CN1155734C - Process and apparatus for preparing porous metal by combined physical gas-phase deposition techinque - Google Patents
Process and apparatus for preparing porous metal by combined physical gas-phase deposition techinque Download PDFInfo
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- CN1155734C CN1155734C CNB021141533A CN02114153A CN1155734C CN 1155734 C CN1155734 C CN 1155734C CN B021141533 A CNB021141533 A CN B021141533A CN 02114153 A CN02114153 A CN 02114153A CN 1155734 C CN1155734 C CN 1155734C
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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
- 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
- C23C14/56—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks
- C23C14/562—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks for coating elongated substrates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
- H01M4/808—Foamed, spongy materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/24—Alkaline accumulators
- H01M10/30—Nickel accumulators
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Abstract
The present invention relates to a preparation method of multiporous metals by a combined physical vapor deposition technology and an apparatus thereof. The present invention is characterized in that any two of the evaporator method, the sputtering plating method and the ion plating method are respectively combined in a coiled vacuum coating machine, particularly relates to the methods of combining the electric arc evaporation plating with the magnetron sputtering plating, and combining the electric arc ion plating and the magnetron sputtering plating. The coiled vacuum coating machine comprises a coiling-uncoiling chamber, a coiling-uncoiling roller, a measuring roller, a magnet controlled plating chamber, magnet controlled targets, an electric arc evaporation plating chamber, electric arc evaporation targets, a spacer plate, a cooling water jacket, a pre-treatment chamber, a guide roller, an uncoiling-coiling chamber and an uncoiling-coiling roller. The present invention has the advantages of reasonable design, good effect on conductive treatment and good technical performance, and overcomes the defect of single technology in the prior art.
Description
Technical field
The present invention relates to a kind of physical gas phase deposition technology, be specifically related to a kind ofly in producing continuous band-shaped porous matter metal process, adopt the built-up type physical gas phase deposition technology, the method and apparatus that organic porous matter band is carried out the continuous conduction processing.
Background technology
Usually, the evaporation plating under the vacuum condition, sputter plating, ion plating are called physical vapor deposition (Physical Vapor Deposition) technology, be called for short PVD.The evaporation plating comprises resistance heating evaporation plating, electron beam evaporation plating, laser evaporation plating, ion beam evaporation plating, induction evaporation mode plating, the plating of hollow cathode plasma electrons beam evaporation, the plating of hot-cathode plasma electrons beam evaporation, arc evaporation plating etc.Sputter plating comprises direct current secondary sputter plating, asymmetrical alternating current sputter plating, bias sputtering plating, three grades of sputter platings, ion beam sputtering plating, radio-frequency sputtering plating, magnetron sputtering etc.Ion plating comprises hallow cathode deposition, HCD, multi-arc ion coating, ion beam assisted depositing etc.
Before this, except that the present invention, also have other method to be used for organic porous matter band is carried out the continuous conduction processing, as chemically coated nickel method, coated with conductive glue method, nickle carbonoxide nickel deposited single stage method and adopt the magnetron sputtering method of single PVD technology or vacuum vapour deposition etc.
Porous matter metal is a kind of novel engineering materials owing to have a porous tridimensional network, specific surface is big, tensile strength and snappiness is good, porosity is high, permeability is strong, in light weight, energy absorption is good, purposes is very extensive.Be widely used as at present the material-nickel foam of ni-mh, nickel-cadmium cell electrode base board in the world, because of making core rod with non-metallic material polyurethane sponge (comprising polyester and polyethers sponge), electroforming metal nickel moulding and gaining the name.The manufacturing technology of nickel foam mainly comprises core rod conductionization, galvanic deposit (claiming electroforming or plating again), thermal treatment three parts.Wherein the core rod conductionization is divided into chemically coated nickel method, coated with conductive glue method, nickle carbonoxide nickel deposited single stage method again and adopts single magnetron sputtering method or vacuum vapour deposition etc.Above-mentioned technology cuts both ways.From the end of the eighties so far, be that the enterprise of several in the world families mass-producing production nickel foam adopts successively.Wherein Ri Ben Sumitomo company, sheet mountain company, company of Chinese Changsha power unit, the general company in Jinchang, Chinese Shenyang, the U.S. former RETEC company adopt chemically coated nickel method and/or coated with conductive glue method technology; France former NITEC company adopts magnetron sputtering method technology; Canada INCO company utilizes the nickel production technology of self, has adopted and diverse nickel foam production technique of above-mentioned technological line and equipment, comprises the conductionization processing mode, i.e. nickle carbonoxide nickel deposited single stage method.
