JPS63184207A - Composite wire for sealing glass and manufacture thereof - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a composite wire material for glass sealing and a method for manufacturing the same. The present invention relates to a composite wire for glass sealing and a method for manufacturing the same.

[Prior Art] Generally, a FeNi alloy, a FeCr alloy, or a FeNiCr alloy is used as a lead wire material for glass sealing. This type of alloy has a thermal expansion coefficient similar to that of glass, which is an insulating material, and also produces surface oxides that bond with glass. A suitable alloy is selected from

Furthermore, glass sealed parts require airtight sealing, and in order to achieve airtight sealing between the glass and the lead wire,
The surface of the glass sealing alloy is treated to form an oxide film in a temperature range that reaches .

In addition, composite wire rods with Cu in their cores are used to improve functionality and make them more compact. One of the manufacturing methods is to fit a glass sealing alloy tubular material and a Cu rod material. They are combined, jointly drawn, and heat treated for diffusion bonding during the drawing process. As another manufacturing method, a cylindrical glass sealing alloy material and a columnar Cu material are fitted together and then extruded under high-temperature heating conditions.

As explained above, in the highly conductive composite wire for glass sealing, Cu used for the core has excellent conductivity, but on the other hand, it has a high thermal expansion coefficient that is 2 to 4 times that of the glass sealing alloy. . This difference in thermal expansion coefficient results in a difference in thermal contraction after the glass sealing alloy is heated to a high temperature to form an oxide film on its surface, and stress is generated in a state where the interface between the outer skin and the core is likely to separate when cooled. When using a composite wire for glass sealing, the composite lead wire may leak at the interface after glass sealing.

This composite wire material for glass sealing is required to have not only high conductivity but also leak resistance.Although high conductivity is designed in advance by the combination ratio of the outer skin and core, good products must be selected by inspection for leak resistance. First, if a defective inspection occurs regarding leak resistance, it has a large impact on the manufacturing process, such as loss of labor, time, and materials. Moreover, the cost is high.

If the leak resistance of the composite wire for glass sealing is unreliable, there is a method of melting the ends of the composite wire for glass sealing to form an alloy. There are problems such as a decrease in yield due to shape defects, and improving leak resistance is a major industrial issue.

In addition, for interfacial leakage of composite lead wire for glass sealing,
There are various causes. If wire rods are manufactured with foreign substances such as organic or inorganic substances mixed into the interface, bonding defects at the interface will occur.
The occurrence of defects due to this cause can be completely eliminated by controlling the manufacturing process.

However, even if the manufacturing process is controlled, some products may have poor leak resistance.This is due to the high temperature heating required for surface treatment of the glass sealing alloy during the manufacturing process. There is a problem in the formation of a low melting point alloy due to the difference in thermal expansion coefficient between the alloy and the core Cu, and the reaction between the impurity composition of the outer glass sealing alloy and the core Cu.

[Problems to be Solved by the Invention] The present invention is directed to the above-described conventional glass sealing composite wire material and its manufacturing method, by lowering the temperature during surface treatment of the glass sealing alloy, and by reducing the temperature of the glass sealing alloy. Is it conceivable to strictly limit the composition, or are these things already widely used as glass sealing alloys?
In view of the large amount of research and development costs required, as well as the large costs associated with changing the manufacturing process, the present inventor conducted independent research and after repeated consideration, developed a structure with a relatively simple structure and manufacturing process. We have developed a composite wire for glass sealing that requires few changes, has high conductivity, and has excellent leak resistance, and a method for manufacturing the same.

[Means for Solving the Problems] The composite wire for glass sealing and the manufacturing method thereof according to the present invention are as follows: (1) The glass sealing alloy, FeNi alloy, FeCr alloy, or FeNiCr alloy, is used as the outer skin, and Cu is used as the core. In the highly conductive composite wire, N is added to the interface between the outer skin and the core.
The first invention is a composite wire for glass sealing characterized by having an i-layer interposed therebetween; Before conducting repeated drawing and annealing to reduce the diameter of the conductive composite wire, a cylindrical material of the glass sealing alloy for the outer skin, a columnar material of Cu for the core, and a Ni
By combining thin plates of or thin cylinders of Ni in a laminated manner,
This invention consists of two inventions, the second invention being a method for manufacturing a composite wire for glass sealing, which is characterized by heating to a temperature of 800 to 1050°C and performing hydrostatic extrusion.

