WO2007142257A1 - スポット溶接用電極 - Google Patents
スポット溶接用電極 Download PDFInfo
- Publication number
- WO2007142257A1 WO2007142257A1 PCT/JP2007/061432 JP2007061432W WO2007142257A1 WO 2007142257 A1 WO2007142257 A1 WO 2007142257A1 JP 2007061432 W JP2007061432 W JP 2007061432W WO 2007142257 A1 WO2007142257 A1 WO 2007142257A1
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- WO
- WIPO (PCT)
- Prior art keywords
- electrode
- core material
- spot welding
- base alloy
- alloy
- Prior art date
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K11/00—Resistance welding; Severing by resistance heating
- B23K11/30—Features relating to electrodes
- B23K11/3009—Pressure electrodes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K11/00—Resistance welding; Severing by resistance heating
- B23K11/30—Features relating to electrodes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0255—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in welding
- B23K35/0261—Rods, electrodes, wires
- B23K35/0266—Rods, electrodes, wires flux-cored
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/32—Selection of soldering or welding materials proper with the principal constituent melting at more than 1550 degrees C
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
Definitions
- the present invention relates to a resistance welding electrode having a double structure in which a W, Mo, W-base alloy or Mo-base alloy is embedded as a core material in a surrounding material made of Cu or Cu alloy.
- the assembly line for automobiles, home appliances, etc. has high working efficiency among the resistance welding methods, and spot welding is frequently used.
- spot welding is frequently used.
- Electrodes for continuous spot welding are subject to repeated high heat and high load during use and are easily deformed. Therefore, excellent deformation resistance is required for electrode materials.
- the spot welding electrode must also have excellent electrical conductivity, thermal conductivity, strength, and wear resistance, which are the original required characteristics. Therefore, hard alloys such as Al-O, such as 01 alloys such as Cu-Cr, 01-0: -21:
- Dispersed Cu material is used for the electrode material.
- Cu-Cr alloys are frequently used from the comprehensive viewpoints of thermal conductivity, strength, and cost.
- a plated steel sheet on which Zn plating, Zn alloy plating, or the like has been applied is often used for improving durability.
- the plated steel sheets are spot-welded, so that the electrode tip is exposed to more severe conditions.
- the plating layer components such as Zn and Al, the base material component Fe of the plated steel sheet, and the Cu, the main component of the electrode, undergo an alloying reaction, Cu-Zn, Cu-Zn-Al-Fe Intermetallic compounds such as are easily formed.
- the produced intermetallic compound causes a large diameter at the tip of the electrode, which is a cause of a decrease in current density, which is very brittle to the extent that it is peeled off by pressure during welding.
- the electrode life is shortened as compared with the case of spot welding of cold-rolled steel sheets such as plain steel and stainless steel.
- the shortening of the electrode life has a significant adverse effect on the workability of spot welding, where the number of electrodes used is increasing.
- the present inventors have previously proposed a dual-structure spot welding electrode in which a core material is embedded in the center of the electrode tip with the aim of extending the life of the electrode.
- a core material is embedded in the center of the electrode tip with the aim of extending the life of the electrode.
- Cu or Cu alloy is used as the electrode body, and a core made of W, Mo, W-base alloy or Mo-base alloy is embedded in the contact surface where the electrode contacts the workpiece.
- the area ratio of the material Z contact surface is adjusted to the range of 0.7 to 3.0.
- the core material contains 0.5 to 10% by volume of at least one kind of fine particles selected from oxides, nitrides, carbides and borides of Group 2A elements, Group 4A elements, Group 5A elements, Group 6A elements or rare earth elements. Disperse at the rate of.
- the spot welding electrode of Patent Document 2 is a dual structure electrode developed for spot welding of Mg-containing Zn-based alloy steel plates. Be, Mg, Ca, Sr, Ti, Zr, Y W, Mo, W-based alloy or Mo-based alloy in which one or more fine particles selected from the oxides of Ce and Ce are dispersed at a ratio of 0.5 to 10% by volume is used as the core material. .
- a double-structured core material has a group 2A element, group 4A element, group 5A element, group 6A element, rare earth element oxide, nitride, carbide, boride.
- a W-based alloy in which fine particles with a melting point of 2400 ° C or more and an average particle size of 2 m or less are dispersed in a total proportion of 0.5 to 10% by volume with one or more selected compounds.
- Each electrode maintains a relatively high strength (high hardness) even at high temperatures and is difficult to alloy with a plated metal.
