CN106460216B - Aluminium plating solution, the manufacture method of aluminium film and aluminium porous body - Google Patents
Aluminium plating solution, the manufacture method of aluminium film and aluminium porous body Download PDFInfo
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- CN106460216B CN106460216B CN201580033821.8A CN201580033821A CN106460216B CN 106460216 B CN106460216 B CN 106460216B CN 201580033821 A CN201580033821 A CN 201580033821A CN 106460216 B CN106460216 B CN 106460216B
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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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/42—Electroplating: Baths therefor from solutions of light metals
- C25D3/44—Aluminium
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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
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
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- Electroplating And Plating Baths Therefor (AREA)
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Abstract
The present invention provides a kind of aluminium plating solution that can continuously manufacture aluminium film, the surface of the aluminium film is smooth and the aluminium film has excellent elongation.The aluminium plating solution for being capable of electric deposition aluminum on the surface of the substrate includes following components：(A) aluminum halide；(B) selected from least one of the group being made of alkyl halide imidazoles, alkylpyridinium halides and carbamide compound compound；And (C1) is selected from least one of group being made of ammonium salt, microcosmic salt, sulfonium salt, amine compounds, phosphine compound and sulfide compound；The component (C1) has C8‑36Straight or branched alkyl is as at least one side chain；With molar ratio computing, the mixing ratio of the component (A) and the component (B) is 1:1 to 3:In the range of 1；The concentration of the component (C1) is 1.0g/L to 45g/L.
Description
Technical field
The present invention relates to the aluminium plating solution that can manufacture aluminium film, which has good surface smoothness and well soft
Property.The invention further relates to the method for manufacturing aluminium film, this method includes the use of aluminium plating solution, and is related to by using the aluminium
The aluminium porous body that plating solution obtains.
Background technology
Aluminium has many good characteristics, such as electric conductivity, corrosion resistance, Lightness and non-toxic, and aluminium is wide
It is general be used in (such as) in the plating of metal product.However, aluminium is high to the compatibility of oxygen, and its oxidation-reduction potential is less than hydrogen
Oxidation-reduction potential.Therefore, it is difficult to electroplated aluminum is carried out in water solution system plating bath.
Therefore, the method for carrying out electroplated aluminum is used as using the method using molten salt bath.However, include fuse salt
Existing plating bath needs to be heated to high temperature.Therefore, when with electroplated aluminum resin, it is understood that there may be melting and nothing occur for resin
The problem of method is electroplated.
In view of the problem of such, Japanese Unexamined Patent Application Publication No.2012-144763 (patent document 1) is described
By the organic chloride salt of such as 1- ethyls -3- methylimidazolium chlorides (EMIC) or 1- butyl pyridinium chloride (BPC) etc
With aluminium chloride (AlCl3) mixing come prepare be at room temperature liquid aluminium plating bath, and electroplated aluminum can set using the plating bath
On the surface of fat formed body.
Specifically, the EMIC-AlCl described in patent document 13It is that plating solution has good SOLUTION PROPERTIES and very
It is suitable as aluminium plating solution.Patent document 1 describe that coughed up by the way that 1,10- phenanthroline is added to 1,10- phenanthrene in the aluminium plating solution
Quinoline concentration reaches 0.25g/L to 7.0g/L, so as to form smooth aluminium film.
On the metal porous body with tridimensional network, the aluminium manufactured by the method described in patent document 1 is more
Hole body (such as) as improve lithium ion battery positive electrode capacity right and wrong often with promising.Since aluminium has good characteristic,
Such as electric conductivity, corrosion resistance and Lightness, therefore active material (such as cobalt oxidate for lithium) will be coated with surface at present
Aluminium foil is used as the cathode of lithium ion battery.The cathode is formed by using the porous body formed by aluminium, surface area increase and
The inside of aluminium can also equally be filled by active material.By means of the structure, even if when the thickness increase of electrode, active material
Utilization rate will not reduce.Therefore, the utilization rate of the active material of unit area improves, and can improve the appearance of cathode
Amount.
As described above, the aluminium porous body with tridimensional network is highly useful.Pass through patent document 1 however, working as
Described in method when being largely continuously manufactured by this aluminium porous body, the flatness of obtained aluminium film gradually reduces, therefore root
According to needs, plating solution needs to be replaced by new plating solution.
In view of the above problems, Japanese Unexamined Patent Application Publication No.2014-058715 (patent document 2) describe by
The concentration control of 1,10- phenanthroline monohydrates in aluminum plating liquid is effective for more than 0.05g/L below 7.5g/L.
Reference listing
Patent document
Patent document 1：Japanese Unexamined Patent Application Publication No.2012-144763
Patent document 2：Japanese Unexamined Patent Application Publication No.2014-058715
The content of the invention
Technical problem
As described in patent document 2, by the way that 1,10- phenanthroline monohydrates are added in aluminium plating solution, and by 1,10-
The concentration control of phenanthroline monohydrate carries out aluminium plating while being more than 0.05g/L below 7.5g/L, can connect in large quantities
It is continuous to form smooth aluminium film.There is the aluminium film obtained by this way good flatness (to have reached the journey that its surface is minute surface
Degree).However, aluminium film is hard and has high intensity, therefore with the property for being not easy to be elongated.
In some applications of the aluminium porous body with tridimensional network, aluminium film needs flexible and extensibility, therefore this
The inventor of invention has been carried out by applying heat to aluminium porous body so that aluminium has flexible research.In general, metal have due to
The property for being heat-treated and softening.It is however, hot even in carrying out by the aluminium porous body that the method described in patent document 2 is obtained
Also without flexibility after processing.
Therefore, it is an object of the invention to provide a kind of aluminium plating solution that can continuously manufacture aluminium film, the surface of the aluminium film is
The smooth and aluminium film has good elongation.
Solution to problem
The aluminium plating solution of embodiment is according to the present invention
(1) it is capable of the aluminium plating solution of electric deposition aluminum on the surface of the substrate,
The aluminium plating solution includes following components：
(A) aluminum halide；
(B) selected from least one of group being made of alkyl halide imidazoles, alkylpyridinium halides and carbamide compound
Compound；And
(C1) in the group being made of ammonium salt, microcosmic salt, sulfonium salt, amine compounds, phosphine compound and sulfide compound extremely
Few one,
Wherein described component (C1) is with the straight or branched alkyl that carbon number is less than more than 8 36 as at least one
Side chain,
With molar ratio computing, the mixing ratio of the component (A) and the component (B) is 1:1 to 3:In the range of 1, and
The concentration of the component (C1) is more than 1.0g/L below 45g/L.
In aluminium plating solution described in above-mentioned (1), the term " side chain " in component (C1) refers to and every kind of salt or compound
N atoms, P atoms or S atom bonding group.
The aluminium plating solution of embodiment is according to the present invention
(2) it is capable of the aluminium plating solution of electric deposition aluminum on the surface of the substrate,
The aluminium plating solution includes following components：
(A) aluminum halide；
(B) selected from least one of group being made of alkyl halide imidazoles, alkylpyridinium halides and carbamide compound
Compound；
(C2) in the group being made of ammonium salt, microcosmic salt, sulfonium salt, amine compounds, phosphine compound and sulfide compound extremely
Few one, and
(D) selected from least one of group being made of alkyl halide, alkynes, alkene and alkane；
Wherein described component (C2) is with the straight or branched alkyl that carbon number is less than more than 1 36 as at least one
Side chain,
The component (D) is the straight-chain or branched-chain compound that carbon number is less than more than 3 36,
With molar ratio computing, the mixing ratio of the component (A) and the component (B) is 1:1 to 3:In the range of 1,
The concentration of the component (C2) is more than 1.0g/L below 45g/L, and
The concentration of the component (D) is more than 0.5g/L below 8.5g/L.
In aluminium plating solution described in above-mentioned (2), the term " side chain " in component (C2) refers to and every kind of salt or compound
N atoms, P atoms or S atom bonding group.
Beneficial effects of the present invention
According to the present invention it is possible to provide a kind of aluminium plating solution that can continuously manufacture aluminium film, the surface of the aluminium film is smooth
And the aluminium film has good elongation.
