CN109652837A - A kind of hole sealing agent of ultralow nickel content and the method that sealing of hole is carried out to anodic oxidation workpiece with it - Google Patents
A kind of hole sealing agent of ultralow nickel content and the method that sealing of hole is carried out to anodic oxidation workpiece with it Download PDFInfo
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- CN109652837A CN109652837A CN201910034736.3A CN201910034736A CN109652837A CN 109652837 A CN109652837 A CN 109652837A CN 201910034736 A CN201910034736 A CN 201910034736A CN 109652837 A CN109652837 A CN 109652837A
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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
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/24—Chemical after-treatment
- C25D11/246—Chemical after-treatment for sealing layers
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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
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
- C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
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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
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/16—Pretreatment, e.g. desmutting
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Abstract
The present invention relates to a kind of hole sealing agent of ultralow nickel content and the methods for carrying out sealing of hole to anodic oxidation workpiece with it.The hole sealing agent includes each raw material of following parts by weight: 0.5-2.0 parts of nickel salt film forming agent, 0.2-1.5 parts of coalescing agent, and 0.01-0.06 parts of wetting agent, alkaline-resisting elevator 0.5-1.0 parts.It is made into fluting liquid using Shi Jiashui, nickel content is generally in 0.2-0.8g/L in liquid of slotting, and fluorine content is in 0.05-0.09g/L.Hole sealing agent provided by the invention individually can carry out high temperature sealing of hole to alumilite process workpiece, can also be used cooperatively with conventional cold seal and silicate high temperature hole sealing.Beneficial effect is: its nickel content only has the 1/10 of most products in the market, largely reduces the cost of wastewater treatment；It is used alone or is used cooperatively with traditional cold seal agent, the agent of silicate high temperature hole sealing and without silicate hole sealing agent, can reach preferable sealing of hole effect.
Description
Technical field
The invention belongs to the technical field of surface of automobile industry anodic oxidation workpiece, and in particular to a kind of ultralow nickel contains
The hole sealing agent of amount and the method that sealing of hole is carried out to anodic oxidation workpiece with it.
Background technique
Aluminium surface carries out at sealing of hole after oil removing, washing, alkaline etching, washing, chemical polishing, washing, ash disposal, anodic oxidation
The neutral salt spray ability, copper accelerated acetic acid salt spray ability, condensation outlet capacity, specking ability, acid resistance of aluminium material surface can be improved in reason
Solution ability, alkali resistance solution ability, heat-resisting ability.Traditional sealing pores are mainly the cold seal and acetic acid of nickel fluoride system
The cold seal of the heat-sealing of nickel system, nickel fluoride system can react with anode oxidation membrane and form Al (OH)3、Ni(OH)2And AlF3,
Fast Filling anode oxidation membrane, to make anode oxidation membrane from various corrosion；The heat-sealing of nickel acetate system can be with anode
Oxidation film layer reacts and forms Al (OH)3、Ni(OH)2, Fast Filling anode oxidation membrane, can also make anode oxidation membrane from
Various corrosion.The fluting concentration nickel content of traditional nickel fluoride system generally in 1-1.5g/L, fluorine content in 0.5-0.9g/L, but
It is that one side nickel, fluorine content are high, and the cost of wastewater treatment also can be accordingly higher, on the other hand since the gadget of nickeliferous metal is long
Phase contacts with human skin, can induce Allergic contact dermatitis, is forbidden to use by many countries in Europe, has put into effect correlation
Limitation standard, including BS EN 1811:1999 and EN12472:2005.Meanwhile in addition to the nickel content of nickel fluoride cold seal system height
Deficiency it is outer, there are the partially soft problems of film layer for traditional heat-sealing system.
Summary of the invention
A kind of method that the present invention provides ultralow nickel content hole sealing agent and carries out sealing of hole to anodic oxidation workpiece with it, can
Effectively overcome the deficiencies of high bring of nickel content increases cost for wastewater treatment and induces dermatitis in traditional cold seal technique, solves simultaneously
The partially soft problem of film layer in traditional hot sealing process.
The technical scheme to solve the above technical problems is that a kind of ultralow nickel content hole sealing agent comprising as follows
Each raw material of parts by weight: 0.5-2.0 parts of nickel salt film forming agent, 0.2-1.5 parts of coalescing agent are 0.01-0.06 parts of wetting agent, alkaline-resisting
0.5-1.0 parts of elevator.Water is added to prepare fluting liquid when use, generally in 0.2-0.8g/L, fluorine content exists nickel content in liquid of slotting
0.05-0.09g/L, between operating temperature 60-95 degree, 10-15min, can independent sealing of hole, can also again with traditional cold seal and silicate
High temperature hole sealing is used cooperatively, when improving the performances such as the acidproof, alkaline-resisting of anode oxidation membrane, salt spray resistance ability and solving high temperature hole sealing
The problems such as film layer is partially soft.
Preferably, the nickel salt film forming agent is one of four hydration nickel fluorides and four hydration nickel acetates or a variety of.
Preferably, the coalescing agent is fluorine zirconic acid, potassium fluorozirconate, ammonium fluozirconate, sodium bifluoride, potassium fluosilicate, fluorine silicon
Sour sodium, fluosilicic acid, potassium fluoborate, sodium fluoborate, fluoboric acid, ammonium titanium fluoride, potassium fluotitanate, fluotitanic acid, potassium floutaramite and fluorine tantalum
One of sour ammonium is a variety of.