Chemically coated nickel method technical maturity, investment of production equipment are less, constant product quality and good uniformity, polyurethane sponge conductionization treatment effect thicker and that the aperture is very little are good; But must drop into bigger expenses of environmental protection, and contain a spot of phosphorus in the nickel foam.Coated with conductive glue method technology is simple, investment of production equipment is little, not phosphorous in environmentally friendly, the nickel foam; But therefore product lack of homogeneity, the sponge conductionization poor processing effect that carbon content is higher, thicker and the aperture is less should not be made thick and nickel foam that the aperture is little.PVD technical finesse polyurethane sponge is thick not as the coating of chemically coated nickel method, and quality product and homogeneity PVD method should not be handled sponge thicker and that the aperture is very little a little less than chemically coated nickel method and PVD method.But environmentally friendly, the acyclic substantially premium usefulness of PVD technology, not phosphorous in the nickel foam, carbon containing not, the physicals excellence of material.Therefore have a good application prospect.
Magnetron sputtering in the PVD technology and arc evaporation plating also respectively have relative merits, though magnetron sputtering has low temperature sputtering sedimentation, membrane-coating granules exquisiteness, the organic porous body not advantages of higher that heats up, but exist still that sedimentation rate is lower, production cost is higher, polyurethane sponge is easily aging and make defective such as tensile strength reduction, single magnetron sputtering technique, because of being subjected to the unsuitable long restriction of sputtering time, relatively poor to the saturating property of the plating of sponge, the nickel deposited amount is lower on the unit surface, even the galvanic deposit production line of low walking speed also is difficult for directly mating and works continuously.After the magnetron sputtering, need on other pre-coating apparatus, make auxiliary treatment, could enter the galvanic deposit production line smoothly.And for the galvanic deposit production line of high walking speed, preplating is essential especially.Though single arc evaporation plating sedimentation rate is higher, metallic particles is bigger, and plated film is usually inhomogeneous, and the cathodic arc spot particle sponge of easily burning.
The domestic technique approaching with the present invention is Jilin University " a kind of preparation method of sponge nickel foam " patent of invention, the patent No.: ZL 95102640.2; The utility model patent of Changchun Information Technology Development Co., Ltd. " vacuum anagnetically controlled sputtering foamed metalizing machine ", the patent No.: ZL 00212809.8; The utility model patent of Xia Zhengxun " magnetron sputtering nickel foam winding film coating machine ", the patent No.: ZL00246953.7.1 etc.Above-mentioned patent all belongs to general, simple magnetically controlled sputter method does the conductionization processing to sponge nickel plating, bad with follow-up galvanic deposit operation matching.This be because: on the one hand sponge is the 3 D complex surface, and all plating property is relatively poor, and the magnetron sputtering time is short, and last nickel amount is low, and as galvanic deposit tape running speed 〉=0.2m/min, the deposition of nickel on sponge just is difficult to accomplish continuously even; Sponge is subjected to the detrimentally affect to sponge intensity such as thermal radiation, particle incident bombardment, nickel particles condensation heat again on the other hand, and sputtering time is unsuitable long, otherwise the tensile strength of sponge will significantly reduce.Therefore, adopt single, simple magnetron sputtering technique, the difficult large-scale production that directly realizes effective continuous band-shaped sponge nickel foam.
Another domestic technique approaching with the present invention is Shenyang Jinchang Puxin Material Co. Ltd's " a kind of equipment and technology of producing porous sponge metal " patent of invention, application number: 01128040.9, and publication number: CN 1341773A.This invention also is a kind of single magnetron sputtering equipment and technology, is used for the conduction processing of polyurethane sponge, as an operation of producing the sponge kind metal.The housing of the vacuum apparatus that relates in the invention, the pumped vacuum systems that links to each other with housing, the plug-type dolly of shipment rolling band, the magnetron sputtering cathode target of the parallel installation of two row, and, be the combination technique of conventional magnetic-control sputtering coiling formula coating equipment as plated film power, voltage etc. by the selected processing parameter of folding and unfolding material roller, take off roll, transition roller, pressure roll, linear velocity trans and shielding power supply that servomotor or stepper-motor drag.Polyurethane sponge with this equipment and technology nickel plating does not reach desired nickel layer thickness of high speed electro-deposition nickel equipment and homogeneity.So-called high speed electro-deposition nickel equipment is meant the patent " the whole plating tank of serialization strip foaming nickel " of patent for invention people Zhong Faping, license notification number CN2337160Y, September 8 1999 Granted publication day.
