CN101257119B - Double polar plates for fuel battery and method for making surface azote nickel-chromium thin film - Google Patents
Double polar plates for fuel battery and method for making surface azote nickel-chromium thin film Download PDFInfo
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- CN101257119B CN101257119B CN2008100863759A CN200810086375A CN101257119B CN 101257119 B CN101257119 B CN 101257119B CN 2008100863759 A CN2008100863759 A CN 2008100863759A CN 200810086375 A CN200810086375 A CN 200810086375A CN 101257119 B CN101257119 B CN 101257119B
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- 229910018487 Ni—Cr Inorganic materials 0.000 title claims description 23
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 title claims description 23
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- 238000007733 ion plating Methods 0.000 claims description 16
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Physical Vapour Deposition (AREA)
- Fuel Cell (AREA)
Abstract
The invention provides a bipolar plate for fuel cell and a surface nitric-nickel-chrome film preparation method which belong to fuel cell technique field. The bipolar plate is composed of a stainlesssteel thin plate substrate and its two sides nitric-nickel-chrome film; the nitric-nickel-chrome film thickness is micro-nanometer magnitude and is prepared by using electric arc ion filming method, therein, substrate passive film is removed by using ion sputtering method before filming, used ion comes from glow plasma of inert gases or electric arc plasma vaporized from metal target; a simple substance film with even component, a grads film with component changed continuously from inside to outside, or a multi-layer film with component changed alternately can be obtained by controlling filmingparameter in film depositing process. The substrate provided by the invention is the stainless steel thin plate, and has a nitric-nickel-chrome film on surface. The stainless steel thin plate and ini tric-nickel-chrome film match connects in atom dimension because of ion film depositing, thereby, the bipolar plate has characteristics of low-cost besides complex characteristics, for example, corrosion resistance, electrical conduction, strengthen and hydrophobic etc. The bipolar plate and preparation method are mainly suitable for fuel cell manufacturing field.
Description
Technical field
The invention belongs to the fuel cell technology field, relate to a kind of bipolar plates and technology of preparing thereof of used in proton exchange membrane fuel cell.
Background technology
Fuel cell (Fuel Cell) can will be stored in fuel and the oxidant chemical energy be converted into electric energy, its transformation efficiency height, environmental friendliness, good reliability are considered to the sustainable efficiently generation technology of 21 century first-selection.In each types of fuel cells, Proton Exchange Membrane Fuel Cells (Proton Exchange MembraneFuel Cell, PEMFC) have start fast, the life-span is long, the specific power advantages of higher, except that being applicable to the terrestrial power generation station, also be particularly suitable for removable power source and various portable power supplies, be one of ideal source of electric motor car and other vehicles or even weapon carrying, so the development of Proton Exchange Membrane Fuel Cells have very important effect to the development of whole technical field of new energies.
Bipolar plates is the critical piece of Proton Exchange Membrane Fuel Cells, account for more than 70% of battery weight, also account in the battery total cost near half, its effect is to separate reacting gas, collected current, each monocell is together in series and provides passage etc. by the flow field for the discharge that reaction gas passes in and out electrode and water.In order to satisfy these functions, bipolar plates should have characteristics such as very high conductivity, corrosion resistance, low-density, high mechanical properties, high choke ability, low cost and easy processing.The bipolar plate material of Proton Exchange Membrane Fuel Cells mainly contains three classes: graphite-like bipolar plates, metal double polar plates and composite material double pole plate.Graphite is good conductivity, corrosion-resistant after high-temperature process, is used widely in the Proton Exchange Membrane Fuel Cells early stage of development.But such materials processing cost is too high, and can't realize sheet, can't realize the commercialization application.With carbon dust and resin is major ingredient, can prepare bipolar plate material cheaply in enormous quantities through methods such as mold pressings, but conductivity and choke ability have much room for improvement.