Embodiment
[description of embodiment of the present invention]
First, it will list and describe embodiment of the present invention.
(1) the aluminium plating solution of embodiment is according to the present invention
It is capable of the aluminium plating solution of electric deposition aluminum on the surface of the substrate,
The aluminium plating solution includes following components：
(A) aluminum halide；
(B) selected from least one of group being made of alkyl halide imidazoles, alkylpyridinium halides and carbamide compound
Compound；And
(C1) in the group being made of ammonium salt, microcosmic salt, sulfonium salt, amine compounds, phosphine compound and sulfide compound extremely
Few one,
Wherein described component (C1) is with the straight or branched alkyl that carbon number is less than more than 8 36 as at least one
Side chain,
With molar ratio computing, the mixing ratio of the component (A) and the component (B) is 1:1 to 3:In the range of 1, and
The concentration of the component (C1) is more than 1.0g/L below 45g/L.
According to embodiment of the present invention described in above-mentioned (1), a kind of aluminium that can continuously manufacture aluminium film can be provided
Plating solution, the surface of the aluminium film is smooth and the aluminium film has good elongation.
(2) according to the present invention the aluminium plating solution of embodiment to be capable of the aluminium plating solution of electric deposition aluminum on the surface of the substrate,
The aluminium plating solution includes following components：
(A) aluminum halide；
(B) selected from least one of group being made of alkyl halide imidazoles, alkylpyridinium halides and carbamide compound
Compound；
(C2) in the group being made of ammonium salt, microcosmic salt, sulfonium salt, amine compounds, phosphine compound and sulfide compound extremely
Few one, and
(D) selected from least one of group being made of alkyl halide, alkynes, alkene and alkane；
Wherein described component (C2) is with the straight or branched alkyl that carbon number is less than more than 1 36 as at least one
Side chain,
The component (D) is the straight-chain or branched-chain compound that carbon number is less than more than 3 36,
With molar ratio computing, the mixing ratio of the component (A) and the component (B) is 1:1 to 3:In the range of 1,
The concentration of the component (C2) is more than 1.0g/L below 45g/L, and
The concentration of the component (D) is more than 0.5g/L below 8.5g/L.
According to embodiment of the present invention described in above-mentioned (2), can provide one kind with relatively low cost can be continuous
The aluminium plating solution of aluminium film is manufactured, the surface of the aluminium film is smooth and the aluminium film has good elongation.
(3) in the aluminium plating solution described in above-mentioned (1) or (2), component (A) is preferably aluminium chloride, and component (B) is preferred
For 1- ethyl -3- methylimidazolium chlorides.
According to embodiment of the present invention described in above-mentioned (3), can provide one kind can stablize and continuously obtain
The aluminium plating solution of aluminium film, the aluminium film have preferable surface smoothness.
(4) method for manufacturing the aluminium film of embodiment according to the present invention, this method are used to manufacture aluminium film to be such a
Method, this method include by using the aluminium plating solution according to any one of above-mentioned (1) to (3) it is electric on the surface of the substrate
Deposition of aluminum.
According to embodiment of the present invention described in above-mentioned (4), can provide one kind has excellent surface for manufacturing
The method of flatness and the aluminium film of good elongation.
(5) the aluminium porous body of embodiment is by using according to any one of above-mentioned (1) to (3) according to the present invention
The aluminium porous body that the aluminium plating solution obtains, the aluminium porous body have tridimensional network and more than 1.5% elongation.
Aluminium porous body described in above-mentioned (5) is soft and has good elongation, therefore it can be used for applying
Added with the aluminium porous body in the application of bending or vibration.
Shadow of the elongation of the aluminium porous body of embodiment according to the present invention by the coating weight of the aluminium of per unit area
Ring.Therefore, elongation is identified as when the coating weight of the aluminium of the per unit area of aluminium porous body is 100g/m2Above 180g/m2
Elongation when below and thickness is more than 0.95mm below 1.05mm.
Term " elongation " refers to the elongation of the measure when carrying out tension test according to JIS Z 2241, and refers to position
Shifting amount is relative to the distance between mark (gauge length (Gage Length)：GL ratio).
(6) in the aluminium porous body described in above-mentioned (5), the crystallite dimension in the cross section of skeleton is preferably more than 1 μm
Less than 50 μm.
Aluminium porous body described in above-mentioned (6) has larger crystallite dimension, therefore the aluminium porous body is soft and has
The aluminium porous body of good elongation.
(7) in the aluminium porous body described in above-mentioned (5) or (6), the content of aluminium carbide is preferably below 0.8 mass %.
On the aluminium porous body described in above-mentioned (7), since the content of aluminium carbide contained in aluminium film is few, so passing through heat
Processing carries out the recrystallization of aluminium.Therefore, it is possible to provide the aluminium porous body including softer aluminium film.
[details of embodiment of the present invention]
The aluminium plating solution of embodiment according to the present invention, the method for manufacturing aluminium film and aluminium is described in more detail below
The specific example of porous body.The present invention is not limited to these examples, but it is defined by the claims.It is intended that the present invention
Scope including claims equivalents and claims in the range of all changes.
In order to make the aluminium porous body obtained by using existing aluminium plating solution have flexibility, the present inventor is porous to aluminium
Body is heat-treated.However it has been found that even if after heat treatment, aluminium porous body still keeps high intensity and the property of low elongation.
Its reason is studied in detail in inventor.According to the research as a result, finding due to heat treatment and in the crystalline substance of aluminium crystal
Aluminium carbide is formd at boundary, so cannot be recrystallized.It was found that the aluminium carbide is absorbed in aluminium film during being formed from film
1,10- phenanthroline.
<Aluminium plating solution>
In view of the foregoing, the present inventor has carried out further further investigation, it turns out that component (C1) is made
It is effective to contribute to the additive of the flatness of aluminium film.
Specifically, as described above, the aluminium plating solution of embodiment is by mixing at least following components according to the present invention
Aluminium plating solution obtained from (A) to (C1).
Component (A)：Aluminum halide
Component (B)：In the group being made of alkyl halide imidazoles, alkylpyridinium halides and carbamide compound at least
A kind of compound
Component (C1)：In the group being made of ammonium salt, microcosmic salt, sulfonium salt, amine compounds, phosphine compound and sulfide compound
At least one
Component (C1) is with the straight or branched alkyl that carbon number is less than more than 8 36 as at least one side chain.
The aluminium plating solution of embodiment according to the present invention can include the other components as inevitable impurity.Not
Damage in the range of aluminium film effect according to embodiments of the present invention, aluminium plating solution can intentionally include other components, aluminium plating
Liquid energy enough forms the aluminium film with good flatness and good elongation.
Aluminum halide for the fuse salt that less than about 110 DEG C are formed when being mixed with component (B), it is suitable as serving as group
Divide the aluminum halide of (A).Its example includes aluminium chloride (AlCl3), aluminium bromide (AlBr3) and silver iodide (AlI3).Wherein, most preferably
Aluminium chloride.
Similarly, for when being mixed with component (A) formed less than about 110 DEG C fuse salt alkylpyridinium halides,
It is suitable as the alkylpyridinium halides for serving as component (B).
Its example is included in the 1 and 3 upper imidazolitm chloride with alkyl (with 1 to 5 carbon atom), 1,2
Position and 3 upper imidazolitm chlorides with alkyl (with 1 to 5 carbon atom), and there is alkyl (tool on 1 and 3
Have 1 to 5 carbon atom) iodate imidazoles.
More specifically, its example includes 1- ethyl -3- methylimidazolium chlorides (EMIC), 1- butyl -3- methyl chlorides
Imidazoles (BMIC) and 1- methyl -3- propyl group imidazolitm chlorides (MPIC).Wherein it is possible to most preferably with 1- ethyls -3- first
Base imidazolitm chloride (EMIC).
The alkylpyridinium halides of less than about 110 DEG C of fuse salt are formed during for being mixed with component (A), it can be fitted
Share the alkylpyridinium halides for serving as component (B).
