CN111636078B - Method for electroplating porous aluminum in water - Google Patents
Method for electroplating porous aluminum in water Download PDFInfo
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- CN111636078B CN111636078B CN202010726053.7A CN202010726053A CN111636078B CN 111636078 B CN111636078 B CN 111636078B CN 202010726053 A CN202010726053 A CN 202010726053A CN 111636078 B CN111636078 B CN 111636078B
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 83
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 238000009713 electroplating Methods 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 14
- -1 aluminum ions Chemical class 0.000 claims abstract description 17
- 239000002738 chelating agent Substances 0.000 claims abstract description 14
- 238000004040 coloring Methods 0.000 claims abstract description 9
- BGZZWXTVIYUUEY-UHFFFAOYSA-N fomesafen Chemical compound C1=C([N+]([O-])=O)C(C(=O)NS(=O)(=O)C)=CC(OC=2C(=CC(=CC=2)C(F)(F)F)Cl)=C1 BGZZWXTVIYUUEY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 238000005269 aluminizing Methods 0.000 claims 1
- 238000007747 plating Methods 0.000 abstract description 46
- 125000006575 electron-withdrawing group Chemical group 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 238000000151 deposition Methods 0.000 description 10
- 230000008021 deposition Effects 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 9
- 239000003446 ligand Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000004696 coordination complex Chemical class 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- ZUGAOYSWHHGDJY-UHFFFAOYSA-K 5-hydroxy-2,8,9-trioxa-1-aluminabicyclo[3.3.2]decane-3,7,10-trione Chemical compound [Al+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O ZUGAOYSWHHGDJY-UHFFFAOYSA-K 0.000 description 1
- 229910016706 AlCl3—NaCl Inorganic materials 0.000 description 1
- 229910016747 AlCl3—NaCl—KCl Inorganic materials 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- 229940118662 aluminum carbonate Drugs 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- VJLOFJZWUDZJBX-UHFFFAOYSA-N bis(2-hydroxyethyl)azanium;chloride Chemical compound [Cl-].OCC[NH2+]CCO VJLOFJZWUDZJBX-UHFFFAOYSA-N 0.000 description 1
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- XHFGWHUWQXTGAT-UHFFFAOYSA-N dimethylamine hydrochloride Natural products CNC(C)C XHFGWHUWQXTGAT-UHFFFAOYSA-N 0.000 description 1
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- CBPYOHALYYGNOE-UHFFFAOYSA-M potassium;3,5-dinitrobenzoate Chemical compound [K+].[O-]C(=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 CBPYOHALYYGNOE-UHFFFAOYSA-M 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 238000009333 weeding Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- C25D5/18—Electroplating using modulated, pulsed or reversing current
Abstract
The invention provides an aqueous electroplating porousA machine electroplating method of an aluminum plating solution comprises aluminum ions, water, 5-30g/L of chelating agent 5- (2-chloro-4-trifluoromethylphenoxy) -N-methylsulfonyl-2-nitrobenzamide, pH of the plating solution is 5-6, and current density is 20-30A/dm 2 . Preferably, the chelating agent is added to the aluminum ion in a molar ratio of 6-1:1. Through the selection of specific electron withdrawing groups, an aluminum compact layer and a porous layer can be simply, conveniently and efficiently deposited from the plating solution, and the plating solution is suitable for plating and coloring of shells of mobile phones, notebook computers and the like.
Description
Technical Field
The invention relates to a method for manufacturing an aluminum deposition layer, in particular to a method for electroplating aluminum, in particular to a method for electroplating porous aluminum in water.
