CN103590086B - Aluminium alloy is without nickel hole sealing agent and hole-sealing treatment process thereof - Google Patents
Aluminium alloy is without nickel hole sealing agent and hole-sealing treatment process thereof Download PDFInfo
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- CN103590086B CN103590086B CN201310567738.1A CN201310567738A CN103590086B CN 103590086 B CN103590086 B CN 103590086B CN 201310567738 A CN201310567738 A CN 201310567738A CN 103590086 B CN103590086 B CN 103590086B
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Abstract
The invention discloses a kind of aluminium alloy without nickel hole sealing agent, including the aqueous solution of fluotitanic acid, corrosion inhibiter and chelating agen, on the basis of the volume of hole sealing agent, the concentration of described fluotitanic acid is 6.0 9.0g/L, and the concentration of described corrosion inhibiter is 1.0 3.0g/L, and the concentration of described chelating agen is 1.0 3.0g/L；The hole sealing agent of the present invention uses fluotitanic acid as the main component of hole sealing agent, completely eliminates nickel salt from source to aluminium alloy and the pollution of water quality.The present invention also provides for a kind of using this aluminium alloy without the hole-sealing treatment process of nickel hole sealing agent, simple to operate, energy-conserving and environment-protective, waste water processes easily, it is prone to large-scale production, build aluminium alloy finished surface processing procedure, aluminium alloy use and the nickel contamination of waste treatment process by thoroughly terminating, solve the bottleneck problem restricting industry development for many years.
Description
Technical field
The invention belongs to the chemically treated technical field of metal material surface, particularly to a kind of hole sealing agent without nickel and hole-sealing treatment process thereof that Process on Aluminum Alloy Oxidation Film layer is carried out sealing pores.
Background technology
At present, China's building aluminium alloy anode oxide sealing of hole mainly uses cold hole-sealing technology and middle temperature hole-sealing technology, and nickel salt is the main component of hole sealing agent.
The aluminium alloy sealing technological process of prior art as shown in Figure 1, first carries out aluminium alloy pretreatment, then carries out anodic oxidation and electrolytic coloring, carry out sealing pores the most again.After sealing of hole, needs rinsing bowl more than washing 1 and washing 2 twice carries out washing process, and during cleaning anodic oxidation sealing of hole, the nickeliferous sealing of hole medicinal liquid of aluminum alloy surface residual, can descend wire wrapping.This sealing pores mode, can produce following both sides metallic nickel compounds and pollute: one is the nickel contamination in rinse water, and two is the nickel contamination of the aluminum alloy surface that sealing pores is crossed.At present, various Al-alloy products, the daily life of ordinary populace is day by day goed deep into including various electronic products, and international cancer research general administration (IARC), as far back as nineteen ninety, nickel compound is classified as the most sufficient first group of carcinogen of cancer evidence with people and animal, therefore, the potential injury that environment and human body are caused by nickeliferous hole sealing technology must cause the great attention of aluminum processing industry.
Summary of the invention
The problem that the invention aims to solve to there is serious nickel contamination in existing aluminium alloy sealing processing procedure, it is provided that a kind of aluminium alloy, without nickel hole sealing agent and hole-sealing treatment process thereof, promotes aluminum alloy surface treatment technology to environmental protection, efficient, energy saving direction development.
The technical scheme is that and be achieved in that:
The present invention provide a kind of aluminium alloy without nickel hole sealing agent, including the aqueous solution of fluotitanic acid, corrosion inhibiter and chelating agen, on the basis of the volume of hole sealing agent, the concentration of described fluotitanic acid is 6.0-9.0g/L, and the concentration of described corrosion inhibiter is 1.0-3.0g/L, and the concentration of described chelating agen is 1.0-3.0g/L.
Preferably, described corrosion inhibiter be ethylene glycol, glycerol and sorbitol one or more.
Preferably, one or more during described chelating agen is triethanolamine, ethylenediaminetetraacetic acid, sodium tripolyphosphate, sodium pyrophosphate, Polymeric sodium metaphosphate., ATMP and phosphonobutane tricarboxylic acid.
Preferably, described hole sealing agent operating temperature is 20-30 DEG C, and the pH value of described hole sealing agent is 3.0-4.0.
Present invention also offers a kind of aluminium alloy without nickel hole-sealing treatment process, by aluminum alloy base material by processing without nickel process unit, comprise the steps:
(1) will be heated to 15-35 DEG C without nickel hole sealing agent, and be immersed in hole sealing agent without nickel by the aluminum alloy base material after anodic oxidation, sealing of hole speed is 1-3 μm/min；
(2) hole sealing agent of the aluminum alloy base material remained on surface through soaking without nickel hole sealing agent of step (1) gained is washed, dry up after flushing, pack.