Its example includes 1- butyl pyridinium chloride (BPC), 1- ethyl pyridinium chlorides (EPC) and 1- butyl -3- methyl
Pyridinium chloride (BMPC).Wherein, most preferably 1- butyl pyridinium chloride.
Serving as the carbamide compound of component (B) includes urea and its derivative.About 110 DEG C are formed during for being mixed with component (A)
The carbamide compound of following fuse salt, it can be suitable as the carbamide compound for serving as component (B).
For example, it is preferable to use the compound represented by following formula (1).
[chemical formula 1]
In formula (1), R each represents hydrogen atom, has the alkyl or phenyl of 1 to 6 carbon atom, and R can be each other
It is identical or different.
In above-mentioned carbamide compound, urea or dimethyl urea can be particularly preferably used.
In aluminium plating solution, with molar ratio computing, the mixing ratio of the component (A) and the component (B) is 1:1 to 3:1 model
In enclosing.Therefore, the aluminium plating solution being suitable for by aluminium film electro-deposition on substrate surface is obtained.
In the case where the ratio of component (B) is assumed to be 1, when the molar ratio of compound (A) is less than 1, will not occur
The electrodeposit reaction of aluminium.In the case where the ratio of component (B) is assumed to be 1, when the molar ratio of compound (A) is more than 3, chlorine
Change aluminium to deposit and mixed in the aluminium film of gained in aluminium plating solution, and the quality of the film reduces.
Component (C1) is selected from the group being made of ammonium salt, microcosmic salt, sulfonium salt, amine compounds, phosphine compound and sulfide compound
At least one of.There is the component (C1) straight or branched alkyl that carbon number is less than more than 8 36 to be used as at least one
A side chain, and other side chains are had no particular limits.It is former that the example of other side chains includes hydrogen, the group with phenyl ring and carbon
Son is less than more than 1 36 straight or branched alkyl.
The alkyl for serving as at least one side chain of component (C1) can be branched alkyl, but preferably straight chained alkyl.Carbon is former
Subnumber is that more than 8 alkyl can aid in the flatness of aluminium film.The alkyl that carbon number is less than 36 can prevent aluminium plating solution
Viscosity it is excessive.From the above point of view, the carbon number for serving as the alkyl of the side chain of component (C1) be preferably more than 8 22 with
Under, more preferably less than more than 12 18.
When component (C1) is salt, component (C1) is preferably halogen.In particular it is preferred to it is chlorion (Cl-), bromide ion
(Br-) or iodide ion (I-) salt.
Specifically, the example of component (C1) include stearylamine, dimethyl stearamine, N- docosyl-N- methyl isophthalic acids-
Docosane amine, dimethyl distearyl ammonium chloride, dodecyl trimethyl ammonium chloride, octyltrimethylammonium chloride and tributyl
Tetradecylphosphonium chloride.
When the concentration of the component (C1) in aluminium plating solution is more than 1.0g/L below 45g/L, it can be formed smooth and extended
The good aluminium film of rate.When the concentration of component (C1) is less than 1.0g/L, it is impossible to obtain aluminium film smooth enough.When component (C1)
When concentration is more than 45g/L, component (C1) can be mixed in aluminium film.Therefore, aluminium film is hardened, but aluminium film is crisp and is stretched with low
Long rate.The concentration of component (C1) is preferably more than 5g/L below 25g/L, more preferably more than 7.5g/L below 20g/L.
When carrying out prolonged plating using the aluminium plating solution containing component (C1), the amount of component (C1) reduces.Therefore, root
According to needs, it is necessary to addO-on therapy (C1) into aluminium plating solution.As described above, in situation about being added to component (C1) in aluminium plating solution
Under, it is more than 1.0g/L below 45g/L by the concentration control of the component (C1) in aluminium plating solution.
The reason for amount that the present inventor have studied component (C1) in aluminium plating solution is reduced.According to the research as a result,
The inventors found that this is because component (C1) side chain (i.e. carbon number be less than more than 8 36 straight or branched
Alkyl) decompose, although the decomposition gradually occurs.It has also been found that in separated alkyl incorporation aluminium film, so as to contribute to aluminium
The flatness of film.
As described above, when carrying out prolonged plating using the aluminium plating solution containing component (C1), the chain length of alkyl by
Gradual change is short, and is being accumulated with the alkyl that carbon number is less than 7 as the component of side chain.In such a case, it is possible to will
Following components (D) are added in aluminium plating solution instead of component (C1).Note that the component (C1) in aluminium plating solution at this time is changed into following
Component (C2).
Specifically, in addition to component (A) and component (B), the aluminium plating solution of embodiment according to the present invention is also to wrap
Aluminium plating solution containing at least following components (C2) and component (D).
Component (C2)：In the group being made of ammonium salt, microcosmic salt, sulfonium salt, amine compounds, phosphine compound and sulfide compound
At least one
Component (D)：Selected from least one of group being made of alkyl halide, alkynes, alkene and alkane
Component (C2) is with the straight or branched alkyl that carbon number is less than more than 1 36 as at least one side chain.Group
It is the straight-chain or branched-chain compound that carbon number is less than more than 3 36 to divide (D).
In component (C2), have carbon number be less than more than 8 36 straight or branched alkyl as side chain salt or
Compound contributes to the flatness and elongation of aluminium film, and additionally aids the dissolubility of component (D).In component (C2), tool
The straight or branched alkyl for having carbon number to be less than more than 17 contributes to the dissolving of component (D) as the salt or compound of side chain
Property.I.e., it is possible to by mixing component (C2) in aluminium plating solution come easily dissolved constituent (D).
Component (C2) is selected from the group being made of ammonium salt, microcosmic salt, sulfonium salt, amine compounds, phosphine compound and sulfide compound
At least one of.Component (C2) is with the straight or branched alkyl that carbon number is less than more than 1 36 as at least one side
Chain, and other side chains are had no particular limits.The example of other side chains includes hydrogen, has the group and carbon number of phenyl ring
For the straight or branched alkyl below more than 1 36.
The alkyl for serving as at least one side chain of component (C2) can be branched alkyl, but preferably straight chained alkyl.Carbon is former
Subnumber is that more than 1 alkyl can aid in the dissolubility of component (D).The alkyl that carbon number is less than 36 can prevent aluminium from plating
The viscosity of liquid is excessive.
To find out from above-mentioned viewpoint, the carbon number of the alkyl in component (C2) is preferably less than more than 1 18, and more preferably
For less than more than 3 12.
When component (C2) is salt, component (C2) is preferably the salt of halogen.In particular it is preferred to it is chlorion (Cl-), bromine from
Son (Br-) or iodide ion (I-) salt.
Specifically, the example of component (C2) includes trimethylamine, trimethyl-phosphine, Ethyl methyl sulfide, stearylamine, dimethyl
Stearylamine, N- docosyls-N- methyl isophthalic acids-docosane amine, dimethyl distearyl ammonium chloride, trimethyl chlorine
Change ammonium, octyltrimethylammonium chloride, tetrabutylammonium chloride, tetrabutyl phosphorus chloride, tributyl tetradecylphosphonium chloride and triethyl group
Phenyl chloride.
The concentration of component (C2) in aluminium plating solution is more than 1.0g/L below 45g/L.When the concentration of component (C2) is less than
During 1.0g/L, it is difficult to which component (D) is dissolved in aluminium plating solution.When the concentration of component (C2) is more than 45g/L, the viscosity of plating solution becomes
Obtain excessive.
The concentration of component (C2) is preferably more than 5.0g/L below 30g/L, more preferably more than 10g/L and below 15g/L.
Component (D) be selected from least one of group being made of alkyl halide, alkynes, alkene and alkane, it is all this
A little carbon numbers is less than more than 3 36, and can have straight or branched structure.Since component (D) has low polarity, institute
It is practically insoluble in component (D) in the aluminium plating solution being made of component (A) and component (B).However, when aluminium plating solution contains component (C2)
When, component (C2) plays the role of surfactant, therefore component (D) is easily dissolved in aluminium plating solution.In addition, component (D)
It is more cheap than component (C1) and be easily obtained.Therefore, component (C1) is replaced by addO-on therapy (D), can with it is low into
The aluminium plating solution of this production embodiment according to the present invention.