Other relevant patent, also have Tandani Vacuum Surface Technology Co., Ltd., Shenzhen City patent of invention " vacuum vapour deposition and the equipment of the processing of organic foam conductionization " (application for a patent for invention number: 01119666.1, publication number: CN1327081A).This invention does not reach the degree of large-scale production yet because of the shortcoming that has above-mentioned single PVD technology.With one of the most approaching foreign patents of the present invention be the patent of Frenchman in 1985 in Japanese publication, the patent No.: clear 61-76686, its european patent number is: EP0151064B1, U.S. Patent number: 4,882,232.This patent name is: " manufacture method of porous matter metal structure ", its technical characterictic relates to following content: 1. be a kind of method that is used to make the porous metal framework material of nickel electrode or cadmium electrode.Its manufacture method comprises conductionization, galvanic deposit, the thermal treatment of substrate core rod.Core rod can be felt, fabric, sponge.Electricity conduction method is vacuum cathode sputter or ion plating.2. the intermediate steps that between galvanic deposit and conductionization, also comprises an electroless copper or chemical nickel plating.3. its conductionization processing can be deposited copper or nickel, and deposit thickness is the 0.05-1 micron, and the conductionization processing can be to make bottom with copper earlier.
Summary of the invention
Technical problem to be solved by this invention is: solve the problems of the prior art that organic porous matter carrying material is carried out the continuous conduction processing: such as, chemically coated nickel method must drop into big expenses of environmental protection, and contain a spot of phosphorus in the nickel foam, coated with conductive glue method product lack of homogeneity, carbon content is higher, thicker and aperture sponge conductionization poor processing effect, the magnetron sputtering deposition speed of single PVD technology is low, the cost height, the polyurethane sponge is easily aging, plating property is relatively poor, and single arc evaporation plated film metallic particles is bigger, plated film is inhomogeneous, the sponge of easily burning, and the present invention aims to provide a kind of above-mentioned shortcoming that monotechnics exists that overcomes, reach even metal lining, realize the method and apparatus of the preparing porous metal by combined physical gas-phase deposition techinque of two-sided continuous band-shaped sponge conductionization purpose.
The technical solution used in the present invention is: in devices of coiled vacuum coating machine, employing magnetron sputtering, evaporation are plated, the ion plating three is combined or wherein any both combined built-up type physical gas-phase deposite methods carry out the continuous conduction processing to organic porous matter band.
The equipment of aforesaid method of the present invention is devices of coiled vacuum coating machine, two ends are respectively the rolling chamber and unreel the chamber, the indoor rolling roller that is equipped with of rolling, unreel indoor being equipped with and unreel roller, rolling chamber and unreel and be connected and installed with magnetic control film coating chamber, electric arc deposited chamber or magnetic control film coating chamber, arc ion plating chamber and dividing plate, cold cover, pretreatment chamber, guide roller, measuring roller, the indoor magnetic controlling target that is equipped with of magnetron sputtering between the chamber, the indoor arc evaporation target that is equipped with of electric arc deposited chamber and arc ion plating.
" organic porous matter band " of the present invention comprises single or multiple lift non-woven fabrics, polyurethane sponge (comprising polyester or polyether-type), cotton or chemical ﹠ blended fabric, felt, fibrous reticulum of mean pore size≤2mm etc.Be particularly related to polyurethane sponge, and fabric width is more than the 0.3-1.5m, length 30-300m.
" metal of plating " of the present invention comprises nickel, copper, tin, zinc, aluminium, titanium, silver, gold etc.; Or the composite deposite of above-mentioned metal, for example, make the bottom another kind of metal of plating again with a kind of metal wherein.Be particularly related on polyurethane sponge metal lining nickel, copper, silver, tin and be the composite deposite of bottom with aluminium.
" built-up type PVD technology " of the present invention, particularly arc evaporation plates the technology that makes up with magnetron sputtering, the technology of arc ion plating and magnetron sputtering combination.
" two-sided even two-forty metal lining " of the present invention is meant: the two-sided metal lining of property once on organic porous matter band, the particularly disposable two-sided plating of polyurethane sponge nickel plating, last nickel amount 〉=4g/m
2, all plating property is good, and can be directly with at a high speed (〉=0.6m/min) the galvanic deposit production line interlock operation of tape transport, promptly between PVD and galvanic deposit without any chemistry and/or electrochemical treatment
The host machine part that is meant integral device of the present invention.Host machine part comprises and unreels chamber, rolling chamber, coating chamber, housing.Except that main frame, integral device also comprises supporting parts such as pumped vacuum systems, cooling system, power-supply system.Host machine part is as one of example of built-up type PVD technology, particularly by arc evaporation coating chamber, magnetron sputtering plating chamber, unreel the unitized construction of chamber, rolling chamber, as Fig. 1.The feature of this technology is: the both sides of magnetic control film coating chamber 4 and arc coating deposition chamber 6 respectively dispose 8 groups of above magnetron sputtering target 5 and some groups of arc evaporation targets 7, use perpendicular to the watercooling jacket 9 of target surface in the middle of the target up and down and be separated by, form several plated film intervals, avoid accumulation of heat, can in time each interval heat that produces be taken away.Effectively improved the situation that polyurethane sponge is long because of the plating time and the too high sponge of causing of sputtering chamber temperature is aging, tensile strength reduces.Polyurethane sponge passes through from the centre of coating chamber, and the particle of accepting magnetic control spattering target and arc evaporation target continuously deposits and the formation metal conductive film.Owing to adopted and part power unwinding and rewinding device and vertical body design a little, make stretched state behind the sponge metal lining can be controlled at the state of starting material sponge.