Metal is the bipolar plate material of desirable Proton Exchange Membrane Fuel Cells, and it has conduction, the heat conductivility that high intensity is become reconciled, and reserves are abundant, easily processing, be suitable for producing in batches, can reduce thickness and improve power density, have the great potential that reduces the bipolar plates cost; In addition, metal can also prevent in the water cavity cooling agent to the diffusion at battery the two poles of the earth, but is particularly useful for the fuel cell system of cold-starting.So metal is considered to the inevitable choice that Proton Exchange Membrane Fuel Cells is realized industrialization.But, the subject matter of metal is easily to corrode under the Proton Exchange Membrane Fuel Cells environment, and its consequence is not only and is made the bipolar plates disabler, but also can cause proton exchange membrane " to poison ", its electric conductivity reduces power output rapidly also owing to surface corrosion descends simultaneously; Can improve the corrosion resistance of metal by modes such as alloyings, but often brought the reduction of its conductivity again, material corrosion resistance and electric conductivity are two aspects of contradiction generally speaking, when the anti-corrosion capability of material is strong (as some metal oxide etc.), its conductive capability is just poor, and the good material of conductive capability, its corrosion process is just more active, that is be difficult for getting both in same material conduction and corrosion resisting property; Some noble metals (such as gold, silver etc.) can to a certain degree be alleviated this contradiction, but directly use noble metal can bring the raising greatly of material cost.The common metal surface all has natural hydrophily in addition, and the obstruction that causes bipolar plate flow field therefrom also is to cause one of subject matter of bipolar plates operation stability decline.
Metal is had on the general metallicity basis at the reservation base material, and again the modification processing being carried out on its surface is the effective means of dealing with problems.Therefore, become the focus of this area in recent years by the research of metal-modified raising metal double polar plates decay resistance and conductive capability, how tame research institute, each big motor corporation are all carrying out related work both at home and abroad.Select by basis material as U.S. Oak Ridge National Laboratory, find the nichrome better performances, then nichrome being carried out high-temperature ammonolysis handles, under the PEMFC environment, show favorable conductive ability and decay resistance, but still have problems such as the higher and complex process of material cost, processing energy consumption be excessive.
Replace rare metal and alloy thereof to have advantage cheaply with stainless steel as bipolar plates, but the intrinsic one deck passivating film that exists of stainless steel surfaces, though play positive role to improving corrosion resisting property, but increased the contact resistance of bipolar plates greatly, to such an extent as to battery generates heat in running, power reduces and corrosion is quickened, so stainless steel is if must carry out surface modification treatment as bipolar plates.ZL200410082726.0 electricity consumption chemical synthesising technology is being obtained good effect at stainless steel surfaces electropolymerization conductive polymer membrane aspect the corrosion resisting property raising, but is being still waiting to improve aspect the reduction contact resistance; ZL200510119646.2 removes the passivating film of stainless steel surfaces with the chemical pickling method, the chromium content that improves stainless steel surfaces with heat-treating methods is aided with and oozes the conductivity that silver process improves bipolar plates, its beneficial effect is that the stainless contact resistance that is untreated has reduced an order of magnitude, then adopt passivating technique that non-conducting portion is carried out passivation again and improve corrosion resisting property, solved the contradictory problems between anti-corrosion and the conductivity to a certain extent.
At present, how further improving electric conductivity and anti-corrosion capability and other correlated performance of bipolar plates, is the urgency common problem to be solved that the Proton Exchange Membrane Fuel Cells field is faced.
Summary of the invention
The purpose of this invention is to provide a kind of cheaply, material consumption quantity low, high-quality, the used in proton exchange membrane fuel cell bipolar plates and the method for making surface azote nickel-chromium thin film thereof that are easy to produce in batches.Adopt the bipolar plates of structure of the present invention and method preparation, have anti-corrosion, conduction, reinforcement and the composite performance such as hydrophobic of high target simultaneously, service requirement when satisfying long in Proton Exchange Membrane Fuel Cells.
Technical conceive of the present invention is, increases the modified film of the micro-nano magnitude thickness of one deck again in the both side surface of stainless sheet steel bipolar plates, played effects such as support, trapping like this by base material, plays anti-corrosion, conduction, reinforcement, effect such as hydrophobic by superficial film.Wherein particularly crucial is that the surface modification film prepares with electric arc ion electroplating method deposition.
Ion plating technique is used for the history that the material surface modifying depositing of thin film has had decades.Arc ion plating is one of the most representative ion plating technique, is the highest ion plating form of ionization level, and it is fast to have deposition velocity, film density height, and combination reaction fully waits advantage; Because the orderly deposition that film growth mechanism is carried energy particle (ion) for atom level, thereby material is the continuous coupling connection of atomic scale between the film base, has half characteristics that metallurgy connects, adhesion is strong; In addition, arc ion plating modification rete is because thickness be micro-nano magnitude only, so material consumption quantity is low and effect is remarkable, is typical physical method masking technique owing to arc ion plating particularly, do not have the discharging of dusty gas and residual article, have the advantage of cleaning, environmental protection.Arc ion plating is widely used in tool and mould surface deposition synthetic compound class ganoine thin film field, is also bringing into play important effect in ornamental plated film field.If the preparation of arc ion plating membrane technology and bipolar plate of stainless steel and surface modification film thereof is combined, then be expected to realize the unification of the low cost of bipolar plates, anti-corrosion, conduction and hydrophobic performance.