When by Aliminuium electrodeposition on the surface of the substrate, in component (D) incorporation aluminium film, so as to contribute to the smooth of aluminium film
Property.However, since component (D) has low-down heat decomposition temperature and low-down boiling point, so when by being flared off filling
When the resin of base material, at the low temperature of the temperature than forming aluminium carbide, component (D) can be removed from aluminium film.Therefore, with 1,
10- phenanthroline is different, and component (D) is not remain in aluminium film or is not formed aluminium carbide.
When removing component (D) from aluminium film, small gap is formed in aluminium film, although the quantity in gap is few.As long as
The concentration of component (D) in aluminium plating solution is in the scope of more than 0.5g/L below 8.5g/L, then the flatness and elongation of aluminium film
It will not be reduced due to these gaps.
Carbon number is that more than 3 component (D) can aid in the flatness of aluminium film.Carbon number is less than 36 component
(D) it can prevent that the viscosity of aluminium plating solution is excessive.Find out from above-mentioned viewpoint, the carbon number of component (D) be preferably more than 5 24 with
Under, more preferably less than more than 8 18.
Because component (D) is easily dissolved in aluminium plating solution, component (D) is preferably liquid or solid at room temperature.
Halogen atom contained in alkyl halide is had no particular limits.However, for example, halogen atom is preferably chlorine
(Cl), bromine (Br) or iodine (I).The number of halogen atom contained in alkyl halide is had no particular limits, and preferably
It is about more than 1 about less than 2.
Because alkynes molecule can not possibly react with each other, the number of three keys included in alkynes is preferably 1.
Because olefin hydrocarbon molecules can not possibly react with each other, the number of the double bond included in alkene is preferably 1.
Specifically, the example of component (D) includes propane, butane, octane, pentane, the tetradecane, octadecane, chloropropane, chlorine
Butane, lauryl chloride, stearyl chloride, amylene, hexene, decene, propine, pentyne and butine.
, can when the concentration of component (D) is more than 0.5g/L below 8.5g/L in the aluminium plating solution containing component (C2)
Form smooth and good elongation aluminium film.When the concentration of component (D) is less than 0.5g/L, foot cannot be obtained in some cases
Enough smooth aluminium films.When the concentration of component (D) is more than 8.5g/L, when by being flared off base material, formed in aluminium film
The quantity in gap becomes too much.Find out from above-mentioned viewpoint, the concentration of component (D) is preferably more than 0.85g/L below 4.5g/L, more
Preferably more than 1.0g/L below 3.0g/L.
As noted previously, as component (D) is incorporated into aluminium film, so when being aluminized for a long time, in aluminium plating solution
The amount of component (D) gradually decreases.In the case that the amount of component (D) in aluminium plating solution is reduced, suitably addO-on therapy (D) causes
The concentration of component (D) reaches above range.
By using the aluminium plating solution of embodiment according to the present invention, smooth surface can be formed and there is good elongation
Aluminium film.
<The method for manufacturing aluminium film>
Method for manufacturing aluminium film according to embodiments of the present invention is such aluminium film manufacture method, the method bag
Include by using aluminium plating solution according to embodiments of the present invention electric deposition aluminum on the surface of the substrate.
It is used to manufacture the method for aluminium film according to embodiments of the present invention, in order to Aliminuium electrodeposition exists in aluminium plating solution
On the surface of base material, aluminium electrode (anode) is set in aluminium plating solution, and establishes and is electrically connected so that the base material in aluminium plating solution is as cloudy
Pole, and power.
In such a situation it is preferred to by Aliminuium electrodeposition on the surface of the substrate so that current density 0.5A/dm2More than
10.0A/dm2Below.When current density within the range when, the aluminium film with better smooth can be obtained.Current density is more
Preferably 1.5A/dm2Above 6.0A/dm2Hereinafter, it is even more preferably 2.0A/dm2Above 4.0A/dm2Below.
Preferably, while by the temperature adjustment of aluminium plating solution to less than more than 15 DEG C 110 DEG C, on the surface of the substrate
Carry out the electro-deposition of aluminium.By the way that the temperature adjustment of aluminium plating solution to more than 15 DEG C, can be reduced fully the viscosity of aluminium plating solution, and
The electrodeposition efficiency of aluminium can be improved.By the way that to less than 110 DEG C, the temperature adjustment of aluminium plating solution can be suppressed waving for aluminum halide
Hair.The temperature of aluminium plating solution is more preferably less than more than 30 DEG C 80 DEG C, still more preferably less than more than 40 DEG C 70 DEG C.
During by surface of the Aliminuium electrodeposition in base material, aluminium plating solution can be stirred as needed.
The method for manufacturing aluminium film of embodiment according to the present invention, can manufacture such smooth aluminium film, the aluminium
The arithmetic average roughness (Ra) of film surface is less than about 0.2 μm.
Base material is had no particular limits, as long as the base material has the purposes for forming aluminium film in its surface.For example,
Copper coin, steel band, copper wire, steel wire or resin through conductive treatment can be used as base material.It is, for example, possible to use through conduction
Change polyurethane, melmac, polypropylene or the polyvinyl resin of processing as the resin through conductive treatment.
The resin for serving as base material can have arbitrary shape.Preferably using the resin molded body with tridimensional network,
This is because can finally manufacture with tridimensional network and such as filter, catalyst carrier, electrode for cell it
The aluminium porous body of superperformance is shown in the application of class.Using the resin with non-woven fabrics can also finally provide with
The aluminium porous body of loose structure.The aluminium porous body manufactured with non-woven fabrics and by this way can also be preferred for all
As filter, catalyst carrier and battery electrode etc application in.
The example of resin molded body with tridimensional network include by using (such as) polyurethane or melamine
The foamed resin products of resin manufacture., can although the example of resin molded body is described as " foamed resin products "
To select the resin molded body with arbitrary shape, as long as the resin molded body has intercommunicating pore (continuous aperture).Can also
Using by winding the fibrous resin of such as polypropylene or polyethylene Foamex is replaced the non-woven fabric-like material that obtains
Formed body.
Hereinafter, the porous body with tridimensional network can also referred to as " porous body ".
The porosity of the porous body is preferably less than more than 80% 98%.The aperture of the porous body is preferably more than 50 μm
Less than 500 μm.Polyurethane foam and melamine foamed plastic can be preferably used as foamed resin products, this is because they have
High porosity, its hole have connectedness, and they have good thermal degradation.From (such as) homogeneity in hole and easily obtain
From the viewpoint of property, preferred polyurethane foam.From obtaining from the viewpoint of there is the resin molded body of small-bore, preferred trimerization
Cyanamide foam.By (such as) foamed resin products that are formed of polyurethane foam or melamine foamed plastic generally comprise and such as foam
During the residue of the foam stabiliser that uses and unreacted monomer etc, therefore preferably carry out cleaning treatment in advance.
The porosity of porous body is defined by the formula：
Porosity=(1- (the weight [g] of the porous body/(volume [cm of porous body3The density of] × raw material))) × 100
[%]
Aperture is determined by following methods：By means of (such as) light microscope amplifies the surface of porous body, count per English
The hole count of very little (25.4mm) calculates average value as the small number of chambers of average pore size=25.4mm/ as the small number of chambers.
The resin molded body with tridimensional network is used as using the resin molded body through conductive treatment.
The conductive treatment of resin surface can be selected from the method including known method.Can use includes leading to
Cross chemical plating or gas phase process formed by (such as) method of metal layer that is formed of nickel and include the use of electrically-conducting paint and form gold
The method of category or carbon-coating.
By forming metal layer on resin surface by chemical plating or vapor phase method, the electric conductivity of resin surface can be improved.
On the other hand, although from the viewpoint of electric conductivity, the conductive treatment for the resin surface being coated with by carbon is somewhat poor,
It is that can carry out the conductive treatment so that after aluminium film is formed, will not be mixed into addition to aluminum in obtained constructed of aluminium
Metal.Therefore, the structure substantially only formed by aluminium as metal can be manufactured.The advantages of this method also reside in can with it is low into
This offer electric conductivity.
