JP2005081371A - Electrode material and its production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrode material high in toughness and electric conductivity, suppressed in alloying with the material to be welded and improved in the number of spotting on welding (welding resistance), and to provide its production method. <P>SOLUTION: An alloy stock expressed by general formula: Cu<SB>bal.</SB>X<SB>a</SB>(wherein, X is at least one kind of element selected from Cr, Zr, Fe, P and Ag; a is ≤1.5% by mass%; and the balance Cu with inevitable impurities) is extruded at a heating temperature of 300 to 500°C by applying shear deformation thereto in such a manner that the extrusion direction is changed to the side direction of <180° in an internal angle on the way. Thus, the electrode material with a structure in which fine grains with a mean grain size of ≤50 nm are precipitated into the structure composed of equi-axed crystal grains with a mean crystal grain size of ≤3 μm is obtained. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an electrode material used when welding a material to be welded made of aluminum, magnesium, iron and alloys thereof, and further, a metal plating material thereof, and a manufacturing method thereof.

Conventionally, as this type of electrode material, a material made of chromium copper (Cu—Cr) and alumina-dispersed copper (Al ₂ O ₃ -dispersed copper) has been used.

  For example, Patent Document 1 has a drawback in that a welding electrode material made of a Cr—Cu alloy is manufactured at a high temperature of about 1000 ° C., so that crystal grains in the alloy become coarse and wear resistance and heat resistance become low. However, it is described that by adding 0.01 to 0.2% by weight of boron to this Cr—Cu alloy, crystal grains of the alloy are refined to improve heat resistance and high temperature hardness.

  In Patent Document 2, the alloy composition of the welding electrode material is 0.4 to 1.0% by weight of Cr, 0.05 to 0.2% by weight of Sn, and the balance is made of copper containing inevitable impurities. It is described that the life of the tip is improved by reducing deformation and wear of the tip.

  In Patent Document 3, the composition of the welding electrode material is an alloy composition composed of 0.05 to 1% by weight of Zr, 3 to 20% by weight of Cr, and the remaining Cu, thereby increasing the electrical conductivity and improving the wear resistance. Thus, it is described that the number of spot welding spots is increased.

  However, the electrode material made of chrome copper has a problem that the electrical conductivity and thermal conductivity are low because of the large amount of Cr dissolved, and the toughness is low because the crystal grain size is as large as several tens of μm. In addition, when used as an electrode material, since the conductivity and thermal conductivity are low, the electrode tip diameter is expanded with a small number of spots and the welding current density is lowered, so the continuous spotting property is low. Since it has low thermal conductivity and toughness, it has a problem that it is easily alloyed with the material to be welded and the number of welding hit points is low.

  On the other hand, the electrode material made of alumina-dispersed copper is fragile, and when used as an electrode material, the electrode tip is significantly worn. Furthermore, since electrical conductivity and thermal conductivity are low, there is a problem that the continuous spotting property and the number of welding spots are low.

In recent years, an alloy material composed of Cu-0.44% Cr-0.2% Zr has been subjected to lateral extrusion (ECAP: equal-channel angular pressing) to refine the crystal grain size, mechanical strength and heat resistance. It has been proposed to provide an electrode material with high conductivity (see Non-Patent Document 1).
Although the alloy described in Patent Document 1 has excellent mechanical strength and heat resistance, the electrical conductivity is as low as 75 to 80% IACS, and it is easy to form an alloy with the material to be welded. I'm leaving.

Japanese Patent Publication No.56-31196 Japanese Patent Application Laid-Open No. 62-3885 JP-A-6-73473 Acta Materialia 50 (2002) 1639-1651 “Structure and properties of ultra-fine grain Cu-Cr-Zr alloy produced by equal-channel angular pressing”

  Accordingly, the present invention has been made to solve the above-mentioned problems, and improves the toughness by refining crystal grains, further improves the conductivity by promoting the precipitation of fine precipitates, and provides an electrode material. It is an object of the present invention to provide an electrode material and a method for producing the same that can improve the continuous spotting property (electrode life) and the number of welding points (welding resistance).