Preferably, the wetting agent is fatty alcohol polyoxyethylene ether, oxo-alcohols polyoxyethylene ether, alkylphenol-polyethenoxy
One of ether, coco amine, alkylphenol sulfate, alkyl sulfate, alkylbenzene sulfonate and polyvinyl alcohol are a variety of.
Preferably, the alkaline-resisting elevator is ammonium acetate, potassium acetate, lithium nitrate, potassium nitrate, sodium nitrate, ammonium nitrate, sulfuric acid
The substances such as ammonium.In the system, the addition of alkaline-resisting elevator can be obviously improved the alkali resistance of the workpiece after hole sealing agent sealing of hole.
Above-mentioned " a variety of " refer to the mixing of two or more arbitrary proportion.
The method that the ultralow nickel content hole sealing agents stated the present invention also provides more than one carry out sealing of hole to anodic oxidation workpiece,
It includes the following steps:
S1. aluminum or aluminum alloy workpiece obtains anodic oxidation workpiece through pre-treatment and anodic oxidation；The pre-treatment and anodic oxygen
Changing is specially by aluminum alloy surface through oil removing, washing alkaline etching, washing, chemical polishing, washing, ash disposal, in 190 ± 10g/L of concentration
Sulfuric acid solution in, be powered 30min under voltage 13.4V, obtains anodic oxidation workpiece.
S2. the ultralow nickel content hole sealing agent and water mixed preparing are slotted liquid, nickel content is 0.2- in the fluting liquid
0.8g/L, fluorine content 0.05-0.09g/L；
S3. sealing pores are carried out to the anodic oxidation workpiece of S1 using the fluting liquid of S2, the sealing pores can be from following
It chooses any one kind of them in four kinds of selections: the fluting liquid high temperature sealing of hole is used only；The fluting liquid high temperature sealing of hole is first used, then is made
With silicate hole sealing agent high temperature hole sealing；Nickel fluoride cold seal agent cold seal is first used, the fluting liquid high temperature sealing of hole is reused；First make
With nickel fluoride cold seal agent cold seal, the fluting liquid high temperature sealing of hole is reused, finally uses silicate hole sealing agent high temperature hole sealing.
Hole sealing agent of the present invention can be used for carrying out sealing pores to the film layer after various aluminium alloy anode oxides, such as
It can be any aluminium alloy of 1-7 system.1 line aluminium alloy is the rafifinal containing 99.00% or more aluminium；2 line aluminium alloy:
It is the main aluminium-containing alloy for closing element with copper；3 line aluminium alloy: being the main aluminium-containing alloy for closing element with manganese；Described 4 be aluminium
Alloy is based on silicon；5 line aluminium alloy is based on magnesium；6 line aluminium alloy is based on magnesium and silicon；7 line aluminium alloy with
Based on zinc, but also to add magnesium, copper on a small quantity sometimes.
Specifically, the sealing of hole temperature of the fluting liquid high temperature sealing of hole is 60-95 DEG C, the sealing of hole time is 10-15min.
Specifically, the sealing of hole temperature of the silicate hole sealing agent high temperature hole sealing is 95-100 DEG C, the sealing of hole time is 15-
30min。
Preferably, the silicate hole sealing agent is Phoenix Seal 290A/E.Phoenix Seal 290A/E is force
The commercially available hole sealing agent based on sodium metasilicate of Han Feinike Chemical Co., Ltd. production, can form on anodic oxidation workpiece
Very good alkaline-resisting film layer.
Specifically, the sealing of hole temperature of the nickel fluoride cold seal agent cold seal is 26-30 DEG C, the sealing of hole time is 15-30min.
Preferably, the nickel fluoride cold seal agent is Phoenix Seal 180 or Phoenix Seal 183.Phoenix
Seal 180 and Phoenix Seal 183 is the production of Wuhan Fei Nike Chemical Co., Ltd. based on fluorine and nickel salt
Commercially available low temperature pore sealing agent has excellent salt fog performance, and operation temperature is usually 26-30 DEG C, operation concentration 3.0-6.0g/L.
Compared with prior art, the beneficial effects of the present invention are: providing a kind of hole sealing agent of ultralow nickel content, it is opened
Tank liquor nickel content and fluorinated volume only have the 1/10 of most products in the market, largely reduce the cost of wastewater treatment,
The corrosion resistance of anodic oxidation workpiece film layer can be effectively promoted simultaneously, be used alone or is used cooperatively with traditional cold seal agent,
It can achieve even more than traditional cold seal effect；It is used alone or with traditional cold seal agent, the agent of silicate high temperature hole sealing and without silicic acid
Salt hole sealing agent is used cooperatively, and can solve the problems, such as that film layer generally existing in high temperature hole sealing technique is partially soft, and Shi Ketong is used alone
Alkaline-resisting 12.5 test is crossed, and workpiece surface is in hydrophobic state；Cooperate silicate high temperature hole sealing or other no silicate sealing of holes reachable
To excellent CASS performance, 5 be 6 be that aluminum profile CASS can reach 72h or more；Hole sealing agent provided by the invention can be closed according to aluminium
The demand of gold anode oxidation workpiece performance, there are four types of alternative hole-sealing treatment process, applicability is good.
