WO2015133263A1 - 電極材料の製造方法 - Google Patents
電極材料の製造方法 Download PDFInfo
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- WO2015133263A1 WO2015133263A1 PCT/JP2015/054258 JP2015054258W WO2015133263A1 WO 2015133263 A1 WO2015133263 A1 WO 2015133263A1 JP 2015054258 W JP2015054258 W JP 2015054258W WO 2015133263 A1 WO2015133263 A1 WO 2015133263A1
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- H01H1/00—Contacts
- H01H1/02—Contacts characterised by the material thereof
- H01H1/0203—Contacts characterised by the material thereof specially adapted for vacuum switches
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/11—Making porous workpieces or articles
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
- B22F3/26—Impregnating
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- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/008—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression characterised by the composition
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/045—Alloys based on refractory metals
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- C22C1/04—Making non-ferrous alloys by powder metallurgy
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- C—CHEMISTRY; METALLURGY
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- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/04—Alloys based on tungsten or molybdenum
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- C—CHEMISTRY; METALLURGY
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- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/06—Alloys based on chromium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H33/00—High-tension or heavy-current switches with arc-extinguishing or arc-preventing means
- H01H33/60—Switches wherein the means for extinguishing or preventing the arc do not include separate means for obtaining or increasing flow of arc-extinguishing fluid
- H01H33/66—Vacuum switches
- H01H33/662—Housings or protective screens
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H33/00—High-tension or heavy-current switches with arc-extinguishing or arc-preventing means
- H01H33/60—Switches wherein the means for extinguishing or preventing the arc do not include separate means for obtaining or increasing flow of arc-extinguishing fluid
- H01H33/66—Vacuum switches
- H01H33/664—Contacts; Arc-extinguishing means, e.g. arcing rings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
Definitions
- the present invention relates to a composition control technique for electrode materials.
- Electrode materials used for electrodes such as vacuum interrupter (VI) include (1) large breaking capacity, (2) high withstand voltage performance, (3) low contact resistance, and (4) welding resistance. It is required to satisfy the following characteristics: (5) low contact consumption, (6) low cutting current, (7) excellent workability, (8) high mechanical strength, etc. .
- a copper (Cu) -chromium (Cr) electrode has characteristics such as a large breaking capacity, a high withstand voltage performance, and a high resistance to welding, and is widely used as a contact material for a vacuum interrupter.
- Cu—Cr electrodes it has been reported that the smaller the particle size of Cr particles, the better in terms of breaking current and contact resistance (for example, Non-Patent Document 1).
- a solid phase sintering method mixes Cu with good conductivity and Cr with excellent arc resistance at a constant ratio, presses the mixed powder, and then sinters in a non-oxidizing atmosphere such as in a vacuum.
- a non-oxidizing atmosphere such as in a vacuum.
- the sintering method has an advantage that the composition of Cu and Cr can be freely selected, the gas content is higher than the infiltration method, and the mechanical strength may be lowered.
- infiltration is performed by pressing Cr powder (or without molding), filling the container, and heating it above the melting point of Cu in a non-oxidizing atmosphere, such as in a vacuum.
- Cu is infiltrated into the electrode to produce an electrode.
- the infiltration method cannot freely select the composition ratio of Cu and Cr, but has the advantage that a material with less gas and voids can be obtained and the mechanical strength is higher than the solid phase sintering method.
- a Cr powder that improves electrical characteristics and a finer Cr particle are used as the base Cu powder.
- heat-resistant element mobdenum (Mo), tungsten (W), niobium (Nb), tantalum (Ta), vanadium (V), zirconium (Zr), etc.
- the mixed powder is inserted into a mold and added.
- Patent Documents 1 and 2 There is a method of manufacturing an electrode that is compacted to form a sintered body.
- a heat-resistant element is added to a Cu—Cr-based electrode material made from Cr having a particle size of 200 to 300 ⁇ m, and Cr is refined through a microstructure technique. That is, alloying of Cr and a heat-resistant element is promoted, and precipitation of fine Cr—X (X is a heat-resistant element) particles is increased inside the Cu base material structure. As a result, Cr particles having a diameter of 20 to 60 ⁇ m are uniformly dispersed in the Cu substrate structure in a form having a heat-resistant element therein.
- the content of Cr and heat-resistant elements in the Cu base material is increased, and Cr and Cr and heat-resistant elements are in solid solution. It is required to make the particle size of the fine particles uniformly dispersed in the Cu base material.
- the particle diameter of the Cr-based particles in the electrode material of Patent Document 1 is 20 to 60 ⁇ m, and further refinement is required to improve electrical characteristics such as current interruption performance and withstand voltage performance.
- An object of the present invention is to provide a technique that contributes to improvement of the withstand voltage performance and current interruption performance of an electrode material.
