CN100494481C - Ion-implanted electroformed structural material and method of producing the structural material - Google Patents
Ion-implanted electroformed structural material and method of producing the structural material Download PDFInfo
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- CN100494481C CN100494481C CNB2004100896491A CN200410089649A CN100494481C CN 100494481 C CN100494481 C CN 100494481C CN B2004100896491 A CNB2004100896491 A CN B2004100896491A CN 200410089649 A CN200410089649 A CN 200410089649A CN 100494481 C CN100494481 C CN 100494481C
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- ion
- implanted
- electroformed
- electroforming
- electroforming device
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/48—Ion implantation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/30—Electron-beam or ion-beam tubes for localised treatment of objects
- H01J37/317—Electron-beam or ion-beam tubes for localised treatment of objects for changing properties of the objects or for applying thin layers thereon, e.g. for ion implantation
- H01J37/3171—Electron-beam or ion-beam tubes for localised treatment of objects for changing properties of the objects or for applying thin layers thereon, e.g. for ion implantation for ion implantation
Abstract
An ion-implanted electroformed structural material is made of an electroformed body formed by electroforming and has an ion-implanted layer formed by implanting ions into the electroformed body. In the electroformed structural material, the microstructure is modulated at a position deeper than the ion-implanted layer, and the hardness becomes higher than that of the original electroformed body even at a position deeper than the ion-implanted layer.
Description
Technical field
The present invention relates to ion-implanted electroformed structured material (ion-implanted electroformedstructural material) and preparation method thereof, more specifically, the present invention relates to the electroforming structured material made by electroforming device (electroformed body), wherein at surface portion, hardness than the part of ion implantation layer depth increases, and the method for preparing this structured material.
Background technology
LIGA (abbreviation of lithographic printing electrotyping forming (lithography electroforming molding)) technology can be used to prepare high-precision metal microstructure (micro-structural body) on the scale operation basis.LIGA technology is used synchrotron light (synchrotron radiation) (SR), and it is the X ray of high directivity.Therefore, LIGA technology can be carried out dark lithographic printing.More specifically, this technology can be processed and be had the structure hundreds of micrometer depth, the micron number order of magnitude precision.In other words, it can prepare the metal micro structure body with big thickness at an easy rate.It also has other characteristics.Therefore, the expection of LIGA technology may be used on very extensive fields.
LIPG technology be combine lithographic printing, as the processing technology of the plating and the moulding of electroforming.In LIPG technology, for example the absorption mask (light net (reticle)) by having predetermined pattern is used the resist layer of SR irradiation in electrically-conductive backing plate formation.According to the pattern (mask pattern) that absorbs mask, this lithographic printing has formed resist structure body (resin mold).When during at the open place of mask pattern metal refining, accessing the metal micro structure body by electroforming.When this high-precision metal microstructure during as molding die, can use preparation microstructure formed bodys such as injection moulding, this formed body is made by synthetic resins.When making up the microstructure formed body that so obtains, can access micromotor (micromachine).Above-mentioned technical description in, ManabuYasui for example, the report of Yasuo Hirabayashi and Hiroyuki Fujita (734～737, No.11, Vol.52,2001, " Journal of the Surface Finishing Society of Japan ").
But in above-mentioned LIGA technology, be confined to the metal that electroforming handle to form can be by electroplated metal, for example nickel (Ni), iron (Fe), cobalt (Co) and Ni-Fe alloy.When higher hardness of needs or higher intensity, use the more material of high rigidity sometimes, for example Ni-Mn (manganese) alloy or Ni-W (tungsten) alloy.But in the case, need more advanced technology to be used to control electroplating solution or the like.This requirement has limited its range of application.
In addition, when micro-structural components needed wear resistance, its surface can be equipped with hard coat, and this coating forms by technologies such as for example plating, physical vapor deposition (PVD) or chemical vapor deposition (CVD)s.But in the case, the enough cohesive strengths that how to obtain between this article body and the coating are problems.In addition, when complex-shaped, when vapour deposition, may be difficult to form coating at dash area (shaded portion) and small sunk part.