Background
Aluminum is light, nontoxic, good in heat conduction and electric conduction, corrosion-resistant and oxidation-resistant, is an excellent surface coating material, and can particularly give metal texture and various color systems after coloring. It is a common requirement to deposit aluminum layers on electronic components such as cell phones, which are difficult to electroplate out by aqueous solutions due to the reactivity of aluminum. The existing method for depositing the aluminum layer mainly comprises hot dip plating, hot spraying, rolling, physical vapor deposition, chemical vapor deposition and the like, but it is known that electroplating aluminum is generally carried out at a temperature close to normal temperature, so that the mechanical properties of a matrix material are not affected by higher working temperature, expensive instruments and equipment are not needed, and the obtained plating layer is high in purity, low in porosity and easy to control in thickness and quality, so that the electroplating process is more advantageous. Unfortunately, aluminum plating is mostly available only in non-aqueous systems. Nonaqueous solvent systems that have been successfully used in electrolytic aluminum plating studies to date are organic solvents and molten salts. This study is relatively extensive and has been reported by many skilled artisans, liu Quan et al, the progress of which is described in detail herein, and the present invention is incorporated herein as an illustration of the case of aluminum plating: 1. an organic solvent system. The organic solvent system is adopted, the electroplating temperature is generally lower than 100 ℃, hydrogen is not generated, corrosive products are not generated, and the current efficiency is high. However, the stability of the organic solvent is poor, the organic solvent is sensitive to water and oxygen, the electroplating must be performed under the protection of inert gas, the deposition rate of aluminum is low, and the quality of the obtained coating is unstable. 2. And (5) electroplating aluminum with inorganic molten salt. Common systems are AlCl3-NaCl, alCl3-NaCl-KCl, etc. The plating temperature is usually between 100 and 200 ℃, and the plating quality is good, but the selection of the matrix material is limited due to the high plating temperature. 3. Ionic liquids, generally composed of metal halides and organic salts, are most studied with halogen as the organic salt anion, but are unstable to air and water. Anionic substitution of halogen such as BF-4, PF-6 and TFSI can enhance the stability of ionic liquid to air and water, but the research is still in progress. The electroplating temperature of the ionic liquid is room temperature, so that the energy consumption and the cost can be reduced, the toxicity is low, and the environmental pollution is low.
The existing method for electroplating aluminum by water is boring, though some researches are available. In order to solve the problem of aqueous aluminum electroplating, dream in the electroplating industry is always required. But more practitioners have not held much hope for this and so fewer people in the industry are doing so. The invention technology CN201410476312X of Zhu Zhongliang relates to a water-phase electrolytic aluminum plating solution, a method for forming an aluminum plating film and an aluminum plating article formed by the method. The electrolytic aluminum plating solution contains 1.5 to 4.0moL of aluminum halide relative to 10.0moL of dimethyl sulfone, and contains 1/20 to 1/2 by mole of dimethylamine hydrochloride, diethylamine hydrochloride, diethanolamine hydrochloride, or a mixture thereof relative to the aluminum halide. The electrolytic aluminum plating solution of the present invention can provide a plating solution which can stably perform an electrolytic aluminum plating treatment for a long period of time even when the amount of water mixed in is gradually increased, and can form a uniform aluminum plating film on an object to be plated even by a barrel-type plating treatment. It is not aqueous electroplated aluminum in nature, but is an extended study of the water-solvent miscibility resistance of conventional plating processes. The process of US20190256994A1 for electroplating aluminum from an aqueous solution, in particular, a process for electrodepositing aluminum onto a surface of a conductive substrate, the electrodeposition being carried out at a temperature of from about 10 ℃ to about 70 ℃, at a pressure of from about 0.5 atmospheres to about 5 atmospheres, in an atmosphere comprising oxygen. The deposition potential is changed by mainly using a metal complex dissolved in an aqueous medium, so that the reduction potential of the metal in the metal complex is lowered below the overpotential for hydrogen evolution due to water splitting. The metal complex includes a metal center and ligands, wherein at least one of the ligands is an electron withdrawing ligand, and the ligands are sulfonate ligands and sulfonimide ligands. But it is not capable of achieving electrodeposited aluminum at low current densities (less than 40A/dm 2).
With the development of the electronic industry, especially the popularization of portable mobile devices such as mobile phones and notebook computers, the portable materials such as various composite materials are increasingly used, however, the lack of metal texture is a common treatment mode, however, the existing aluminum plating cannot be conveniently separated from an aqueous solution as described above, and the existing aluminum plating is usually formed into a porous layer through anodic oxidation to meet various requirements on color, so that the color is colored. The complexity and inconvenience of the above-described process results in an inadvisable extended application.
Disclosure of Invention
In view of the above-mentioned drawbacks and deficiencies, the present invention provides an aqueous plating solution for plating porous aluminum, a method of using the same, and a component such as a mobile phone case manufactured thereby.
