CN105980606A - Aluminum film manufacturing method and manufacturing device - Google Patents
Aluminum film manufacturing method and manufacturing device Download PDFInfo
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- CN105980606A CN105980606A CN201580007478.XA CN201580007478A CN105980606A CN 105980606 A CN105980606 A CN 105980606A CN 201580007478 A CN201580007478 A CN 201580007478A CN 105980606 A CN105980606 A CN 105980606A
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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
- C25D1/00—Electroforming
- C25D1/08—Perforated or foraminous objects, e.g. sieves
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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
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/004—Sealing devices
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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
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/04—Removal of gases or vapours ; Gas or pressure control
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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
- C25D3/00—Electroplating: Baths therefor
- C25D3/66—Electroplating: Baths therefor from melts
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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
- C25D3/00—Electroplating: Baths therefor
- C25D3/66—Electroplating: Baths therefor from melts
- C25D3/665—Electroplating: Baths therefor from melts from ionic liquids
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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
- C25D5/003—Electroplating using gases, e.g. pressure influence
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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
- C25D5/54—Electroplating of non-metallic surfaces
- C25D5/56—Electroplating of non-metallic surfaces of plastics
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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
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
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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
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
- C25D7/0621—In horizontal cells
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- Electroplating Methods And Accessories (AREA)
Abstract
The purpose of the present invention is to provide an aluminum film manufacturing method and manufacturing device with which there is no intrusion of moisture or oxygen into a plating chamber. Provided is an aluminum film manufacturing method in which, in a molten salt electrolytic solution, aluminum is electrodeposited onto the surface of a long and elongated porous resin substrate to which conductivity was imparted. The aluminum film manufacturing method includes the following: a step in which a substrate (W) passes through a seal chamber (4) disposed at the entrance side of a plating chamber (1) and is thereby loaded into the plating chamber; a step in which an aluminum film is electrodeposited onto the surface of the substrate (W) in the plating chamber (1); and a step in which the substrate onto which the aluminum film was electrodeposited passes through a seal chamber (5) disposed at the exit side of the plating chamber (1) and is thereby loaded out of the plating chamber (1). An inert gas is supplied into the plating chamber so that the plating chamber has a positive pressure with respect to the outside air, and the inert gas is forcibly exhausted from inert gas exhaust pipes (7) provided to each of the two seal chambers.
Description
Technical field
The present invention relates to the manufacture method of a kind of aluminum film and the manufacture device of aluminum film, wherein, at strip porous resin matrix
Electroplating Aluminum on the surface of material, thus on base material, form aluminum film.
Background technology
Aluminum is passivated by forming the oxidation film of densification in its surface, thus shows the corrosion resistance of excellence.Cause
This, by the surface with aluminum coated steel strip etc., thus improve corrosion resistance.
Such as, in order to carry out aluminum plating on the surface of steel band, first, steel band is continuously supplied to plating room, by leading
Electricity roller, and make to run between steel band anode in impregnated in the electroplate liquid that plating is indoor.Now, steel band itself is electrical connection
, thus steel band oneself serves as negative electrode.Therefore, it is being electrolysed as between steel band and the anode of negative electrode, and by aluminum electricity
Deposit to the surface of steel band, thus realize aluminum plating.By rotating the direction that roller change steel band is advanced in the plating solution, then,
Steel band runs up.In this case, between negative electrode and anode, plating is still carried out.Plating room is left at the steel band aluminized
After, by another conductive rollers transmission, take it out system (with reference to patent documentation 1 and 2).
Additionally, for improving the positive electrode capacity of lithium ion battery, the aluminum porous body with tridimensional network is one
Plant promising material.At present, by utilizing the good characteristic (such as electric conductivity, corrosion resistance and light weight) of aluminum, by surface
The aluminium foil being coated with active substance (such as lithium and cobalt oxides) is used as the positive pole of lithium ion battery.The porous being made up of aluminum by use
Body forms positive pole, can increase surface area, and the inside of aluminum porous body can also be filled with active substance.Thus, though electric
The thickness of pole increases, and does not the most reduce the utilization rate of active substance, and also improves the profit of the active substance of per unit area
By rate such that it is able to improve the capacity of positive pole.
As the method preparing such aluminum porous body, the applicant has been proposed for one electroplated aluminum and has three dimensional network
The method (with reference to patent documentation 3) of the resin-formed body of shape structure.Existing aluminum molten salt bath needs to be heated to high temperature.Therefore,
One problem is that resin can not bear high temperature and melt when attempting the surface with electroplated aluminum resin-formed body.But, according to
Method described in patent documentation 2, by by such as 1-ethyl-3-methylimidazolium chloride (EMIC) or 1-butyl chlorination
The organic chloride salt of pyridine (BPC) etc and aluminum chloride (AlCl3) mixing, the aluminum bath at room temperature for liquid can be formed,
It is thus possible to use electroplated aluminum resin-formed body.Especially, EMIC-AlCl3It is that solutions display goes out good characteristics of liquids, and can
As aluminum plating solution.
At use fuse salt as in the continuous electroplating apparatus of plating solution, when the fuse salt as plating solution is with air contact,
It is by the moisture absorbed in air and reacts, thus produces product.As a result of which it is, the function needed for plating solution is impaired.
Especially, when chlorine compound system fuse salt is used for aluminum system plating, fuse salt can form chlorination with the reaction of moisture in air
Hydrogen, causes the problem such as the deterioration of such as working environment and the corrosion of electroplanting device assembly.Additionally, due to metallic aluminium is easy to by oxygen
Changing, the aluminum film formed on substrate surface also can react with a small amount of dissolved oxygen of comprising in plating solution, thus forms aluminium oxide.
When the growth of such reaction Yu plated film occurs simultaneously, aluminium grain changes, and causes the mechanical strength of such as plated film to reduce
Occur with degradation problem under electrical conductivity.