Specific embodiment
Of the invention is described in further detail below in conjunction with specific embodiment, example is served only for explaining this hair
It is bright, it is not intended to limit the scope of the present invention.
Drug without specific instruction used is commercial product in following embodiment and comparative example, and it is special that method therefor is not made
Explanation is conventional method.
In following embodiment, embodiment 1 to 3 is using only ultralow nickel content hole sealing agent provided by the invention to anodic oxidation
Workpiece carries out high temperature sealing of hole, only a step sealing pores；Embodiment 4 to 6 is first using in hole sealing agent provided by the invention progress
High temperature hole sealing carries out silicate high temperature hole sealing again later, is two step sealing of holes, and the alkaline-resisting of film layer can be made by increasing silicate high temperature hole sealing
Sexuality enhancing；Embodiment 7 to 9 is first to be reused hole sealing agent of the invention later using conventional cold seal and carried out high temperature sealing of hole,
It also is two step sealing of holes, high temperature sealing of hole is the aging step after cold seal, and further promotion can be obtained in cold seal performance；Embodiment 10-
12, first to use conventional cold seal, reuse hole sealing agent of the invention later and carry out high temperature sealing of hole, finally reuse silicate height
Warm sealing of hole is three step sealing of holes, and high temperature sealing of hole forms barrier layer between cold seal and high temperature hole sealing, can effectively promote sealing of hole effect
Fruit.
Embodiment 1
A method of sealing of hole is carried out to anodic oxidation workpiece with ultralow nickel content hole sealing agent, is included the following steps:
(1) aluminium and aluminum alloy surface are through oil removing, washing, alkaline etching, washing, chemical polishing, washing, ash disposal, in sulfuric acid concentration
In 190g/L, under voltage 13.4V, after energization 30min anodic oxidation, measuring film thickness is 8 μm, and is cleaned up.
(2) by nickel salt film forming agent: four hydration nickel fluoride 0.5g, coalescing agent: fluorine zirconic acid 0.7g, wetting agent: oxo-alcohols are poly-
Ethylene oxide ether 0.03g and alkaline-resisting elevator: ammonium acetate 0.5g, compounding after mixing evenly ultralow nickel content hole sealing agent, then use
The hole sealing agent is made into the fluting liquid of 50g/L by pure water of the conductivity less than 30 μ S/cm, and wherein the content of nickel is about 0.2g/L.
(3) 10min will be handled in above-mentioned fluting liquid by the Al alloy parts of step (1) processing, 75 DEG C of sealing of hole temperature,
And pure water cleans 3 times, drying.
Embodiment 2
A method of sealing of hole is carried out to anodic oxidation workpiece with ultralow nickel content hole sealing agent, is included the following steps:
(1) aluminium and aluminum alloy surface are through oil removing, washing, alkaline etching, washing, chemical polishing, washing, ash disposal, in sulfuric acid concentration
In 190g/L, under voltage 13.4V, after energization 30min anodic oxidation, measuring film thickness is 8 μm, and is cleaned up.
(2) by nickel salt film forming agent: four hydration nickel acetate 0.5g, coalescing agent: fluorine zirconic acid 1.5g, wetting agent: oxo-alcohols are poly-
Ethylene oxide ether 0.06g and alkaline-resisting elevator: 0.8g ammonium sulfate, compounding after mixing evenly ultralow nickel content hole sealing agent, then use
The hole sealing agent is made into the fluting liquid of 50g/L by pure water of the conductivity less than 30 μ S/cm, and wherein the content of nickel is about 0.8g/L.
(3) 15min will be handled in above-mentioned fluting liquid by the Al alloy parts of step (1) processing, sealing of hole temperature 60 C,
And pure water cleans 3 times, drying.
Embodiment 3
A method of sealing of hole is carried out to anodic oxidation workpiece with ultralow nickel content hole sealing agent, is included the following steps:
(1) aluminium and aluminum alloy surface are through oil removing, washing, alkaline etching, washing, chemical polishing, washing, ash disposal, in sulfuric acid concentration
In 190g/L, under voltage 13.4V, after energization 30min anodic oxidation, measuring film thickness is 8 μm, and is cleaned up.
(2) by nickel salt film forming agent: four hydration nickel acetate 1.5g, coalescing agent: fluorine zirconic acid 1.5g, wetting agent: oxo-alcohols are poly-
Ethylene oxide ether 0.01g and alkaline-resisting elevator: 1.0g ammonium acetate, balance of water after mixing evenly ultralow nickel content hole sealing agent,
Then the hole sealing agent is made into the fluting liquid of 50g/L by the pure water with conductivity less than 30 μ S/cm, and wherein the content of nickel is about
0.6g/L。
(3) 12min will be handled in above-mentioned fluting liquid by the Al alloy parts of step (1) processing, 95 DEG C of sealing of hole temperature,
And pure water cleans 3 times, drying.
Embodiment 4
A method of sealing of hole is carried out to anodic oxidation workpiece with ultralow nickel content hole sealing agent, is included the following steps:
(1) aluminium and aluminum alloy surface are through oil removing, washing, alkaline etching, washing, chemical polishing, washing, ash disposal, in sulfuric acid concentration
In 190g/L, under voltage 13.4V, after energization 30min anodic oxidation, measuring film thickness is 8 μm, and is cleaned up.