Technical solution of the present invention is, a kind of bipolar plate for fuel cell, constitute by stainless sheet steel bipolar plates base material 1 and connected both side surface modified film 2,3 thereof, the modified film the 2, the 3rd on surface, azote nickel-chromium thin film, the thickness of film are 0.1 μ m-5 μ m.
Described connection is that base material 1 adopts the arc ion plating membrane deposition method to be connected with 2,3 of modified films, for the continuous coupling of material on atomic scale connects.
Described azote nickel-chromium thin film is the uniform nitrogen nickel chromium triangle of a composition monofilm, and the relative atom percentage composition of nitrogen is 0%-55%, and the relative atom percentage composition of nickel is 0%-90%.
Described azote nickel-chromium thin film is the nitrogen nickel chromium triangle gradient film that composition outwards changes from the lining, changes in 0%-55% with the relative atom percentage composition of the increase nitrogen of film thickness, and the relative atom percentage composition of nickel changes in 0%-90%.
Described azote nickel-chromium thin film is that composition is periodically variable nitrogen nickel chromium triangle nano-multilayer film alternately with thickness, the atomic percentage conc of nitrogen is alternately step variation between 0%-33% and 33%-55%, and alternately the elementary layer periodic thickness of step variation is 10nm-200nm.
A kind of method for making surface azote nickel-chromium thin film of bipolar plate for fuel cell, be with the preparation method of arc ion plating (aip) at bipolar plates substrate surface deposition azote nickel-chromium thin film, comprise following technical process: with bipolar plate of stainless steel thin plate base material after ultrasonic cleaning and oven dry are handled, be placed in the vacuum chamber of arc ion plating, the vacuum chamber vacuum be extracted into 5 * 10 by vacuum system
-3Pa charges into working gas, starter cathode target electric arc and biasing afterwards and begins to carry out substrate passivating film removal processing; Reduce then and be biased into-300V--500V, adjust operating air pressure to 0.2Pa-0.8Pa, adjust arc stream simultaneously, send into reacting gas nitrogen and begin to carry out film deposition process, deposition 20min-120min decontrols vacuum through the cold back of abundant stove again and takes out the bipolar plates of plated film; Wherein said substrate passivating film is removed to handle and is adopted the method for ion sputtering to carry out, ion comes from the glow discharge plasma of inert gas and the arc discharge plasma of metal targets arc evaporation, the working gas that for this reason charges into is an inert gas argon, air pressure is 0.3Pa-5Pa, the negative electrode target electric arc that starts is pure chromium metallic target electric arc and nichrome target electric arc, and the composition of nichrome target is Ni
90Cr
10-Ni
10Cr
90, arc current is 0A-80A, biasing is-500V--1500V; Film deposition process adopts the matching process of adjusting arc stream to carry out, and the arc current ratio of chromium target arc current and nickel chromium triangle target is 1A/2A-2A/1A;
Described adjustment arc current adopts with the method for the time arc stream variation of plated film and carries out, and begins to change 35A-150A to finishing the arc evaporation electric current from plated film.
Described feeding reacting gas adopts with the method for the time batch (-type) feeding of plated film and carries out, and the feeding amount is 0sccm-400sccm, and the make-and-break time cycle is 1min-10min.
The invention has the beneficial effects as follows, at bipolar plate of stainless steel surface deposition synthetic nitrogen nickel chromium triangle homogeneous membrane, nickel chromium triangle/nitrogen nickel chromium triangle multilayer film, nitrogen nickel chromium triangle gradient film, change the surface property of bipolar plate of stainless steel, hardness is reached more than the 10GPa, corrosion resistance improves 3 orders of magnitude, and contact resistance is reduced to 15m Ω cm
2Below (under the 0.8MPa thrust), water contact angle is greater than 90 °.
Description of drawings
The present invention is further described below in conjunction with the drawings and specific embodiments.
Fig. 1 is the cross-sectional profile structure chart of bipolar plates of the present invention.
Among the figure, 1. Thin Stainless Steel plate substrate, 2. surface nitrogen nickel chromium triangle modified film, 3. surface nitrogen nickel chromium triangle modified film.