In the case where carrying out conductive treatment by carbon coating, first, the carbon coating for serving as conductive coating paint is prepared.
In addition to carbon particle, the suspension for serving as carbon coating preferably comprises adhesive, dispersant and decentralized medium.
When using the resin molded body with tridimensional network, in order to which carbon particle is equably applied to porous body,
Suspension is needed to keep even suspension state.For this reason, suspension preferably remains in 20 DEG C to 40 DEG C.By by the temperature of suspension
More than 20 DEG C are maintained at, even suspension state can be kept, can prevent that only adhesive is forming the net structure of porous body
Enrichment and forming layer on skeleton surface, so as to equably carbon particles.Due to the carbon of even spread in this way
The layer of particle is not readily separated, it is possible to forms the coat of metal for being firmly attached to carbon particle layer.On the other hand, due to suspension
Temperature below 40 DEG C, it is possible to suppress the evaporation of dispersant.Therefore, suspension is not easy to coating processing time
Elapse and concentrate.
The particle diameter of carbon particle is 0.01 μm to 5 μm, is preferably 0.01 μm to 0.5 μm.When particle diameter is excessive, carbon particle may
The hole of porous resin formed body can be blocked or suppress smooth plating.When particle diameter is too small, it is difficult to ensure sufficient electric conductivity.
<Aluminium porous body>
The aluminium porous body of embodiment according to the present invention is the aluminium porous body that elongation is more than 1.5%.By using
The aluminium porous body that the manufacture method of known aluminium plating solution obtains has high intensity and low elongation.In contrast, it is real according to the present invention
The aluminium porous body for applying scheme is the soft aluminium porous body that elongation is more than 1.5%.
Elongation be 1.5% above is preferable, this is because aluminium porous body can effectively to counter-bending and vibration, because
This expands the application range of aluminium porous body.Therefore, the elongation of aluminium porous body is preferably as high as possible.The elongation of aluminium porous body
More preferably more than 1.8%, even more preferably more than 2.5%.It is used to make according to invention described below embodiment
The method for making aluminium porous body, can manufacture the aluminium porous body that elongation is about more than 1.5% about less than 5.0%.
As described above, the elongation of aluminium porous body refers to that the coating weight of the aluminium when the per unit area of aluminium porous body is
100g/m2Above 180g/m2Elongation when below and thickness is more than 0.95mm below 1.05mm.Pass through JIS Z 2241
Specified in stretching test measurement aluminium porous body elongation.
Crystallite dimension in the cross section of the skeleton of aluminium porous body is preferably less than more than 1 μm 50 μm.Crystallite dimension is 1 μm
Above is it is preferable, this is because aluminium film softens and the elongation of aluminium porous body is changed into more than 1.5%.On the other hand, crystal grain
Size is preferable for less than 50 μm, this is because can suppress due to the excessively soft caused intensity decreases of aluminium porous body.From above-mentioned
Viewpoint finds out that the crystallite dimension in the cross section of the skeleton of aluminium porous body is more preferably less than more than 1.5 μm 25 μm, even more preferably from
For less than more than 2 μm 15 μm.
By using aluminium plating solution, the aluminium porous body with relatively large crystallite dimension can be obtained.For further increasing
The example of the method for crystallite dimension includes：Including carrying out heat-treating methods to aluminium porous body；It is included in the manufacture of aluminium porous body
The method of the middle fluid temperature for improving aluminium plating solution；And the method for current density during including reducing plating.
The content of aluminium carbide in aluminium porous body is preferably below 0.8 mass %.In aluminium porous body, the content of aluminium carbide
It is preferable for below 0.8 mass %, this is because aluminium film softens and the elongation of aluminium porous body is changed into more than 1.5%.Aluminium
The content of aluminium carbide in porous body is more preferably below 0.5 mass %, still more preferably below 0.3 mass %.
When manufacturing aluminium porous body by using aluminium plating solution according to embodiments of the present invention, substantially, passing through burning
During removing base material, at the low temperature of the temperature than forming aluminium carbide, the carbonaceous component in aluminium film is removed.Therefore,
The content of aluminium carbide in aluminium porous body is 0 mass %.However, during by the removal base material that burns, mix in aluminium film
Carbonaceous component may react with aluminium, and although the amount of carbonaceous component is very small, but still can in aluminium film shape
Into aluminium carbide.In addition, component (B) can be incorporated into aluminium film and can cause the formation of aluminium carbide.
(manufacture method of aluminium porous body)
Aluminium porous body can be manufactured by following steps：Electroplated by fusion electrolysis, with tridimensional network
The step of aluminium film is to form resin structure is formed on the surface of electroconductive resin formed body；And from the resin structure
The step of except electroconductive resin formed body.
These steps are described more fully below.
- forming step of aluminium film-
The step is such step, i.e., by carrying out electrolysis plating in fuse salt (that is, aluminium plating solution) with three
Tie up and form aluminium film on the surface of the electroconductive resin formed body of net structure.Electroconductive resin shaping with tridimensional network
Body can be above-mentioned and what is obtained by carrying out conductive treatment on the surface of the resin molded body with tridimensional network
Resin molded body.
By forming aluminium film in aluminium plating solution, even in the formed body with complicated skeleton structure (such as with three dimensional network
The electroconductive resin formed body of shape structure) skeleton surface on can also be formed uniformly the larger aluminium film of thickness.In order to carry out
Fusion electrolysis is electroplated, and is made electroconductive resin formed body as cathode and aluminium is applied direct current in aluminium plating solution as anode
Stream.
The mixing of moisture and oxygen in aluminium plating solution deteriorates plating solution.It is therefore preferable that in inert gas (such as nitrogen or argon
Gas) atmosphere in and sealing environment in carry out plating.
The temperature of aluminium plating solution can be 15 DEG C to 110 DEG C, be preferably 25 DEG C to 45 DEG C.With the reduction of temperature, Ke Yijin
The current density range of row plating narrows, and the whole surface become more difficult in the skeleton of electroconductive resin formed body is enterprising
Row plating.By carrying out plating in the scope below 110 DEG C, it can prevent from serving as the shape of the electroconductive resin formed body of base material
Shape is damaged the generation of this problem.
By above-mentioned steps, such resin structure can be obtained：It has the surface that is formed by aluminium film, and including
Core of the electroconductive resin formed body as its skeleton.
- removal step of electroconductive resin formed body-
By (such as) it is heated in nitrogen atmosphere or air being equal to or more than 370 DEG C (temperature of resin decomposition), excellent
Temperature of the choosing equal to or more than 500 DEG C, so as to be heat-treated to the resin structure obtained as described above.Therefore, resin and
Conductive layer is burned off, so as to obtain aluminium porous body.In this step, the carbonaceous component in incorporation aluminium film can also be removed.
Embodiment
Embodiment will be used below, and the present invention will be described in more detail.These embodiments for illustration purposes, also,
For example, the aluminium plating solution of the present invention is not limited to this.The scope of the present invention is defined by the claims, and including right
All deformations in the implication and Claims scope of the equivalent form of claim.
[embodiment 1]
(aluminium plating solution)
By aluminium chloride (AlCl3) it is used as component (A), and 1- ethyl -3- methylimidazolium chlorides (EMIC) are used as group
Divide (B).Component (A) and component (B) are mixed so that mixing ratio 2:1 (with molar ratio computing), to prepare fuse salt.To melting
In salt addition as component (C1) reagent dimethyl distearyl ammonium chloride (by Tokyo Chemical Industry Co.,
Ltd. manufacture) so that its concentration is 15g/L.Thus aluminium plating solution 1 is obtained.
(formation of aluminium film)
Base material is used as using the copper coin that size is 20mm × 40mm × 1.0mm.In the aluminium plating solution 1 of above-mentioned preparation, by copper
Plate is connected to the cathode side of rectifier, is connected to its anode-side using as the aluminium sheet (purity 99.99%) to electrode, and apply electricity
Press so that Aliminuium electrodeposition is on the surface of copper coin.It is 45 DEG C by the temperature control of aluminium plating solution 1, and is by current density control
3.0A/dm2。
<The evaluation of aluminium film>
(evaluation method)
Aluminium film is formed on the surface of 50 pieces of copper coins by method same as described above.Measure the surface roughness of each aluminium film
(arithmetic average roughness Ra).