- One aspect of the method for producing the electrode material of the present invention that achieves the above object is to temporarily sinter a mixed powder containing a heat-resistant element powder and a Cr powder to obtain a solid solution in which the heat-resistant element and Cr are in solid solution.
- Another aspect of the method for producing an electrode material of the present invention that achieves the above object is that in the method for producing an electrode material, in the preliminary sintering step, a peak corresponding to a Cr element in an X-ray diffraction measurement of the solid solution. Alternatively, the mixed powder is sintered until any of the peaks corresponding to the refractory elements disappears completely.
- the sintering temperature in the preliminary sintering step is in the range of 1250 ° C. or more and the melting point of Cr or less. is there.
- the sintering temperature in the main sintering step is in a range from the melting point of Cu to the melting point of Cr. It is.
- the mixed powder in the electrode material production method, in the preliminary sintering step, is sintered in a vacuum heating furnace, and at least The vacuum degree of the vacuum heating furnace after sintering the mixed powder is set to 5.0 ⁇ 10 ⁇ 3 Pa or less.
- the mixed powder is pressure-molded in the preliminary sintering step.
- the other aspect of the manufacturing method of the electrode material of this invention which achieves the said objective WHEREIN:
- molding pressure of the said mixed powder shall be 0.1 t / cm ⁇ 2 > or less.
- Electron micrograph of mixed powder of Mo powder and Cr powder (b) Electron micrograph of MoCr powder. 2 is a cross-sectional photomicrograph (magnification ⁇ 400) of the electrode material of Example 1, and a cross-sectional photomicrograph (magnification ⁇ 800) of the electrode material of Example 1.
- 4 is an electron micrograph (magnification ⁇ 500) of the MoCr powder of Reference Example 1.
- 4 is an electron micrograph (magnification ⁇ 500) of the MoCr powder of Reference Example 2. It is a flowchart of the manufacturing method of the electrode material which concerns on a comparative example.
- 2 is a cross-sectional photomicrograph (magnification ⁇ 800) of the electrode material of Comparative Example 1.
- the average particle diameter (median diameter d50) and the volume relative particle amount are values measured by a laser diffraction particle size distribution analyzer (Cirrus Corporation: Cirrus 1090L). .
- the inventors examined the correlation between the occurrence of re-ignition and the distribution of heat-resistant elements (Mo, Cr, etc.) and Cu.
- heat-resistant elements Mo, Cr, etc.
- Cu heat-resistant elements
- minute protrusions for example, minute protrusions of several tens to several hundreds of micrometers
- a high electric field is generated at the tip of the protruding portion, it can be a factor that degrades the breaking performance and the withstand voltage performance.
- the protrusions are formed because the electrodes are melted and welded by the input current, and the melted parts are peeled off when the current is interrupted thereafter.
- the particle size of the heat-resistant element in the electrode is reduced and finely dispersed, and the Cu region in the electrode surface is made fine and uniform.
- dispersion it was found that the generation of minute protrusions in the Cu region is suppressed and the probability of re-ignition is reduced.
- the electrode contact is ruptured by repeatedly opening and closing the contact, whereby the heat-resistant element particles on the electrode surface are crushed and become fine particles that are detached from the electrode surface.
- the particle size of the heat-resistant element in the electrode material is reduced and finely dispersed, and further, the Cu region is finely dispersed, thereby achieving heat resistance.
- the present inventors have found that an effect of suppressing the breakage of elemental particles can be obtained. Based on these findings, the inventors have intensively studied the particle size of the heat-resistant element, the dispersibility of Cu, the voltage resistance of the electrode of the vacuum interrupter, and the like, and as a result, the present invention has been completed.
- the present invention relates to a composition control technique for a Cu—Cr—heat-resistant element (Mo, W, V, etc.) electrode material, wherein the particles containing Cr are finely dispersed and uniformly dispersed, A certain Cu structure is also finely and uniformly dispersed and the content of the heat-resistant element is increased to improve, for example, the withstand voltage performance and current interruption performance of the electrode material for a vacuum interrupter.
- Mo Cu—Cr—heat-resistant element
- refractory elements examples include molybdenum (Mo), tungsten (W), tantalum (Ta), niobium (Nb), vanadium (V), zirconium (Zr), beryllium (Be), hafnium (Hf), and iridium (Ir).
- Mo molybdenum
- tungsten W
- tantalum Ti
- niobium Nb
- vanadium V
- zirconium zirconium
- Be zirconium
- Be zirconium
- Be zirconium
- Be hafnium
- Hf iridium
- Ir iridium
- elements selected from elements such as platinum (Pt), titanium (Ti), silicon (Si), rhodium (Rh), and ruthenium (Ru) can be used alone or in combination.