On the other hand, when replacing solution to carry out electroforming as the electroforming bath by the use fused salt, compare with conventional nickel-base alloy, this technology can produce the very hard electroforming device of being made by chromium (Cr), titanium (Ti), molybdenum (Mo) etc.But the fused salt that can be used in the electroforming of using above-mentioned metal is limited to 250 ℃ or higher.Therefore, in the lithographic printing of using conventional photo-resist, resist causes and can't use owing to heat is out of shape.In addition, fused salt is height moisture absorption and chemically active.This character has produced the requirement that for example need carry out electroforming in inert atmosphere.
Consider above-mentioned situation, industrial requirement exploitation can be by the electroforming structured material of ordinary method formation, and it is easy to improve intensity, and the method for preparing this structured material.
Summary of the invention
The purpose of this invention is to provide a kind of ion-implanted electroformed structured material that can be easy to improve intensity, and the method for preparing this structured material.
According to the present invention, aforementioned purpose is finished by following ion-implanted electroformed structured material is provided.Ion electroforming structured material is formed by electroforming device by electroforming.The electroforming structured material has by will speed up the ion implantation ion implanted layer that forms in the electroforming device.
In the electroforming structured material, have high-intensity ion implanted layer and form at surface portion, the modulated structure (modulated structure) with meticulousr (finer) structure forms in the position than ion implantation layer depth.As a result, in surface portion and the dark part of specific surface part, can gain in strength.
According to an aspect of the present invention, the invention provides the method for the following ion-implanted electroformed structured material of preparation.This method comprises step that forms electroforming device and the step that will speed up ion implantation this electroforming device.The combination of abovementioned steps can form has the more modulated structure of fine structure, and it is positioned at the position darker than ion implanted layer at surface portion.
According to the present invention, when using ion-implanted electroformed structured material and preparing the method for this material, the weather resistance of electroforming structured material is easy to improve.So, can use this structured material and this method to calcine with structured material that improves intensity and the micro electroforming structured material that is used for micromotor usually as need so far always.Therefore, expection be can be used in the application widely by the technology of the present invention's exploitation, comprises the application of eliminating calcining step and other the unknown.
Description of drawings
In the accompanying drawings:
Fig. 1 is the synoptic diagram of the method for the ion-implanted electroformed structured material of preparation, and it is one embodiment of the present invention.
Fig. 2 is the depth profile synoptic diagram of the hardness of ion-implanted electroformed structured material of the present invention.
The microstructure synoptic diagram of material when Fig. 3 is electroforming.
Fig. 4 is after ion implantation, the microstructure synoptic diagram of electroforming device.
Fig. 5 is when the electroforming, apart from the synoptic diagram of focused ion beam (FIB) photo of material surface 40 micrometer depth positions.
Fig. 6 is the string diagram (line drawing) of microstructure of " A " part of showing among Fig. 5.
Fig. 7 is the FIB photo that ion implantation back is taken in 40 microns dark positions, distance electroforming device surface.
Fig. 8 is the string diagram of microstructure of " A " part of Fig. 7 demonstration.
Preferred implementation
The inventor finds when ion implantation in electroforming device the time, and this injection causes the phenomenon in the hardness raising that exceeds the position that ion arrives.But the mechanism that produces this phenomenon is not clear.The inventor has studied lot of documents, but can not affirm that above-mentioned phenomenon delivered.However, by changing the repeatability that experimental results show that this phenomenon that various experiment conditions carry out.
Below with reference to accompanying drawing, explain embodiments of the present invention.Fig. 1 is the synoptic diagram of the method for the ion-implanted electroformed structured material of preparation in embodiment.According to the pattern (not shown) of resist layer, on metal substrate 3, form electroforming device 1.With 10kV or higher acceleration voltage ion 2 is pushed in the electroforming device 1, make these ions be injected into.This is ion implantation to have increased the hardness of the darker position of the ion implanted layer that shows in than Fig. 2.Compare with untreated electroforming device, being increased under most of situation of hardness is 30%, in some cases up to 50%.This increase is significant.Ion implanted layer is 5 microns or more shallow zone formation in the degree of depth.Fig. 2 does not point out the hardness of ion implantation layer region.