Therefore, use fuse salt as in the continuous electroplating apparatus of plating solution, as it is shown in fig. 7, (following at strip plate W
The intake section of plating room 1 also referred to as " workpiece ") and exit portion are configured with closed chamber 4 and 5, and wherein closed chamber 4 and 5 is respectively
It is provided with two pairs of sealed rollers, thus, completely and the closed system of extraneous air isolation carries out plating (with reference to patent documentation
4)。
Reference listing
Patent documentation
Patent documentation 1: Unexamined Patent 05-222599 publication
Patent documentation 2: Unexamined Patent 05-186892 publication
Patent documentation 3: JP 2012-007233 publication
Patent documentation 4: JP 2000-87287 publication
Summary of the invention
Technical problem
As it is shown in fig. 7, the present inventor has made aluminum film manufacturing device, this device includes plating room 1 and is configured at institute
Stating the workpiece intake section of plating room 1 and the closed chamber 4 and 5 of workpiece exit portion, wherein each to have two right for closed chamber 4 and 5
Sealed roller is also filled with N2Gas.By using this device, there is the resin-formed body of tridimensional network by electroplated aluminum, its
In in the apparatus, in order to further ensure that moisture and oxygen do not enter in plating room from extraneous air, by plating room
N2Air pressure is set to malleation.As a result of which it is, the problem found is still to have the moisture of trace and oxygen to invade in tank house.
In view of the above problems, it is an object of the invention to provide the manufacture method of a kind of aluminum film and manufacture device, Qi Zhongshui
Divide and oxygen will not invade in electroplating chamber.
The solution of problem
The present inventor conducts in-depth research to solve the problems referred to above, and it has been found that by plating room
Base material entrance side and base material outlet side arrange closed chamber, by noble gas supply to described plating room so that plating room is relative to outward
Portion's air has malleation, and by described indifferent gas from the noble gas exhaustor being separately positioned on said two confined chamber
Body is forced to discharge, such that it is able to prevent moisture from invading in plating room.Thus, the present invention is completed.
In order to solve the problems referred to above, present invention employs following characteristics.
That is, according to a kind of method manufacturing aluminum film of the present invention, wherein in molten salt electrolyte by Aliminuium electrodeposition to quilt
Imparting on the surface of strip porous resin base material of electric conductivity, the method includes: makes described base material transport through and is configured at
The closed chamber of the entrance side of plating room is also sent to the step of described plating room；By aluminum film electrodeposition to institute in described plating room
State the step on the surface of base material；And its substrates has the base material of described aluminum film send out from described plating room and pass through
It is arranged in the step of the closed chamber of described plating room outlet side, wherein, to described plating room supplying inert gas, so that described
Plating room has malleation relative to outside air, and from the noble gas exhaustor being separately positioned on said two closed chamber
Middle by the pressure discharge of described noble gas.
In a still further aspect thereof, the manufacture device of a kind of aluminum film, wherein sinks aluminum electricity in molten salt electrolyte
Amassing on the surface of strip porous resin base material having been assigned electric conductivity, this device includes: plating room；It is configured at described plating
The closed chamber covering the base material entrance side of room and the closed chamber of the base material outlet side being configured at described plating room；Noble gas supplies
Ying Guan, it is arranged on described plating room, and is fed to by noble gas in described plating room；And noble gas aerofluxus
Pipe, it is separately positioned on said two closed chamber, and forces to discharge by the described noble gas in described closed chamber.
The beneficial effect of the invention
According to the present invention, in the manufacture method and manufacture device of aluminum film, employ molten salt electrolyte by Aliminuium electrodeposition
On base material such that it is able to be reliably prevented moisture and oxygen invades in plating room.
Accompanying drawing explanation
Fig. 1 is the figure of the example showing aluminum film manufacturing device according to embodiments of the present invention.
Fig. 2 is the figure of the example showing aluminum film manufacturing device according to embodiments of the present invention.
Fig. 3 is the figure of the example showing aluminum film manufacturing device according to embodiments of the present invention.
Fig. 4 is the figure of the example showing aluminum film manufacturing device according to embodiments of the present invention.
Fig. 5 is the figure of the example showing aluminum film manufacturing device according to embodiments of the present invention.
Fig. 6 is the figure of an example of the structure showing closed chamber used in the present embodiment.
Fig. 7 is the figure of the aluminum film manufacturing device showing and not having feature of present invention.
Fig. 8 shows the flow chart of the manufacturing process of aluminum porous body.
Fig. 9 includes the schematic cross-section showing aluminum porous body manufacture process.
Figure 10 is to show by using electrically-conducting paint to give the step of electric conductivity continuously to the surface of resin porous body
Figure.
Figure 11 is the figure showing the metal porous body with the tridimensional network including intercommunicating pore.
Detailed description of the invention
First, will enumerate and describe the content of embodiment of the present invention.
(1) according to a kind of method manufacturing aluminum film of embodiment of the present invention, wherein by aluminum in molten salt electrolyte
Electro-deposition is on the surface of strip porous resin base material having been assigned electric conductivity, and the method includes
Described base material is made to transport through the closed chamber of the entrance side being configured at plating room and be sent to the step of described plating room
Suddenly；
By the step on aluminum film electrodeposition to the surface of described base material in described plating room；And
The base material that its substrates has described aluminum film sends out from described plating room and by being arranged in described plating room
The step of the closed chamber of outlet side,
Wherein, to described plating room supplying inert gas, so that described plating room has malleation relative to outside air,
And
Force to discharge by described noble gas from the noble gas exhaustor being separately positioned on said two closed chamber.
According to this embodiment, force to discharge by the moisture and oxygen that have invaded closed chamber by means of inert gas,
It is thus possible to the moisture being reliably prevented in extraneous air and oxygen invade in plating room.Therefore, it is possible to obtain high-quality
Aluminum plated film, and it is possible to prevent the generation of the harmful substances such as hydrogen chloride.
(2) method manufacturing aluminum film according to one embodiment of the invention is the manufacture aluminum film described in above-mentioned (1)
Method, wherein, the base material entrance side at the described closed chamber being configured at described entrance side is provided with noble gas exhaustor, and
And the base material outlet side of the described closed chamber being configured at described outlet side is provided with noble gas exhaustor.