- Mo, W, Ta, Nb, V, or Zr which has a remarkable effect of refining Cr particles.
- the average particle size of the heat-resistant element powder is, for example, 2 to 20 ⁇ m, more preferably 2 to 10 ⁇ m, so that the electrode material contains particles containing Cr (a solid solution of the heat-resistant element and Cr).
- the electrode material contains particles containing Cr (a solid solution of the heat-resistant element and Cr).
- 6 to 76% by weight, more preferably 32 to 68% by weight, of the heat-resistant element with respect to the electrode material the withstand voltage performance and current interruption performance of the electrode material are improved without impairing the mechanical strength and workability. Can be made.
- Cr is contained in an amount of 1.5 to 64% by weight, more preferably 4 to 15% by weight with respect to the electrode material, so that the withstand voltage performance and current interruption performance of the electrode material can be reduced without impairing the mechanical strength and workability. Can be improved.
- the particle size of Cr powder is, for example, ⁇ 48 mesh (particle size less than 300 ⁇ m), more preferably ⁇ 100 mesh (particle size less than 150 ⁇ m), and still more preferably ⁇ 325 mesh (particle size less than 45 ⁇ m). By doing so, an electrode material excellent in withstand voltage performance and current interruption performance can be obtained.
- the particle size of the Cr powder By setting the particle size of the Cr powder to ⁇ 100 mesh, it is possible to reduce the amount of residual Cr that causes the particle size of Cu infiltrated into the electrode material to increase.
- the oxygen content contained in the electrode material increases. As a result, the current interruption performance decreases.
- the increase in the oxygen content of the electrode material by reducing the particle size of the Cr particles is considered to be caused by the oxidation of Cr when finely pulverizing Cr.
- a Cr powder having a particle size of less than ⁇ 325 mesh may be used. It is preferable to use a Cr powder having a small particle diameter in order to disperse the particles containing modified Cr.
- the contact resistance of the electrode material can be reduced without impairing the withstand voltage performance or the current interruption performance.
- the total of the heat-resistant elements, Cr and Cu added to the electrode material does not exceed 100% by weight. Absent.
- heat-resistant element powder for example, Mo powder
- Cr powder heat-resistant element powder
- the average particle size of the Mo powder and the Cr powder is not particularly limited, but the average particle size of the Mo powder is 2 to 20 ⁇ m, and the average particle size of the Cr powder is ⁇ 100 mesh, so that the Cu phase has MoCr.
- An electrode material in which a solid solution is uniformly dispersed can be formed.
- the Mo powder and the Cr powder are mixed such that the weight ratio of Cr to Mo1 is 4 or less, more preferably, Cr is 1/3 or less to Mo1, so that withstand voltage performance and current interruption performance are achieved. It is possible to manufacture an electrode material excellent in the above.
- the mixed powder of Mo powder and Cr powder (hereinafter referred to as mixed powder) obtained in the mixing step S1 is filled into a container (for example, an alumina container) that does not react with Mo and Cr, Temporary sintering is performed at a predetermined temperature (for example, 1250 ° C. to 1500 ° C.) in a non-oxidizing atmosphere (hydrogen atmosphere, vacuum atmosphere, or the like).
- a predetermined temperature for example, 1250 ° C. to 1500 ° C.
- a non-oxidizing atmosphere hydrogen atmosphere, vacuum atmosphere, or the like.
- the sintering temperature and time in the preliminary sintering step S2 are selected so that at least the peak corresponding to the Mo element disappears in the X-ray diffraction measurement of the solid solution of MoCr. Is done.
- the mixed powder may be pressure-formed (pressed) before pre-sintering.
- pressure forming interdiffusion between Mo and Cr is promoted, so that the pre-sintering time can be shortened or the pre-sintering temperature can be reduced.
- the pressure at the time of pressure molding is not particularly limited, but is preferably 0.1 t / cm 2 or less.
- the MoCr solid solution is pulverized using a pulverizer (for example, a planetary ball mill) to obtain a MoCr solid solution powder (hereinafter referred to as MoCr powder).
- the pulverizing atmosphere in the pulverizing step S3 is preferably a non-oxidizing atmosphere, but may be pulverized in the air.
- the pulverization conditions may be such that the particles (secondary particles) in which the MoCr solid solution particles are bonded to each other are pulverized.
- the longer the pulverization time the smaller the average particle diameter of the MoCr solid solution particles.
- the MoCr powder by setting the pulverization conditions such that the volume relative particle amount of particles having a particle size of 30 ⁇ m or less (more preferably, particles having a particle size of 20 ⁇ m or less) is 50% or more, MoCr particles ( Particles in which Mo and Cr are dissolved and dissolved in each other) and an electrode material in which the Cu structure is uniformly dispersed (that is, an electrode material excellent in withstand voltage performance) can be obtained.