" equipment " of the present invention also is particularly related to the structure design of novel magnetic control mosaic target.This design had both improved target utilization and sedimentation rate; Conveniently change target again, saved the time of changing target.As Fig. 2 is novel magnetic control mosaic target structure iron, and target plate 14 is fixed on the dividing plate 15 by middle press strip 17 and limit press strip 20, and when target plate etched into the degree that needs replacing, as long as press strip is unclamped, the target plate of changing same size got final product.
" preparation method and equipment " of the present invention also is particularly related to following technology:
The method of igniting of arc source, adoptable a kind of method are that trigger in the gap, promptly by providing impulse of current to make its conducting to an auxiliary triggering utmost point, thereby ignite electric arc between the main electrode; Another kind method is that machinery triggers, and promptly relies on contacting and draw back and realizing igniting of arc electrode and cathode surface moment.
The arrangement mode of magnetron sputtering plating and arc evaporation plated film, can be two kinds of plated film modes alternately, also can be again with the two combination after a kind of plated film mode is arranged continuously.
The cathode material of arc evaporation source can be made into the right cylinder bulk, also can be for planar rectangular tabular; The cathode sputtering material of magnetron sputtering plating can be made into circular flat or rectangle plane or cylindrical;
D.c. sputtering can be adopted, also radio-frequency sputtering can be adopted.
The present invention compares with prior art and existing patent, has following novelty, creativeness, practicality:
1. built-up type PVD and follow-up galvanic deposit operation have good matching.Adopt after the processing of built-up type PVD technology conductionization, can directly enter the galvanic deposit operation of fast feed.And general magnetron sputtering must be done preplating with galvanic deposit or electroless plating to handle, and just can enter the high speed electro-deposition operation.The present invention make the conduction processing of polyester sponge can be in PVD equipment disposable finishing, simplified production process, avoided doing preplating and handled trade effluent problem with fork-like farm tool used in ancient China because of galvanic deposit or electroless plating.
2. combination PVD technology is compared (for example patent ZL95102640.2) with single magnetron sputtering, and its sedimentation rate can improve about 3～5 times.When especially organic porous matter band is polyurethane sponge, adopt single evaporation coating technology that sponge is burnt; Adopt single magnetron sputtering technique, because sponge is complex-shaped, plating property is relatively poor, and sedimentation rate is low, can't link with the high speed tape transport matched of the subsequent handling-galvanic deposit of conductionization processing.Thereby single PVD technology production efficiency is lower, quality product be cannot say for sure card.
3. magnetic filter has been installed on arc evaporation source, has been made the burn drawback of sponge of evaporation particle obtain effectively overcoming.
4. adopted cooling system efficiently between each relatively independent coating chamber, guaranteed sponge reason influence of thermal effect not in coating process, effusion small molecules organic gas influences the change of carrying out and cause the sponge physical and chemical performance smoothly of coating process.Polyurethane sponge is a macromolecular compound, drawback such as very easily produce venting, bond rupture in the PVD process, wear out, burn.Use perpendicular to the watercooling jacket 9 of target surface in the middle of the target about the present invention has designed and be separated by, form several plated film intervals, avoid heat accumulation, each interval heat isolation that produces is also in time taken away, thereby improved the situation that polyurethane sponge is long because of the plating time and the too high sponge of causing of coating chamber temperature is aging, tensile strength reduces effectively.The band speed of travel can be increased to more than the 200cm/min by 30-60cm/min second (for example patent ZL 95102640.2) during plated film, and the tensile strength of sponge still keeps good.The metallic nickel of every square metre of plating is increased to more than 4 grams, thereby has been improved the saturating property of plating of sponge by 1 gram following (for example patent ZL 95102640.2), has guaranteed that the direct coupling of sponge in high speed tape transport galvanic deposit operation after the conductionization processing moved.The alligatoring pre-treatment (for example patent ZL 95102640.2) that need not adopt single magnetron sputtering to carry out sponge; Also need not increase the preplating operation one after single magnetron sputtering, the galvanic deposit operation with the high speed tape transport is complementary by this.
5. " spongy foam nickel that can prepare bulk, every area can reach 1m with the feature of patent ZL 95102640.2
2More than " difference, because this patent has adopted the combination technique of PVD and parted force actuators a little, the conduction treating processes of polyester sponge can be carried out in the serialization of wide cut degree.Fabric width is that the above whole volume length of 0.3-1.5m can reach 30～300m.The nickel foam of producing is continuous band-shaped, and every volume area can reach 150m
2More than, rather than block.