According to this embodiment, before the moisture and oxygen invading each closed chamber from outside invades electroplating chamber, will
It is discharged jointly with noble gas.
(3) method manufacturing aluminum film according to one embodiment of the invention is the manufacture described in above-mentioned (1) or (2)
The method of aluminum film, wherein, the noble gas arranging supplying inert gas in each of said two closed chamber further supplies
Ying Guan.
According to this embodiment, owing to the flow velocity of the noble gas in each closed chamber can be improved, therefore, it is possible to more
It is reliably prevented moisture and oxygen invades in plating room.
(4) method manufacturing aluminum film according to one embodiment of the invention is the manufacture aluminum film described in above-mentioned (3)
Method, wherein, the base material outlet side at the described closed chamber being configured at described entrance side is provided with described noble gas supply
Pipe, and the base material entrance side of the described closed chamber being configured at described outlet side is provided with described noble gas supply pipe.
According to this embodiment, owing to the noble gas in plating room can be improved further in each closed chamber
The flow velocity of aerofluxus tube side, therefore, it is possible to be more reliably prevented from moisture and oxygen invades in plating room.
(5) method manufacturing aluminum film according to one embodiment of the invention is any one institute in above-mentioned (1) to (4)
The method manufacturing aluminum film recorded, wherein, utilizes sealed roller by the respective described base material entrance of said two closed chamber and institute
State base material exit seal.
According to this embodiment, owing to obtaining the effect stoping extraneous air to invade by means of sealed roller, therefore, it is possible to
It is reliably prevented moisture further and oxygen invades in plating room.
(6) according to a kind of aluminum film manufacturing device of one embodiment of the invention, wherein will in fuse salt electroplate liquid
Aliminuium electrodeposition is on the surface of strip porous resin base material having been assigned electric conductivity, and this device includes
Plating room；
It is configured at the closed chamber of the base material entrance side of described plating room and is configured at the base material outlet side of described plating room
Closed chamber；
Noble gas supply pipe, it is arranged on described plating room, and is fed to by noble gas in described plating room；
And
Noble gas exhaustor, it is separately positioned on said two closed chamber, and by the inertia in described closed chamber
Gas is forced to discharge.
According to this embodiment, by means of inert gas, the moisture invaded in closed chamber and oxygen are forced row
Go out, it is possible to the moisture being reliably prevented in outside air and oxygen invade in plating room.Therefore, it is possible to obtain high-quality aluminum
Plated film, and it is possible to prevent the generation of the harmful substances such as such as hydrogen chloride.
It should be noted that no matter base material is with or without being sent in plating room in order to prevent plating solution and moisture and oxygen mix,
It is required to constantly be fed in plating room or closed chamber by noble gas, and the noble gas in closed chamber is forced row
Go out.Reason for doing so is that and prevent when moisture is mixed into plating solution, plating solution and moisture react to each other formation product also
And the impaired phenomenon needed for plating solution, and prevent when oxygen is mixed into plating solution, the aluminum film formed during plating
React with a small amount of dissolved oxygen included in plating solution and form the phenomenon of aluminium oxide.
The manufacture method of the aluminum film according to the present invention described in detail below and manufacture device.
It is intended to illustrate that the scope of the present invention is not or not to be determined by appended claim therefrom, and the model of the present invention
Enclose all changes including in the equivalents of claim and scope.
In the case of forming aluminum film by plating on conventional substrate, it is provided only with the closed chamber of sealed roller by utilization
Just can intercept moisture fully.But, there is the resin-formed body of tridimensional network (hereinafter also referred to as with electroplated aluminum
" resin porous body ") in the case of, the most only sealed roller can not provide sufficient moisture barrier effect.
Its reason is by inference: the resin-formed body being placed between sealed roller is the porous former with intercommunicating pore, and
And moisture and the oxygen being retained in intercommunicating pore is introduced in plating room.It is assumed that the other reasons of this phenomenon is: due to
Exist dense between moisture or the concentration of oxygen in moisture under the nitrogen atmosphere of plating room and the concentration of oxygen and extraneous air
Degree gradient, therefore moisture and oxygen through intercommunicating pore and are diffused in plating room.
Especially, the downstream at outlet side closed chamber is provided with flusher to remove the base material being formed with aluminum film on it
In the case of the plating solution remained on surface, it is assumed that due to above-mentioned phenomenon, moisture can invade in plating room.
Therefore, the present inventor constructs such device, joins at the entrance side of plating room and outlet side accommodating plating solution
Put closed chamber, each of described closed chamber arranges exhaustor, and lazy by blow out from plating room by this exhaustor
Property gas force discharge, in described closed chamber formed air-flow.Thus, it is possible to prevent aqueous vapor and oxygen from invading in plating room.
By to have with electroplated aluminum tridimensional network resin-formed body (hereinafter also referred to " resin porous body ") thus
The summary of the step manufacturing aluminum film is described, and is described in detail the ad hoc structure of closed chamber in the present invention.
(summary of Lv Mo manufacturing process)
In the manufacture device of the aluminum film according to the present invention, it is sent to base material be contained in the plating solution of plating room, and
By Aliminuium electrodeposition on base material, thus on base material, form aluminum film.
Fig. 8 shows the flow chart of the manufacturing process of aluminum porous body.Additionally, the Fig. 9 corresponding to this flow chart includes as follows
Schematic diagram, the schematic shows and use porous resin base material (the most alternatively referred to as " resin the porous body ") conduct serving as base material
Core thus form the state of aluminum film.With reference to the two accompanying drawing, the flow process of whole manufacturing process is illustrated.
First, the preparation of resin porous body 101 is carried out.Fig. 9 (a) is for show an example as resin porous body
There is the enlarged diagram on the surface of the resin porous body of intercommunicating pore.Resin porous body 31 is utilized to form hole as skeleton.So
After, the surface of resin porous body 102 is carried out the imparting of electric conductivity.As shown in Fig. 9 (b), via the step for, in resin porous
The conductive layer 32 being made up of electric conductor is defined thinly on the surface of body 1.
