WO2004108988A1 - 放電表面処理方法および放電表面処理装置 - Google Patents
放電表面処理方法および放電表面処理装置 Download PDFInfo
- Publication number
- WO2004108988A1 WO2004108988A1 PCT/JP2004/001318 JP2004001318W WO2004108988A1 WO 2004108988 A1 WO2004108988 A1 WO 2004108988A1 JP 2004001318 W JP2004001318 W JP 2004001318W WO 2004108988 A1 WO2004108988 A1 WO 2004108988A1
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- WIPO (PCT)
- Prior art keywords
- electrode
- discharge
- surface treatment
- voltage
- discharge surface
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Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
Definitions
- the present invention relates to a discharge surface treatment technology, and more particularly, to a powder compact electrode obtained by compression-molding a metal powder, a metal compound powder, or a ceramic powder, as an electrode.
- the present invention relates to a discharge surface treatment method and a discharge surface treatment apparatus for generating a pulsed discharge and forming a film made of an electrode material or a substance in which the electrode material has reacted by the discharge energy on a work surface by using the energy.
- Patent Document 1 The conventional discharge surface treatment focuses on abrasion resistance at room temperature and forms a coating of a hard material such as TiC (titanium carbide) (for example, see Patent Document 1).
- Patent Document 1 a hard material such as TiC (titanium carbide)
- an electrode different from a ceramic-based electrode for forming a hard ceramic film is used.
- An electrode formed by performing a heat treatment as necessary is used.
- the hardness of the electrode must be reduced to some extent. It is necessary to give the electrode certain characteristics such as This is because it is necessary to supply a large amount of electrode material to the workpiece by a discharge pulse.
- the discharge surface treatment can usually form a stable film, the film formation suddenly becomes unstable, and once it becomes unstable, it cannot be easily recovered to a stable state.
- This is considered for the following reasons. That is, the sudden occurrence of the unstable state is due to the concentration of the discharge.
- the portion of the electrode where the discharge is concentrated widely melts and re-solidifies.
- the portion of the electrode melts, the shape of the electrode at that portion is deformed, and a state in which discharge is likely to occur is obtained.
- the discharge is likely to be generated, and the damage of the portion is increased, so that it is difficult to recover the film formation to a stable state.
- the present invention has been made in view of the above, and accurately detects an unstable phenomenon of film formation, and performs an appropriate response process before the state of the film and the state of the electrode are deteriorated due to the unstable phenomenon. It is an object of the present invention to provide a discharge surface treatment method and a discharge surface treatment device for enabling to carry out the above. Disclosure of the invention
- the metal powder or the metal compound Using a powder or a compact formed by compressing ceramic powder as an electrode, a pulse-like discharge is generated between the electrode and the work, and the energy of the discharge forms a film made of the electrode material on the work surface or the material of the electrode.
- a discharge surface treatment method for forming a film made of a substance reacted by discharge energy wherein a voltage between an electrode and a workpiece during discharge is detected, and when a decrease in the voltage is detected, a discharge surface is detected. It is characterized in that the processing state is determined to be abnormal.
- an unstable phenomenon of the discharge surface treatment is accurately detected during the discharge surface treatment.
- FIG. 1 is a diagram showing a process of manufacturing a discharge surface treatment electrode
- FIG. 2 is a diagram showing a discharge surface treatment performed by a discharge surface treatment apparatus using a discharge surface treatment electrode for forming a thick film.
- FIG. 3 is a diagram showing the electric circuit of FIG. 2
- FIG. 4A is a characteristic diagram showing a voltage waveform when the discharge surface treatment is performed normally.
- FIG. 4B is a characteristic diagram showing a current waveform corresponding to the voltage waveform of FIG. 4A
- FIG. 5A is a characteristic diagram showing a voltage waveform when the discharge surface treatment is abnormal.
- FIG. 5B is a characteristic diagram showing a current waveform corresponding to the voltage waveform of FIG. 5A
- FIG. 6 is a diagram showing a state where a negative part of the electrode is melted by excessive heat.