(2) by nickel salt film forming agent: by nickel salt film forming agent: four hydration nickel fluoride 0.5g, coalescing agent: fluorine zirconic acid 0.7g moistens
Humectant: oxo-alcohols polyoxyethylene ether 0.03g and alkaline-resisting elevator: 0.5g ammonium acetate, compounding after mixing evenly ultralow nickel content
Hole sealing agent, then the hole sealing agent is made into the fluting liquid of 1g/L by the pure water with conductivity less than 30 μ S/cm, wherein the content of nickel
About 0.2g/L.
(3) 10min will be handled in above-mentioned fluting liquid by the Al alloy parts of step (1) processing, 75 DEG C of sealing of hole temperature,
And pure water cleans 3 times, drying carries out sealing pores, sealing of hole temperature using silicate sealing of hole Phoenix Seal 290A/E later
95 DEG C, sealing of hole time 30min, pure water cleans 3 times, takes out drying.
Embodiment 5
A method of sealing of hole is carried out to anodic oxidation workpiece with ultralow nickel content hole sealing agent, is included the following steps:
(1) aluminium and aluminum alloy surface are through oil removing, washing, alkaline etching, washing, chemical polishing, washing, ash disposal, in sulfuric acid concentration
In 190g/L, under voltage 13.4V, after energization 30min anodic oxidation, measuring film thickness is 8 μm, and is cleaned up.
(2) by nickel salt film forming agent: four hydration nickel acetate 2.0g, coalescing agent: fluorine zirconic acid 1.5g, wetting agent: oxo-alcohols are poly-
Ethylene oxide ether 0.06g and alkaline-resisting elevator: 0.8g ammonium sulfate, compounding after mixing evenly ultralow nickel content hole sealing agent, then use
The hole sealing agent is made into the fluting liquid of 0.5g/L by pure water of the conductivity less than 30 μ S/cm, and wherein the content of nickel is about 0.8g/L.
(3) 15min will be handled in above-mentioned fluting liquid by the Al alloy parts of step (1) processing, sealing of hole temperature 60 C,
And pure water cleans 3 times, drying carries out sealing pores, sealing of hole temperature 98 using silicate sealing of hole Phoenix Seal 183 later
DEG C, sealing of hole time 23min, pure water cleans 3 times, takes out drying.
Embodiment 6
A method of sealing of hole is carried out to anodic oxidation workpiece with ultralow nickel content hole sealing agent, is included the following steps:
(1) aluminium and aluminum alloy surface are through oil removing, washing, alkaline etching, washing, chemical polishing, washing, ash disposal, in sulfuric acid concentration
In 190g/L, under voltage 13.4V, after energization 30min anodic oxidation, measuring film thickness is 8 μm, and is cleaned up.
(2) by nickel salt film forming agent: four hydration nickel acetate 1.5g, coalescing agent: fluorine zirconic acid 1.5g, wetting agent: oxo-alcohols are poly-
Ethylene oxide ether 0.01g and alkaline-resisting elevator: 1.0g ammonium acetate, balance of water after mixing evenly ultralow nickel content hole sealing agent,
Then the hole sealing agent is made into the fluting liquid of 0.5g/L by the pure water with conductivity less than 30 μ S/cm, and wherein the content of nickel is about
0.6g/L。
(3) 12min will be handled in above-mentioned fluting liquid by the Al alloy parts of step (1) processing, 95 DEG C of sealing of hole temperature,
And pure water cleans 3 times, drying carries out sealing pores, sealing of hole temperature using silicate sealing of hole Phoenix Seal 290A/E later
100 DEG C, sealing of hole time 15min, pure water cleans 3 times, takes out drying.
Embodiment 7
A method of sealing of hole is carried out to anodic oxidation workpiece with ultralow nickel content hole sealing agent, is included the following steps:
(1) aluminium and aluminum alloy surface are through oil removing, washing, alkaline etching, washing, chemical polishing, washing, ash disposal, in sulfuric acid concentration
In 190g/L, under voltage 13.4V, after energization 30min anodic oxidation, measuring film thickness is 8 μm, and is cleaned up.
(2) by nickel salt film forming agent: four hydration nickel fluoride 0.5g, coalescing agent: fluorine zirconic acid 0.7g, wetting agent: oxo-alcohols are poly-
Ethylene oxide ether 0.03g and alkaline-resisting elevator: 0.5g ammonium acetate, compounding after mixing evenly ultralow nickel content hole sealing agent, then use
The hole sealing agent is made into the fluting liquid of 1g/L by pure water of the conductivity less than 30 μ S/cm, and wherein the content of nickel is about 0.14g/L.
(3) it will be placed in commercially available 180 solution of Phoenix Seal at cold seal by the Al alloy parts of step (1) processing
Reason, operation temperature are 26 DEG C, operation concentration 4.5g/L, and the sealing of hole time is 20min, and after the completion of sealing of hole, pure water is cleaned 3 times, it
10min is handled in above-mentioned fluting liquid afterwards, 75 DEG C of sealing of hole temperature, and pure water cleaning 3 times, is dried up.