The first aspect of the present invention is an aqueous electrolytic aluminum plating bath comprising: comprises aluminum ion, water, 5-30g/L chelating agent 5- (2-chloro-4-trifluoromethyl phenoxy) -N-methanesulfonyl-2-nitrobenzamide, and electroplating solution pH 5-6 with current density 20-30A/dm 2 . Preferably, the chelating agent is added to the aluminum ion in a molar ratio of 6-1:1.
The aluminum source is usually a substance capable of providing aluminum ions as described in the art, and is not particularly limited, but anions other than aluminum, which do not indirectly affect the reduction potential of aluminum, may be used, and examples thereof include organic aluminum, which is aluminum acetate, aluminum citrate, etc., preferably an inorganic aluminum salt, particularly preferably aluminum chloride, aluminum sulfate, aluminum carbonate, aluminum nitrate, etc.
The chelating agent, which is essentially a potential modifier, is added to chelate aluminum ions to generate a positive potential, thereby preferentially decomposing hydrogen to electrodeposit. However, substances which can meet the basic principle are difficult to screen, more electron withdrawing group substances are preferably adopted according to the general requirement on electronegativity, but are not always desirable, only screening is carried out as much as possible, and it is difficult to understand that the electron withdrawing groups under the same condition are not always perfectly matched, so that the invention adopts 5- (2-chloro-4-trifluoromethyl phenoxy) -N-methanesulfonyl-2-nitrobenzamide (which is abbreviated as FMSAF for describing the invention), and the FMSAF contains the electron withdrawing groups of trifluoromethyl, methanesulfonyl, nitro and the like, and the substances are difficult to screen. However, its proportion to aluminum ions and pH solution significantly affect the deposition and morphology of aluminum, and thus has not been found to be applied to aqueous electrodeposition of aluminum based on the above principles prior to the present invention.
In the Ag/AgCl (0.1M KCl) electrode test, a potential theoretically more positive than about-1.52V may precipitate metallic aluminum, whereas a large amount of hydrogen gas may be observed.
Moreover, unfortunately, there is no literature about the application of FMSAF in electroplating other than aluminum, and in order to understand other physical properties, it has been unexpectedly found that this material has been used in a large amount in the field of agricultural chemical weeding, but is far from the present invention, however, since the basic physical parameters are studied in this field, it is convenient to obtain other beneficial aids besides electronic adsorptivity in the practice of the present invention, without the need of measurement and physical and chemical studies, such as its melting point is 220-221 ℃, molecular weight is about 438, solubility in water is closely related to pH, can reach 600 g or more near neutral, and is not easily hydrolyzed in acidic and alkaline solutions.
The invention further includes another embodiment, a method for electroplating porous aluminum in an aqueous solution, comprising the steps of:
1) Preparing aqueous electroplating solution, aluminum ion Al 3+ The concentration is 4.5-27g/L, the chelating agent is 73-500g/L of 5- (2-chloro-4-trifluoromethyl phenoxy) -N-methanesulfonyl-2-nitrobenzamide, and the pH value is adjusted to 5.1-6.3;
2) Pretreating a substrate to form a surface suitable for electroplating;
3) Graphite or aluminum plate is used as anode, pretreated substrate is used as cathode, and current density is 20-30A/dm 2 Electroplating for 40-90min at 20-35 deg.C.
The implementation aspect of the invention further resides in: electroplating is carried out for 30-50min under low current density, and then electroplating is carried out for 10-40min under high current density. The low current density is less than the high current density. The low current density is 20-24A/dm2 and the high current density is 26-30A/dm2. The plating time is longer at low current densities than at high current densities.
Electrolytic coloring is also included according to the color requirements. The aluminum plating does not need to be anodized. No additional porosification step is included, such as a porosification step via anodic oxidation.
Another aspect of the present invention is to manufacture a part comprising an aluminum layer obtained by electroplating aluminum from an aqueous solution, wherein the aluminum layer is preferably a dense aluminum metal layer as the lower layer and a porous aluminum metal layer as the upper layer; more preferably, the aluminum layer is formed by the low and high current density plating method, more preferably the part is a decorative part, more preferably the decorative part is an electronic product housing, more preferably the electronic product housing is a mobile phone housing or a notebook computer housing.