- MoCr powder is formed.
- the MoCr powder is molded by, for example, pressure molding at a pressure of 2 t / cm 2 .
- the formed MoCr powder is subjected to main sintering to obtain a MoCr sintered body (MoCr skeleton).
- the main sintering is performed, for example, by sintering a compact of MoCr powder in a vacuum atmosphere at 1150 ° C. for 2 hours.
- the main sintering step S5 is a step of obtaining a denser MoCr sintered body by deformation and joining of the MoCr powder.
- the sintering of the MoCr powder is desirably performed under the temperature condition of the next infiltration step S6, for example, at a temperature of 1150 ° C. or higher.
- the sintering temperature of the present invention is higher than the temperature at the time of Cu infiltration and is equal to or lower than the melting point of Cr, preferably in the range of 1150 to 1500 ° C., so that densification of MoCr particles proceeds and MoCr particles Degassing proceeds sufficiently.
- Cu is infiltrated into the MoCr sintered body.
- Infiltration of Cu is performed, for example, by placing a Cu plate material on a MoCr sintered body and holding it in a non-oxidizing atmosphere at a temperature equal to or higher than the melting point of Cu for a predetermined time (for example, 1150 ° C.-2 hours).
- a vacuum interrupter can be comprised using the electrode material (henceforth the electrode material which concerns on embodiment of this invention) manufactured with the manufacturing method of the electrode material which concerns on embodiment of this invention.
- a vacuum interrupter 1 having an electrode material according to an embodiment of the present invention includes a vacuum vessel 2, a fixed electrode 3, a movable electrode 4, and a main shield 10.
- the vacuum vessel 2 is configured by sealing both open end portions of the insulating cylinder 5 with a fixed side end plate 6 and a movable side end plate 7, respectively.
- the fixed electrode 3 is fixed in a state of passing through the fixed side end plate 6.
- One end of the fixed electrode 3 is fixed so as to face one end of the movable electrode 4 in the vacuum vessel 2, and the end of the fixed electrode 3 facing the movable electrode 4 is in accordance with the embodiment of the present invention.
- An electrode contact material 8 which is an electrode material is provided.
- the movable electrode 4 is provided on the movable side end plate 7.
- the movable electrode 4 is provided coaxially with the fixed electrode 3.
- the movable electrode 4 is moved in the axial direction by an opening / closing means (not shown), and the fixed electrode 3 and the movable electrode 4 are opened and closed.
- An electrode contact material 8 is provided at the end of the movable electrode 4 facing the fixed electrode 3.
- a bellows 9 is provided between the movable electrode 4 and the movable side end plate 7, and the movable electrode 4 is moved up and down while keeping the inside of the vacuum vessel 2 in a vacuum, so that the fixed electrode 3 and the movable electrode 4 can be opened and closed. Done.
- the main shield 10 is provided so as to cover a contact portion between the electrode contact material 8 of the fixed electrode 3 and the electrode contact material 8 of the movable electrode 4, and is insulated from an arc generated between the fixed electrode 3 and the movable electrode 4.
- Example 1 A specific example is given and the manufacturing method of the electrode material which concerns on embodiment of this invention and the electrode material produced by the said method are demonstrated in detail.
- the electrode material of Example 1 was produced according to the flowchart shown in FIG.
- the Mo powder used had a particle size of 2.8 to 3.7 ⁇ m.
- the Cr powder -325 mesh (a sieve opening of 45 ⁇ m) was used.
- the mixed powder of Mo powder and Cr powder was transferred into an alumina container and pre-sintered in a vacuum heating furnace. If the degree of vacuum after maintaining for a predetermined time at the presintering temperature is 5 ⁇ 10 ⁇ 3 Pa or less, the oxygen content in the electrode material produced using the obtained presintered body is reduced, The current interruption performance of the electrode material is not impaired.
- the mixed powder was pre-sintered at 1250 ° C. for 3 hours.
- the degree of vacuum of the vacuum heating furnace after sintering at 1250 ° C. for 3 hours was 3.5 ⁇ 10 ⁇ 3 Pa.
- the MoCr preliminary sintered body was taken out from the vacuum heating furnace and pulverized for 10 minutes using a planetary ball mill to obtain MoCr powder.
- XRD X-ray diffraction
- the lattice constant a (Mo) of the Mo powder was 0.3151 nm, and the lattice constant a (Cr) of the Cr powder was 0.2890 nm.
- FIG. 3 (a) is an electron micrograph of a mixed powder of Mo powder and Cr powder.
- the particles having a relatively large particle size of about 45 ⁇ m seen in the lower left and upper center are Cr powders, and the fine particles that are aggregated are Mo powders.