Embodiment 8
A method of sealing of hole is carried out to anodic oxidation workpiece with ultralow nickel content hole sealing agent, is included the following steps:
(1) aluminium and aluminum alloy surface are through oil removing, washing, alkaline etching, washing, chemical polishing, washing, ash disposal, in sulfuric acid concentration
In 190g/L, under voltage 13.4V, after energization 30min anodic oxidation, measuring film thickness is 8 μm, and is cleaned up.
(2) by nickel salt film forming agent: four hydration nickel acetate 2.0g, coalescing agent: fluorine zirconic acid 1.5g, wetting agent: oxo-alcohols are poly-
Ethylene oxide ether 0.06g and alkaline-resisting elevator: 0.8g ammonium sulfate, compounding after mixing evenly ultralow nickel content hole sealing agent, then use
The hole sealing agent is made into the fluting liquid of 0.5g/L by pure water of the conductivity less than 30 μ S/cm, and wherein the content of nickel is about 0.8g/L.
(3) it will be placed in commercially available 183 solution of Phoenix Seal at cold seal by the Al alloy parts of step (1) processing
Reason, operation temperature are 30 DEG C, operation concentration 6g/L, and the sealing of hole time is 20min, and after the completion of sealing of hole, pure water cleans 3 times, later
It handles 15min, sealing of hole temperature 60 C, and pure water in above-mentioned fluting liquid to clean 3 times, drying.
Embodiment 9
A method of sealing of hole is carried out to anodic oxidation workpiece with ultralow nickel content hole sealing agent, is included the following steps:
(1) aluminium and aluminum alloy surface are through oil removing, washing, alkaline etching, washing, chemical polishing, washing, ash disposal, in sulfuric acid concentration
In 190g/L, under voltage 13.4V, after energization 30min anodic oxidation, measuring film thickness is 8 μm, and is cleaned up.
(2) by nickel salt film forming agent: four hydration nickel acetate 1.5g, coalescing agent: fluorine zirconic acid 1.5g, wetting agent: oxo-alcohols are poly-
Ethylene oxide ether 0.01g and alkaline-resisting elevator: 0.8g ammonium acetate, balance of water after mixing evenly ultralow nickel content hole sealing agent,
Then the hole sealing agent is made into the fluting liquid of 0.5g/L by the pure water with conductivity less than 30 μ S/cm, and wherein the content of nickel is about
0.6g/L。
(3) it will be placed in commercially available 180 solution of Phoenix Seal at cold seal by the Al alloy parts of step (1) processing
Reason, operation temperature are 26 DEG C, operation concentration 3g/L, and the sealing of hole time is 20min, and after the completion of sealing of hole, pure water cleans 3 times, later
12min is handled in above-mentioned fluting liquid, 95 DEG C of sealing of hole temperature, and pure water cleaning 3 times, is dried up.
Embodiment 10
A method of sealing of hole is carried out to anodic oxidation workpiece with ultralow nickel content hole sealing agent, is included the following steps:
(1) aluminium and aluminum alloy surface are through oil removing, washing, alkaline etching, washing, chemical polishing, washing, ash disposal, in sulfuric acid concentration
In 190g/L, under voltage 13.4V, after energization 30min anodic oxidation, measuring film thickness is 8 μm, and is cleaned up.
(2) by nickel salt film forming agent: four hydration nickel fluoride 0.5g, coalescing agent: fluorine zirconic acid 0.7g, wetting agent: oxo-alcohols are poly-
Ethylene oxide ether 0.03g and alkaline-resisting elevator: 0.5g ammonium acetate, compounding after mixing evenly ultralow nickel content hole sealing agent, then use
The hole sealing agent is made into the fluting liquid of 50g/L by pure water of the conductivity less than 30 μ S/cm, and wherein the content of nickel is about 0.2g/L.
(3) it will be placed in commercially available 180 solution of Phoenix Seal at cold seal by the Al alloy parts of step (1) processing
Reason, operation temperature are 26 DEG C, operation concentration 4.5g/L, and the sealing of hole time is 20min, and after the completion of sealing of hole, pure water is cleaned 3 times, it
10min is handled in above-mentioned fluting liquid afterwards, 75 DEG C of sealing of hole temperature, and pure water cleaning 3 times, finally uses silicate sealing of hole
Phoenix Seal 290A/E carries out sealing pores, and 95 DEG C of sealing of hole temperature, sealing of hole time 30min, pure water cleans 3 times, and taking-up is blown
It is dry.
Embodiment 11
A method of sealing of hole is carried out to anodic oxidation workpiece with ultralow nickel content hole sealing agent, is included the following steps:
(1) aluminium and aluminum alloy surface are through oil removing, washing, alkaline etching, washing, chemical polishing, washing, ash disposal, in sulfuric acid concentration
In 190g/L, under voltage 13.4V, after energization 30min anodic oxidation, measuring film thickness is 8 μm, and is cleaned up.
(2) by nickel salt film forming agent: four hydration nickel acetate 2g, coalescing agent: fluorine zirconic acid 1.5g, wetting agent: oxo-alcohols polyoxy
Vinethene 0.06g and alkaline-resisting elevator: 0.8g ammonium sulfate, compounding after mixing evenly ultralow nickel content hole sealing agent, then electricity consumption
The hole sealing agent is made into the fluting liquid of 50g/L by pure water of the conductance less than 30 μ S/cm, and wherein the content of nickel is about 0.8g/L.