Subsequently, fuse salt 103 carries out aluminum plating, thus is formed on the surface of resin porous body with conductive layer
Aluminum film 33 (Fig. 9 (c)).Thus, obtained including the resin porous body as base material and being formed at the aluminum film 33 on its surface
Constructed of aluminium body.As required, from described constructed of aluminium body, substrate resin 104 is removed.
Resin porous body 31 is made to disappear by decomposition etc. such that it is able to only to be remained with the aluminum porous body 33 of metal level
(Fig. 9 (d)).
Each step will be described the most in order.
(preparation of porous resin base material)
Prepare the resin porous body with tridimensional network and intercommunicating pore.Any resin can be selected as resin
The material of porous body.It is, for example possible to use the resin molded foam body of polyurethane, melamine, polypropylene, polyethylene etc..Although table
State as resin molded foam body, but the resin-formed body with arbitrary shape can be selected, as long as it has (the connection of continuous print hole
Hole).It is, for example possible to use there is the entangled to each other molded body being similar to non-woven fabrics of resin fibre to substitute resin
Expanded moldings.Preferably, the porosity of resin molded foam body is 80% to 98%, and aperture is that 50 μm are to 500 μm.Poly-
Urethane foam and melamine foam have the connectedness in high porosity and hole, and have excellent resistance to pyrolytic, therefore fit
Share and make resin molded foam body.
The aspects such as the polyurethane foam uniformity in hole, accessibility are preferred, and melamine foam is being obtained in that have
The hole aspect of small-bore is preferred.
In many cases, resin porous body has the residue in foam manufacture process, such as foaming agent and unreacted
Monomer, and carry out subsequent step again after preferably carrying out cleaning process.Substrate resin as skeleton forms three-dimensional grid, because of
This, be integrally formed continuous print hole as one.In the skeleton of polyurethane foam, the cross section being perpendicular to skeleton bearing of trend has
Generally triangular shape.Here, porosity is defined by the formula:
Porosity=(1-(the weight [g] of resin porous body/(volume [cm of resin porous body3] × density of material))) ×
100 [%]
Additionally, determined aperture by following methods, in the method, putting of resin porous body is obtained by optical microscope etc.
Big surface, calculates the number number as cell of per inch (25.4mm) mesopore, and obtains meansigma methods by following formula: be average
Aperture=25.4mm/ cell number.
(giving the surface of resin porous body with electric conductivity)
In order to electroplate, the surface to resin porous body carries out electric conductivity imparting process in advance.In the present invention, pass through
The conductive coating paint of the conductive particle containing carbon etc. is coated in the surface of resin porous body, thus carries out at electric conductivity imparting
Reason.
First, the carbon coating as conductive coating paint is prepared.As the suspension of conductive coating paint preferably comprise carbon granule,
Binding agent, dispersant and disperse medium.In order to carry out the coating of conductive particle equably, suspension needs to keep even suspension
State.Therefore, suspension preferably remains in 20 DEG C to 40 DEG C.Reason for this is that, when the temperature of suspension is less than 20 DEG C,
Even suspension state disappears, and forms such layer so that only has binding agent and concentrates on composition resin porous body network structure
Skeleton surface on.In this case, coated carbon granule layer is easily peeled off, and is difficult to be formed the gold of firm attachment
Belong to coating.On the other hand, when the temperature of suspension is more than 40 DEG C, the evaporation capacity of disperse medium is big, along with the coating processing time
Passage, suspension concentrate, thus the coated weight of carbon be likely to change.Additionally, the granularity of carbon granule be 0.01 μm to 5 μm,
And preferably 0.01 μm to 0.5 μm.When grain graininess is big, granule may block the hole of resin porous body and hinder smooth plating
Cover.When grain graininess is too small, then it is difficult to ensure that enough electric conductivity.
Then can carry out extruding and being dried such that it is able to by carbon by impregnating target resin porous body in suspension
Granule is applied on resin porous body.
Figure 10 shows and gives the band resin porous body as skeleton with the structure example of the processing equipment of electric conductivity
Schematic diagram, it is an example of actual manufacture process.As it can be seen, this equipment includes: supply long strip base material resin is (following
The supply drum 52 of also referred to as " band resin ") 51；Accommodate the groove 55 of conductive coating paint suspension 54；It is positioned at above groove 55
To compression roller 57；It is configured at multiple hot air nozzles 56 of the both sides of the band resin 51 of traveling in an opposing fashion；It is used for rolling up
Take the band resin 51 that processed batches drum 58.The slewing rollers 53 being used for guiding band resin 51 are additionally, proper set.
In the equipment with said structure, the band resin 51 with tridimensional network is launched by supply drum 52, diverted roller
53 guide, and are immersed in the suspension 54 in groove 55.The band resin 51 being immersed in the suspension 54 in groove 55 is directed
The compression roller 57 of suspension 54 surface it is positioned to upwardly direction being advanced through.Between this stage, compression roller 57
Distance less than the thickness of band resin 51, band resin 51 is compressed.Therefore, containing the excess suspension being immersed in band resin 51
Liquid is extruded and returns in groove 55.
Subsequently, the direct of travel of band resin 51 changes again.Then, by from the hot air nozzle including multiple nozzle
In 56, the disperse medium of suspension etc. is removed by the hot-air of ejection, and after band resin 51 is completely dried, is batched
Batching on drum 58.It should be noted that the temperature range of the hot-air of ejection is preferably 40 DEG C from hot air nozzle 56
To 80 DEG C.By using this equipment, can automatically and continuously complete electric conductivity imparting and process, and can be formed and have not
The network structure that can block and the skeleton with uniform conductive layer.Therefore, it is possible to successfully carry out metal deposition after this
Continuous step.
(formation of aluminum film: fuse salt plating)
Then, electroplate in fuse salt, thus on the surface of resin porous body, form aluminum film.
By carrying out aluminum plating in molten salt bath, enable in particular to (such as there is three-dimensional netted knot in complicated framing structure
The resin porous body of structure) formed uniformly over the surface thickness aluminum film.