The present invention solves the above-described problems, and the configuration thereof is as described below.
(1) General formula: Cu _bal. X _a (where X is at least one element selected from Cr, Zr, Fe, P, and Ag, a is 1.5% by mass or less, and the balance Is a composition having a composition represented by the following formula: a structure in which fine particles having an average particle diameter of 50 nm or less are precipitated in a structure composed of equiaxed crystal grains having an average crystal grain size of 3 μm or less. An electrode material comprising:
(2) The electrode material according to (1), wherein the fine particles are dispersed and dispersed in an average interparticle distance of 200 nm or less.
(3) The electrode according to (1) or (2), wherein the fine particles are at least one selected from Cr, Cu ₃ Zr, Cu ₉ Zr ₂ , Fe, Cu ₃ P, and Ag. material.

(4) General formula: Cu _bal. X _a (where X is at least one element selected from Cr, Zr, Fe, P, Ag, a is 1.5% by mass or less, and the balance Is a Cu-based alloy material having a heating temperature of 300 to 500 ° C., and the shearing deformation is applied by changing the extrusion direction to the side with an inner angle of less than 180 ° in the middle. A method for producing an electrode material, wherein:
(5) The method for producing an electrode material according to the above (4), wherein plastic deformation (strain) corresponding to elongation of 220% or more is given to the alloy material by the shear deformation.
(6) The method for producing an electrode material according to the above (4) or (5), wherein the alloy material is preliminarily heat-treated at a temperature of 350 to 700 ° C. before performing the extrusion.
(7) The method for producing an electrode material according to any one of (4) to (6), wherein heat treatment is performed at a temperature of 350 to 700 ° C. after the extrusion.

  According to the electrode material and the manufacturing method thereof of the present invention, the toughness is improved by refining crystal grains, and the conductivity is improved by promoting the precipitation of fine precipitates. It is possible to provide an electrode material capable of improving (electrode life) and the number of welding hit points (welding resistance). Furthermore, an electrode material having the excellent characteristics can be easily produced.

  In the present invention, a lateral extrusion method (ECAE method: equal-channel angular extrusion) is effective as a specific means for imparting shear deformation to the alloy material. The ECAE method changes the extrusion direction to the side of an inner angle of less than 180 ° (more preferably in the range of an inner angle of 60 to 120 °) in the middle without changing the cross-sectional area of the alloy material. It is possible to give plastic deformation (strain) corresponding to elongation of 220% or more, further 10,000% or more. Thereby, precipitation of fine particles having an equiaxed shape with an average crystal grain size of 3 μm or less and an average particle diameter of 50 nm or less can be promoted, and high strength and heat resistance can be imparted to the material.

  In the ECAE method of the present invention, as shown in FIG. 1, two extruded containers having the same cross-sectional area on the inner surface, or the container 1 and the die 2 are joined at an appropriate angle (2φ) of less than 180 °, and one container is This is a method in which the alloy material S is inserted into 1 and extruded toward the next container 1 or die 2 by the ram 3 to apply a shear deformation in the lateral direction to the material, and this step is preferably performed a plurality of times. By applying this method to the alloy material, the crystal grains can be refined to 3 μm or less by a very simple process and without reducing the cross-sectional area, and the toughness can be greatly improved (Japanese Patent Laid-Open No. 9-1990). No. 133244).

  The process also has an effect on fracture and homogenization of cast structure, macro of alloy components, micro segregation, and omits high temperature and long time homogenization heat treatment that is generally performed for alloy materials. It is also possible. Furthermore, even if the die 2 is accompanied by a reduction in the cross-sectional area, the effect does not change.

The amount of shear deformation applied to the alloy material by the ECAE method in the present invention varies depending on the bonding angle between the two containers or the container and the die. In general, the strain amount Δε _i per one extrusion due to such shear deformation is given by the following equation (1).

Δε _i = (2 / √3) · cotanφ (1)
ERR = (A ₀ / A) = exp (Δε _i ) (2)
EAR = {1- (1 / ERR)} × 100 (3)
EE = (ERR-1) × 100 (4)
(Where Δε _i is the strain amount, φ is 1/2 of the joining angle, ERR is the area ratio before and after processing, A ₀ is the cross-sectional area before processing, A is the cross-sectional area after processing, and EAR is the equivalent cross-section before and after processing) (Decrease rate, EE represents equivalent strain (synonymous with elongation).)