(3) it will be placed in commercially available 183 solution of Phoenix Seal at cold seal by the Al alloy parts of step (1) processing
Reason, operation temperature are 30 DEG C, operation concentration 6g/L, and the sealing of hole time is 20min, and after the completion of sealing of hole, pure water cleans 3 times, later
15min, sealing of hole temperature 60 C, and pure water are handled in above-mentioned fluting liquid to clean 3 times, finally use silicate sealing of hole Phoenix
Seal 290A/E carries out sealing pores, and 98 DEG C of sealing of hole temperature, sealing of hole time 23min, pure water cleans 3 times, takes out drying.
Embodiment 12
A method of sealing of hole is carried out to anodic oxidation workpiece with ultralow nickel content hole sealing agent, is included the following steps:
(1) aluminium and aluminum alloy surface are through oil removing, washing, alkaline etching, washing, chemical polishing, washing, ash disposal, in sulfuric acid concentration
In 190g/L, under voltage 13.4V, after energization 30min anodic oxidation, measuring film thickness is 8 μm, and is cleaned up.
(2) by nickel salt film forming agent: four hydration nickel acetate 1.5g, coalescing agent: fluorine zirconic acid 1.5g, wetting agent: oxo-alcohols are poly-
Ethylene oxide ether 0.01g and alkaline-resisting elevator: 1.0g ammonium acetate, compounding after mixing evenly ultralow nickel content hole sealing agent, then use
The hole sealing agent is made into the fluting liquid of 50g/L by pure water of the conductivity less than 30 μ S/cm, and wherein the content of nickel is about 0.6g/L.
(3) it will be placed in commercially available 180 solution of Phoenix Seal at cold seal by the Al alloy parts of step (1) processing
Reason, operation temperature are 26 DEG C, operation concentration 3g/L, and the sealing of hole time is 20min, and after the completion of sealing of hole, pure water cleans 3 times, later
12min is handled in above-mentioned fluting liquid, 95 DEG C of sealing of hole temperature, and pure water cleaning 3 times, finally uses silicate sealing of hole Phoenix
Seal 290A/E carries out sealing pores, and 100 DEG C of sealing of hole temperature, sealing of hole time 15min, pure water cleans 3 times, takes out drying.
Comparative example 1
Sealing pores are carried out to anodic oxidation workpiece using commercially available nickel fluoride cold seal agent, are included the following steps:
(1) aluminium and aluminum alloy surface are through oil removing, washing, alkaline etching, washing, chemical polishing, washing, ash disposal, in sulfuric acid concentration
In 190g/L, under voltage 13.4V, after energization 30min anodic oxidation, measuring film thickness is 8 μm, and is cleaned up.
(2) it will be placed in commercially available 180 solution of Phoenix Seal and carried out at sealing of hole by the aluminium alloy of step (1) processing
Reason, operation temperature are 26 DEG C, operation concentration 4.5g/L, and the sealing of hole time is 20min, and after the completion of sealing of hole, pure water is cleaned 3 times, are taken
It dries up out.
Comparative example 2
Cold seal is carried out to anodic oxidation workpiece using commercially available nickel fluoride cold seal agent, reuses commercially available silicate hole sealing agent later
High temperature hole sealing is carried out, is specifically comprised the following steps:
(1) aluminium and aluminum alloy surface are through oil removing, washing, alkaline etching, washing, chemical polishing, washing, ash disposal, in sulfuric acid concentration
In 190g/L, under voltage 13.4V, after energization 30min anodic oxidation, measuring film thickness is 8 μm, and is cleaned up.
(2) it will be placed in commercially available 180 solution of Phoenix Seal and carried out at sealing of hole by the aluminium alloy of step (1) processing
Reason, operation temperature are 26 DEG C, operation concentration 4.5g/L, and the sealing of hole time is 20min, and after the completion of sealing of hole, pure water is cleaned 3 times, it
Sealing pores are carried out using silicate sealing of hole Phoenix Seal 290A/E afterwards, it is 95 DEG C of sealing of hole temperature, sealing of hole time 30min, pure
Water cleans 3 times, takes out drying.
The correlated performance of anodic oxidation workpiece film layer after 1 to 2 sealing pores of embodiment 1 to 12 and comparative example is carried out
Test, specific test content are as follows:
One, pH1: acid resistance test
The acid solution (HCl:0.1mol/L) for preparing pH=1, workpiece is soaked in the acid solution after 10min and is taken
Out, dried up after flowing water is rinsed well, observation workpiece surface appearance whether there is or not significant changes, if without significant change, workpiece it is acidproof
PH=1.0 test passes through, and does not otherwise pass through.
Two, pH12.5:
The alkaline solution (NaOH:1.27g/L, sodium phosphate: 2g/L, NaCl:0.33g/L) for preparing pH=12.5, by workpiece
It is soaked in the alkaline solution and is taken out after 10min, flowing water dries up after rinsing well, and observation workpiece surface appearance becomes whether there is or not obvious
Change, if the alkaline-resisting pH=12.5 test of workpiece passes through without significant change, does not otherwise pass through.
Three, pH13.5: alkali resistance test
The alkaline solution (NaOH:12.7g/L, sodium phosphate: 2g/L, NaCl:0.33g/L) for preparing pH=13.5, by workpiece
It is soaked in the alkaline solution and is taken out after 10min, flowing water dries up after rinsing well, and observation workpiece surface appearance becomes whether there is or not obvious
Change, if the alkaline-resisting pH=13.5 test of workpiece passes through without significant change, does not otherwise pass through.