- a carbon such as Co (cobalt), Ni (nickel), and Fe (iron) is used. It has been found that it is difficult to form a stable and dense thick film unless a material that is difficult to form is included in the electrode.
- a thick film that the above-mentioned material containing about 40% by volume or more that hardly forms carbide is contained.
- a material that hardly forms carbide is contained in the electrode in an amount of 40% by volume or more, a dense and thick film can be stably formed.
- the particle size is smaller than 1 izm, a thick film may be formed in some cases even if these materials are not necessarily included in the above amounts.
- FIG. 1 is a cross-sectional view showing the concept of a method for manufacturing an electrode for discharge surface treatment according to Embodiment 1 of the present invention.
- a Co alloy powder is used as an electrode material
- the space surrounded by the upper punch 2 of the die, the lower punch 3 of the die, and the die 4 of the die is filled with the Co alloy powder 1.
- a compact is formed by compression molding the Co alloy powder 1.
- this green compact is used as a discharge electrode.
- the manufacturing process of the electrode shown in FIG. 1 is as follows.
- the Co alloy powder 1 is put into a mold, and the upper punch 2 and the lower punch 3 apply pressure to the Co alloy powder 1 and press it. By applying a predetermined press pressure to the Co alloy powder 1 in this manner, The Co alloy powder 1 solidifies and becomes a green compact.
- the green compact that has been compression-molded as described above can be used as it is as an electrode for discharge surface treatment if a predetermined hardness is obtained by compression. Further, the compression molded green compact does not have a predetermined hardness, in which case the strength, that is, the hardness of the green compact can be increased by heating.
- FIG. 2 is a conceptual diagram showing how a discharge surface treatment is performed by the discharge surface treatment apparatus according to the present invention using the low-level discharge surface treatment electrode having a high hardness for forming a thick film manufactured in the above process. Show. FIG. 2 shows a state in which a pulsed discharge is generated. FIG. 3 is a diagram showing the electric circuit of FIG.
- the discharge surface treatment apparatus is an electrode for discharge surface treatment described above, and is a green compact obtained by compression-molding Co alloy powder 1 or a heat treatment of this green compact.
- the electrode for discharge surface treatment 11 (which may be simply referred to as the electrode 11 hereinafter), which is made of a green compact, and the oil which is the working fluid 13, and the voltage between the electrode 11 and the workpiece 12.
- a discharge surface treatment power supply device 14 for generating a pulse-like discharge (arc column 15) by applying a voltage.
- the power supply device 14 for discharging surface treatment is connected to the power supply body 14a, the voltage detection device 14b, the switching elements SI, S2, and the respective switching elements shown in FIG. And a control circuit .14c for turning on and off the switching elements S1, S2,... In FIG. 3, they are separated for easy understanding.
- members that are not directly related to the present invention such as a driving device that controls a relative position between the electrode 11 and the work 12 and a working fluid tank that stores the working fluid 13 are omitted.
- the electrode 11 and the workpiece 12 are arranged to face each other in the working fluid 13.
- a pulse-like discharge is generated between the electrode 11 and the work 12 by using the power supply device for discharge surface treatment 14.
- a voltage is applied between the electrode 11 and the work by turning on and off the switching element S 1 or S 2 by the control circuit 14 c to generate a discharge.
- the arc column 15 of the discharge is generated between the electrode 11 and the work 12 as shown in FIG.
- the switching element to be turned on and off is determined by the current to be flowed when discharged. More specifically, in FIG. 3, each switching element is connected to a resistor having a predetermined resistance value, and when a discharge occurs while each switching element is ON, the resistance value and the voltage of the power supply are changed.
- the current flowing when the switching element S 1 is turned on is (E ⁇ V g) ZR 1.
- the value of the current flowing when the switching element S2 is turned on is (E-Vg) / R2.