  In other words, when the inner angle of two containers or container-die joint is a right angle (90 °), the strain amount is 1.15 (equivalent elongation: 220%) by one side extrusion, and when 120 °, the strain amount is 120 °. Is given by 0.67 (equivalent elongation: 95%). By performing side extrusion at a right angle while maintaining the same cross-sectional area, it is possible to add a process corresponding to a rolling reduction (cross-sectional reduction rate) of 69% by rolling.

By repeating the above process, infinite strain can be accumulated in the material without changing the cross-sectional area of the material. The accumulated strain amount ε _t given to the material by the repetition is given by the following equation (5).
ε _t = Δε _i × N (5)
(However, ε _t represents the amount of accumulated strain, and N represents the number of extrusions.)

  The number of repetitions (N) is theoretically better as much as possible, but in reality, the effect is saturated in a certain number of times depending on the alloy. With a general wrought alloy material, a sufficient effect can be obtained with 4 repetitions (when the joining angle is a right angle, the cumulative strain amount is 4.6 and the equivalent elongation is 10,000%). Infinite strain can also be accumulated by rolling, but in that case, the cross-sectional area becomes infinitely small, which is in contrast to the side extrusion method.

  In the present invention, it is important that the ECAE method is performed at a temperature of 300 to 500 ° C. This temperature range is because when the temperature is less than 300 ° C., the mechanical strength is improved, but the precipitation cannot be sufficiently promoted to prevent the precipitation of fine precipitates, and the conductivity cannot be improved. When the temperature exceeds 500 ° C., the crystal grains cannot be refined, and the precipitated particles cannot be refined, the mechanical strength and the like cannot be improved, and re-dissolution of the precipitated dispersed particles occurs. This is because the conductivity cannot be improved.

  Furthermore, in the present invention, it is preferable to perform a heat treatment (hereinafter also referred to as a pre-heat treatment) within a temperature range of 350 to 700 ° C. before performing the ECAE method. By performing this preliminary heat treatment, fine precipitates are dispersed, contributing to pinning such as dislocations introduced in the ECAE process, and crystal grains can be refined. When the temperature is less than 350 ° C., precipitation does not occur, and when the temperature exceeds 700 ° C., the crystal grain size and the precipitate are too coarse, and even if the ECAE method is applied, an appropriate crystal grain size or precipitate is obtained. It becomes impossible to control to the size of. About the prior heat processing time, the said effect can be anticipated if it is at least 30 minutes or more. In addition, although there is no restriction | limiting in particular about an upper limit, when it considers economical efficiency etc., it is desirable that it is less than 100 hours.

  In the present invention, after the ECAE method, it is preferable to perform a heat treatment (hereinafter also referred to as a post-heat treatment) within a temperature range of 350 to 700 ° C. Since it can be uniformly and finely deposited and dispersed, the electrical conductivity can be improved as an electrode material. When the temperature is lower than 350 ° C., the amount of the precipitate deposited is insufficient, and the conductivity is not improved. On the other hand, when the temperature exceeds 700 ° C., the precipitated dispersed particles are re-dissolved and the conductivity tends to decrease. About the heat processing time, the said effect can be anticipated if it is at least 10 minutes or more. In addition, although there is no restriction | limiting in particular about an upper limit, when it considers economical efficiency etc., it is desirable that it is less than 50 hours.

  In the present invention, the combined use of the pre-heat treatment and the post-heat treatment controls the average crystal grain size and fine precipitates to an appropriate size, and uniformly finely disperses the fine precipitates. It is particularly preferable for controlling the amount.

The Cu-based alloy material to which the present invention is applied has a general formula: Cu _bal. X _a (where X is at least one element selected from Cr, Zr, Fe, P, and Ag, and a is mass%. 1.5% or less, and the balance is preferably Cu containing inevitable impurities). The X element is at least one element selected from Cr, Zr, Fe, P, and Ag, and these elements contribute to the improvement of heat resistance, which is an object of the present invention, when added in an amount of 1.5% by mass or less. Fine precipitates can be deposited. The lower limit is not particularly specified, but is preferably 0.01% by mass or more from the viewpoint of depositing fine precipitates.

  Further, specific compositions thereof include Cu-(-1.5%) Cr, Cu-(-0.2%) Zr, Cu-(-1.3%) Cr-(-0.2%) Zr. Cu- (˜1.0%) Fe— (˜0.2%) P, Cu— (˜0.5%) Ag and other alloys are particularly preferred.