Use the laser microscope measurement surface roughness (arithmetic mean roughness manufactured by Keyence Corporation
Spend Ra).
(evaluation result)
The average value of the arithmetic average roughness Ra on the surface of aluminium film is 0.11 μm.
[embodiment 2]
<The preparation of aluminium porous body>
(forming aluminium film on substrate surface)
By using the aluminium plating solution 1 prepared in embodiment 1, so that electric deposition aluminum is to prepare resin knot on the surface of the substrate
Structure body.Base material is used as using the resin molded body with tridimensional network and through conductive treatment.It the use of thickness is 1mm, hole
Gap rate is the polyurethane foam (100mm × 30mm's is square) that the hole count (the small number of chambers) of 95% and per inch is about 50 as tree
Fat formed body.Carried out by the way that polyurethane foam is immersed in the polyurethane foam in carbon suspension liquid and obtained by drying at conducting
Reason.The carbon suspension liquid includes following components：25% graphite and carbon black, resin binder, bleeding agent and defoamer.The grain of carbon black
Footpath is 0.5 μm.
Base material is connected to the cathode side of rectifier, its sun is connected to using as the aluminium sheet (purity 99.99%) to electrode
Pole side.It is 45 DEG C by the temperature control of aluminium plating solution 1, and is 6.0A/dm by current density control2.Stirring aluminium plating solution causes rotating speed
For 100rpm.
(removal of base material)
When the coating weight of the aluminium of per unit area reaches 140g/m2When, take out resin structure from aluminium plating solution 1.It is right
The resin structure carries out washing process, then in atmosphere, is heat-treated 20 minutes at 610 DEG C.Thus base material has been burnt up, and
Aluminium porous body 1 is obtained.
<The evaluation of aluminium porous body>
(evaluation method)
15 aluminium porous bodies 1 are prepared for by method same as described above.Measure elongation, the crystal grain ruler of each aluminium porous body
The very little and content of aluminium carbide.
Tension test is carried out according to JIS Z 2241 to measure the elongation of each aluminium porous body 1.Using by Shimadzu
The Autograph of Corporation manufactures is as testing machine.
By cutting each aluminium porous body 1, then manufactured with Hitachi High-Technologies Corporation
Scanning electron microscope observes cross section, measures the crystallite dimension of the aluminium on the cross section of skeleton.
Carbon contained in each aluminium porous body 1 is measured using the X-ray diffractometer manufactured by Shimadzu Corporation
Change the amount of aluminium.
(evaluation result)
The elongation ratio of GL (displacement relative to) minimum 1.8% of aluminium porous body 1, up to 3.3%.Elongation
Average value be 2.6%.
The average grain size of aluminium on the cross section of the skeleton of aluminium porous body 1 is 3.5 μm.In addition, institute in aluminium porous body 1
The amount of the aluminium carbide contained is 0.35 mass %.
[embodiment 3]
Aluminium plating solution 2 is obtained according to mode in the same manner as in Example 1, difference is：By reagent dodecyl front three
Ammonium chloride (being manufactured by Tokyo Chemical Industry Co., Ltd.s) is used as the component (C1) in aluminium plating solution, and adds
Add component (C1) so that its concentration is 20g/L.
15 aluminium porous bodies 2 are prepared according to mode in the same manner as in Example 2, difference is：Use aluminium plating solution 2.
Measure the content of the elongation of each aluminium porous body 2, crystallite dimension and aluminium carbide.
(evaluation result)
The elongation ratio of GL (displacement relative to) minimum 1.9% of aluminium porous body 2, up to 2.8%.Elongation
Average value be 2.3%.
The average grain size of aluminium on the cross section of the skeleton of aluminium porous body 2 is 3 μm.It is in addition, contained in aluminium porous body 2
The amount of aluminium carbide be 0.34 mass %.
[embodiment 4]
Aluminium plating solution 3 is obtained according to mode in the same manner as in Example 1, difference is：By reagent octyl trimethyl chlorine
Change ammonium (being manufactured by Tokyo Chemical Industry Co., Ltd.s) and be used as the component (C1) in aluminium plating solution, and addition group
Divide (C1) so that its concentration is 15g/L.
15 aluminium porous bodies 3 are prepared according to mode in the same manner as in Example 2, difference is：Use aluminium plating solution 3.
Measure the content of the elongation of each aluminium porous body 3, crystallite dimension and aluminium carbide.
(evaluation result)
The elongation ratio of GL (displacement relative to) minimum 1.6% of aluminium porous body 3, up to 3.0%.Elongation
Average value be 2.5%.
The average grain size of aluminium on the cross section of the skeleton of aluminium porous body 3 is 3.2 μm.In addition, institute in aluminium porous body 3
The amount of the aluminium carbide contained is 0.37 mass %.
[embodiment 5]
Aluminium plating solution 4 is obtained according to mode in the same manner as in Example 1, difference is：By the reagent tributyl tetradecane
Base phosphorus chloride (being manufactured by Kanto Chemical Co., Inc.) is used as the component (C1) in aluminium plating solution, and addO-on therapy
(C1) so that its concentration is 5.0g/L.
15 aluminium porous bodies 4 are prepared according to mode in the same manner as in Example 2, difference is：Use aluminium plating solution 4.
Measure the content of the elongation of each aluminium porous body 4, crystallite dimension and aluminium carbide.
(evaluation result)
The elongation ratio of GL (displacement relative to) minimum 1.8% of aluminium porous body 4, up to 3.4%.Elongation
Average value be 2.8%.
The average grain size of aluminium on the cross section of the skeleton of aluminium porous body 4 is 3.5 μm.In addition, institute in aluminium porous body 4
The amount of the aluminium carbide contained is 0.34 mass %.
[embodiment 6]
Aluminium plating solution 5 is obtained according to mode in the same manner as in Example 1, difference is：By reagent dimethyl stearamine
(being manufactured by Tokyo Chemical Industry Co., Ltd.s) is used as the component (C1) in aluminium plating solution, and addO-on therapy
(C1) so that its concentration is 15g/L.
15 aluminium porous bodies 5 are prepared according to mode in the same manner as in Example 2, difference is：Use aluminium plating solution 5.
Measure the content of the elongation of each aluminium porous body 5, crystallite dimension and aluminium carbide.
(evaluation result)
The elongation ratio of GL (displacement relative to) minimum 1.7% of aluminium porous body 5, up to 2.8%.Elongation
Average value be 2.2%.
The average grain size of aluminium on the cross section of the skeleton of aluminium porous body 5 is 4.0 μm.In addition, in aluminium porous body 5
The amount of contained aluminium carbide is 0.28 mass %.
[embodiment 7]
Aluminium plating solution 6 is obtained according to mode in the same manner as in Example 1, difference is：In embodiment 1, addition group
Divide (C1) so that its concentration is 1.0g/L.
15 aluminium porous bodies 6 are prepared according to mode in the same manner as in Example 2, difference is：Use aluminium plating solution 6.
Measure the content of the elongation of each aluminium porous body 6, crystallite dimension and aluminium carbide.
(evaluation result)
The elongation ratio of GL (displacement relative to) minimum 1.5% of aluminium porous body 6, up to 2.7%.Elongation
Average value be 2.1%.
The average grain size of aluminium on the cross section of the skeleton of aluminium porous body 6 is 4.0 μm.In addition, institute in aluminium porous body 6
The amount of the aluminium carbide contained is 0.24 mass %.
[embodiment 8]
Aluminium plating solution 7 is obtained according to mode in the same manner as in Example 1, difference is：In embodiment 1, addition group
Divide (C1) so that its concentration is 45g/L.
15 aluminium porous bodies 7 are prepared according to mode in the same manner as in Example 2, difference is：Use aluminium plating solution 7.
