized that it can implement with a various aspect in the range which does not deviate from the summary of this invention.

It is explanatory drawing which fractures | ruptures and shows the principal part of the conjugate | zygote of Example 1. FIG. 1 is a perspective view showing a joined body of Example 1. FIG. It is explanatory drawing which shows the measuring method of the joint strength of the joined body of Example 1. FIG. It is explanatory drawing which fractures | ruptures and shows the principal part of the conjugate | zygote of Example 2. FIG. It is explanatory drawing which fractures | ruptures and shows the vacuum switch of Example 3. FIG. It is explanatory drawing which fractures | ruptures and shows the principal part of the vacuum switch of Example 3. FIG. It is explanatory drawing which fractures | ruptures and shows the principal part of the vacuum switch of Example 4. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Ceramic member for joining 3 ... Metal member 5, 35, 162, 219, 221 ... Raw material 7, 37 ... Joined body 9 ... Ceramic base material 11 ... Metallized layer 13 ... Plating layer 31 ... 1st ceramic member for joining 33 ... Second bonding ceramic member 39 ... First ceramic substrate 41 ... First metallized layer 45 ... Second ceramic substrate 47 ... Second metallized layer 161, 207 ... Arc shield 101 ... Insulating valve 100 , 200 ... Vacuum switch (high load switch)
171, 211, 213 ... Metallized layer 201 ... Upper insulating valve 203 ... Lower insulating valve 205 ... Connection member

Claims (6)

A mixture containing a refractory metal powder of W and / or Mo and Ni powder is mixed with an organic binder to produce a metallized ink as a paste, and the metallized ink is applied to a ceramic substrate which is a ceramic fired body. A method of manufacturing a ceramic member for bonding, wherein a metallized layer is formed by baking ,
As the mixture, a mixture containing 70 to 97 wt% of the refractory metal powder of W and / or Mo and 1 to 10 wt% of the Ni powder is used,
Using the ceramic substrate containing SiO ₂ ,
A bonding temperature in which baking is performed at 1150 ° C. or more and 1250 ° C. or less, and SiO ₂ in the ceramic base is infiltrated between particles of the refractory metal of the metallized layer during the baking. Of manufacturing ceramic member for use. A bonding ceramic member manufactured by the method for manufacturing a bonding ceramic member according to claim 1 . A bonded body comprising a metal member bonded to the bonding ceramic member according to claim 2 via the metallized layer. The joined ceramic member according to claim 2 , wherein another joining ceramic member is joined via the metallized layer. A vacuum switch comprising the joined body according to claim 3 or 4 . A vacuum vessel comprising the joined body according to claim 3 or 4 .

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