- FIG. 3 (b) is an electron micrograph of MoCr powder.
- a relatively large powder having a particle size of about 45 ⁇ m could not be confirmed, and it was confirmed that Cr was not present in the raw material as it was (size).
- the average particle diameter (median diameter d50) of the MoCr powder was 15.1 ⁇ m.
- the MoCr powder obtained in the pulverization step is pressure-molded using a press at a press pressure of 2 t / cm 2 to form a compact, and this compact is subjected to main firing in a vacuum atmosphere at 1150 ° C. for 2 hours. As a result, a MoCr sintered body was produced.
- a relatively white region is an alloy structure in which Mo and Cr are solid solution
- a relatively black portion is a Cu structure.
- a fine alloy structure (white portion) of 1 to 10 ⁇ m was uniformly refined and dispersed. Further, the Cu structure was not evenly distributed and was uniformly dispersed.
- N L n L / L (2)
- n L and n S were divided by L and S, respectively, to obtain N L and N S. Further, by substituting the N L and N S in (1) to determine the average particle diameter dm.
- the average particle diameter dm of the MoCr particles of the electrode material of Example 1 was 3.8 ⁇ m.
- the average particle size of the MoCr powder obtained by pre-sintering the mixed powder at 1250 ° C. for 3 hours and pulverizing it using a planetary ball mill was 15.7 ⁇ m.
- the cross-sectional observation after Cu infiltration was conducted, and the average particle diameter of the MoCr particles obtained from the Fullman equation was 3.8 ⁇ m. Therefore, it is considered that the refinement of the MoCr particles further progressed in the Cu infiltration step S6. .
- the average particle diameter of the MoCr particles obtained from the Fullman equation was 15 ⁇ m or less.
- the dispersion state index of the MoCr particles in the electrode material of Example 1 was calculated from the SEM images of FIGS. 5A and 5B, and the micro-dispersion state of the electrode structure was evaluated.
- the dispersion state index was calculated according to the method described in JP-A-4-74924.
- the electrode material of Example 2 was prepared by using the same material as that of Example 1 except that the mixing ratio of Mo powder and Cr powder was different, and the same material as that of Example 1 was used.
- the X-ray diffraction (XRD) measurement of the MoCr powder obtained by pulverizing the temporary sintered body of Example 2 was performed to determine the lattice constant a of the MoCr powder.
- the electrode material of Example 3 was prepared using the same material as that of Example 1 except that the mixing ratio of Mo powder and Cr powder was different, and the electrode material was produced by the same method as Example 1.
- the X-ray diffraction (XRD) measurement of the MoCr powder obtained by pulverizing the pre-sintered body of Example 3 was performed to obtain the lattice constant a of the MoCr powder.
- the electrode material of Example 4 was made of the same material as that of Example 1 except that the mixing ratio of Mo powder and Cr powder was different, and the electrode material was produced by the same method as Example 1.
- pulverized the temporary sintered compact of Example 4 was performed, and the lattice constant a of MoCr powder was calculated
- the electrode material of Example 5 was prepared using the same material as that of Example 1 except that the mixing ratio of Mo powder and Cr powder was different, and the same material as that of Example 1 was used.
- the X-ray diffraction (XRD) measurement of the MoCr powder obtained by pulverizing the temporary sintered body of Example 5 was performed to determine the lattice constant a of the MoCr powder.
- the electrode material of Example 6 was prepared by using the same material as that of Example 1 except that the mixing ratio of Mo powder and Cr powder was different, and the same material as that of Example 1 was used.
- the X-ray diffraction (XRD) measurement of the MoCr powder obtained by pulverizing the temporary sintered body of Example 6 was performed to determine the lattice constant a of the MoCr powder.
- the electrode material of Example 7 was prepared by using the same material as that of Example 1 except that the mixing ratio of Mo powder and Cr powder was different, and the same material as that of Example 1 was used.
- pulverized the temporary sintered compact of Example 7 was performed, and the lattice constant a of MoCr powder was calculated
- Reference Example 1 The electrode material of Reference Example 1 is obtained by performing preliminary sintering at 1200 ° C. for 30 minutes in the preliminary sintering step.
- the electrode material of Reference Example 1 was prepared using the same material as that of Example 1 as a raw material, except that the temperature and time in the preliminary sintering step were different, and was produced by the same method as in Example 1.
- the MoCr temporary sintered body was taken out from the vacuum heating furnace, and the temporary sintered body was pulverized using a planetary ball mill to obtain MoCr powder.
- XRD X-ray diffraction
- Reference Example 2 The electrode material of Reference Example 2 is obtained by performing preliminary sintering at 1200 ° C. for 3 hours in the preliminary sintering step.