Fig. 3 is the synoptic diagram of the microstructure of electroforming device.Might even in electroforming device, obtain fine structure.More specifically, apply pulse-like voltage between the electrode in bathing by electroforming, when carrying out electroforming so that the pulse type electric current to be provided, electroforming device from electroforming solution, deposit come out in, be used for the density increase of sedimentary nucleation site.As a result, can obtain to have the electroforming device of fine structure.The synoptic diagram of Fig. 3 has shown the electroforming device with this fine structure.Under the situation of this electroforming device, crystal is grown continuously from the surface of electrode.Therefore, be formed on styloid long on the direction of growth sometimes, it is orientation not.The synoptic diagram of Fig. 3 can be interpreted as showing the schematic cross-section of equiaxed crystal (equiaxed crystals) or styloid.Under the situation of styloid, the crystal grain diameter of average crystal grain diameter on the vertical section, measuring.
In the middle of the fine grain 5 in the crystalline structure that Fig. 3 shows, there is space 4 (being also referred to as hole or hole).On the other hand, Fig. 4 shows modulated structure.It has meticulousr structure in the part than ion implantation layer depth.Crystal grain when as shown in Figure 4, crystal grain 5 becomes than electroforming is meticulousr.Thus, space 4 becomes littler.As if when crystal grain became meticulousr, imperfection (defective) (for example space) part consumed and is the increment of grain boundary, it is a class imperfection (defective).But as mentioned above, this may be the phenomenon of meeting first in the long history of bulk metal material.Therefore, the inventor avoids providing clearly and explains.Above description only be interpreted as the fact of explaining that the inventor finds.
Fig. 5 is the synoptic diagram of focused ion beam (FIB) photo of electroforming device.Fig. 6 is the string diagram of microstructure of " A " part of showing among Fig. 5.Electroforming device is formed styloid, and the average crystal grain diameter of this styloid is less than 1 micron.Though this electroforming device contains the space,, in Fig. 5, can not observe them because ratio of enlargement is not enough.
Fig. 7 injects FIB photo behind the ion from above-mentioned electroforming device face side." A " string diagram partly that Fig. 8 shows for Fig. 7.Among Fig. 6 and 8 string diagram comparison shows that this structure is modulated, and apart from the surface 40 microns inside far away, promptly ion not have arrival interior location become meticulousr.As can be observed from Fig. 8, seeming synthetic mode will influence original styloid.More specifically, along the longitudinal axis of styloid, this structure seems and becomes meticulousr, has kept elongated shape simultaneously slightly.The degree that becomes meticulousr is significant, and average crystal grain diameter seems and is far smaller than 0.5 micron.
As mentioned above, might be by forming the above-mentioned increase that modulated structure obtains hardness, this structure has meticulousr structure in the position darker than ion implanted layer.
Embodiment
Under 55 ℃, 5A electric current, form with following plating bath (electroforming bath), by using 10 centimetres square nickel plate as negative electrode, nickel carries out electroplating in 100 minutes (electroforming) as anode:
[plating bath]
Nickel sulfamic acid: 300g/l (g/dm
3)
Thionamic acid manganese: 40g/l
First brightener (brightener) (sodium saccharate (sodium saccharic acid): an amount of
Second brightener (butynediol): an amount of
Tensio-active agent (laureth sodium sulfate): an amount of
Then, downcut 2 centimetres square segment from the centre portions of sample (electroforming device).This segment is halved, make each partly all have 1 centimetre width.Half is as the sample (1) that is used to measure hardness and crystal grain diameter.Second half is as ion implantation sample (2).