- the current flowing when the switching element S1 and the switching element S2 are simultaneously turned on is (E ⁇ V g) / R 1 + (E ⁇ V g) ZR 2.
- this circuit uses a resistor to limit the current, it is also possible to use a circuit system that determines the flowing current to a desired value.
- a film of the electrode material is formed on the surface of the work by the discharge energy of the discharge generated between the electrode 11 and the work 12, or a film of the substance reacted with the electrode material is formed on the surface of the work by the discharge energy.
- the electrode 11 side is used as negative polarity and the work 12 side is used as positive polarity.
- FIGS. 4A and 4B show examples of discharge pulse conditions when performing a discharge surface treatment in a discharge surface treatment apparatus having such a circuit configuration.
- Fig. 4 A and 4 FIG. B is a diagram showing an example of a discharge pulse condition at the time of discharge surface treatment.
- FIG. 4A shows a voltage waveform applied between the electrode 11 and the work 12 at the time of discharge. Shows the current waveform of the current flowing through the discharge surface treatment apparatus during discharge. As shown in FIG. 4A, a no-load voltage ui is applied between the electrodes at time t0, but discharge occurs between the electrodes at time t1 after the discharge delay time td has elapsed, and a current flows.
- the voltage at this time is the discharge voltage ue, and the current flowing at this time is the peak current value ie. Then, when the supply of the voltage between both electrodes is stopped at time t2, no current flows.
- Time t 2 -t 1 is referred to as pulse width te.
- the voltage waveform from time t0 to time t2 is repeatedly applied between both electrodes with a pause time to. That is, as shown in FIG. 4A, a pulse-like voltage is applied between the electrode 11 and the work 12.
- the voltage during discharge shows a value of about 50 V when the discharge surface treatment is performed normally, and a range of about 40 V to 60 V in many cases. However, there may be a slight shift up and down depending on various conditions such as the molding conditions of the electrode 11.
- the electrode 11 has a high hardness, the voltage between the electrode 11 and the work 12 is low. On the other hand, when the electrode 11 is made to have a soft hardness, the voltage between the electrode 11 and the work 12 becomes high.
- the voltage between the electrode 11 and the work 12, that is, the arc voltage itself is usually about 25 V to 3 OV.
- the electrode 11 for forming a thick film used in the present invention has a high electric resistance because it is made by solidifying powder.
- the measurement results of the voltage detector 17 in Fig. 3 indicate that the voltage drop at the electrode 11 is a brass voltage in the arc voltage, and the electric resistance value of the electrode is low, and it is higher than the case. Obviously, the measurement results of the voltage detector 17 in Fig. 3 indicate that the voltage drop at the electrode 11 is a brass voltage in the arc voltage, and the electric resistance value of the electrode is low, and it is higher than the case. Obviously, the measurement results of the voltage detector 17 in Fig. 3 indicate that the voltage drop at the electrode 11 is a brass voltage in the arc voltage, and the electric resistance value of the electrode is low, and it is higher than the case. Become.
- the detected voltage between the electrodes during the discharge that is, the voltage V1 between the electrode 11 and the work 12 is the fourth voltage.
- the force becomes a high value. If the film cannot be formed stably, As shown in FIG. 5A, it was found that the voltage of the voltage between the electrodes during discharge, that is, the voltage V 1 between the electrode 11 and the work 12 was reduced.
- the voltage between the electrode 11 and the workpiece 12 during discharge is stabilized by the voltage detection device 14b shown in FIG. 3, that is, the discharge surface treatment is performed stably. It detects that it has fallen below the time it has been. For example, a pulse at the gap voltage detection timing is generated a predetermined time after the occurrence of electric discharge, and the gap voltage is compared with a threshold value, which is the voltage at the boundary between stable machining and unstable machining, at that pulse And other methods.
- the timing of the above detection may be a predetermined time from the occurrence of discharge, for example, 1 ⁇ s to several seconds, or may be a process such as the middle of the discharge duration time.