Measure the content of the elongation of each aluminium porous body 7, crystallite dimension and aluminium carbide.
(evaluation result)
The elongation ratio of GL (displacement relative to) minimum 1.9% of aluminium porous body 7, up to 3.6%.Elongation
Average value be 2.7%.
The average grain size of aluminium on the cross section of the skeleton of aluminium porous body 7 is 3.2 μm.In addition, institute in aluminium porous body 6
The amount of the aluminium carbide contained is 0.39 mass %.
[comparative example 1]
Aluminium plating solution A is obtained according to mode in the same manner as in Example 1, difference is：1,10- phenanthroline one is hydrated
Thing is used as the component (C1) in aluminium plating solution, and addO-on therapy (C1) is so that its concentration is 0.5g/L.
15 aluminium porous body A are prepared according to mode in the same manner as in Example 2, difference is：Use aluminium plating solution A.
Measure the content of the elongation of each aluminium porous body A, crystallite dimension and aluminium carbide.
(evaluation result)
The elongation ratio of GL (displacement relative to) minimum 0.6% of aluminium porous body A, is even up to only
1.2%.The average value of elongation is 0.8%.
The average grain size of aluminium on the cross section of the skeleton of aluminium porous body A is 1.0 μm.In addition, institute in aluminium porous body A
The amount of the aluminium carbide contained is 1.2 mass %.
[comparative example 2]
Aluminium plating solution B is obtained according to mode in the same manner as in Example 1, difference is：In embodiment 1, addition group
Divide (C1) so that its concentration is 0.6g/L.
15 aluminium porous body B are prepared according to mode in the same manner as in Example 2, difference is：Use aluminium plating solution B.
Measure the content of the elongation of each aluminium porous body B, crystallite dimension and aluminium carbide.
(evaluation result)
The elongation ratio of GL (displacement relative to) minimum 0.5% of aluminium porous body B, is even up to only
1.3%.The average value of elongation is 0.7%.
The average grain size of aluminium on the cross section of the skeleton of aluminium porous body B is 4.0 μm.In addition, institute in aluminium porous body B
The amount of the aluminium carbide contained is 0.24 mass %.
[comparative example 3]
Aluminium plating solution C is obtained according to mode in the same manner as in Example 1, difference is：In embodiment 1, addition group
Divide (C1) so that its concentration is 50g/L.
15 aluminium porous body C are prepared according to mode in the same manner as in Example 2, difference is：Use aluminium plating solution C.
Measure the content of the elongation of each aluminium porous body C, crystallite dimension and aluminium carbide.
(evaluation result)
The elongation ratio of GL (displacement relative to) minimum 0.8% of aluminium porous body C, is even up to only
1.2%.The average value of elongation is 1.0%.
The average grain size of aluminium on the cross section of the skeleton of aluminium porous body C is 1.2 μm.In addition, institute in aluminium porous body C
The amount of the aluminium carbide contained is 0.84 mass %.
[embodiment 9]
The aluminium plating solution 1 for preparing in 1 liter of embodiment 1 is prepared, and it is porous according to mode in the same manner as in Example 2 to obtain aluminium
Body.Then while the electric current flowing of 3.6A is controlled, when progress aluminium plating 42 is small.When the coating weight of the aluminium of per unit area
Amount reaches 140g/m2When, change base material, and continue aluminium plating.
The elongation ratio of GL (displacement relative to) of the aluminium porous body 2' obtained after measuring when 42 is small.According to above-mentioned
Identical method prepares 20 aluminium porous body 2'.The elongation minimum 1.2% of aluminium porous body 2'.When even up to, elongation
Rate is also reduced to 1.6%.The average value of elongation reaches 1.3%.
Aluminium plating solution at this time is known as aluminium plating solution 1', and by liquid chromatography-mass spectrography (LC/MS) analyze aluminium plating solution 1' into
Point.According to the result, it was confirmed that the alkyl as the side chain of the component (C1) initially included shortens, and changes into former with carbon
Component (C2) of the alkyl that subnumber is less than 7 as side chain.The concentration of component (C2) is 15g/L.
(aluminium plating solution)
It will be added to as the stearyl chloride (being manufactured by Tokyo Chemical Industry Co., Ltd.) of component (D)
In aluminium plating solution 1', so that its concentration is 1g/L.Thus, aluminium plating solution 8 is obtained.
<The preparation of aluminium porous body>
15 aluminium porous bodies 8 are prepared according to mode in the same manner as in Example 2, difference is：Use aluminium plating solution 8.
Measure the content of the elongation of each aluminium porous body 8, crystallite dimension and aluminium carbide.
(evaluation result)
The elongation ratio of GL (displacement relative to) minimum 2.0% of aluminium porous body 8, up to 3.5%.Elongation
Average value be 2.3%.
The average grain size of aluminium on the cross section of the skeleton of aluminium porous body 8 is 4.2 μm.In addition, institute in aluminium porous body 8
The amount of the aluminium carbide contained is 0.3 mass %.
[embodiment 10]
Aluminium plating solution 9 is obtained according to mode in the same manner as in Example 9, difference is：Serve as the stearoyl of component (D)
The concentration of chlorine is 8.3g/L.
15 aluminium porous bodies 9 are prepared according to mode in the same manner as in Example 2, difference is：Use aluminium plating solution 9.
Measure the content of the elongation of each aluminium porous body 9, crystallite dimension and aluminium carbide.
(evaluation result)
The elongation ratio of GL (displacement relative to) minimum 1.6% of aluminium porous body 9, up to 2.5%.Elongation
The average value of rate is 1.8%.
The average grain size of aluminium on the cross section of the skeleton of aluminium porous body 9 is 3.2 μm.In addition, institute in aluminium porous body 9
The amount of the aluminium carbide contained is 0.6 mass %.
[embodiment 11]
Aluminium plating solution 10 is obtained according to mode in the same manner as in Example 10, difference is：By the tetradecane (by Wako
Pure Chemical Industries, Ltd. manufacture) be used as the component (D) in aluminium plating solution, and addO-on therapy (D) so that its
Concentration is 1g/L.
15 aluminium porous bodies 10 are prepared according to mode in the same manner as in Example 2, difference is：Use aluminium plating solution
10.Measure the content of the elongation of each aluminium porous body 10, crystallite dimension and aluminium carbide.
(evaluation result)
The elongation ratio of GL (displacement relative to) minimum 2.5% of aluminium porous body 10, up to 3.9%.Elongation
The average value of rate is 2.8%.
The average grain size of aluminium on the cross section of the skeleton of aluminium porous body 10 is 4.0 μm.In addition, in aluminium porous body 10
The amount of contained aluminium carbide is 0.3 mass %.
[embodiment 12]
Aluminium plating solution 11 is obtained according to mode in the same manner as in Example 10, difference is：By decene (by Tokyo
Chemical Industry Co., Ltd.s manufacture) it is used as the component (D) in aluminium plating solution, and addO-on therapy (D) is so that its is dense
Spend for 0.8g/L.
15 aluminium porous bodies 11 are prepared according to mode in the same manner as in Example 2, difference is：Use aluminium plating solution
11.Measure the content of the elongation of each aluminium porous body 11, crystallite dimension and aluminium carbide.
(evaluation result)
The elongation ratio of GL (displacement relative to) minimum 1.8% of aluminium porous body 11, up to 2.8%.Elongation
The average value of rate is 2.2%.
The average grain size of aluminium on the cross section of the skeleton of aluminium porous body 11 is 3.6 μm.In addition, in aluminium porous body 11
The amount of contained aluminium carbide is 0.34 mass %.
[embodiment 13]
Aluminium plating solution 12 is obtained according to mode in the same manner as in Example 10, difference is：By two chloro-octanes (by
Tokyo Chemical Industry Co., Ltd.s manufacture) be used as aluminium plating solution in component (D), and addO-on therapy (D) with
It is 3.0g/L to make its concentration.
15 aluminium porous bodies 12 are prepared according to mode in the same manner as in Example 2, difference is：Use aluminium plating solution
12.Measure the content of the elongation of each aluminium porous body 12, crystallite dimension and aluminium carbide.