Make and measure hardness in the following method.Sample (1) vertically is inserted in the Resins, epoxy, make the cross section can with the surface level of resin.By continuously changing the granularity to 4000 of abrasive grain, use the abrasive polishing cross section.Then, obtain the surface of minute surface precision work (mirror-finished) by the polishing cross section.Use the Vickers hardness-testing device, in the position measurement hardness of 25 microns far away of the plate surfaces of distance sample.Carry out ten times and measure, obtain mean value.Measure crystal grain diameter with X-ray diffraction.
Under the condition below, it is ion implantation that sample (2) (electroforming device) is carried out omnidirectional (omnidirectional):
[omnidirectional's ion implanting conditions]
Voltage: 30kV
The ionic type that injects: carbon (C)
Pulse-repetition: 150kHz
Treatment time: 60 minutes
Maximum vacuum: 6.7 * 10
-4Pa or lower
Temperature: with 25 ℃ coolant cools substrate holder
After ion implantation, measure Vickers hardness and crystal grain diameter according to sample (1).
(measuring result)
The Vickers hardness (Hv) of sample (1) is 439, and crystal grain diameter is 10～1000nm.Handle the back observation by scanning ion microscope (SIM) at FIB and confirmed to exist nano level slight void.
On the other hand, in the position than ion implantation layer depth, ion-implanted electroformed structured material has the Vickers hardness of increase, and its Hv is 511.Under same position, crystal grain diameter is reduced to the scope of 5～250 nanometers.After FIB handles, observe discovery observed space in sample (1) by SIM and become littler, and its density significantly reduces.
Calculating on the basis, the discovery that obtains from other embodiment of the present invention and above-mentioned embodiment is explained as follows:
(1) in above-mentioned ion-implanted electroformed structured material, in from the surface to 5 microns the surface portion scope of the degree of depth at the most, can form ion implanted layer, and can prepare in position that wherein microstructure is modulated than ion implantation layer depth structure.
Above-mentioned structure (wherein the microstructure of electroforming device is modulated) refers to a kind of structure, the microstructure when wherein having changed electroforming, and the meticulousr crystal grain of the crystal grain when making than electroforming constitutes major portion.This structure can prepare the microtexture material with superior weather resistance.If ion implantation will reaching apart from the degree of depth of surface greater than 5 microns needs very large extensive accelerator.This system has departed from purpose of the present invention, and it can be gained in strength easily.
Can be by carrying out the modulation of microstructure in the kernel of section position, this position is in the depths of distance electroforming structured material interior surface.
As mentioned above, why by the above-mentioned modulated structure of ion implantation generation, how dark the modulated structure of formation is or the like not clear apart from the surface.But modulated structure can form at the whole thickness of electroforming structured material (thickness is approximately 80 microns).In case the formation modulated structure, it can form in the gross section.That is, the depth profile of modulated structure can not be controlled.But when at least on kernel of section part, when forming the modulated structure with fine structure more, this structure helps to improve the weather resistance of electroforming structured material very much.
(2), can have 0.5 micron average crystal grain diameter at the most in the synthetic part that produces above-mentioned microstructure according to the present invention.Formation has more, and the modulated structure of fine structure can improve intensity.Shown in Fig. 5～8, when modulation had the structure of electroforming device of columnar crystal structure, styloid had kept the shape of styloid, and it becomes meticulousr simultaneously.In styloid, average crystal grain diameter is the average crystal grain diameter that is parallel to the section of the styloid direction of growth.
As mentioned above, according to the present invention, the modulation of microstructure and on than the position of ion implantation layer depth the part that reduces to cause having modulated microstructure of average crystal grain diameter have the higher hardness of electroforming device when forming by electroforming.
(3) electroforming device that forms by electroforming is that ion will inject material wherein.When electroforming device itself has fine structure, be easy in inside by ion implantation preparation modulated structure.Compare with electroforming device, the modulated structure by ion implantation preparation has meticulousr structure and the intensity of Geng Gao.