Embodiment
Embodiment 1
With putting into the vacuum chamber of arc ion plating apparatus after the pre-treatments such as stainless sheet steel bipolar plates process cleaning-drying, pure chromium target is installed on all tops, cathode arc source position, part is installed the nichrome target, is evacuated down to 5 * 10
-3Pa; logical argon gas is to 0.4Pa; start chromium target and nickel chromium triangle target electric arc and obtain arc-plasma; arc stream is 50A; add-800V * 20kHz * 60% pulsed bias; carry out ion sputtering with the ion pair bipolar plates in the plasma and remove passivating film processing 10 minutes; falling the bias voltage amplitude arrives-300V; adjust chromium negative electrode target and nichrome target arc stream to 80A, feed nitrogen then, flow is 100sccm; begin to deposit the nitrogen nicr layer; time is 40 minutes, unloads bias voltage after then; stop arc; stop the supple of gas or steam; keep 1 hour reprocessing of melted and cooled in vacuum, bleed off vacuum at last and take out the bipolar plates of plated film.So be 1 micron nitrogen nickel chromium triangle modified film, make bipolar plates contact resistance≤15m Ω cm at the synthetic thickness of bipolar plate surfaces deposition
2(under the 0.8MPa), corrosion current i under the simulation PEMFC corrosive environment
Cor≤ 1.0 * 10
-6A/cm
2, water contact angle 〉=90 °, surface microhardness Hk 〉=15GPa, film/basic adhesion 〉=70N.
With putting into the vacuum chamber of arc ion plating apparatus after the pre-treatments such as stainless sheet steel bipolar plates process cleaning-drying, pure chromium target is installed on top, cathode arc source position, part is installed the nichrome target, is evacuated down to 5 * 10
-3Pa; logical argon gas is to 0.8Pa; add-800V * 20kHz * 40% pulsed bias causes the glow plasma of inert gas argon; carry out ion sputtering with the ion pair bipolar plates in the plasma and remove passivating film processing 10 minutes; falling the bias voltage amplitude arrives-300V; changing partial pressure of ar gas is 0.4Pa; start chromium cathode arc and nickel chromium triangle cathode arc, arc stream fixes on 80A, begins to deposit pure chromium layer; time is 5 minutes; feed nitrogen then, flow is 100sccm, begins to deposit the nitrogen nicr layer; duration also is 5 minutes; after stop to send nitrogen again, logical again nitrogen after 5 minutes ... so alternate repetition carries out, and total deposition plating time is 40 minutes; unload bias voltage then; stop arc; stop the supple of gas or steam; keep 1 hour reprocessing of melted and cooled in vacuum, bleed off vacuum at last and take out the bipolar plates of plated film.Be the modified film of nickel chromium triangle/nitrogen nickel chromium triangle nano-multilayered structures of 1 micron so, make bipolar plates contact resistance≤15m Ω cm at the synthetic thickness of bipolar plate surfaces deposition
2(under the 0.8MPa), corrosion current i under the simulation PEMFC corrosive environment
Cor≤ 1.0 * 10
-6A/cm
2, water contact angle 〉=90 °, surface microhardness Hk 〉=15GPa, film/basic adhesion 〉=70N.
With putting into the vacuum chamber of arc ion plating apparatus after the pre-treatments such as stainless sheet steel bipolar plates process cleaning-drying, pure chromium target is installed on top, cathode arc source position, part is installed the nichrome target, is evacuated down to 5 * 10
-3Pa; logical argon gas is to 0.8Pa; the pulsed bias that adds 800V * 20kHz * 40% causes the glow plasma of inert gas argon; carry out ion sputtering with the ion pair bipolar plates in the plasma and remove passivating film processing 10 minutes; the bias voltage amplitude is fallen to 300V; changing partial pressure of ar gas is 0.4Pa; start chromium cathode arc and nickel chromium triangle cathode arc; arc stream fixes on 80A, begins to deposit pure chromium layer, and the time is 5 minutes; feed nitrogen then; flow is 100sccm, adjusts chromium negative electrode arc stream subsequently once more, and method of adjustment is carried out according to continually varying mode in time; in 35 minutes; arc stream is evenly adjusted to 120A from 80A continuously, unloads bias voltage after then; stop arc; stop the supple of gas or steam; keep 1 hour reprocessing of melted and cooled in vacuum, bleed off vacuum at last and take out the bipolar plates of plated film.So be 1 micron chromium constituent content continually varying nitrogen nickel chromium triangle gradient modified film, make bipolar plates contact resistance≤15m Ω cm at the synthetic thickness of bipolar plate surfaces deposition
2(under the 0.8MPa), corrosion current i under the simulation PEMFC corrosive environment
Ocr≤ 1.0 * 10
-6A/cm
2, water contact angle 〉=90 °, surface microhardness Hk 〉=15GPa, film/basic adhesion 〉=70N.