  In addition, the structure of the electrode material effective for the present invention is such that fine particles having an average particle diameter (dispersion particle diameter) of 50 nm or less are precipitated in a structure composed of equiaxed crystal grains having an average crystal grain size of 3 μm or less. It is an organization structure. By adopting such a structure, the room temperature hardness (Hv) can be 100 or more, the conductivity (IACS) can be 90% or more, and the average crystal grain size is 1 μm or less, the size of fine precipitates. By adopting a structure having a (dispersed particle diameter) of 25 nm or less, the room temperature hardness (Hv) can be 120 or more and the conductivity (IACS) can be 90% or more.

Moreover, the dispersion state of fine precipitates that contribute to the improvement of heat resistance is 200 nm or less, preferably 100 nm or less, in terms of the average interparticle distance. Dispersion of particles having a diameter of 50 nm or less at the above intervals makes it possible to suppress a decrease in hardness after being held at 600 ° C. for several hours. In the present invention, specific examples of the fine precipitate to be precipitated include Cu—Zr series such as Cr, Cu ₃ Zr and Cu ₉ Zr ₂ , Fe, Cu ₃ P, Ag and the like.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example and a comparative example, it cannot be overemphasized that this invention is not limited to the specific aspect shown in the following Examples.

  In a high frequency melting furnace, electrolytic copper and various gold were melted in an argon atmosphere and cast into a graphite mold to obtain an ingot having a diameter of 40 mm and a length of 300 mm. Table 1 shows the composition of the obtained ingot. The ingot was extruded into a 25 mm square bar at a temperature of 900 ° C. After extrusion, solution treatment was performed at 1000 ° C. for 2 hours, and heat treatment (pre-heat treatment) shown in Table 2 was performed. After the preliminary heat treatment, each material was inserted into one of two containers connected at a right angle shown in FIG. 1 and subjected to side extrusion under the conditions shown in Table 3 to obtain a 25 mm square side extruded material. After the side extrusion treatment, each material was subjected to heat treatment (post heat treatment) under the conditions shown in Table 4 to obtain a final treated material.

  A structural photograph of the final treated material is shown in FIG. The crystal grain size before lateral extrusion was 50 to 100 μm, but the average crystal grain size of the final treated material was equiaxed to 3 μm or less, and the size of fine precipitates was refined to 50 nm or less. Further, the distance between the particles of the fine precipitate is 200 nm or less, and the fine precipitate is uniformly and finely dispersed in the structure.

  Table 5 (Tables 5-1 to 5-8) shows the measurement results of room temperature hardness (Hv) and electrical conductivity at room temperature (% IACS) of the final treated material. Compared with the conventional material (comparative material) shown in Table 5-9, the material of the present invention has the same or slightly lower room temperature hardness (Hv), but the conductivity (% IACS) is increased to 90% or more. I understand. The hardness measurement is the result of measuring the hardness with a micro Vickers hardness tester with a load of 50 gf. Further, the conductivity measurement is a result of mirror polishing the surface of the final treatment material, measuring the numerical value by bringing the measurement probe of a digital conductivity meter (Auto Sigma 3000) into contact with the sample surface.

<Electrode life evaluation>
In order to evaluate the life of the electrode, it is molded into an electrode having a tip diameter of 6 mm (40R), and after pickling the shot-dull finish material of an Al-Mg alloy plate having a plate thickness of 1 mm as a welding base material, a commercially available low viscosity mineral The oil-coated one was used, and a spot welding test was performed using a single-phase alternating current stationary spot welder while water cooling the electrodes. The welding current was 26 kA, the energization time was 4 cycles, and the applied pressure was 400 kgf. Welding conditions were in accordance with WES7302 so that a nugget with a diameter of 5 mm was obtained, and the continuous welding speed was 1 time / 2 s. The electrode life was evaluated by the number of hits when the welded part was peeled off and the nugget diameter (the value obtained by adding the major axis and the minor axis divided by 2) was less than 5 mm. The electrode life was evaluated according to the following evaluation criteria.
(Electrode life evaluation criteria)
○: More than 1000 consecutive hit points ×: Less than 1000 consecutive hit points