People wish 1 micron at the most of the average crystal grain diameter of the electroforming device that forms by electroforming.Under the situation of styloid, average crystal grain diameter is the mean value of crystal grain diameter of the vertical section of styloid.Above-mentioned requirements can obtain by applying pulse-like voltage when the electroforming.Degree of supersaturation when the applying of pulse-like voltage or pulse type electric current can increase from solution deposition.This increase can increase the density of nucleus development, causes electroforming device to have meticulousr structure.When ion implantation, this operation has promoted to have the more modulated structure of fine structure in the position formation than ion implantation layer depth.
(4) in ion implantation step, with ion implantation to the hardness that can improve the part darker from the surface to 5 microns the scope of the degree of depth at the most than this zone.That is, the modulated structure of fine structure can form in the position darker than ion implanted layer because have more, and the inside outside the part that ion arrives can have higher intensity.
In above-mentioned ion implantation step, with ion implantation to from the surface to the structure of can this part of the modulation ratio dark part of 5 microns the scope of the degree of depth at the most.According to present method, even when ion implanted layer forms, for example can have the more modulated structure of fine structure in the position at 40 microns places in from the surface to 5 microns depth range at the most in the degree of depth apart from the surface.
(5) in ion implantation step, the temperature of electroforming device can remain on the material that forms electroforming device fusing point (representing) with K at the most 1/3.In having the modulated structure of fine structure more, this condition has kept the diameter that reduces of each crystal grain, increases and roughen so can prevent fine grain.
(6) in ion implantation step, wish that ion quickens under the voltage of 10kV at least.If acceleration voltage is less than 10kV, ion can not fully inject, and formation has the more modulated structure of fine structure in inside so be difficult to (if not impossible words).
(7) in ion implantation step, wish to use omnidirectional's plasma ion implantation apparatus.Even for the electroforming device with complicated shape, this device can form the uniform ion input horizon on whole surface, and does not produce dash area.As a result, having more, the modulated structure of fine structure can form in the whole positions than ion implantation layer depth.
(8) wish that electroforming device made by the material that is selected from Ni, Fe, copper (Cu), zinc (Zn), tin (Sn), Mn, Co, silver (Ag), gold (Au) and alloy thereof.The ion implantation processing of the electroforming device of being made by previous materials can prepare the ion electroforming structured material with superior weather resistance.
(9) in the above-described embodiment, carbon (C) ion is as the ion that will be injected in the electroforming device.But, can use other ion.For example can use nitrogen (N) ion.This ion can be atomic ion or molion.Certainly, also can use other ion except carbon and nitrogen.
Embodiments of the present invention have been explained as mentioned above.Above-mentioned embodiment of the present invention only limits to the purpose of illustration.Scope of the present invention is not subjected to the restriction of above-mentioned embodiment.Scope of the present invention is by the range describe of appended claims.The invention is intended to comprise the implication of the scope that is equivalent to claim and all improvement in the scope.
Claims (8)
1. ion-implanted electroformed structured material, it is made by the electroforming device that forms by electroforming, and this ion-implanted electroformed structured material has the ion implanted layer by forming in the ion-implanted electroformed body,
Wherein, described electroforming device forms by applying pulse-like voltage;
The average crystal grain diameter of described electroforming device is 1 micron or less than 1 micron;
Forming described ion implanted layer from the surface of ion-implanted electroformed structured material to the surface portion of 5 micrometer depth at the most; And
In microstructure than the ion-implanted electroformed structured material of position modulation of ion implantation layer depth.
2. ion-implanted electroformed structured material as claimed in claim 1 is wherein in the cross section middle position modulation microstructure from the surface to the deep inside.
3. ion-implanted electroformed structured material as claimed in claim 1, the average crystal grain diameter of wherein having modulated the part of microstructure are 0.5 micron or less than 0.5 micron.
4. ion-implanted electroformed structured material as claimed in claim 1 has wherein been modulated the hardness height of the electroforming device that the hardness ratio electroforming of the part of microstructure forms.