(evaluation result)
The elongation ratio of GL (displacement relative to) minimum 2.1% of aluminium porous body 12, up to 2.8%.Elongation
The average value of rate is 2.4%.
The average grain size of aluminium on the cross section of the skeleton of aluminium porous body 12 is 6.0 μm.In addition, in aluminium porous body 12
The amount of contained aluminium carbide is 0.52 mass %.
[embodiment 14]
Aluminium plating solution 13 is obtained according to mode in the same manner as in Example 10, difference is：By chloropropane (by Tokyo
Chemical Industry Co., Ltd.s manufacture) it is used as the component (D) in aluminium plating solution, and addO-on therapy (D) is so that its is dense
Spend for 3g/L.
15 aluminium porous bodies 13 are prepared according to mode in the same manner as in Example 2, difference is：Use aluminium plating solution
13.Measure the content of the elongation of each aluminium porous body 13, crystallite dimension and aluminium carbide.
(evaluation result)
The elongation ratio of GL (displacement relative to) minimum 1.7% of aluminium porous body 13, up to 2.9%.Elongation
The average value of rate is 2.3%.
The average grain size of aluminium on the cross section of the skeleton of aluminium porous body 13 is 12 μm.In addition, in aluminium porous body 13
The amount of contained aluminium carbide is 0.46 mass %.
[comparative example 4]
Aluminium plating solution D is obtained according to mode in the same manner as in Example 9, difference is：In embodiment 9, addition group
Divide (D) so that its concentration is 0.3g/L.
15 aluminium porous body D are prepared according to mode in the same manner as in Example 2, difference is：Use aluminium plating solution D.
Measure the content of the elongation of each aluminium porous body D, crystallite dimension and aluminium carbide.
(evaluation result)
The elongation ratio of GL (displacement relative to) minimum 0.8% of aluminium porous body D, is even up to only
1.6%.The average value of elongation is 1.1%.
The average grain size of aluminium on the cross section of the skeleton of aluminium porous body D is 4.8 μm.In addition, institute in aluminium porous body D
The amount of the aluminium carbide contained is 0.12 mass %.
[comparative example 5]
Aluminium plating solution E is obtained according to mode in the same manner as in Example 9, difference is：In embodiment 9, addition group
Divide (D) so that its concentration is 9g/L.
15 aluminium porous body E are prepared according to mode in the same manner as in Example 2, difference is：Use aluminium plating solution E.
Measure the content of the elongation of each aluminium porous body E, crystallite dimension and aluminium carbide.
(evaluation result)
The elongation ratio of GL (displacement relative to) minimum 1.2% of aluminium porous body E, is even up to also only
1.8%.The average value of elongation is 1.4%.
The average grain size of aluminium on the cross section of the skeleton of aluminium porous body E is 0.6 μm.In addition, institute in aluminium porous body E
The amount of the aluminium carbide contained is 2.6 mass %.
Claims (7)
1. a kind of aluminium plating solution, its can electric deposition aluminum on the surface of the substrate,
The aluminium plating solution is composed of the following components：
(A) aluminum halide；
(B) selected from least one of the group being made of alkyl halide imidazoles, alkylpyridinium halides and carbamide compound chemical combination
Thing；And
(C1) at least one in the group being made of ammonium salt, microcosmic salt, sulfonium salt, amine compounds, phosphine compound and sulfide compound
Person,
Wherein described component (C1) is with the straight or branched alkyl that carbon number is less than more than 8 36 as at least one side
Chain, wherein " side chain " refers to the group being bonded with every kind of salt or the N atoms of compound, P atoms or S atom,
With molar ratio computing, the mixing ratio of the component (A) and the component (B) is 1:1 to 3:In the range of 1, and
The concentration of the component (C1) is more than 1.0g/L below 45g/L.
2. a kind of aluminium plating solution, its can electric deposition aluminum on the surface of the substrate,
The aluminium plating solution includes following components：
(A) aluminum halide；
(B) selected from least one of the group being made of alkyl halide imidazoles, alkylpyridinium halides and carbamide compound chemical combination
Thing；
(C2) at least one in the group being made of ammonium salt, microcosmic salt, sulfonium salt, amine compounds, phosphine compound and sulfide compound
Person, and
(D) selected from least one of group being made of alkyl halide, alkynes, alkene and alkane；
Wherein described component (C2) is with the straight or branched alkyl that carbon number is less than more than 1 36 as at least one side
Chain, wherein " side chain " refers to the group being bonded with every kind of salt or the N atoms of compound, P atoms or S atom,
The component (D) is the straight-chain or branched-chain compound that carbon number is less than more than 3 36,
With molar ratio computing, the mixing ratio of the component (A) and the component (B) is 1:1 to 3:In the range of 1,
The concentration of the component (C2) is more than 1.0g/L below 45g/L, and
The concentration of the component (D) is more than 0.5g/L below 8.5g/L.
3. aluminium plating solution according to claim 1 or 2, wherein the component (A) is aluminium chloride, and the component (B) is
1- ethyl -3- methylimidazolium chlorides.
4. a kind of method for manufacturing aluminium film, the described method includes by using according to any one of claims 1 to 3
Aluminium plating solution electric deposition aluminum on the surface of the substrate.
5. a kind of aluminium porous body, it is obtained by using aluminium plating solution according to any one of claim 1 to 3, described
Aluminium porous body has tridimensional network and more than 1.5% elongation, wherein the elongation is identified as working as aluminium porous body
The coating weight of aluminium of per unit area be 100g/m2Above 180g/m2Below and thickness is more than 0.95mm 1.05mm
Elongation when following, it refers to the elongation of the measure when carrying out tension test according to JIS Z 2241, and refers to displacement
Measure the ratio relative to the distance between graticule.
6. aluminium porous body according to claim 5, crystallite dimension in the cross section of its middle skeleton for more than 1 μm 50 μm with
Under.
7. the aluminium porous body according to claim 5 or 6, the wherein content of aluminium carbide are below 0.8 mass %.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
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| JP2014-128803 | 2014-06-24 | ||
| JP2014128803 | 2014-06-24 | ||
| JP2015053299A JP2016027190A (en) | 2014-06-24 | 2015-03-17 | Aluminum plating solution, aluminum film manufacturing method, and porous aluminum object |
| JP2015-053299 | 2015-03-17 | ||
| PCT/JP2015/066132 WO2015198819A1 (en) | 2014-06-24 | 2015-06-04 | Alluminum plating solution, aluminum film manufacturing method, and porous aluminum object |
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| CN106460216A CN106460216A (en) | 2017-02-22 |
| CN106460216B true CN106460216B (en) | 2018-05-04 |
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| US (1) | US20170121835A1 (en) |
| JP (1) | JP2016027190A (en) |
| KR (1) | KR20170021252A (en) |
| CN (1) | CN106460216B (en) |
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| WO (1) | WO2015198819A1 (en) |
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| CN110462106A (en) * | 2017-04-05 | 2019-11-15 | 住友电气工业株式会社 | Aluminium porous body and method for producing aluminium porous body |
| CN110536978A (en) * | 2017-05-22 | 2019-12-03 | 住友电气工业株式会社 | The manufacturing method of metal porous body and metal porous body |
| CN110536979A (en) * | 2017-05-22 | 2019-12-03 | 住友电气工业株式会社 | The manufacturing method of porous body of composite metal and porous body of composite metal |
| US11142841B2 (en) | 2019-09-17 | 2021-10-12 | Consolidated Nuclear Security, LLC | Methods for electropolishing and coating aluminum on air and/or moisture sensitive substrates |
| KR20230074944A (en) | 2021-11-22 | 2023-05-31 | 주식회사 알링크 | Manufacturing method for aluminum plating solution and plating method using the same |
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| Publication number | Publication date |
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| DE112015003017T5 (en) | 2017-03-09 |
| KR20170021252A (en) | 2017-02-27 |
| CN106460216A (en) | 2017-02-22 |
| US20170121835A1 (en) | 2017-05-04 |
| WO2015198819A1 (en) | 2015-12-30 |
| JP2016027190A (en) | 2016-02-18 |
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