<Evaluation of welding resistance>
The welding resistance was evaluated by the following method. In the electrode life evaluation test, when the electrode material and the material to be welded adhered, the load when the electrode material was pulled and separated by a tensile tester was measured, and when the load exceeded 10 kgf, it was defined as “welding”. Further, the number of hitting points until welding was taken as the number of welding hits, and the average value of the welding hit points was called “average welding hitting point”, which was used as an index indicating the frequency of occurrence of welding. The larger the average number of welding points, the harder it is to weld. The welding resistance was evaluated according to the following evaluation criteria.
(Welding resistance evaluation criteria)
○: Average number of welding hit points 500 times or more Δ: Average number of welding hit points 100 to 499 times ×: Average number of welding hit points 100 times or less

<Comprehensive evaluation>
The results of comprehensive evaluation of continuous spotting property (electrode life) and welding resistance were comprehensively evaluated according to the following criteria, and are shown in the bottom column of Table 5.
(Comprehensive evaluation criteria)
A: Both continuous dot resistance and welding resistance are evaluated.
○: Evaluation of continuous dot resistance and welding resistance is ○ or △
X: x is included in the evaluation of continuous spotting property and welding resistance

  Invention material Nos. 15, 18, 24 to 26, 29, 32, 35, 37, 38, 41, 43, 44, 46, 47, 49 to 52, 58, 61, 63, 64, 67, 70, 72 , 73, 76, and 78 have low conductivity (% IACS) (not shown in the table but low thermal conductivity), so Joule heat generation is high, and because the heat removal rate is low, crystal grains grow. The toughness was lowered and it became easy to alloy with the material to be welded, and the average welding interval was less than 500 times.

  Comparative material No. No. 1 has a large amount of solid solution of Cr and its conductivity (% IACS) is too low (not shown in the table but the thermal conductivity is too low), so Joule heating is very high, and the cooling efficiency is poor. The temperature of the material increased and the hardness decreased significantly. As a result, the electrode material tip diameter is enlarged and the welding current density is lowered with a small number of hitting points, so that the continuous spotting property is low. As for the welding resistance, the electrical conductivity (% IACS) is too low (not shown in the table but the thermal conductivity is too low), and the toughness is low due to the large crystal grain size of several tens of μm. Therefore, it is easy to alloy with the material to be welded, and the average number of welding points is small.

Comparative material No. No. 2 is brittle and wears at the tip of the electrode, and the conductivity (% IACS) is too low (not shown in the table, but the thermal conductivity is too low), and is easily welded.
From the above, it has been clarified that a material having high hardness, high conductivity (% IACS) and fine crystal grains is excellent in welding characteristics.

A bar made of Cu-1.0% Cr was prepared in the same manner as in Example 1, and after extrusion, solution treatment was performed at 1000 ° C. for 2 hours, and pre-heat treatment was performed at 450 ° C. for 2 hours.
After the preliminary heat treatment, the room temperature hardness and conductivity were measured. As a result, the hardness was 160 and the conductivity was 80%. Each material was inserted into one of two containers connected at a right angle shown in FIG. 1 and subjected to side extrusion at a temperature of 350 ° C. to obtain a 25 mm square side extruded material. After the side extrusion treatment, the room temperature hardness and conductivity were measured. As a result, the hardness was 143 and the conductivity was 90%.
Furthermore, each material was heat-treated under the conditions of (1) 425 ° C. for 10 minutes and (2) 425 ° C. for 8 hours to obtain final treated materials.
The final treated material is (1) hardness 156, conductivity 90%, average recrystallized particle size 1 μm or less, fine precipitate average particle size 1-20 nm, fine precipitate Cr average interparticle distance 100 nm or less, (2) The hardness was 120, the conductivity was 93%, the average recrystallization particle size was 1 μm or less, the average particle size of fine precipitates was 5 to 40 nm, and the average interparticle distance of the fine precipitates Cr was 150 nm or less.

  A bar made of Cu-1.0% Cr was prepared in the same manner as in Example 1, and after extrusion, solution treatment was performed at 1000 ° C. for 2 hours, and pre-heat treatment was performed at 450 ° C. for 2 hours. After the preliminary heat treatment, each material was inserted into one of two containers connected at right angles shown in FIG. 1 and subjected to side extrusion under the condition of a temperature of 500 ° C. to obtain a 25 mm square side extruded material. The obtained side extrusion processing material was used as the final processing material. The final treated material had a hardness of 110, an electrical conductivity of 95%, an average recrystallized particle size of 3 μm or less, an average particle size of fine precipitates of 5 to 40 nm, and an average interparticle distance of fine precipitates Cr of 150 nm or less.