6. this patent " the organic porous body band " that relate to comprises non-woven fabrics, polyester or polyether(poly)urethane sponge, cotton or chemical ﹠ blended fabric, felt, fibrous reticulum of mean pore size≤2mm etc.Adopt the metal of combination PVD method plating, comprise the composite deposite of nickel, copper, tin, zinc, aluminium, titanium, silver, gold or above-mentioned metal, for example, make bottom plating another kind metal etc. again with a kind of metal wherein.
7. this patent adopts novel magnetic control mosaic target to improve target utilization and sedimentation rate.Fig. 2 is novel magnetic control mosaic target structure iron, and target plate 14 is fixed on the dividing plate 15 by middle press strip 17 and limit press strip 20, when target plate etches into the degree that needs replacing, as long as press strip is unclamped, the target plate of changing same size gets final product, and has both improved target utilization, has saved the time of changing target again.The power of magnetic controlling target depends on target refrigerative effect.In Fig. 2, provide big flow cooling water by water pipe 10, reach the ideal cooling performance.
8. adopt to part the power train system a little, guarantee that the hole of sponge is indeformable, walking speed is even.
9. adopt combination PVD technology as follows to the technical process of organic porous material work conductionization processing:
Organic porous matter band → unreel → guide roller → pre-treatment → built-up type PVD plated film → measuring roller → rolling.Whole process is all carried out under vacuum state.Fig. 1 is for adopting one of combination PVD The Application of Technology example, and its main equipment structural principle is as figure.Among Fig. 1: reeling(unreeling)chamber 1 both can have been done rolling with receipts (putting) scroll 2 and also can unreel, and the position of magnetic control film coating chamber 4 will be adjusted up and down when adopting different tape transport directions; 3 pairs of sponges of measuring roller do the technology control survey, as length metering; Magnetic control film coating chamber 4 is finished the magnetron sputtering operation; Magnetic controlling target 5 provides the metal for the treatment of plating; The operation of electric arc evaporation is finished in arc coating deposition chamber 6; Electric arc target 7 provides plating metal; Dividing plate 8 separates magnetron sputtering chamber 4 and arc evaporation coating chamber 6; Watercooling jacket 9 is mainly used in and reduces the coating chamber temperature; There is the special foamed metal of asking that has in 10 pairs of pretreatment chamber, and as condition of surface, make special pre-treatment; Guide roller 11 prevents that band from wandering off; Put (receipts) volume chamber 12 and put (receipts) scroll 13 and work (receipts) volume effect of putting.
In the electric arc deposited chamber, igniting of arc source generally has two kinds of methods: a kind of is that trigger in the gap, promptly by providing impulse of current to make its conducting to an auxiliary triggering utmost point, thereby ignites electric arc between the main electrode; Another kind is that machinery triggers, i.e. contacting and drawing back and realize by arc electrode and cathode surface moment.In the electric arc deposited chamber, metal draws pin cause arc discharge with pulsed current after, the arc light bright spot on cathode surface intensely, irregularly motion, radiate a large amount of cathode material particle and ion simultaneously, in the effect of electric field deposit to sponge.Magnetron sputtering plating chamber and arc evaporation coating chamber can also can be arranged recombinant alternately separately continuously.The cathode material of arc evaporation source can be made into the right cylinder bulk, also can be the tabular of planar rectangular; The cathode sputtering material of magnetron sputtering plating can be made into circular flat or rectangle plane or cylindrical, but d.c. sputtering, but also radio-frequency sputtering.
The present invention is environmentally friendly, and the porous matter continuous metal band of production, foamed metal are without phosphorus carbon-free, and plated film is even, fine and smooth, and plating property is good, bonding force and tensile strength are strong.Metal deposition rates height, target utilization height, can work continuously.Be that electrodip process is produced porous insert sheet metal strip ideal conductionization pretreatment procedure.
The porous insert sheet metal strip that adopts the present invention's manufacturing also is used for manufacturing and prevents hertzian wave and rf wave interferential porous matter metallic substance except that the substrate as ni-mh, nickel-cadmium cell pole plate; High temperature filtration medium porous matter metallic substance; Good conduction, heat conduction porous matter metallic substance.
Description of drawings
Fig. 1 is an embodiment of the invention synoptic diagram
Fig. 2 is a magnetic controlling target new texture synoptic diagram among Fig. 1
Embodiment
Embodiment:
Referring to Fig. 1, the 1-reeling(unreeling)chamber, 2-receives (putting) scroll, 3-measuring roller, 4-magnetic control film coating chamber, the 5-magnetic controlling target, 6-electric arc deposited chamber 7-arc evaporation target, 8-dividing plate, 9-cold water jacket, 10-pretreatment chamber, 11-guide roller, 12-are put (receipts) volume chamber, and 13-is put (receipts) scroll.