Four, pH1+13.5: continuous acid-proof alkaline test
Workpiece is first impregnated into 10min in the acid solution of pH=1 (HCl:0.1mol/L), after rinsing well, is placed into
10min is impregnated in the solution of pH=13.5 (NaOH:12.7g/L, sodium phosphate: 2g/L, NaCl:0.33g/L), is seen after rinsing well
Examine surface have it is unchanged.
Five, specking
Six, CASS: copper accelerated acetic acid salt spray test
This method executes national standard: GB/T 12967.3-2008: " aluminium and aluminium alloy anode oxide film detection method the 3rd
Part: copper accelerated acetic acid salt spray tests (CASS test) ".
Specifically, carried out in dedicated CASS salt fog cabinet, under conditions of (50 scholar 2) DEG C, by compressed air by pH=
3.05 ± 0.05 acid solution atomization, it is continuous spraying.Acid mist is deposited in specimen surface, and sample is made to generate certain variation.Acid
Property solution manufacturing method: prepare the sodium chloride solution of 50 ± 5g/L, the copper chloride of (0.26 ± 0.02) g/L be added, then thereto
Suitable glacial acetic acid adjustment pH to 3.05 ± 0.05 or so is added.
Seven, NSS: neutral salt spray test
This detection method executes: GB/T 10125-2012: " artificial atmosphere corrosion test (salt spray test) ".
Specifically, carried out in dedicated salt fog cabinet, under conditions of (35 scholar 2) DEG C, by compressed air by neutral chlorine
Change sodium solution (its concentration is 50g/L scholar 5g/L) atomization, is then deposited in specimen surface.
Eight, Huimidity: anti-moisture test
It is carried out in dedicated resistance to wet tank, sample is placed on to temperature is 40 ± 2 DEG C, relative humidity is 98% ± 2%
In condensed water experimental box.Arrangement angle of the test specimen in chamber should be greater than or be equal to 60 DEG C, and in this case
In order to sufficient heat release, they cannot mutually be abutted.
It is as shown in the table (wherein to the result of the film performance test of the workpiece after each embodiment and comparative example sealing pores
OK is represented to be tested by this, and NG is not tested by this, and number represents the maximum hourage that test can pass through):
By upper table data it is found that when conventional cold seal or conventional cold seal and silicate high temperature hole sealing are used in combination, anodic oxidation
The film layer of workpiece only has preferable acid-fast ability and basic CASS, NSS and Huimidity ability, alkaline-resisting, resistance to continuous soda acid
And the performances such as specking are poor.Ultralow nickel content hole sealing agent provided by the invention individually can carry out sealing of hole, envelope to anodic oxidation workpiece
Workpiece behind hole has certain alkaline-resisting (pH12.5) and surface hydrophobic, the alkaline-resisting nickel acetate or fluorine for being better than traditional high nickel content
Change the systems such as nickel, and surface soapy feeling is more preferable.Its specking, the more conventional cold seal of CASS, NSS and Huimidity ability or high temperature envelope
The workpiece of hole processing is more outstanding, i.e., when ultralow nickel content hole sealing agent provided by the invention is used alone, is highly suitable for need
The workpiece to use under certain alkaline condition is handled.The high temperature of ultralow nickel content hole sealing agent provided by the invention is sealed
Hole when being used cooperatively with conventional cold seal or silicate high temperature hole sealing, can preferably be promoted by the properties of sealing of hole workpiece,
Especially CASS performance can accomplish 72h or more.Traditional cold seal cooperation heat-sealing CASS can only generally accomplish 24-36h or so
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (11)
1. a kind of ultralow nickel content hole sealing agent, which is characterized in that each raw material including following parts by weight: nickel salt film forming agent 0.5-
2.0 parts, 0.2-1.5 parts of coalescing agent, 0.01-0.06 parts of wetting agent, alkaline-resisting elevator 0.5-1.0 parts.
2. a kind of ultralow nickel content hole sealing agent according to claim 1, which is characterized in that the nickel salt film forming agent is four water
Close one of nickel fluoride, four hydration nickel acetates, nickel sulfamic acid, nickelous carbonate or a variety of.
3. a kind of ultralow nickel content hole sealing agent according to claim 1, which is characterized in that the coalescing agent is fluorine zirconium
Acid, potassium fluorozirconate, ammonium fluozirconate, sodium bifluoride, potassium fluosilicate, prodan, fluosilicic acid, potassium fluoborate, sodium fluoborate, fluorine boron
One of acid, ammonium titanium fluoride, potassium fluotitanate, fluotitanic acid, potassium floutaramite and fluorotantalic acid ammonium are a variety of.
4. a kind of ultralow nickel content hole sealing agent according to claim 1, which is characterized in that the wetting agent is poly alkyl alcohol
Ethylene oxide ether, oxo-alcohols polyoxyethylene ether, alkyl phenol polyoxyethylene ether, coco amine, alkylphenol sulfate, alkyl sulfate, alkane
One of base benzene sulfonate and polyvinyl alcohol are a variety of.