The composite wire for glass sealing and the manufacturing method thereof according to the present invention will be explained in detail below.

That is, it is a composite wire material for glass sealing in which a thin layer of pure Nl is interposed between a glass sealing alloy of FeNi alloy, FeCr alloy, or FeNiCr alloy as the outer skin and Cu as the core.

The thermal expansion coefficient of pure Ni is 12~l 3 x 10-'/d
eg, an FeNi alloy as an alloy for glass sealing of the outer skin,
Since the coefficient of thermal expansion is intermediate between the FeCr alloy or FeNiCr alloy and the core Cu, the tensile force that acts on the interface due to thermal contraction during the thermal history (heat treatment) of the glass sealing alloy of the outer skin is By interposing the Ni layer, the FeNi of the glass sealing alloy of the outer shell is concentrated at the boundary between the glass sealing alloy of the wire and the Cu of the core.
It is dispersed at two locations: the boundary between the alloy, PeCr alloy, or FeNiCr alloy and the pure Nl thin layer, and the boundary between the Ni thin layer and the core Cu, thereby significantly improving the leak resistance of the composite wire material for sealing the outer glass with glass.

Generally, there are many unpredictable phenomena that occur regarding the properties of alloy products of metals, but in the composite wire for glass sealing according to the present invention, the main component of the alloy for glass sealing of the outer cover is It is clear from a metallurgical point of view that it must be interposed with a certain element in a high purity state.

In addition, FeNi alloy, Fe
Regarding the metallurgical reaction between impurities in Cr alloys and FeNiCr alloys and Cu in the core, impurities in various glass sealing alloys are controlled, but by interposing a pure Ni0 layer, pure N1
can be used instead of impurity control.

In this way, the combination of metal materials is strictly selected, and the pure Ni thin layer is coated with FeNi alloy, FeCr alloy, and
By interposing a pure Ni thin layer between the glass sealing alloy (FeNiCr alloy) and the Cu core, the number of bonding surfaces increases to two, which increases the reliability of leak resistance (on the other hand, the number of dangerous parts increases). .

Therefore, the reliability of the above-mentioned leak resistance was ensured by using the hot isostatic extrusion method, which is fully applicable to joining such dissimilar metals.

It is generally known that placing a clean interface under high temperature and pressure is effective for joining dissimilar metals, but since extrusion involves heavy processing, a new surface is generated at the interface, and dissimilar metals are bonded together. Since the composite wire for glass sealing can be easily joined, the extrusion temperature was also selected for the composite wire for glass sealing, and it was achieved that the composite wire for glass sealing could be manufactured by the hydrostatic extrusion method.

That is, FeNi alloy, FeC, which is the alloy for glass sealing of the outer skin.
A cylindrical material made of R alloy or FeNiCr alloy, a pure Ni thin plate, and a highly conductive Cu columnar material at the core are fitted concentrically, and the entire surface except the extrusion die side is made into a liquid-tight seal structure, and extrusion is performed. This is a method in which the material is heated to a temperature of 800 to 1050° C. and isostatically extruded prior to heating.

The upper limit of this heating temperature is 1050°C.
If extruded at a temperature exceeding 1050°C, the core Cu will be extruded first, making it impossible to extrude a composite wire for glass sealing that maintains the designed composite ratio. The upper limit of the temperature at which the composite ratio can be extruded as designed is 1050°C. In addition, the lower limit of the heating temperature of 800°C is determined by the need to reduce the deformation resistance of the glass sealing alloy and process it at a high extrusion ratio. Because the wear alloy has high deformation resistance, the extrusion ratio is 6 or more, and the low temperature makes it difficult to bond dissimilar metals, the lower limit of heating temperature is 800°C to obtain a sound interface bond. do.