The present invention will be evaporated a certain method above-mentioned in plating, sputter plating, the ion plating and be made up respectively, for example arc evaporation plating and magnetron sputtering combination, and arc ion plating and magnetron sputtering combination form specific preparation method and equipment.This class PVD technology is because of the PVD technology of the single form that is different from common employing, so claim PVD built-up type technology.The present invention be more particularly directed to the technology of arc evaporation plating and magnetron sputtering combination, the technology of arc ion plating and magnetron sputtering combination is used for polyurethane sponge metal lining nickel, as a pretreatment procedure in the nickel foam production process, i.e. the conduction treatment process of polyester sponge.
The present invention be more particularly directed to be used to make novel secondary cell, a production process during as the positive pole of ni-mh, nickel-cadmium cell and/or negative electrode substrate foam nickel material, promptly to organic porous matter continuous band, for example polyurethane sponge is made a kind of method and apparatus of conductionization processing.This patent will be illustrated as key content with porous insert metal-nickel foam.In order to produce continuous band-shaped porous matter metallic substance, after organic porous matter band is carried out the continuous conduction treatment process, also must pass through galvanic deposit, two master operations of thermal treatment.Except that above-mentioned battery pole plates was used the baseplate material nickel foam, this patent also will be referred to adopt above-mentioned " conductionization processing-galvanic deposit-thermal treatment " technological process, made to be used to prevent hertzian wave and rf wave interferential porous matter metal base; High temperature filtration medium porous insert metal; When good conduction, heat conduction porous matter metal, to the preparation method and the equipment of organic porous matter band conduction processing.
Essential characteristic of the present invention: in devices of coiled vacuum coating machine, the PVD technology of adopt magnetron sputtering, evaporate plating, ion plating is combined (being particularly related to the technology that the plating of magnetron sputtering and arc evaporation combines, the technology that magnetron sputtering and arc ion plating are combined) reaches even metal lining, the two-sided continuous band-shaped sponge of realization is led electrochemical purpose.Adopt built-up type PVD technology, can solve the above-mentioned shortcoming that existing monotechnics exists.Make sponge in the PVD process, both reached and carried out subsequent handling-galvanic deposit needed " going up the nickel amount " requirement smoothly, be unlikely again that because of the treatment time is long the intensity of sponge is affected.Therefore, aforesaid combination PVD technology becomes in the large-scale production foam metal nickel process, polyurethane sponge is carried out the fairly perfect method of PVD conductionization processing.
One of application example of the present invention, magnetron sputtering and the combined equipment principle of arc evaporation plating are seen Fig. 1
Present device is meant the host machine part of integral device.Host machine part comprises and unreels chamber, rolling chamber, coating chamber, housing.Except that main frame, integral device also comprises supporting parts such as pumped vacuum systems, cooling system, power-supply system.Host machine part is as one of example of built-up type PVD technology, particularly by arc evaporation coating chamber, magnetron sputtering plating chamber, unreel the unitized construction of chamber, rolling chamber, as Fig. 1.The feature of this technology is: the both sides of magnetic control film coating chamber 4 and arc coating deposition chamber 6 respectively dispose 8 groups of above magnetron sputtering target 5 and some groups of arc evaporation targets 7, use perpendicular to the watercooling jacket 9 of target surface in the middle of the target up and down and be separated by, form several plated film intervals, avoid accumulation of heat, can in time each interval heat that produces be taken away.Effectively improved the situation that polyurethane sponge is long because of the plating time and the too high sponge of causing of sputtering chamber temperature is aging, tensile strength reduces.Polyurethane sponge passes through from the centre of coating chamber, and the particle of accepting magnetic control spattering target and arc evaporation target continuously deposits and the formation metal conductive film.Owing to adopted and part power unwinding and rewinding device and vertical body design a little, make stretched state behind the sponge metal lining can be controlled at the state of starting material sponge.
Referring to the structure sectional view of Fig. 2 magnetic control embedding target, 14-target plate among the figure, press strip in the middle of the magnet in the middle of the 15-dividing plate, 16-, 17-, 18-pole shoe, 19-limit magnet, 20-limit press strip, 21-target frame, 22-target base plate, 23-water pipe, 24-O shape sealing-ring.
Present device also is particularly related to the structure design of novel magnetic control mosaic target.This design had both improved target utilization and sedimentation rate; Conveniently change target again, saved the time of changing target.In the novel magnetic control mosaic target of Fig. 2 structure iron, target plate 14 is fixed on the dividing plate 15 by middle press strip 17 and limit press strip 20, and when target plate etched into the degree that needs replacing, as long as press strip is unclamped, the target plate of changing same size got final product.