5. a kind of ultralow nickel content hole sealing agent according to claims 1, which is characterized in that the alkaline-resisting elevator is
One of ammonium acetate, potassium acetate, lithium nitrate, potassium nitrate, sodium nitrate, ammonium nitrate and ammonium sulfate are a variety of.
6. a kind of carry out sealing of hole to anodic oxidation workpiece with ultralow nickel content hole sealing agent described in any one of claim 1 to 5
Method, which comprises the steps of:
S1. aluminum or aluminum alloy workpiece obtains anodic oxidation workpiece through pre-treatment and anodic oxidation；
S2. the ultralow nickel content hole sealing agent and water mixed preparing are slotted liquid, nickel content is 0.2-0.8g/ in the fluting liquid
L, fluorine content 0.05-0.09g/L；
S3. sealing pores are carried out using anodic oxidation workpiece of the fluting liquid of S2 to S1, the sealing pores can be from following four
It chooses any one kind of them in selection: the fluting liquid high temperature sealing of hole is used only；The fluting liquid high temperature sealing of hole is first used, silicon is reused
Hydrochlorate hole sealing agent high temperature hole sealing；Nickel fluoride cold seal agent cold seal is first used, the fluting liquid high temperature sealing of hole is reused；First use fluorine
Change nickel cold seal agent cold seal, reuse the fluting liquid high temperature sealing of hole, finally uses silicate hole sealing agent high temperature hole sealing.
7. a kind of method that sealing of hole is carried out to anodic oxidation workpiece with ultralow nickel content hole sealing agent according to claim 6,
It is characterized in that, the sealing of hole temperature of the fluting liquid high temperature sealing of hole is 60-95 DEG C, the sealing of hole time is 10-15min.
8. a kind of method that sealing of hole is carried out to anodic oxidation workpiece with ultralow nickel content hole sealing agent according to claim 6,
It is characterized in that, the sealing of hole temperature of the silicate hole sealing agent high temperature hole sealing is 95-100 DEG C, the sealing of hole time is 15-30min.
9. a kind of method that sealing of hole is carried out to anodic oxidation workpiece with ultralow nickel content hole sealing agent according to claim 8,
It is characterized in that, the silicate hole sealing agent is Phoenix Seal 290A/E.
10. a kind of method that sealing of hole is carried out to anodic oxidation workpiece with ultralow nickel content hole sealing agent according to claim 6,
It is characterized in that, the sealing of hole temperature of the nickel fluoride cold seal agent cold seal is 26-30 DEG C, the sealing of hole time is 15-30min.
11. a kind of side for carrying out sealing of hole to anodic oxidation workpiece with ultralow nickel content hole sealing agent according to claim 10
Method, which is characterized in that the nickel fluoride cold seal agent is Phoenix Seal 180 or Phoenix Seal 183.
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| CN110777415A (en) * | 2019-10-29 | 2020-02-11 | 武汉风帆电化科技股份有限公司 | Preparation method of high-temperature-resistant corrosion-resistant anodic oxide film |
| CN110831323A (en) * | 2019-11-12 | 2020-02-21 | 惠州市欣可达科技有限公司 | High heat conduction metal substrate |
| CN111172578A (en) * | 2020-01-17 | 2020-05-19 | 深圳市裕展精密科技有限公司 | Metal product and preparation method thereof |
| CN111188071A (en) * | 2020-02-25 | 2020-05-22 | 上海宇铱新材料有限公司 | High-performance hole sealing process for aluminum alloy anodic oxidation |
| CN111378999A (en) * | 2020-05-12 | 2020-07-07 | 武汉风帆电化科技股份有限公司 | Method for realizing anodic oxide film and phosphorus-nickel alloy composite coating on surface of aluminum alloy |
| CN115029754A (en) * | 2022-06-16 | 2022-09-09 | 江门市优博科技有限公司 | Silvery white normal-temperature high-corrosion-resistance sealing agent for aluminum and aluminum alloy anodic oxide film, and preparation method and application process thereof |
| WO2023188499A1 (en) * | 2022-03-28 | 2023-10-05 | アイシン軽金属株式会社 | Outer casing member and method for producing same |
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| CN110831323A (en) * | 2019-11-12 | 2020-02-21 | 惠州市欣可达科技有限公司 | High heat conduction metal substrate |
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| CN111188071B (en) * | 2020-02-25 | 2021-08-06 | 上海宇铱新材料有限公司 | High-performance hole sealing process for aluminum alloy anodic oxidation |
| CN111378999A (en) * | 2020-05-12 | 2020-07-07 | 武汉风帆电化科技股份有限公司 | Method for realizing anodic oxide film and phosphorus-nickel alloy composite coating on surface of aluminum alloy |
| CN111378999B (en) * | 2020-05-12 | 2021-06-08 | 武汉风帆电化科技股份有限公司 | Method for realizing anodic oxide film and phosphorus-nickel alloy composite coating on surface of aluminum alloy |
| WO2023188499A1 (en) * | 2022-03-28 | 2023-10-05 | アイシン軽金属株式会社 | Outer casing member and method for producing same |
| CN115029754A (en) * | 2022-06-16 | 2022-09-09 | 江门市优博科技有限公司 | Silvery white normal-temperature high-corrosion-resistance sealing agent for aluminum and aluminum alloy anodic oxide film, and preparation method and application process thereof |
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Application publication date: 20190419 |