The invention has the beneficial effects that:
1. the method expands the deposition mode of the aluminum film, particularly provides an attempt for precipitating aluminum from the aqueous solution, and lays an experimental foundation for industrialization; 2. the potential chelating agent for separating out aluminum from a new aqueous solution is screened, so that dense deposition of aluminum can be realized at the initial stage, meanwhile, the hydrogen separation can be well utilized, a porous layer formed by the potential chelating agent is colored, the service life of an electronic component is combined, and the porous performance is enough to meet the updating of the electronic component after the potential chelating agent is used, especially a mobile phone notebook computer and the like; in order to prevent the problem of the porous layer, the porous layer is coated with a polymer varnish, so that the gloss and the color diversity of the metal are not lost, and perspiration etching is prevented. 3. The cathode electrodeposition current density is innovatively reduced, and the deposition of the required aluminum compact layer and the porous layer is realized under the lower two-stage current density.
Detailed Description
Example 1
1) Preparing aqueous electroplating solution, aluminum ion Al 3+ The concentration is 4.5g/L, the chelating agent 5- (2-chloro-4-trifluoromethyl phenoxy) -N-methanesulfonyl-2-nitrobenzamide (FMSAF) is 73-500g/L, and the pH value is adjusted to 6.3;
2) Pretreating a substrate to form a surface suitable for electroplating;
3) Taking an aluminum plate as an anode, taking a pretreated base material as a cathode, and electroplating in the first stage: at a current density of 20A/dm 2 Electroplating for 30min, wherein the temperature of the plating solution is 25 ℃, and electroplating in the second stage: then at a current density of 26A/dm 2 Electroplating for 10min, wherein the temperature of the plating solution is 25 ℃,
4) Coloring.
And (3) plating performance test: during the first stage electroplating operation, no obvious bubbles of the plating solution escape, no hydrogen is separated out, the plating layer of the first stage electroplated aluminum is tested, no obvious pinholes are found by using a pinhole tester, and no hydrogen is separated out. In the second stage of electroplating, the electroplating solution has slowly accumulated hydrogen, but does not precipitate in a large amount, and the electroplating solution is found to have no obvious pinholes through visual inspection, and pinhole tests are carried out on the plating layer, so that uniformly distributed micro pinholes are found. The electroplating process can realize water-based electroplating of aluminum, realizes compact aluminum plating under lower current density without hydrogen precipitation, and realizes porous layer under slightly high current density, wherein the porous layer utilizes hydrogen precipitation to cause pinholes, thereby being beneficial to subsequent electrolytic coloring. The electrolytic coloring is not particularly limited, and may be used for conventional electrolytic coloring, and the thickness of the polymer transparent varnish after the electrolytic coloring is about 1 to 10 μm is applied for corrosion prevention.
The plating solution of example 1 was tested for its precipitation potential under Ag/AgCl (0.1M KCl), the first phase precipitation potential was-1.3V, the second phase precipitation potential was-1.4V, and the scanning was continued to reach about-1.5V to be remarkable. It can be seen that the first stage is mainly aluminum precipitation and deposition, the potential is changed by the chelating agent, precipitation from an aqueous solution can be achieved, and the plating layer is dense, and the second stage is that aluminum can still be precipitated, and hydrogen precipitation is gradually enhanced in consideration of decomposition of the chelating agent and change of the potential, thereby generating a porous layer.
Examples 2-3, comparative examples 1-5 are specifically referred to in Table 1. The remaining parameters are as in example 1.
The plating was tested and examples 2-3 were essentially the same as example 1 to obtain a porous layer and a dense layer. When the aluminum ion content is too low, although a plating layer can be obtained as in comparative example 1, it is economically disadvantageous that a sufficient thickness layer cannot be deposited in the same time, so that the aluminum ion content is not less than 1/6mol of FMSAF and the absolute content should be more than 4.5g/l. The presence of the loose pin-hole layer alone is undesirable. The proposed ratio of FMSAF to aluminum ions is thus 1-6:1.