- the electrode material of Reference Example 2 was prepared using the same material as that of Example 1 as a raw material, except that the temperature in the preliminary sintering step was different, and was produced by the same method as in Example 1.
- the MoCr temporary sintered body was taken out from the vacuum heating furnace, and the temporary sintered body was pulverized using a planetary ball mill to obtain MoCr powder.
- XRD X-ray diffraction
- the Mo powder used had a particle size of ⁇ 4.0 ⁇ m.
- the Cr powder a ⁇ 180 ⁇ m mesh (80 ⁇ m sieve opening) was used.
- this mixed powder of Mo powder and Cr powder was transferred into an alumina container and maintained at 1250 ° C. for 3 hours in a vacuum heating furnace to prepare a temporary sintered body.
- the final degree of vacuum when kept at 1250 ° C. for 3 hours was 3.5 ⁇ 10 ⁇ 3 Pa.
- the MoCr temporary sintered body was taken out from the vacuum heating furnace and pulverized using a planetary ball mill to obtain MoCr powder. After grinding, X-ray diffraction (XRD) measurement of the MoCr powder was performed to determine the crystal constant of the MoCr powder.
- XRD X-ray diffraction
- the MoCr powder was press-molded at a press pressure of 2 t / cm 2 to form a compact, and this compact was subjected to main sintering in a vacuum atmosphere at 1150 ° C. for 2 hours to produce a MoCr sintered body. Thereafter, a Cu plate material was placed on the MoCr sintered body, held in a vacuum heating furnace at 1150 ° C. for 2 hours, and Cu was infiltrated into the MoCr sintered body.
- Comparative Example 1 The electrode material of Comparative Example 1 was produced according to the flowchart shown in FIG.
- the mixed powder of Mo powder and Cr powder is pressure-formed at a press pressure of 2 t / cm 2 to form a formed body (pressure forming step T2), and this formed body is vacuumed at a temperature of 1200 ° C. for 2 hours.
- the main sintering was performed by holding in an atmosphere (sintering step T3), and a MoCr sintered body was manufactured.
- Cu plate material was placed on the MoCr sintered body, and Cu was infiltrated by holding at a temperature of 1150 ° C. for 2 hours in a vacuum heating furnace (Cu infiltration step T4). In this manner, Cu was liquid phase sintered in the MoCr sintered body to obtain a uniform infiltrated body.
- FIG. 9 shows an electron micrograph (magnification ⁇ 800) of the electrode material of Comparative Example 1.
- a region that appears relatively white (white portion) is a structure in which Mo and Cr are dissolved, and a portion that appears relatively black (black portion) is a structure of Cu.
- the electrode material of Comparative Example 1 has a structure in which Cu (black part) having a particle size of 20 to 60 ⁇ m is dispersed in fine MoCr solid solution particles (white part) having a size of 1 to 10 ⁇ m. This is because in the Cu infiltration step T4, the Cr particles are refined by the Mo particles, and Cr diffuses into the Mo particles by the diffusion mechanism, so that the Cu infiltrates into the void portion formed in the step of forming a solid solution structure of Cr and Mo. It is estimated that this is the result.
- Comparative Example 2 The electrode material of Comparative Example 2 was made of the same material as that of Comparative Example 1 except that ⁇ 325 mesh (sieving 45 ⁇ m) was used as the Cr powder, and the electrode material was prepared by the same method as Comparative Example 1. Produced.
- Table 1 shows the withstand voltage performance of the electrode materials of Examples 1-8, Reference Examples 1 and 2, and Comparative Examples 1 and 2.
- the electrode material of Example 1-8 is an electrode material excellent in withstand voltage performance. It can also be seen that the withstand voltage performance of the electrode material improves as the proportion of the heat-resistant element contained in the electrode material increases.
- fine particles solid solution particles of a heat-resistant element and Cr
- a heat-resistant element and Cr are mutually dissolved and dispersed are uniformly dispersed in the electrode material. Therefore, current interruption performance and contact resistance can be reduced.
- the average particle size of the fine particles varies depending on the average particle size of the Mo powder as the raw material and the average particle size of the Cr powder.
- the average particle size of the fine particles dispersed in the electrode material is By controlling the composition so that the average particle size obtained using the above formula is 20 ⁇ m or less, more preferably 15 ⁇ m or less, the current blocking performance of the electrode material can be improved and the contact resistance can be reduced.
- the electrode material which was excellent in the withstand voltage performance and the electric current interruption performance can be obtained because the particle
- the dispersion state index CV obtained from the average value and the standard deviation of the distance between the center of gravity of the fine particles is 2.0 or less, preferably 1.0 or less. Therefore, the composition of the electrode material can be controlled so that an electrode material excellent in current interruption performance and withstand voltage performance can be obtained.