- the voltage detection device 14b transmits a predetermined signal, for example, a signal of a voltage detection result to the control circuit 14c.
- the control circuit 14c determines the quality of the discharge state based on the detection result of the voltage detection device 14b.
- the control circuit 14c When it is determined that the electric body is abnormal (bad), the control circuit 14c further stops the generation of discharge by turning off the switching element S1 or S2 based on the result of the determination. .
- control circuit 14c has a function of determining the quality of the discharge state body based on the detection result of the voltage detection device 14b is described.
- Means having a function of judging pass / fail of the discharge state body based on the detection result may be provided separately from the control circuit 14c.
- the timing for detecting the voltage between the electrode 11 and the work 12 may be selected at one point during the discharge duration, and the voltage between the electrode 11 and the work 12 during the discharge duration may be selected. An average value may be selected.
- the voltage value between the electrode 11 and the workpiece 12 at the time of stable processing differs depending on the electrode used, but is substantially constant for each electrode. Therefore, a threshold value is set for a value lower than the voltage measured and determined in advance, and if it falls below that value, it is determined that there is an abnormality.
- a circuit for calculating the average value of the voltage value during the discharge of a certain number of pulses is arranged, and the discharge of the voltage value occurs at a predetermined rate, for example, 10% lower than the average value calculated by the circuit. It is also possible to determine that it is abnormal when it is generated.
- the following method can be used. For example, if the electrode is made of metal and there is no voltage drop at the electrode, the voltage value between the electrodes during discharge surface treatment, that is, the voltage value between the electrode and the workpiece, is 25 V to 30 V Since the voltage falls within the range of about V, it can be determined that the voltage is normal, for example, if the voltage between the electrodes is 35 V or more.
- discharge conditions such as extending the discharge pause time to
- a method of doubling the pause time from the next pulse when a pulse with a discharge voltage lower than the threshold is generated, etc. is there.
- the technique for preventing electrode damage in the case of forming a film by discharge surface treatment has been described above. From the results of the test for the present invention described above, the following can be understood.
- the voltage drop at the electrode, which causes the discharge voltage to rise during stable machining, that is, when the discharge surface treatment is being performed stably, is not caused by the entire electrode, but by the foot of the arc column on the electrode surface. Waking up in the part. ⁇
- the discharge voltage suddenly jumps out of the predetermined range that is, deviates from the predetermined range, can be determined to be an abnormal state of the electrode during the discharge surface treatment. Further, when the discharge voltage is always outside the predetermined range, it can be determined that the electrode is in an abnormal state from the beginning. This is because, when an electrode manufactured in a normal state is used, the voltage during discharge falls within a predetermined range, and does not always fall within the predetermined range (exceeding the predetermined range or exceeding the predetermined range). In this case, it can be determined that the electrode is in an abnormal state from the beginning.
- the electrode material is melted and moved to the work side.
- the electrode needs to be in a state where the electric resistance is large to some extent.
- an abnormal state occurs, for example, where the discharge concentrates on the local part of the electrode, the melting of that part of the electrode, that is, the part where the discharge concentrates, proceeds. Then, in this case, the electric resistance value of the electrode is reduced.
- the change in the state of this electrode is determined by the discharge voltage, that is, (arc potential between the electrodes)
- a state in which the discharge voltage has decreased indicates that an abnormality has occurred in the electrode, and the phenomenon can be detected at the timing of several discharges. .
- an unstable phenomenon of the discharge surface treatment is accurately detected, and an appropriate countermeasure is performed before the formation state of the film is deteriorated due to the unstable phenomenon. It becomes possible. That is, by determining the stability of the discharge surface treatment, it is possible to prevent the deterioration of the film formation state.
- a sudden occurrence of an unstable phenomenon in the formation of a film can be accurately detected, and appropriate measures can be taken before the state of the film and the state of the electrode become bad due to the unstable phenomenon. Processing can be performed. That is, according to the present invention, it is possible to prevent damage to the coating film and the electrode by determining the stability of the discharge surface treatment.