Next, the composite wire for glass sealing and the manufacturing method thereof according to the present invention will be specifically explained with reference to the drawings.

As shown in Fig. 1, the cylindrical Cu core l (outer diameter 5
A thin pure Ni intermediate layer 2 (thickness O, l mmt) is formed in a cylindrical shape on the radially outer side of the thin pure Ni intermediate layer 2 (7 mmφ), and a FeNi outer skin is formed on the radially outer side of this thin pure Ni intermediate layer 2.
An alloy glass sealing alloy 3 (outer diameter 143II1 m, inner diameter 57.5 mmφ) was formed into a cylindrical shape.

The length of the composite material consisting of the core Cut, the thin pure Ni intermediate layer 2, and the FeNi alloy 3 of the glass sealing alloy of the outer skin is 500 mm, and the core part Cul, the thin pure Ni intermediate layer 2
The mutual relationship between the glass sealing alloy 3 and the FeNi alloy of the outer skin was 0.1 to 0.2 mm.

In FIG. 1, reference numeral 4 denotes a dummy block (made of cupronickel), and an end portion of an FeNi alloy 3, which is an alloy for sealing the glass of the outer skin, is welded and fixed to this dummy block 4.

As illustrated in FIG.
Intervening air between each layer of the intermediate layer 2 and the core portion 3 is removed, and 1
It was degassed to about 0-'Torr and then sealed. In FIG. 1, 6 is a die, 7 is a container, 8 is a seal piston, and 9 is a pressure medium.

Thus, the degassed and sealed composite material was heated to a temperature of 950°C and extruded into a 46 mm diameter bar by hot isostatic extrusion, and then cold drawing and annealing were repeated to obtain a diameter of 3.0 mm diameter. It was processed into a wire rod.

The obtained wire rod was heated to a temperature of 1020° C. in accordance with the temperature conditions for hermetically sealing the glass and the lead wire.

A line analysis of component elements was conducted on a cross section of a heat-treated composite wire material for glass sealing according to the present invention (EP
MA).

As shown in Fig. 2(a), the results show that C of Mn and St
However, for the composite wire for glass sealing without a thin pure Ni intermediate layer, diffusion of Mn and Si into Cu was observed as shown in FIG. 2(b).

In addition, as shown in Table 1, when intermetallic compounds of CuMn and Cu5i are formed, the melting point decreases depending on the composition of the two, and they melt at the temperature when the glass and lead wire are hermetically sealed, leading to leakage. There is.

Table 1 [Effects of the Invention] As explained above, since the composite wire material for glass sealing and the manufacturing method thereof according to the present invention have the above-described configuration, it is possible to avoid heat effects during hermetically sealing the glass and the lead wire. , it has the effects of having high conductivity and excellent leak resistance.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram of the structure and hydrostatic extrusion mechanism of the composite wire for glass sealing according to the present invention, and FIG. 2 is a diagram showing the results of EPMA analysis of various composite wires for glass sealing that have been subjected to heat treatment. ■... Core, 2... Middle layer, 3... Outer skin, 4... Dummy block, 5... Degassing pipe, 6... Dice, 7... Container, 8... Seal piston, 9... Pressure medium. .

Claims (2)

[Claims] (1) In a highly conductive composite wire with an outer skin made of FeNi alloy, FeCr alloy, or FeNiCr alloy, which is an alloy for glass sealing, and a Cu core, N is added to the interface between the outer skin and the core.
A composite wire material for glass sealing characterized by having an i-layer interposed therebetween. (2) In a highly conductive composite wire having an outer shell made of FeNi alloy, FeCr alloy, or FeNiCr alloy, which is an alloy for glass sealing, and a core made of Cu, the outer shell is The glass sealing alloy cylindrical material, the core Cu columnar material, and the Ni
By combining thin plates of or thin cylinders of Ni in a laminated manner,
A method for producing a composite wire for glass sealing, which comprises heating to a temperature of 800 to 1050°C and performing hydrostatic extrusion.