Claims (4)
1. the method for making surface azote nickel-chromium thin film of a bipolar plate for fuel cell, be with the preparation method of arc ion plating (aip) at bipolar plates substrate surface deposition azote nickel-chromium thin film, comprise following technical process: with bipolar plate of stainless steel thin plate base material after ultrasonic cleaning and oven dry are handled, be placed in the vacuum chamber of arc ion plating, the vacuum chamber vacuum be extracted into 5 * 10 by vacuum system
-3Pa charges into working gas, starter cathode target electric arc and biasing afterwards and begins to carry out substrate passivating film removal processing; Reduce then and be biased into-300V--500V, adjust operating air pressure to 0.2Pa-0.8Pa, adjust arc stream simultaneously, send into reacting gas nitrogen and begin to carry out film deposition process, sedimentation time is 20min-120min, bleeds off vacuum through abundant stove after cold again and takes out the bipolar plates of plated film; It is characterized in that: the substrate passivating film is removed to handle and is adopted the method for ion sputtering to carry out, the ion of ion sputtering comes from the glow discharge plasma of inert gas and the arc discharge plasma of metal targets arc evaporation, the working gas that charges into is an inert gas argon, air pressure is 0.3Pa-5Pa, the negative electrode target electric arc that starts is pure chromium metallic target electric arc and nichrome target electric arc, and the composition of nichrome target is Ni
90Cr
10-Ni
10Cr
90, arc stream is 50A-80A, biasing is-500V--1500V; Film deposition process adopts the matching process of adjusting arc stream to carry out, and the arc stream ratio of chromium target arc stream and nickel chromium triangle target is 1A/2A-2A/1A.
2. the method for making surface azote nickel-chromium thin film of a kind of bipolar plate for fuel cell according to claim 1, it is characterized in that: described adjustment arc stream adopts the method with the time arc stream variation of plated film, begins to change 35A-150A to finishing the arc evaporation electric current from plated film.
3. the method for making surface azote nickel-chromium thin film of a kind of bipolar plate for fuel cell according to claim 1, it is characterized in that: the described reacting gas of sending into adopts the method for sending into the time batch (-type) of plated film, the amount of sending into is 5sccm-400sccm, and sending cycle break time is 1min-10min.
4. use the fuel battery double plates of claim 1,2 or 3 described method preparations, constitute by stainless sheet steel bipolar plates base material (1) and connected both side surface modified film (2); It is characterized in that: the modified film on surface is an azote nickel-chromium thin film, and being connected between base material (1) and modified film (2) is the continuous coupling connection of material on atomic scale, and the thickness of film is 0.1 μ m-5 μ m.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2008100863759A CN101257119B (en) | 2007-05-28 | 2008-03-25 | Double polar plates for fuel battery and method for making surface azote nickel-chromium thin film |
Applications Claiming Priority (3)
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CNA2007100115077A CN101092688A (en) | 2007-05-28 | 2007-05-28 | Ion plating modified method for bipolar plate of stainless steel for fuel cell in type of proton exchange membrane |
CN2008100863759A CN101257119B (en) | 2007-05-28 | 2008-03-25 | Double polar plates for fuel battery and method for making surface azote nickel-chromium thin film |
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CN2008100863759A Expired - Fee Related CN101257119B (en) | 2007-05-28 | 2008-03-25 | Double polar plates for fuel battery and method for making surface azote nickel-chromium thin film |
CN200810086374A Active CN100595951C (en) | 2007-05-28 | 2008-03-25 | Double polar plates for fuel battery and method for making surface carbon chromium thin film |
CN200810086373XA Expired - Fee Related CN101257117B (en) | 2007-05-28 | 2008-03-25 | Double polar plates for fuel battery and method for making surface azote chromium thin film |
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CN200810086373XA Expired - Fee Related CN101257117B (en) | 2007-05-28 | 2008-03-25 | Double polar plates for fuel battery and method for making surface azote chromium thin film |
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Family Cites Families (1)
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CN101092688A (en) * | 2007-05-28 | 2007-12-26 | 大连理工大学 | Ion plating modified method for bipolar plate of stainless steel for fuel cell in type of proton exchange membrane |
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2007
- 2007-05-28 CN CNA2007100115077A patent/CN101092688A/en active Pending
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2008
- 2008-03-25 CN CN2008100863759A patent/CN101257119B/en not_active Expired - Fee Related
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CN100595951C (en) | 2010-03-24 |
CN101257119A (en) | 2008-09-03 |
CN101092688A (en) | 2007-12-26 |
CN101257118A (en) | 2008-09-03 |
CN101257117A (en) | 2008-09-03 |
CN101257117B (en) | 2010-12-01 |
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