Polyurethane sponge nickel plating is disposable two-sided plating, last nickel amount 〉=4g/m
2, all plating property is good, and can be directly with at a high speed (〉=0.6min) the galvanic deposit production line interlock operation of tape transport, promptly between PVD and galvanic deposit without any chemistry and/or electrochemical treatment.
Claims (10)
1. the method for a preparing porous metal by combined physical gas-phase deposition techinque, it is characterized in that: in devices of coiled vacuum coating machine, adopt magnetron sputtering, evaporation plating, the ion plating three is combined or both combined built-up type physical gas phase deposition technologies two-sided metal lining of property once on organic porous matter band arbitrarily wherein, and organic porous matter band is carried out the continuous conduction processing.
2. the method for preparing porous metal by combined physical gas-phase deposition techinque according to claim 1, it is characterized in that: disposable two-sided plated nickel on the polyurethane sponge band and directly with tape running speed is 〉=operation that links of the follow-up galvanic deposit production line of 0.6m/min.
3. the method for preparing porous metal by combined physical gas-phase deposition techinque according to claim 1, it is characterized in that described organic porous matter band, comprise single or multiple lift non-woven fabrics, polyurethane sponge, cotton chemical ﹠ blended fabric, felt or the fibrous reticulum of mean pore size≤2mm.
4. organic porous matter band according to claim 3, it is characterized in that: described polyurethane sponge fabric width is 0.3-1.5m, length is 30-300m.
5. the method for preparing porous metal by combined physical gas-phase deposition techinque according to claim 1, the metal that it is characterized in that plating are a kind of in the following metal or their composite deposite: nickel, copper, tin, zinc, aluminium, titanium, silver, gold.
6. the equipment of a preparing porous metal by combined physical gas-phase deposition techinque, it is characterized in that: main process equipment is a devices of coiled vacuum coating machine, adopt vertical main equipment, two ends are respectively the rolling chamber and unreel the chamber up and down, the indoor wind-up roll that is equipped with of rolling, unreel the indoor let off roll that is equipped with, rolling chamber and unreeling is connected and installed with combination coating chamber, pretreatment chamber, guide roller and measuring roller between the chamber; The combination coating chamber is the combination of magnetron sputtering plating chamber and arc evaporation coating chamber or the combination of magnetron sputtering plating chamber and arc ion plating chamber.
7. the equipment of preparing porous metal by combined physical gas-phase deposition techinque according to claim 6 is characterized in that: magnetron sputtering target and arc evaporation targets more than the both sides of the both sides of magnetron sputtering plating chamber and arc coating deposition chamber are installed 8 groups respectively.
8. the equipment of preparing porous metal by combined physical gas-phase deposition techinque according to claim 6 is characterized in that: use perpendicular to the watercooling jacket of target surface in the middle of the target about in the combination coating chamber and be separated by, form relatively independent plated film interval.
9. according to the equipment of claim 6 or 7 described preparing porous metal by combined physical gas-phase deposition techinque, it is characterized in that: the magnetron sputtering chamber target adopts pattern structure, and target plate is fixed on the dividing plate by middle press strip and limit press strip.
10. the equipment of preparing porous metal by combined physical gas-phase deposition techinque according to claim 6, it is characterized in that: the permutation and combination of combination coating chamber, take following both one of, the coating chamber of identical type is arranged the back recombinant continuously, and perhaps two kinds of different coating chambers make up alternately.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021141533A CN1155734C (en) | 2002-05-27 | 2002-05-27 | Process and apparatus for preparing porous metal by combined physical gas-phase deposition techinque |
| PCT/CN2003/000393 WO2003100111A1 (en) | 2002-05-27 | 2003-05-26 | Method for producing porous metal by composite physical vapour deposition and the equipment thereof |
| AU2003242164A AU2003242164A1 (en) | 2002-05-27 | 2003-05-26 | Method for producing porous metal by composite physical vapour deposition and the equipment thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021141533A CN1155734C (en) | 2002-05-27 | 2002-05-27 | Process and apparatus for preparing porous metal by combined physical gas-phase deposition techinque |