- the electric discharge surface treatment method according to the present invention is suitable for use in the surface treatment related industry for forming a film on the surface of a workpiece, and particularly for a surface forming a thick film on the surface of the workpiece. Suitable for use in processing related industries. .
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
Claims
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005506724A JP4523546B2 (ja) | 2003-06-04 | 2004-02-09 | 放電表面処理方法および放電表面処理装置 |
| US10/559,344 US7892410B2 (en) | 2003-06-04 | 2004-02-09 | Discharge surface treatment method and discharge surface treatment apparatus |
| TW093104056A TWI246949B (en) | 2003-06-04 | 2004-02-19 | Surface treating method by electric discharge, and apparatus therefor |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003158896 | 2003-06-04 | ||
| JP2003-158896 | 2003-06-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2004108988A1 true WO2004108988A1 (ja) | 2004-12-16 |
Family
ID=33508494
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2004/001318 Ceased WO2004108988A1 (ja) | 2003-06-04 | 2004-02-09 | 放電表面処理方法および放電表面処理装置 |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US7892410B2 (ja) |
| JP (1) | JP4523546B2 (ja) |
| CN (1) | CN100587113C (ja) |
| TW (1) | TWI246949B (ja) |
| WO (1) | WO2004108988A1 (ja) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9284647B2 (en) * | 2002-09-24 | 2016-03-15 | Mitsubishi Denki Kabushiki Kaisha | Method for coating sliding surface of high-temperature member, high-temperature member and electrode for electro-discharge surface treatment |
| KR101063575B1 (ko) * | 2002-09-24 | 2011-09-07 | 미츠비시덴키 가부시키가이샤 | 고온부재의 슬라이딩면 코팅 방법 및 고온부재와 방전표면 처리용 전극 |
| CN1692179B (zh) * | 2002-10-09 | 2011-07-13 | 石川岛播磨重工业株式会社 | 回转体及其涂覆方法 |
| RU2365677C2 (ru) * | 2005-03-09 | 2009-08-27 | АйЭйчАй КОРПОРЕЙШН | Способ обработки поверхности и способ ремонта |
| KR101192947B1 (ko) * | 2008-05-30 | 2012-10-18 | 케이씨아이 라이센싱 인코포레이티드 | 가슴 조직에서 사용되는 감압,압축 장치 및 방법 |
| JPWO2010134129A1 (ja) * | 2009-05-20 | 2012-11-08 | 三菱電機株式会社 | 表面層形成方法及び耐エロージョン部品の製造方法並びに蒸気タービン翼 |
| WO2011004426A1 (ja) * | 2009-07-07 | 2011-01-13 | 三菱電機株式会社 | ワイヤ放電加工装置 |
| US9308546B2 (en) * | 2012-06-05 | 2016-04-12 | Mitsubishi Electric Corporation | Discharge surface treatment apparatus |
| JP5230848B1 (ja) * | 2012-06-26 | 2013-07-10 | 三菱電機株式会社 | 放電表面処理装置および放電表面処理方法 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0770761A (ja) * | 1993-08-31 | 1995-03-14 | Res Dev Corp Of Japan | アルミニウム及びその合金の液中放電による表面処理方法 |
| JPH08323544A (ja) * | 1995-06-06 | 1996-12-10 | Aisin Aw Co Ltd | 放電加工装置 |
| WO1999058744A1 (en) * | 1998-05-13 | 1999-11-18 | Mitsubishi Denki Kabushiki Kaisha | Electrode for discharge surface treatment and manufacturing method thereof and discharge surface treatment method and device |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4236057A (en) * | 1976-12-14 | 1980-11-25 | Inoue-Japax Research Incorporated | Apparatus for detecting gap conditions in EDM processes with monitoring pulses |