The resin porous body using surface to have been assigned electric conductivity is negative electrode, and with aluminum as anode, thus at fuse salt
Middle applying DC current.
It addition, as fuse salt, it is possible to use as organohalogen compounds and the eutectic salts of aluminum halide organic fuse salt or
Person is as alkali halide and the inorganic molten salt of the eutectic salts of aluminum halide.When using melt at relatively low temperatures to have
During machine molten salt bath, the resin porous body as base material can be plated in the case of Undec, thus is preferred.Permissible
Use imidazole salts, pyridiniujm etc. as organohalogen compounds.And specifically, it is preferable to 1-ethyl-3-methylimidazolium chloride
And butyl pyridinium chloride (BPC) (EMIC)..
When moisture or oxygen are mixed into fuse salt, fuse salt deteriorates.It is therefore preferable that at the indifferent gas of such as nitrogen or argon
In bromhidrosis atmosphere, and under closed environment, carry out plating.
Molten salt bath is preferably nitrogenous molten salt bath, and imidazoles salt bath is especially preferably used.Melt under using high temperature
In the case of the salt melted is as fuse salt, resin melts fuse salt or its speed decomposed is faster than the growth of plated film, and not
Plated film may be formed on the surface of resin porous body.Imidazoles salt bath even can use at relatively low temperatures without
Affect resin.As imidazole salts, it is preferably used containing the salt at 1 and 3 glyoxaline cation with alkyl.Especially
Ground, most preferably with aluminum chloride-1-ethyl-3-methylimidazolium chloride (AlCl3+ EMIC) it is fuse salt, this is because it is steady
Qualitative height and be not easy to decompose.Plating can be carried out in polyurethane foam, melamine foam etc..The temperature of molten salt bath is 10 DEG C
To 100 DEG C, and preferably 25 DEG C to 45 DEG C.Along with the reduction of temperature, the current density range that can carry out plating narrows, and
And become to be difficult to carry out plating on the whole surface of resin porous body.Under the high temperature more than 100 DEG C, it is likely that resin occurs
The problem of porous body deformation.
Fuse salt for metal surface is aluminized, it has been reported for improve coating surface flatness purpose to
AlCl3-EMIC adds the additives such as dimethylbenzene, benzene, toluene or 1,10-phenanthroline.Present inventor have discovered that particularly right
Having the resin porous body of tridimensional network when aluminizing, add 1,10-phenanthroline is formed with spy for aluminum porous body
Other effect.In other words, obtained the 1st feature of the aluminum skeleton not easy fracture constituting porous body, and plating can have been carried out, made
Obtain the 2nd feature that the plated thickness difference between surface portion and the inside of porous body is little.
On the other hand, in the range of resin does not dissolves and waits, it is possible to use inorganic salt bath is as fuse salt.Inorganic salt bath generation
Table have AlCl3-XCl (X: alkali metal) binary salt system or multicomponent salt system.In such inorganic salt bath, although its
Melt temperature is usually above organic salt baths such as imidazoles salt baths, but the restriction of the environmental condition of such as moisture and oxygen etc is few,
And generally put into actually used with low cost.In the case of resin is melamine foam, compared to polyurethane foam, Ke Yi
Use under high temperature, and use inorganic salt bath at 60 DEG C to 150 DEG C.
(plater)
Fig. 1 shows an example of aluminum film manufacturing device according to embodiments of the present invention.
Aluminum film manufacturing device include plating room 1, the entrance side closed chamber 4 being arranged at the base material entrance side of plating room 1 and
It is arranged at the outlet side closed chamber 5 of the base material outlet side of plating room 1.
Base material W (hereinafter also referred to " workpiece ") by supply drum 20 launch, this supply drum 20 base material is sent to through
Entrance side closed chamber 4 is also sent in plating room 1.On its in plating room 1, the workpiece W already formed with aluminum film passes outlet side
Closed chamber 5, is washed with water in flusher 22, is then taken up and is batching on drum 21.
-plating room-
As it is shown in figure 1, plating room 1 comprises anode 2 and plating solution 3.Plating room 1 is provided with noble gas supply to plating room
The noble gas supply pipe 6 of 1.Thus, the inside of plating room is in inert gas atmosphere, and has relative to extraneous air
Malleation.Noble gas can be the gas not reacted with fuse salt, such as nitrogen or argon, and comes from the viewpoint of cost
See, nitrogen is preferably used.
Will be described below the situation using nitrogen as noble gas.
Can use any existing plating room as plating room 1, and can use be powered in a liquid be
System or the system being powered outside liquid.
Although fig 1 illustrate that the base material in plating room is with horizontal direction transmission, but such plating room can also be used,
When along the circumferential surface conveying work pieces of conveying roller, wherein form aluminum film.
-entrance side closed chamber and outlet side closed chamber-
Fig. 1 shows closed chamber according to embodiments of the present invention.
Nitrogen exhaust pipe 7 it is provided with in each of closed chamber 4 and 5, and will be from plating room by nitrogen exhaust pipe 7
The noble gas of 1 blowout is forced to discharge, and forms stream of nitrogen gas in each of closed chamber 4 and 5.Preferably away from plating room
Position configuration nitrogen exhaust pipe 7.That is, in entrance side closed chamber, nitrogen exhaust pipe 7 is preferably configured in the position near base material entrance
Put place, and in outlet side closed chamber, nitrogen exhaust pipe 7 is preferably configured in the position near base material outlet.By upper
Rheme puts configuration nitrogen exhaust pipe 7, is formed with the air-flow flowing to base material entrance from plating room 1 in entrance side closed chamber, and
The air-flow flowing to base material outlet side from plating room 1 it is formed with in outlet side closed chamber.This improves and prevent moisture and oxygen
Invade the effect in plating room.
Fig. 2 and 3 shows the closed chamber according to other embodiments of the present invention.
In example as shown in Figures 2 and 3, each of closed chamber 4 and 5 is provided with nitrogen supply (NS) pipe 8.