- W, Mo, W-base alloy or Mo-base alloy core material is made of Cu or Cu. It has a double structure embedded in the electrode body made of alloy. Since the W, Mo, W-base alloy or Mo-base alloy core material is also embedded, it is easy to secure a current-carrying path with a certain area, so that the decrease in welding current density is suppressed and the life of the electrode is extended.
- W and Mo which are inherently hard materials, have been thought to be a defect that cracks are likely to occur due to the impact of electrode pressurization during spot welding, but they are easily damaged. Stopping action can suppress crack generation and propagation. By adding fine particles, the core material is not partly lost, the expansion of the current path is suppressed, and an almost constant nugget diameter can be obtained. Such effects greatly improve the electrode life compared to conventional Cu alloy electrodes.
- Patent Document 1 Japanese Unexamined Patent Application Publication No. 2006-15349
- Patent Document 2 Japanese Patent Laid-Open No. 2006-95549
- Patent Document 3 Japanese Unexamined Patent Publication No. 2006-102775 Disclosure of the invention
- the present invention has been devised to solve such a problem, and as a spot welding electrode to which heating and pressurization are repeatedly applied, it suppresses degranulation wear and chipping on the electrode tip surface and is durable.
- the purpose is to provide an inexpensive spot welding electrode embedded with W or Mo core material with improved stability.
- the electrode for spot welding of the present invention uses Cu or a Cu alloy as an electrode body (peripheral material), and a W, Mo, W base on the surface where the electrode body abuts the material to be welded. It has a double structure in which a core material made of an alloy or Mo base alloy is embedded.
- the core W, Mo, W-base alloy or Mo-base alloy has a structure extending in the direction of the electrode axis so that the average particle diameter is 50 m or more and the aspect ratio is 1.5 or more.
- a material in which a fibrous structure is prepared by sintering, swaging and then annealing W, Mo, a W-based alloy or a Mo-based alloy is preferable.
- the hardness at room temperature is in the range of HV300 to 430.
- the hardness at room temperature is preferably in the range of HV180 to 260.
- W, Mo, W-base alloys or Mo-base alloys include Group 2A elements, Group 4A elements, Group 5A elements, Group 6A elements, rare earth oxides, nitrides, carbides, borides. Fine particles of seeds or more may be dispersed. When the fine particles are dispersed, the fine particles having an average particle diameter of 2 m or less are preferably dispersed in a total proportion of 0.5 to 10% by mass.
- the core material on the contact surface where the electrode main body contacts the material to be welded so that the area ratio of the core material Z contact surface is 0.7 to 3.0.
- the electrode life is improved, such as reactivity with the plating metal and suppression of expansion of the current path. The same applies not only to welding electrodes but also to other resistance welding methods.
- the core material of the double electrode is preferably manufactured by heat-treating a W, Mo, W-base alloy or Mo-base alloy into a predetermined shape through current sintering and swaging.
- Heat treatment removes residual stresses introduced during swaging 'releasing the external ratio of the crystal grains of the fibrous tissue that is released by the force of release, and increasing the average cross-sectional average particle size Has an effect. Residual stress is removed by heat treatment and the fibrous structure is modified to give a stable durability to the S spot welding electrode.
- FIG. 1 is a diagram for explaining the structure of a double-structured embedded electrode.
- Fig. 2 is a schematic diagram for explaining the state of wear at the tip of a core member in a conventional electrode.
- FIG. 3 is a schematic diagram for explaining the state of wear at the tip of the core material in the electrode of the present invention.
- FIG. 4 is a view for explaining the relationship between the core material and the contact surface in the electrode of the present invention.
- the W rod used for the core material 3 is usually manufactured by electric current sintering and swaging, and has a fine fibrous structure. Shika is also hardened in the manufacturing process, so there is residual processing stress and it is very hard. If a hardened W rod is used as the core material 3, repeated stress is applied to the electrode tip due to the heating and pressurization during welding, and cracks occur in the initial stage of welding, combined with residual stress in the manufacturing process. However, it is assumed that cracks propagate gradually. [0021] It is necessary to control the propagation and connection of cracks c and c in order to suppress the wear and loss of the electrode tip.
- the fibrous structure built by swaging is modified by annealing (heat treatment) into an effective structure for suppressing the connection of cracks C and C, and the occurrence of cracks itself is eliminated by removing residual stress.