The pH is more serious for aqueous electroplated aluminum, preferably 5.1 to 6.3 in the observable range, as in comparative examples 3 to 4, no significant aluminum plating is observed, while bubbles in the solution escape.
The influence of the current density is not more than 20A/dm as shown in comparative example 5 2 When the plating test shows that a sufficient aluminum compact layer is not seen, and when the plating is higher than 30, the visible plating is larger loose and porous. The optimum current density is 20-30A/dm2. In particular, the high current density in the second stage may induce pinholes, and may be caused by trace carbon impurities generated by electrolysis of FMSAF in solution, and more likely the decomposition causes positive electrode potential shift, and although aluminum deposition can be generated, the potential is close to the hydrogen gas precipitation potential, so that a small amount of hydrogen is precipitated, and pinholes are caused. The defect is generally taken as a defect in the field, the defect is creatively utilized as an advantage, so that a colorable porous aluminum compact layer is formed, and the lower aluminum compact layer is taken as a protective layer, and the thin coating of the high-molecular transparent varnish is adopted to prevent the electronic component from being bright, not discolored and sweat from invading, and can meet the requirement of using the electronic component for 3-5 years under the general condition after the standard salt spray test is carried out for more than 96 hours. This essentially meets the frequency of updating alternatives for cell phones and notebook computers. While maintaining the color unchanged.
Table 1 implementation of the operating parameters
It will be apparent to those skilled in the art that various modifications to the above embodiments may be made without departing from the general spirit and concepts of the invention. Which fall within the scope of the present invention. The protection scheme of the invention is subject to the appended claims.
Claims (3)
1. A method for electroplating porous aluminum in an aqueous solution, comprising the steps of:
1) Preparing an aqueous electroplating solution containing aluminum ions and water, wherein Al 3+ The concentration is 4.5-27 g-The concentration of the chelating agent 5- (2-chloro-4-trifluoromethyl phenoxy) -N-methanesulfonyl-2-nitrobenzamide is 73-500g/L, and the pH value is adjusted to 5.1-6.3; wherein, the chelating agent and aluminum ions are added in a molar ratio of 6-1:1;
2) Pretreating a substrate to form a surface suitable for electroplating;
3) Graphite or aluminum plate is used as anode, pretreated substrate is used as cathode, and current density is 20-30A/dm 2 Electroplating for 40-90min at 20-35deg.C; concretely, electroplating is carried out for 30-50min under low current density, then electroplating is carried out for 10-40min under high current density, and the low current density is 20-24A/dm 2 The high current density is 26-30A/dm 2 And the electroplating time is longer than the high current density time at low current density.
2. The method according to claim 1, characterized in that: electrolytic coloring is also included.
3. A method according to any one of claims 1-2, characterized in that: the anodic oxidation treatment is not carried out after the aluminizing.
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| CN102770160A (en) * | 2009-03-06 | 2012-11-07 | 先正达参股股份有限公司 | Compatibilized electrolyte formulations |
| CN103849911A (en) * | 2012-12-07 | 2014-06-11 | 中国科学院过程工程研究所 | Ionic liquid electroplating solution for preparing bright aluminum coating at low temperature and using method of ionic liquid electroplating solution |
| CN105297082A (en) * | 2015-11-05 | 2016-02-03 | 华南理工大学 | Method for preparing super-hydrophobic film layers on metal surfaces through one-step method |
| CN108779566A (en) * | 2016-02-16 | 2018-11-09 | 鲁米士德科技公司 | The electrochemical deposition of element in water-bearing media |
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| CN102770160A (en) * | 2009-03-06 | 2012-11-07 | 先正达参股股份有限公司 | Compatibilized electrolyte formulations |
| CN103849911A (en) * | 2012-12-07 | 2014-06-11 | 中国科学院过程工程研究所 | Ionic liquid electroplating solution for preparing bright aluminum coating at low temperature and using method of ionic liquid electroplating solution |
| CN105297082A (en) * | 2015-11-05 | 2016-02-03 | 华南理工大学 | Method for preparing super-hydrophobic film layers on metal surfaces through one-step method |
| CN108779566A (en) * | 2016-02-16 | 2018-11-09 | 鲁米士德科技公司 | The electrochemical deposition of element in water-bearing media |
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