By by nitrogen supply (NS) pipe 8 the supply of nitrogen, the flow velocity of the air-flow formed in each of closed chamber 4 and 5 is able to
Improve, and further increase the effect preventing moisture and oxygen from invading in plating room.
The nitrogen supplied by nitrogen supply (NS) pipe 8 is preferably blown to workpiece in the way of relative to workpiece inclination.By with so
Mode the supply of nitrogen, easily formed from plating room 1 effluent to the air-flow of nitrogen exhaust pipe 7 side, and by nitrogen from workpiece
Displace the moisture in the hole being present in workpiece W and oxygen and it is discharged from workpiece.The moisture discharged from workpiece and oxygen
Gas is taken away by the air-flow in closed chamber, and is discharged by exhaustor 7.
Figure 4 and 5 show the closed chamber according to other embodiments of the present invention.
In example as shown in Figure 4, each of the closed chamber 4 and 5 in the example shown in Fig. 1 is provided with two right
Sealed roller 9, and in the example shown in Fig. 5, each of the closed chamber 4 and 5 of the example shown in Fig. 2 is provided with two right
Sealed roller 9.
By arranging such sealed roller in closed chamber, it is possible to more efficiently prevent from moisture and oxygen invades plating room
In.
In the example shown in Fig. 6, it is provided with close for prevent extraneous air from invading in the base material porch of closed chamber 4
Shrouding (encapsulant) 10.This sealing plate is arranged so that its end contacts with the surface of workpiece W, thus, prevents outside empty
Gas invades from base material porch.Sealing plate can be made up of the material on not defective work piece surface, and is preferably fabricated from a flexible material.
Additionally, be also provided with the sealing plate (encapsulant) being similarly used for preventing extraneous air from invading in the base material exit of closed chamber 5
10。
(cleaning)
For being formed with the aluminium coated fabric body of aluminum film on the surface of resin porous body, it is carried out nitrogen and purges with fully
Ground removes plating solution, is then carried out obtaining aluminum porous body.
Although by using water as cleanout fluid, but organic solvent can also be used.
By above-mentioned steps, obtain the constructed of aluminium body (aluminum porous body) including resin porous body as skeleton core.Root
Desired use according to the most various filters and catalyst carrier etc, it is possible to use this constructed of aluminium is multiple as resin-metal
Fit.When owing to using the reasons such as environment restriction, when using described constructed of aluminium not include resin as metal structure, permissible
Resin is removed.Resin can be removed by any method, such as, use organic solvent, fuse salt or supercritical water to carry out point
Solve (dissolving) or heat resolve.The method decomposed by high-temperature heating is easy, but can cause the oxidation of aluminum.With nickel etc. no
With, aluminum is just difficult to reduction treatment once oxidized.It is thus possible, for instance the feelings used at the electrode material as battery etc.
Under condition, conductivity is lost due to oxidation, it is thus impossible to use the method that high-temperature heating decomposes.
Therefore, in order to prevent the oxidation of aluminum, it is generally desirable to use the side being removed resin by heat resolve in fuse salt
Method, this will be described below.
(removing of resin: heat resolve in fuse salt)
The heat resolve in fuse salt is carried out by method as described below.The resin porous body that surface configuration has aluminum film soaks
Not in fuse salt, apply nagative potential and heat while aluminum film, so that resin porous body decomposes.When in resin porous
When body is immersed under the state in fuse salt applying nagative potential, it is possible to make resin porous body decompose and not make aluminum oxidation.Can basis
The kind of resin porous body properly selects heating-up temperature.In order to not make aluminum melt, it is necessary at the fusing point (660 DEG C) less than aluminum
At a temperature of process.Preferably temperature range is 500 DEG C to 600 DEG C.Additionally, the amount of the nagative potential applied is relative to aluminum
Reduction potential be positioned at minus side, and be positioned at positive side relative to the reduction potential of fuse salt cationic.
Made by heated resin its decompose used in fuse salt can be the halogenation of alkali metal or alkaline-earth metal
Thing salt, so that aluminum electrode potential becomes relatively low (base).Specifically, it is preferable that fuse salt comprises the free lithium chloride of choosing
(LiCl), potassium chloride (KCl), sodium chloride (NaCl) and aluminum chloride (AlCl3) in the group that constituted at least one or multiple.Logical
Cross this method, it is possible to obtain and there is intercommunicating pore and there is on its surface the aluminum porous of thin oxide layer of low oxygen content
Body.
Embodiment
Hereinafter based on embodiment, the present invention will be further described in more detail.But, these embodiments are only illustrative
, and the invention is not restricted to this.Here, the scope of the present invention is defined by the appended claims, and include that right is wanted
Ask all deformation in book equivalence meaning and scope.
[embodiment 1]
Use the aluminum film manufacturing device according to embodiments of the present invention shown in Fig. 1, porous resin base material is formed aluminum
Plated film.Plating conditions is as follows.
(porous resin base material)
Preparation width is 1m, thickness is 1mm, the number in the hole (cell) of porosity 95 volume % and per inch is big
The polyurethane of about 50 is as base material.By polyurethane foam is immersed in carbon suspension liquid, it is subsequently dried, thus gives it to lead
Electrically.Carbon suspension liquid is made up of the graphite of 17 mass % and the resinoid bond of white carbon black and 7 mass %, and wraps further
Containing penetrating agent and defoamer.The granularity of white carbon black is 0.5 μm.
(closed chamber)
Entrance side closed chamber 4 and the respective a length of 500mm of outlet side closed chamber, and be highly 200mm.
Gas in each closed chamber is by exhaustor 7 sucking-off and is discharged.
(plating room)
With 4.0m3/ minute overall flow rate by two feed tube 6 the supply of nitrogen of plating room 1.