- the fibrous structure generated by swaging gives priority to the propagation of cracks along the electrode axis direction and regulates the propagation in the radial direction. Then, by annealing after swaging and modifying to a fibrous structure with an average particle diameter of 50 m or more and an aspect ratio of 1.5 or more, the radial crack c is reduced and the crack c extending in the electrode axis direction is reduced. Opportunity to connect with radial crack c
- the residual stress of the metal material is usually removed by a heat treatment such as annealing. Even in the case of the W bar used for the core material of the spot welding double electrode, if the bar material from which residual stress has been removed by annealing after strong processing is used as the material, the occurrence of cracks in the initial stage of welding will be suppressed. obtain. In fact, annealed electrodes using W bars as the core material have fewer cracks (Fig. 3).
- the amount of residual stress can be roughly estimated from the normal temperature hardness.
- the normal temperature hardness of a W-bar cross-section that has been subjected to strong swaging is usually about HV450, and after it is fully annealed, it drops to about HV300.
- the same reasoning force is preferably tempered in the range of HV180 to 260.
- the required properties other than hardness can also be deduced from the example of using a W or W-based alloy as the core material.
- the distribution state of the crystal particles (metal structure) on the tip surface of the core material has a great influence on the wear of the tip of the double electrode core material during welding.
- Making the metal structure into a fibrous structure by swaging directs the propagation direction of crack c in the vertical direction (electrode axis direction), which is effective in suppressing degranulation, but is caused by a large processing residual stress.
- the wear at the tip of the material will increase. Since the crystal grains increase with annealing, it is necessary to set the heat treatment conditions so that an appropriate annealing state is obtained.
- the ratio of the major axis Z minor axis ratio of the particles maintaining the fibrous structure must be 1.5 or more, and the average cross-sectional diameter of each particle must be 5 O / zm or more. If the aspect ratio is less than 1.5, flocculation tends to occur at the core material tip. If the average particle size of the cross section is less than 50 m, the particles will easily fall off and the electrical resistance will increase, resulting in severe wear of the core material.
- the average cross-sectional particle diameter can be determined from a microscope image obtained by observing the radial cross section of the electrode core material.
- the grain boundary is a portion where the bond strength between adjacent atoms across the grain boundary is weak, and when the crystal grain size becomes small, the grain boundary area increases and the grains are likely to fall off.
- the influence of the crystal grain size becomes significant when the average cross-sectional particle diameter is less than 50 m, and the particles drop off due to impact and the electrical resistance immediately increases. Therefore, it is preferable that the average cross-sectional particle diameter is 50 m or more. Ideally, a single crystal having no grain boundary is preferable.
- W or Mo has a body-centered cubic lattice crystal structure, is originally a brittle material having no malleability and ductility, and is difficult to be plastically processed. Even when processing at a temperature exceeding the brittle and ductile transition temperature (about 400 ° C), W or Mo particles cannot be extended and cannot be force processed until the aspect ratio becomes 50 because they are cut halfway. From this point of view, it is realistic to set the processing temperature low and to set the aspect ratio to about 20 as the upper limit.
- the alloying reaction with the plating metal is performed by using oxides, nitrides, carbides, borides of 2A group elements, 4A group elements, 5A group elements, 6A group elements, and rare earth elements. It can be suppressed by dispersing fine particles of seeds or more in W, Mo, W-base alloy or Mo-base alloy. These fine particles reduce the wettability of the core material made of W, Mo, W-base alloy or Mo-base alloy to the plating metal which is poor in reactivity with A1 and Zn, and the alloying reaction between the core material and the plating metal It has the effect of suppressing
- the dispersion of the fine particles is also effective in suppressing fine cracks that tend to occur in the core material.
- the propagation of cracks is pinned by fine particles when the core is impacted, resulting in improved crack resistance and impact resistance.
- the fine particles preferably have a particle size of 2 / z m or less. If the particle size exceeds 2 / z m, the fine particles may be the starting point of destruction due to the difference in thermal expansion between the matrix Z fine particles.
- the area ratio of the core material Z contact surface in the electrode body and core material of the present invention that is, in the dual structure electrode 1 as shown in Fig. 4, the core material 3 embedded in the surrounding material 2
- the area ratio of the area indicated by diameter b to the contact surface 2a with the workpiece to be indicated indicated by diameter a is set to 0.7 to 3.0. It is preferable. 1. To exceed 0, use a core material 3 with a diameter b thicker than the diameter a of the contact surface 2a, grind the tip of the electrode including the core material 3, and only the core material 3 will be the contact surface. This means that the tip shape is adjusted.