- the ratio of the heat-resistant element and the Cr element in the solid solution powder is such that the weight ratio of Cr is 4 or less with respect to the heat-resistant element 1, more preferably, Cr is 1/3 or less with respect to the heat-resistant element 1. An electrode material excellent in performance can be obtained.
- the average particle size of the heat-resistant element can be one factor that determines the particle size of the solid solution powder of the heat-resistant element and Cr. That is, Cr particles are refined by heat-resistant element particles, Cr diffuses into the heat-resistant element particles by the diffusion mechanism, and the heat-resistant element and Cr form a solid solution structure. growing. Further, the degree of increase by pre-sintering also depends on the mixing ratio of Cr. Therefore, by setting the average particle diameter of the heat-resistant element powder to, for example, 2 to 20 ⁇ m, more preferably 2 to 10 ⁇ m, the heat-resistant element and Cr for forming an electrode material having excellent withstand voltage performance and current interruption performance The solid solution powder can be obtained.
- the filling rate of the electrode material is 95% or more, which is caused by an arc at the time of current interruption or current switching.
- An electrode material with less surface roughness of the contact surface can be produced. That is, there can be produced an electrode material that is free from fine irregularities on the surface of the electrode material due to the presence of pores and has excellent withstand voltage performance.
- the voids of the porous body by filling the voids of the porous body with Cu, it has excellent mechanical strength and higher hardness than the electrode material manufactured by the sintering method, so it manufactures an electrode material with excellent withstand voltage performance can do.
- the electrode material manufactured by the method for manufacturing an electrode material according to the embodiment of the present invention is provided on at least one of the fixed electrode and the movable electrode of the vacuum interrupter (VI), for example.
- Voltage performance is improved.
- the gap length between the fixed electrode and the movable electrode can be made shorter than the conventional vacuum interrupter, and the gap between the fixed electrode and the movable electrode and the main shield can be narrowed. Therefore, the structure of the vacuum interrupter can be reduced. As a result, the vacuum interrupter can be reduced in size.
- the manufacturing cost of the vacuum interrupter is reduced by downsizing the vacuum interrupter.
- the pre-sintering temperature is 1250 ° C.-3 hours, but the pre-sintering temperature of the present invention is 1250 ° C. or higher and not higher than the melting point of Cr, more preferably 1250
- the preliminary sintering time varies depending on the preliminary sintering temperature. For example, preliminary sintering for 3 hours is performed at 1250 ° C., but preliminary sintering for 0.5 hour is sufficient at 1500 ° C. It is.
- the MoCr solid solution powder is not limited to those manufactured by the manufacturing method described in the embodiment, and the MoCr solid solution powder manufactured by a known manufacturing method (for example, a jet mill method or an atomizing method) is used. Also good.