(plating conditions)
Plating conditions is provided that
Plating solution forms: AlCl3/ EMIC=2mol/1mol
Apply electric current: 1,000A
Workpiece: polyurethane foam (thickness 1mm, width 1,000mm, aperture 0.5mm)
Work speed: 150mm/ minute
The immersion length of workpiece: 2m
(evaluation)
After plater runs 24 hours, utilize air pump, by the atmosphere gas (nitrogen) collected in plating room of bleeding,
This gas is defined as [sample gas 1]；And utilizing air pump, the room being deposited plater by collection of bleeding (is also referred to as below
For " general room ") near supply drum atmosphere gas, this gas is defined as [sample gas 2].
About [sample gas 1], analyze dew point and oxygen concentration respectively by dew point instrument (capacitor type) and oxymeter.
Additionally, about [sample gas 2], analyzed the concentration of hydrogen chloride by hydrogen cloride concentration meter.
Analysis result is shown in Table 1.
[embodiment 2]
Running plater as in Example 1 and collect sample gas, difference is to employ according to the present invention
The aluminum film manufacturing device being provided with sealed roller 9 shown in Fig. 4 of implementation, and with 3.5m3/ minute overall flow rate by plating
Two nitrogen supply (NS) pipe 6 the supply of nitrogen of room 1.
The analysis result of sample gas is shown in Table 1.
[embodiment 3]
Running plater as in Example 1 and collect sample gas, difference is, in embodiment 1, and Fig. 6
Shown sealing plate 10 is respectively arranged at the base material entrance side of closed chamber 4 and the base material outlet side of closed chamber 5, and with 3.5m3/
Minute overall flow rate by two nitrogen supply (NS) pipe 6 the supply of nitrogen of plating room 1.
The analysis result of sample gas is shown in Table 1.
[embodiment 4]
Running plater as in Example 1 and collect sample gas, difference is, employs according to the present invention
Aluminum film manufacturing device shown in Fig. 2 of implementation, with 3.3m3/ minute overall flow rate by two nitrogen supply (NS) pipes of plating room 1
6 the supply of nitrogen, and with 0.2m3/ minute overall flow rate by nitrogen supply (NS) pipe 8 the supply of nitrogen of closed chamber 4 and 5
The analysis result of sample gas is shown in table 1.
[embodiment 5]
Running plater as in Example 1 and collect sample gas, difference is, employs according to the present invention
The aluminum film manufacturing device being provided with sealed roller 9 shown in Fig. 5 of embodiment, with 3.0m3/ minute overall flow rate by plating room 1
Two nitrogen supply (NS) pipe 6 the supply of nitrogen, and with 0.2m3/ minute overall flow rate supplied by the nitrogen supply (NS) pipe 8 of closed chamber 4 and 5
Answer nitrogen.
The analysis result of sample gas is shown in Table 1.
[comparative example 1]
Running plater as in Example 1 and collect sample gas, difference is, in embodiment 1, does not has
By closed chamber 4 and 5 each in air force from nitrogen exhaust pipe 7 discharge.
The analysis result of sample gas is shown in Table 1.
[comparative example 2]
Running plater as in Example 2 and collect sample gas, difference is, in example 2, does not has
By closed chamber 4 and 5 each in air force from nitrogen exhaust pipe 7 discharge.
The analysis result of sample gas is shown in Table 1.
[comparative example 3]
Running plater as in Example 3 and collect sample gas, difference is, in embodiment 3, does not has
By closed chamber 4 and 5 each in air force from nitrogen exhaust pipe 7 discharge.
The analysis result of sample gas is shown in Table 1.
[comparative example 4]
Running plater as in Example 4 and collect sample gas, difference is, in example 4, does not has
By closed chamber 4 and 5 each in air force from nitrogen exhaust pipe 7 discharge.
The analysis result of sample gas is shown in Table 1.
Think that the oxygen concentration of plating room is less than 0.5% for acceptable scope.
Think that plating room dew point is acceptable scope less than-30 DEG C.
When HCl concentration is less than 0.1ppm, then it is assumed that there is not leakage.
[table 1]
Symbol description
1 plating room
2 anodes
3 plating solutions
4 entrance side closed chambers
5 outlet side closed chambers
6 noble gases (nitrogen) supply pipe
7 noble gases (nitrogen) exhaustor
8 noble gases (nitrogen) supply pipe
9 sealed rollers
10 sealing plates
11 hold-down rollers
12 power supply rollers
13 transfer rollers
14 accumulator tanks
15 pumps
20 supply drums
21 batch drum
22 flushers
31 resin porous bodies
32 conductive layers
33 aluminum films
51 strip porous resin base materials (band resin)
52 supply drums
53 slewing rollers
54 electrically-conducting paint suspensions
55 grooves
56 hot air nozzles
57 compression rollers
58 batch drum
W workpiece
Claims (6)
1. the method manufacturing aluminum film, wherein in molten salt electrolyte by Aliminuium electrodeposition to the strip having been assigned electric conductivity
On the surface of shape porous resin base material, the method includes:
Described base material is made to transport through the closed chamber of the entrance side being configured at plating room and be sent to the step of described plating room；
By the step on aluminum film electrodeposition to the surface of described base material in described plating room；And
The described base material that its substrates has described aluminum film sends out from described plating room and by being configured at described plating room
The step of closed chamber of outlet side,
Wherein, to described plating room supplying inert gas, so that described plating room has malleation relative to extraneous air, and
Force to discharge by described noble gas from the noble gas exhaustor being separately positioned on said two closed chamber.
The method of manufacture aluminum film the most according to claim 1, wherein, is being configured at the described closed chamber of described entrance side
Base material entrance side is provided with described noble gas exhaustor, and
Base material outlet side at the described closed chamber being configured at described outlet side is provided with described noble gas exhaustor.
The method of manufacture aluminum film the most according to claim 1 and 2, wherein, enterprising in each of said two closed chamber
One step arranges the noble gas supply pipe of supplying inert gas.
The method of manufacture aluminum film the most according to claim 3, wherein, is being configured at the described closed chamber of described entrance side
Base material outlet side is provided with described noble gas supply pipe, and enters at the base material of the described closed chamber being configured at described outlet side
Mouth side is provided with described noble gas supply pipe.
The method of manufacture aluminum film the most according to any one of claim 1 to 4, wherein, utilizes sealed roller by said two
The respective described base material entrance of closed chamber and described base material exit seal.