- Cu or Cu alloy used in the surrounding material is more susceptible to alloying reactivity than W, Mo, W-based alloy or Mo-based alloy used in the core material. Therefore, when the core material diameter b is larger than the diameter a of the contact surface, Cu as a surrounding material does not come into contact with the metal, and no alloying reaction occurs between Cu and the metal. If the core area is about 30% smaller than the area of the abutment surface, the surrounding material will come into contact with the metal, but since the contact area is small, deformation due to alloying between the surrounding material and the metal is not possible. The diameter does not increase, and the tip shape of the electrode as a whole does not change.
- the W, Mo, W-base alloy or Mo-base alloy for the core material is manufactured by a sintering method, preferably an electric current sintering method.
- a sintering method preferably an electric current sintering method.
- K (potassium) doped with W or Mo in the form of oxides, nitrides, metals, carbides or borides is often used.
- W, Mo, W-base alloy or Mo-base alloy ⁇ is used to include K-doped W and Mo.
- W, Mo, W-base alloy or Mo-base alloy oxide powder or metal powder with fine particles added as necessary is heat-treated in a reducing atmosphere, and the heat-treated powder is formed into an appropriate shape and pre-sintered Then, conduct current sintering. Next, the sintered body is swaged into a rod shape and annealed.
- the average cross-sectional particle size is grown to around 50 m, and then the cross-sectional average particle size is increased to 50 ⁇ m or more by heat treatment above the recrystallization temperature. Even if the growth is not sufficient, grain growth is performed by heat treatment in the subsequent process and crossing Method to make the surface average particle size 50 ⁇ m or more
- HIP hot isostatic pressure
- An aspect ratio of 1.5 or more is obtained by heating the material to at least a ductile brittle transition temperature (about 400 ° C) or more in the swaging process and applying a processing pressure of about a degree that does not cause brittle fracture. This can be achieved by repeating the processing.
- Carrying residual stress introduced by swaging is released by annealing 'Removing force for W and W based alloys 1400 to 3000 ° CX for 1 second to 1 hour in non-oxidizing atmosphere, Mo and Mo based For gold, heat treatment conditions of 980 to 2100 ° CX for 1 second to 1 hour are preferred in a non-acidic atmosphere.
- the balance between the treatment temperature and the treatment time is also effective in maintaining the aspect ratio and cross-sectional average particle diameter of the core material within the specified value range.
- the annealed rod-like W, Mo, W-base alloy or Mo-base alloy is cut to a predetermined length to produce a double-electrode core material.
- the tip is cut or ground and shaped into the required shape, such as the DR shape.
- the next step is a DR-type spot welding electrode with a tip diameter of 6 mm and an overall diameter of 16 mm, with a dual structure spot welding electrode with an arc of 4 Omm radius of curvature at the tip diameter of 6 mm and an arc of curvature radius of 8 mm at the other part Prepared with.
- the electrode with W as the core material with an appropriate heat treatment condition an aspect ratio of the core material of 1.5 or more, and an average cross-sectional diameter of 50 ⁇ m or more is 10000 without any problems. Spot welding exceeding the spot was possible.
- the last column in Table 2 shows a comparative example, which was swaged and centerless polished but annealed.
- the core material 3 annealed at a temperature that is too low or for a time that is too short maintains an aspect ratio of 1.5 or more, but cannot have an average particle diameter of a cross section of 50 m or more.
- the double electrode embedded with degranulation occurred on the tip surface, and spot welding up to 10,000 shots could not be performed.
- the processing temperature is too high or the processing time is too long, the aspect ratio tends to be too small or the average cross-sectional particle diameter tends to be too large.
- Using such a core material results in low hardness. As a result, the core material was greatly deformed, and the desired electrode life could not be obtained.
- a dual-structure spot welding electrode embedded with Mo core material 3 of the same size and shape as in Example 1 was prepared in the following process.
- Example 2 the same Zn—Al—Mg alloy steel plate as in Example 1 was used as a material to be welded, and spot welding was performed at continuous spots under the conditions shown in Table 1, and the electrode life was evaluated in the same manner as in Example 1.
- Table 3 shows the evaluation results. The last column in Table 3 shows the results (comparative example) when spot welding was performed with a double electrode embedded with a core material that was swaging and centerless polished but not annealed.
- the core material is W in which CeO powder with a particle size of 0.5 ⁇ m is dispersed in various proportions.
- Example 2 The same as Example 1 except that the core material contains CeO powder.