The same electrode material as in Example 1 was used, and a hot-dip galvanized steel sheet having a thickness of 0.8 mm (average plating adhesion amount: 60 g / m ² ) was used as the welding base material. In use, spot welding tests were conducted while water cooling the electrodes. The welding current was 8.3 kA, the energization time was 10 cycles (50 Hz), and the applied pressure was 200 kgf. The welding conditions were such that a nugget with a diameter of 5 mm was obtained, and the continuous welding speed was 1 time / 1 s. The electrode life and welding resistance were evaluated by the same method and standard as in Example 1, and the results of comprehensive evaluation by the same standard as in Example 1 were used as comprehensive evaluations. 9 shows.

  Inventive materials 18, 32, 35, 38, 44, 47, 49, 50, 58, 64, 70, 73, 76 have low conductivity (% IACS) (not shown in the table, but heat conduction) Since the rate of Joule heat generation is high and the heat removal rate is low, the crystal grains grow, the toughness decreases, and it becomes easy to alloy with the material to be welded, and the average welding interval becomes less than 500 times.

  Comparative material No. No. 1 has a large amount of solid solution of Cr and its conductivity (% IACS) is too low (not shown in the table but the thermal conductivity is too low), so Joule heating is very high, and the cooling efficiency is poor. The temperature of the material increased and the hardness decreased significantly. As a result, the electrode material tip diameter is enlarged and the welding current density is lowered with a small number of hitting points, so that the continuous spotting property is low. As for the welding resistance, the conductivity (% IACS) is too low (not shown in the table, but the thermal conductivity is too low), and the toughness is low due to the large crystal grain size of several tens of μm. Therefore, it is easy to alloy with the material to be welded, and the average number of welding points is small.

Comparative material No. No. 2 is brittle and wears at the tip of the electrode, and the conductivity (% IACS) is too low (not shown in the table, but the thermal conductivity is too low), and is easily welded.
From the above, it has been clarified that a material having high hardness, high conductivity (% IACS) and fine crystal grains is excellent in welding characteristics.

  The electrode material of the present invention has high toughness and electrical conductivity, and is excellent in continuous spotting performance (electrode life) and number of welding spots (welding resistance), so aluminum, magnesium, iron and alloys thereof, and metal plating materials thereof, etc. It is highly usable as an electrode material used when welding a material to be welded.

It is a figure which shows an example of the ECAE method shaping | molding apparatus. It is a figure which shows the metal structure of a final process material (thing by EBSP).

Explanation of symbols

1 container 2 die 3 ram S alloy material

Claims (7)

General formula: Cu _bal. X _a (where X is at least one element selected from Cr, Zr, Fe, P, Ag, a is 1.5% by mass or less, and the remainder is inevitable) (It is Cu containing impurities) and has a structure in which fine particles with an average particle size of 50 nm or less are precipitated in a structure made of equiaxed crystal particles with an average crystal particle size of 3 μm or less. An electrode material characterized by.   2. The electrode material according to claim 1, wherein the fine particles are deposited and dispersed in an average interparticle distance of 200 nm or less. The electrode material according to claim 1 or 2, wherein the fine particles are at least one selected from Cr, Cu ₃ Zr, Cu ₉ Zr ₂ , Fe, Cu ₃ P, and Ag. General formula: Cu _bal. X _a (where X is at least one element selected from Cr, Zr, Fe, P, Ag, a is 1.5% by mass or less, and the remainder is inevitable) Extruding a Cu-based alloy material represented by (which is Cu containing impurities) at a heating temperature of 300 to 500 ° C. by changing its extrusion direction to the side with an inner angle of less than 180 ° and applying shear deformation. A method for producing a featured electrode material.   5. The method for producing an electrode material according to claim 4, wherein plastic deformation (strain) corresponding to elongation of 220% or more is applied to the alloy material by the shear deformation.   6. The method for producing an electrode material according to claim 4, wherein the extruding is performed in advance at a temperature of 350 to 700 [deg.] C. on the alloy material.   The method for producing an electrode material according to claim 4, wherein a heat treatment is performed at a temperature of 350 to 700 ° C. after the extrusion.