5. method that is used to prepare ion-implanted electroformed structured material, this method comprises following step:
(1) forms electroforming device; And
(2) will speed up ion implantation in electroforming device,
Wherein, in the step that forms electroforming device, described electroforming device forms by applying pulse-like voltage;
In forming the step of electroforming device, the average crystal grain diameter of described electroforming device is 1 micron or less than 1 micron;
In will speed up ion implantation step in this electroforming device, from the surface to injecting ion 5 microns dark zones at the most, with the structure of should the zone dark part of modulation ratio with increase the hardness of the part darker than this zone.
6. the method for the ion-implanted electroformed structured material of preparation as claimed in claim 5, wherein in will speed up ion implantation step in this electroforming device, the temperature of electroforming device remain on the material that forms electroforming device fusing point 1/3 or less than 1/3, wherein fusing point is represented with K.
7. the method for the ion-implanted electroformed structured material of preparation as claimed in claim 5, wherein in will speed up ion implantation step in this electroforming device, speeding-up ion under the voltage of 10kV at least.
8. the method for the ion-implanted electroformed structured material of preparation as claimed in claim 5 wherein in will speed up ion implantation step in this electroforming device, is used omnidirectional's plasma ion implantation apparatus.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003370309 | 2003-10-30 | ||
| JP370309/2003 | 2003-10-30 | ||
| JP370309/03 | 2003-10-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1611632A CN1611632A (en) | 2005-05-04 |
| CN100494481C true CN100494481C (en) | 2009-06-03 |
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ID=34543863
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100896491A Expired - Fee Related CN100494481C (en) | 2003-10-30 | 2004-10-29 | Ion-implanted electroformed structural material and method of producing the structural material |
Country Status (4)
| Country | Link |
|---|---|
| US (2) | US20050092608A1 (en) |
| KR (1) | KR20050041893A (en) |
| CN (1) | CN100494481C (en) |
| DE (1) | DE102004051374A1 (en) |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62122714A (en) * | 1985-11-25 | 1987-06-04 | Canon Inc | Duplicate mold for precision molding |
| US4678680A (en) * | 1986-02-20 | 1987-07-07 | Xerox Corporation | Corrosion resistant aperture plate for ink jet printers |
| US4673467A (en) * | 1986-09-02 | 1987-06-16 | Cbs Inc. | Method of manufacturing fine-grained copper substrate for optical information carrier |
| US4915746A (en) * | 1988-08-15 | 1990-04-10 | Welsch Gerhard E | Method of forming high temperature barriers in structural metals to make such metals creep resistant at high homologous temperatures |
| US5516415A (en) * | 1993-11-16 | 1996-05-14 | Ontario Hydro | Process and apparatus for in situ electroforming a structural layer of metal bonded to an internal wall of a metal tube |
| US5829240A (en) * | 1997-03-17 | 1998-11-03 | A. B. Carter, Inc. | Spinning ring having improved traveler bearing surface |
| US7122760B2 (en) * | 2002-11-25 | 2006-10-17 | Formfactor, Inc. | Using electric discharge machining to manufacture probes |
-
2004
- 2004-10-21 DE DE102004051374A patent/DE102004051374A1/en not_active Withdrawn
- 2004-10-25 KR KR1020040085213A patent/KR20050041893A/en not_active Application Discontinuation
- 2004-10-29 CN CNB2004100896491A patent/CN100494481C/en not_active Expired - Fee Related
- 2004-10-29 US US10/975,435 patent/US20050092608A1/en not_active Abandoned
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2008
- 2008-03-14 US US12/076,154 patent/US20080237049A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| KR20050041893A (en) | 2005-05-04 |
| US20050092608A1 (en) | 2005-05-05 |
| DE102004051374A1 (en) | 2005-06-02 |
| US20080237049A1 (en) | 2008-10-02 |
| CN1611632A (en) | 2005-05-04 |
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