6. a manufacture device for aluminum film, wherein in molten salt electrolyte by Aliminuium electrodeposition to the strip having been assigned electric conductivity
On the surface of shape porous resin base material, this device includes:
Plating room；
The closed chamber being configured at the base material entrance side of described plating room and the base material outlet side being configured at described plating room close
Envelope room；
Noble gas supply pipe, it is arranged on described plating room, and is fed to by noble gas in described plating room；And
Noble gas exhaustor, it is separately positioned on said two closed chamber, and by the described inertia in described closed chamber
Gas is forced to discharge.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014019935 | 2014-02-05 | ||
| JP2014-019935 | 2014-02-05 | ||
| PCT/JP2015/051983 WO2015118977A1 (en) | 2014-02-05 | 2015-01-26 | Aluminum film manufacturing method and manufacturing device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105980606A true CN105980606A (en) | 2016-09-28 |
Family
ID=53777784
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580007478.XA Pending CN105980606A (en) | 2014-02-05 | 2015-01-26 | Aluminum film manufacturing method and manufacturing device |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20170002474A1 (en) |
| EP (1) | EP3103895B1 (en) |
| JP (1) | JP6447928B2 (en) |
| KR (1) | KR20160119089A (en) |
| CN (1) | CN105980606A (en) |
| WO (1) | WO2015118977A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109689941A (en) * | 2016-11-22 | 2019-04-26 | 株式会社Uacj | Electrolytic aluminum foil and its manufacturing method |
| CN110073037A (en) * | 2016-12-16 | 2019-07-30 | 株式会社Uacj | The manufacturing method and manufacturing device of electrolytic aluminum foil |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10954600B2 (en) | 2016-12-16 | 2021-03-23 | Hamilton Sundstrand Corporation | Electroplating systems and methods |
| US11261533B2 (en) | 2017-02-10 | 2022-03-01 | Applied Materials, Inc. | Aluminum plating at low temperature with high efficiency |
| US10240245B2 (en) * | 2017-06-28 | 2019-03-26 | Honeywell International Inc. | Systems, methods, and anodes for enhanced ionic liquid bath plating of turbomachine components and other workpieces |
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| US3167403A (en) * | 1960-06-09 | 1965-01-26 | Nat Steel Corp | Base materials coated with an alloy of aluminum and manganese |
| JP2000087287A (en) * | 1998-09-11 | 2000-03-28 | Sumitomo Metal Ind Ltd | Liquid circulating device between sealed vessels and method therefor |
| JP2012255185A (en) * | 2011-06-08 | 2012-12-27 | Sumitomo Electric Ind Ltd | Manufacturing method and manufacturing apparatus for aluminum porous body |
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| JPS61213389A (en) * | 1985-03-18 | 1986-09-22 | Sumitomo Metal Ind Ltd | Electroplating device by molten salt bath |
| JPH0317292A (en) * | 1989-06-14 | 1991-01-25 | Nisshin Steel Co Ltd | Aluminum electroplating apparatus with molten salt bath |
| JPH04329898A (en) * | 1991-05-07 | 1992-11-18 | Sumitomo Metal Ind Ltd | Device for continuous fused salt electrolytic plating |
| JP2806116B2 (en) | 1992-01-10 | 1998-09-30 | 住友金属工業 株式会社 | Molten salt electroplating equipment |
| JP2943484B2 (en) | 1992-02-17 | 1999-08-30 | 住友金属工業株式会社 | Method and apparatus for hot-dip plating of aluminum |
| JP2002030480A (en) * | 2000-07-11 | 2002-01-31 | Casio Micronics Co Ltd | Plating method and device therefor |
| JP2012007233A (en) | 2010-04-22 | 2012-01-12 | Sumitomo Electric Ind Ltd | Method for manufacturing aluminum structure and the aluminum structure |
-
2015
- 2015-01-26 CN CN201580007478.XA patent/CN105980606A/en active Pending
- 2015-01-26 JP JP2015560925A patent/JP6447928B2/en active Active
- 2015-01-26 KR KR1020167021351A patent/KR20160119089A/en not_active Application Discontinuation
- 2015-01-26 US US15/114,871 patent/US20170002474A1/en not_active Abandoned
- 2015-01-26 EP EP15746409.0A patent/EP3103895B1/en active Active
- 2015-01-26 WO PCT/JP2015/051983 patent/WO2015118977A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3167403A (en) * | 1960-06-09 | 1965-01-26 | Nat Steel Corp | Base materials coated with an alloy of aluminum and manganese |
| JP2000087287A (en) * | 1998-09-11 | 2000-03-28 | Sumitomo Metal Ind Ltd | Liquid circulating device between sealed vessels and method therefor |
| JP2012255185A (en) * | 2011-06-08 | 2012-12-27 | Sumitomo Electric Ind Ltd | Manufacturing method and manufacturing apparatus for aluminum porous body |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109689941A (en) * | 2016-11-22 | 2019-04-26 | 株式会社Uacj | Electrolytic aluminum foil and its manufacturing method |
| US11035047B2 (en) | 2016-11-22 | 2021-06-15 | Uacj Corporation | Electrolytic aluminum foil and method of manufacturing same |
| CN110073037A (en) * | 2016-12-16 | 2019-07-30 | 株式会社Uacj | The manufacturing method and manufacturing device of electrolytic aluminum foil |
| CN110073037B (en) * | 2016-12-16 | 2021-04-30 | 株式会社Uacj | Method and apparatus for manufacturing electrolytic aluminum foil |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20160119089A (en) | 2016-10-12 |
| EP3103895A4 (en) | 2017-02-22 |
| JP6447928B2 (en) | 2019-01-09 |
| WO2015118977A1 (en) | 2015-08-13 |
| EP3103895B1 (en) | 2018-07-18 |
| JPWO2015118977A1 (en) | 2017-03-23 |
| US20170002474A1 (en) | 2017-01-05 |
| EP3103895A1 (en) | 2016-12-14 |
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