Publications (2)
| Publication Number | Publication Date |
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| CN1397654A CN1397654A (en) | 2003-02-19 |
| CN1155734C true CN1155734C (en) | 2004-06-30 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB021141533A Expired - Fee Related CN1155734C (en) | 2002-05-27 | 2002-05-27 | Process and apparatus for preparing porous metal by combined physical gas-phase deposition techinque |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN1155734C (en) |
| AU (1) | AU2003242164A1 (en) |
| WO (1) | WO2003100111A1 (en) |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100447291C (en) * | 2004-03-16 | 2008-12-31 | 茂德科技股份有限公司 | Physical vapor deposition method and device therefor |
| CN100392146C (en) * | 2004-08-27 | 2008-06-04 | 茂德科技股份有限公司 | Physical vapor deposition process and apparatus |
| CN100342924C (en) * | 2004-10-13 | 2007-10-17 | 苏州苏豪生物材料科技有限公司 | Skin substitute and its preparation method |
| DE102008029379A1 (en) * | 2008-06-23 | 2009-08-13 | Von Ardenne Anlagentechnik Gmbh | Arrangement for coating band-shaped film substrates e.g. ferromagnetic metal film, comprises wind-off and take-up rollers guided between the substrates under strip tensile stress and coating station comprising two coating sources |
| CN101649448B (en) * | 2009-08-26 | 2012-05-30 | 兰州大成科技股份有限公司 | Continuous surface vacuum coater of metal sheet strip |
| CN104831527B (en) * | 2015-03-31 | 2017-10-13 | 嘉兴中科奥度新材料有限公司 | The full covered composite yarn ion plating nano-metal technique of aramid fiber or laid fabric surface and its product |
| CN104894514A (en) * | 2015-03-31 | 2015-09-09 | 嘉兴中科奥度新材料有限公司 | Porous metal foil product with metal nanoparticle coating and preparation method thereof |
| CN104831528B (en) * | 2015-03-31 | 2017-10-13 | 嘉兴中科奥度新材料有限公司 | The non-woven fabric compounded ion plating nano-metal technique of highly effective air particulate filter and its product |
| CN104831236B (en) * | 2015-03-31 | 2017-12-22 | 嘉兴中科奥度新材料有限公司 | Waterproof ventilation polyurethane film compound ion plating nano-metal technique and its product |
| CN105239052A (en) * | 2015-11-17 | 2016-01-13 | 广东腾胜真空技术工程有限公司 | Double-release and double-collection winding film coating device and method |
| CN105970157B (en) * | 2016-05-17 | 2018-09-04 | 佛山市顺德区美的电热电器制造有限公司 | Foam metal and preparation method thereof and cooking apparatus |
| CN110066935B (en) * | 2018-01-23 | 2020-05-12 | 清华大学 | Foam metal preparation device and preparation method |
| KR20210091342A (en) * | 2018-12-12 | 2021-07-21 | 어플라이드 머티어리얼스, 인코포레이티드 | Free-span coating systems and methods |
| CN109768334A (en) * | 2018-12-25 | 2019-05-17 | 中国电子科技集团公司第十八研究所 | Preparation method of bipolar solid-state lithium secondary battery |
| CN111058010A (en) * | 2019-09-25 | 2020-04-24 | 广东汇成真空科技股份有限公司 | Metal foil strip winding type vacuum coating equipment |
| CN111020522B (en) * | 2019-12-09 | 2022-05-27 | 王殿儒 | Composite type substrate continuous coating system based on gas discharge type high-power electron gun |
| CN111411923A (en) * | 2020-03-31 | 2020-07-14 | 益阳市菲美特新材料有限公司 | Foamed nickel sand control screen pipe and manufacturing method thereof |
| CN113684454A (en) * | 2020-05-19 | 2021-11-23 | 宝山钢铁股份有限公司 | Method for coating substrate with metal alloy and vacuum deposition device thereof |
| CN112310367A (en) * | 2020-10-09 | 2021-02-02 | 上海交通大学 | Ultrathin porous metal material for lithium battery electrode and preparation method and application thereof |
| CN112210760B (en) * | 2020-10-13 | 2021-05-07 | 廖斌 | Surface treatment method of ultrathin polymer |
| CN113355647B (en) * | 2021-06-07 | 2023-04-11 | 江苏中天科技股份有限公司 | Porous metal, and method and apparatus for producing same |
| CN114737157B (en) * | 2022-04-27 | 2023-10-20 | 重庆金美新材料科技有限公司 | Production and processing equipment for metal film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2558485B1 (en) * | 1984-01-25 | 1990-07-13 | Rech Applic Electrochimique | POROUS METAL STRUCTURE, MANUFACTURING METHOD THEREOF AND APPLICATIONS |
| JPH042795A (en) * | 1990-04-19 | 1992-01-07 | Sumitomo Electric Ind Ltd | Continuous production of metallic porous body |
| JP3413662B2 (en) * | 1992-01-13 | 2003-06-03 | 上村工業株式会社 | Method for producing porous aluminum body |
| JP3344175B2 (en) * | 1995-07-12 | 2002-11-11 | 上村工業株式会社 | Method for producing porous aluminum body |
-
2002
- 2002-05-27 CN CNB021141533A patent/CN1155734C/en not_active Expired - Fee Related
-
2003
- 2003-05-26 AU AU2003242164A patent/AU2003242164A1/en not_active Abandoned
- 2003-05-26 WO PCT/CN2003/000393 patent/WO2003100111A1/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| CN1397654A (en) | 2003-02-19 |
| WO2003100111A1 (en) | 2003-12-04 |
| AU2003242164A1 (en) | 2003-12-12 |
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