- the electrode material may be molded by CIP processing or HIP processing.
- the filling rate of the MoCr sintered body can be increased by performing the HIP treatment after the main sintering and before the Cu infiltration, and as a result, the withstand voltage performance of the electrode material can be increased.
- the electrode material produced by the method for producing an electrode material of the present invention is not limited to those having only heat-resistant elements, Cr and Cu as constituent elements, but contains elements that improve the characteristics of the electrode material. It may be.
- the welding resistance of the electrode material is improved by adding Te to the electrode material.
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Abstract
Description
具体的な実施例を挙げて、本発明の実施形態に係る電極材料の製造方法並びに当該方法により作製される電極材料について詳細に説明する。実施例1の電極材料は、図1に示すフローチャートにしたがって作製したものである。
実施例1の電極材料の断面を電子顕微鏡により観察した。電極材料の断面顕微鏡写真を図4(a)及び図4(b)に示す。
実施例1の電極材料の断面組織をSEM(走査型電子顕微鏡)により観察した。電極材料のSEM像を図5(a)及び図5(b)に示す。
dm=(4/π)×(NL/NS) …(1)
NL=nL/L …(2)
NS=nS/S …(3)
dm:平均粒径、π:円周率、
NL:断面組織上の任意の直線によってヒットされる単位長さ当たりの粒子数、
NS:任意の測定領域内でヒットされる単位面積当たりに含まれる粒子の数、
nL:断面組織上の任意の直線によってヒットされる粒子の数、
L:断面組織上の任意の直線の長さ、
nS:任意の測定領域内に含まれる粒子の数、
S:任意の測定領域の面積
具体的に説明すると、図5(a)のSEM像を用いて、その写真全体を測定領域(面積S)として得られたSEM像に含まれるMoCr粒子数nSを数えた。次に、SEM像を等分に分割する任意の直線(長さL)を引き、その直線にヒットされる粒子の数nLを数えた。
電極材料中にMoCr粒子がどれだけ存在するか、またMoCr粒子の粒径がどの程度のサイズであるかだけでなく、MoCr粒子がどの程度均一に分散されているかにより電極材料の特性が左右される。
CV=σ/ave.X …(4)
その結果、重心間距離Xの平均値ave.Xは5.25μm、標準偏差σは、3.0μmとなり、分散状態指数CVは、0.57となった。
実施例2の電極材料は、Mo粉末とCr粉末の混合比率を重量比率で、Mo:Cr=9:1で混合したものである。実施例2の電極材料は、Mo粉末とCr粉末の混合比率が異なること以外は、実施例1と同じ材料を原料とし、実施例1と同じ方法により電極材料を作製した。
実施例3の電極材料は、Mo粉末とCr粉末の混合比率を重量比率で、Mo:Cr=5:1で混合したものである。実施例3の電極材料は、Mo粉末とCr粉末の混合比率が異なること以外は、実施例1と同じ材料を原料とし、実施例1と同じ方法により電極材料を作製した。
実施例4の電極材料は、Mo粉末とCr粉末の混合比率を重量比率で、Mo:Cr=3:1で混合したものである。実施例4の電極材料は、Mo粉末とCr粉末の混合比率が異なること以外は、実施例1と同じ材料を原料とし、実施例1と同じ方法により電極材料を作製した。
実施例5の電極材料は、Mo粉末とCr粉末の混合比率を重量比率で、Mo:Cr=1:1で混合したものである。実施例5の電極材料は、Mo粉末とCr粉末の混合比率が異なること以外は、実施例1と同じ材料を原料とし、実施例1と同じ方法により電極材料を作製した。
実施例6の電極材料は、Mo粉末とCr粉末の混合比率を重量比率で、Mo:Cr=1:3で混合したものである。実施例6の電極材料は、Mo粉末とCr粉末の混合比率が異なること以外は、実施例1と同じ材料を原料とし、実施例1と同じ方法により電極材料を作製した。
実施例7の電極材料は、Mo粉末とCr粉末の混合比率を重量比率で、Mo:Cr=1:4で混合したものである。実施例7の電極材料は、Mo粉末とCr粉末の混合比率が異なること以外は、実施例1と同じ材料を原料とし、実施例1と同じ方法により電極材料を作製した。
参考例1の電極材料は、仮焼結工程において、1200℃で30分間仮焼結を行ったものである。参考例1の電極材料は、仮焼結工程における温度及び時間が異なること以外は、実施例1と同じ材料を原料とし、実施例1と同じ方法により電極材料を作製した。
参考例2の電極材料は、仮焼結工程において、1200℃で3時間仮焼結を行ったものである。参考例2の電極材料は、仮焼結工程における温度が異なること以外は、実施例1と同じ材料を原料とし、実施例1と同じ方法により電極材料を作製した。
Mo粉末とCr粉末の混合比率を重量比率で、Mo:Cr=1:4として、V型混合器を用いて均一となるように十分に混合した。
図8に示すフローチャートにしたがって、比較例1の電極材料を作製した。
比較例2の電極材料は、Cr粉末として-325メッシュ(ふるい目開き45μm)を用いたこと以外は、比較例1の電極材料と同じ材料を原料とし、比較例1と同じ方法により電極材料を作製した。
Claims (7)
- 耐熱元素の粉末とCr粉末とを含有する混合粉末を焼結して、耐熱元素とCrとが固溶した固溶体を得る仮焼結工程と、
前記固溶体を粉砕して粉末とする粉砕工程と、
前記固溶体の粉末を成形した成形体を焼結して焼結体を得る本焼結工程と、
当該焼結体にCuを溶浸するCu溶浸工程と、を有する、電極材料の製造方法。 - 前記仮焼結工程では、前記固溶体のX線回折測定におけるCr元素に対応するピークまたは耐熱元素に対応するピークのいずれかが完全に消失するまで前記混合粉末を焼結する、請求項1に記載の電極材料の製造方法。
- 前記仮焼結工程の焼結温度は、1250℃以上Crの融点以下の範囲である、請求項1または請求項2に記載の電極材料の製造方法。
- 前記本焼結工程の焼結温度は、Cuの融点以上Crの融点以下の範囲である、請求項1から請求項3のいずれか1項に記載の電極材料の製造方法。
- 前記仮焼結工程では、前記混合粉末を真空加熱炉にて焼結し、
少なくとも、前記混合粉末を焼結後の前記真空加熱炉の真空度を5.0×10-3Pa以下とする、請求項1から請求項4のいずれか1項に記載の電極材料の製造方法。 - 前記仮焼結工程では、前記混合粉末を加圧成形する、請求項1から請求項5のいずれか1項に記載の電極材料の製造方法。
- 前記混合粉末の成形圧力を0.1t/cm2以下とする、請求項6に記載の電極材料の製造方法。
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