| CH662764A5 (fr) * | 1985-03-05 | 1987-10-30 | Charmilles Technologies | Procede pour regler l'usinage par etincelage erosif. |
| JPS63156618A (ja) * | 1986-12-22 | 1988-06-29 | Hoden Seimitsu Kako Kenkyusho Ltd | 放電加工装置 |
| JP3093846B2 (ja) | 1991-11-18 | 2000-10-03 | 科学技術振興事業団 | 金属材料の表面処理方法 |
| JP3363284B2 (ja) | 1995-04-14 | 2003-01-08 | 科学技術振興事業団 | 放電加工用電極および放電による金属表面処理方法 |
| JP3121309B2 (ja) * | 1998-02-16 | 2000-12-25 | 株式会社デンソー | 内燃機関用のスパークプラグ |
| WO1999058743A1 (en) * | 1998-05-08 | 1999-11-18 | Mitsubishi Denki Kabushiki Kaisha | Power source unit for discharge surface treatment |
| US6793982B1 (en) * | 1998-05-13 | 2004-09-21 | Mitsubishi Denki Kabushiki Kaisha | Electrode of green compact for discharge surface treatment, method of producing the same, method of discarge surface treatment, apparatus therefor, and method of recycling electrode of green compact for discharge surface treatment |
| DE19883018C2 (de) * | 1998-11-13 | 2003-10-09 | Mitsubishi Electric Corp | Verfahren zur Bearbeitung einer Oberfläche einer Form unter Verwendung einer elektrischen Entladung, bei einer derartigen Bearbeitung verwendete Elektrode, und Verfahren zur Herstellung einer derartigen Elektrode |
| JP2001034227A (ja) * | 1999-07-15 | 2001-02-09 | Hitachi Ltd | 表示装置及びその駆動方法 |
| CH694120A5 (de) | 1999-07-16 | 2004-07-30 | Mitsubishi Electric Corp | Verfahren zum Herstellen einer Elektrode für Funkenoberflächenbehandlung. |
| DE19983980B3 (de) | 1999-09-30 | 2013-09-05 | Mitsubishi Denki K.K. | Verfahren zur Herstellung einer Entladungs-Oberflächenbehandlungs-Elektrode, hiernach erhaltene Entladungs-Oberflächenbehandlungs-Elektrode und deren Verwendung |
| EP1477257B1 (en) * | 2002-01-24 | 2014-03-12 | Mitsubishi Denki Kabushiki Kaisha | Method and system for electric discharge machining insulating material or high resistance material |
-
2004
- 2004-02-09 CN CN200480021740A patent/CN100587113C/zh not_active Expired - Fee Related
- 2004-02-09 US US10/559,344 patent/US7892410B2/en not_active Expired - Fee Related
- 2004-02-09 WO PCT/JP2004/001318 patent/WO2004108988A1/ja not_active Ceased
- 2004-02-09 JP JP2005506724A patent/JP4523546B2/ja not_active Expired - Fee Related
- 2004-02-19 TW TW093104056A patent/TWI246949B/zh not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0770761A (ja) * | 1993-08-31 | 1995-03-14 | Res Dev Corp Of Japan | アルミニウム及びその合金の液中放電による表面処理方法 |
| JPH08323544A (ja) * | 1995-06-06 | 1996-12-10 | Aisin Aw Co Ltd | 放電加工装置 |
| WO1999058744A1 (en) * | 1998-05-13 | 1999-11-18 | Mitsubishi Denki Kabushiki Kaisha | Electrode for discharge surface treatment and manufacturing method thereof and discharge surface treatment method and device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1829822A (zh) | 2006-09-06 |
| JP4523546B2 (ja) | 2010-08-11 |
| JPWO2004108988A1 (ja) | 2006-07-20 |
| TW200427538A (en) | 2004-12-16 |
| TWI246949B (en) | 2006-01-11 |
| CN100587113C (zh) | 2010-02-03 |
| US7892410B2 (en) | 2011-02-22 |
| US20060213777A1 (en) | 2006-09-28 |
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