- the electrode life of a spot welding electrode with W as the core material in which 1% by mass of fine particles with various particle sizes and materials were dispersed was investigated.
- the particle size of CeO fine particles is changed from 0.5 to 3 ⁇ m, the particle size is 2 m or less.
- Example 2 The conditions are the same as in Example 1 except that the core material diameter is variously changed.
- the core material characteristics were an aspect ratio of 1.7, an average cross-sectional diameter of 100 / m, and a normal temperature hardness of HV380.
- Particle diameter 0.5 111 Same 60 powder dispersed at 1% by mass W is used as the core material, extending the life of the electrode.
- Example 5 The conditions are the same as in Example 5 except that the core material contains CeO powder.
- the electrode for spot welding of the present invention is a W, Mo, W-based alloy or Mo-based alloy having a fibrous texture with an average particle diameter of 50 m or more and an aspect ratio of 1.5 or more. It has a double structure embedded in the surrounding material made of Cu or Cu alloy as a core material! Because of the fibrous texture, the propagation direction of cracks is regulated in the direction of the electrode axis, and degranulation at the tip of the electrode is suppressed, so that a sufficiently large nugget can be formed even if the number of continuous hit points exceeds 10,000. Used as a lifetime electrode.
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/308,088 US8471169B2 (en) | 2006-06-08 | 2007-06-06 | Electrode for spot welding |
EP07744775.3A EP2027964B1 (en) | 2006-06-08 | 2007-06-06 | Electrode for spot welding |
KR1020087032062A KR101281267B1 (ko) | 2006-06-08 | 2007-06-06 | 스폿 용접용 전극 |
CN2007800205353A CN101460279B (zh) | 2006-06-08 | 2007-06-06 | 点焊用电极 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2006159318 | 2006-06-08 | ||
JP2006-159318 | 2006-06-08 |
Publications (1)
Publication Number | Publication Date |
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WO2007142257A1 true WO2007142257A1 (ja) | 2007-12-13 |
Family
ID=38801504
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/JP2007/061432 WO2007142257A1 (ja) | 2006-06-08 | 2007-06-06 | スポット溶接用電極 |
Country Status (5)
Country | Link |
---|---|
US (1) | US8471169B2 (ja) |
EP (1) | EP2027964B1 (ja) |
KR (1) | KR101281267B1 (ja) |
CN (1) | CN101460279B (ja) |
WO (1) | WO2007142257A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2014151337A (ja) * | 2013-02-07 | 2014-08-25 | Toyota Industries Corp | 抵抗溶接用電極 |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101885117B (zh) * | 2010-06-27 | 2012-03-07 | 珠海精易焊接设备有限公司 | 一种点焊机用的点焊刀及其生产方法 |
CN102039479A (zh) * | 2010-12-20 | 2011-05-04 | 福建海峡科化股份有限公司 | 一种储能焊接铜脚线-镍铬合金丝的方法 |
JP2016078036A (ja) * | 2014-10-10 | 2016-05-16 | トヨタ自動車株式会社 | スポット溶接用電極 |
FR3037517B1 (fr) * | 2015-06-16 | 2017-06-16 | Le Bronze Ind | Procede d'obtention d'une electrode de soudage |
CN108237281B (zh) * | 2016-12-23 | 2019-12-13 | 桂林金格电工电子材料科技有限公司 | 一种银钨电极的焊接方法 |
CN108237280B (zh) * | 2016-12-23 | 2019-12-13 | 桂林金格电工电子材料科技有限公司 | 一种铜钨电极的焊接方法 |
CN108237278B (zh) * | 2016-12-23 | 2019-12-13 | 桂林金格电工电子材料科技有限公司 | 一种铜钼电极的焊接方法 |
CN108237284B (zh) * | 2016-12-23 | 2019-12-13 | 桂林金格电工电子材料科技有限公司 | 一种银钼电极的焊接方法 |
KR102176354B1 (ko) * | 2018-12-12 | 2020-11-09 | 주식회사 포스코 | 점 용접용 전극팁 및 그 제조방법 |
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US20100193478A1 (en) | 2010-08-05 |
EP2027964A1 (en) | 2009-02-25 |
CN101460279A (zh) | 2009-06-17 |
CN101460279B (zh) | 2011-12-28 |
KR20090023654A (ko) | 2009-03-05 |
US8471169B2 (en) | 2013-06-25 |
KR101281267B1 (ko) | 2013-07-03 |
EP2027964B1 (en) | 2015-07-22 |
EP2027964A4 (en) | 2010-04-28 |
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