Preferably, described process unit without nickel includes production system, heating system, gas agitating system, filtration system and Waste Water Treatment；
Described production system includes 1# sealing of hole groove, 2# rinsing bowl and 3# rinsing bowl, and described 1# sealing of hole groove is main work nest, has been used for the sealing of hole of Process on Aluminum Alloy Oxidation Film, described 2# rinsing bowl and the 3# rinsing bowl hole sealing agent of aluminum alloy surface residual after cleaning sealing of hole；
Described heating system includes steam-heating pipe and the 8# valve being arranged on described steam-heating pipe, and described steam-heating pipe is respectively arranged at the both sides of described 1# sealing of hole groove, for the heating of described 1# sealing of hole groove；
Described Waste Water Treatment is made up of 2# rinsing bowl, 3# rinsing bowl, 4# stillpot, acid-proof pump, filter, 3# valve, 4# valve, 5# valve and pipeline, described Waste Water Treatment is for purifying the cleanout fluid in described 2# rinsing bowl and 3# rinsing bowl, it is achieved cycling utilization of wastewater；
Described gas agitating system includes air compressor machine, feed channel and the 6# valve being arranged in described feed channel and 7# valve, and described gas agitating system is the uniform stirring of solution in described 1# sealing of hole groove and 4# stillpot；
Described filtration system is connected by 1# sealing of hole groove, 2# rinsing bowl, 3# rinsing bowl, 4# stillpot, acid-proof pump, filter, 1# valve, 2# valve, 3# valve, 4# valve, 5# valve and pipeline and forms, and described filtration system is the filtration of water lotion in described 1# sealing of hole groove, described 2# rinsing bowl and 3# rinsing bowl.
Preferably, open 8# valve, heat described 1# sealing of hole groove, open 3# valve, 4# valve, 5# valve, start acid-proof pump, in the water lotion in 4# stillpot to 2# rinsing bowl and 3# rinsing bowl, return again to 4# stillpot；
After oxidized aluminum alloy, in 1# sealing of hole groove, sealing of hole speed is 1-3 μm/min, after sealing of hole completes, through 2# rinsing bowl and 3# rinsing bowl, cleaning aluminum alloy remained on surface hole sealing agent, then air-dries, packs.
Preferably, during the heating of described 1# sealing of hole groove, described 8# valve automatically controls hole sealing agent temperature between 20-30 DEG C.
Preferably, after adding without nickel hole sealing agent in described 1# sealing of hole groove, open 7# valve, described gas agitating system the hole sealing agent in being stirred by 1# sealing of hole groove is mixed uniformly, continues to produce；Close 3# valve, 4# valve, 5# valve, open gas agitating 6# valve, quick lime is added 4# stillpot, stirring while adding, to pH value be 8.0 time, stop adding quick lime and stirring.
Preferably, the water lotion filter regeneration of the hole sealing agent filter regeneration in 1# sealing of hole groove, 2# rinsing bowl and 3# rinsing bowl is also included；
Hole sealing agent filter regeneration in described 1# sealing of hole groove, closes 3# valve and 4# valve, cleans acid-proof pump, filter and pipeline；Open 1# valve, 2# valve；Start acid-proof pump, circulating filtration hole sealing agent groove, to so clear that you can see the bottom, complete hole sealing agent regeneration；
Described 2# rinsing bowl and the water lotion filter regeneration of 3# rinsing bowl, close 1# valve and 2# valve, opens 3# valve, 4# valve and 5# valve；Start acid-proof pump, after being filtered by the water lotion of 4# stillpot, be evacuated to 3# rinsing bowl, then through 2# rinsing bowl, certainly flow back into 4# stillpot, complete the circulating filtration of rinsing bowl；When the pH value of water lotion is less than 5.0, stop acid-proof pump, close 3# valve, 4# valve and 5# valve, open gas agitating 6# valve, quick lime is added 4# stillpot, stirring while adding, pH value is surveyed on limit, during to pH value close to 8.0, stop adding quick lime and stirring, stand 1 hour, restart Waste Water Treatment, complete to clean the recycling of waste water.
Compared to prior art, the beneficial effects of the present invention is:
1, the present invention completely eliminates nickel salt to aluminium alloy and the pollution of water quality from source, solves pore-sealing liquid and decomposes sedimentation problem, reduces molten aluminum amount, reduce powder on substrate surface, at the sealing of hole film water white transparency that substrate surface is formed, reduce aluminium true qualities, and extend the life-span of tank liquor；Using fluotitanic acid as the main component of hole sealing agent, sealing of hole speed is more than the twice of nickel salt, improves production efficiency；Using fluotitanic acid as the main component of hole sealing agent, sealing of hole temperature can as little as 15 DEG C, saves the energy.
2, the aluminium alloy of the present invention is simple to operate without nickel hole-sealing treatment process, energy-conserving and environment-protective, waste water processes easily, it is prone to large-scale production, build aluminium alloy finished surface processing procedure, aluminium alloy use and the nickel contamination of waste treatment process by thoroughly terminating, solve the bottleneck problem restricting industry development for many years.
Accompanying drawing explanation
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, the accompanying drawing used required in embodiment or description of the prior art will be briefly described below, apparently, accompanying drawing in describing below is only some embodiments of the present invention, for those of ordinary skill in the art, on the premise of not paying creative work, it is also possible to obtain other accompanying drawing according to these accompanying drawings.
Fig. 1 is the aluminium alloy sealing processing technological flow figure of prior art；
Fig. 2 is the aluminium alloy system structure schematic diagram without the hole-sealing treatment process of nickel hole sealing agent of the present invention.
Detailed description of the invention
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is only a part of embodiment of the present invention rather than whole embodiments.Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art are obtained under not making creative work premise, broadly fall into the scope of protection of the invention.
The aluminium alloy that the present invention provides is without nickel hole sealing agent, and including the aqueous solution of fluotitanic acid, corrosion inhibiter and chelating agen, on the basis of the volume of hole sealing agent, the concentration of fluotitanic acid is 6.0-9.0g/L, and the concentration of corrosion inhibiter is 1.0-3.0g/L, and the concentration of chelating agen is 1.0-3.0g/L.Corrosion inhibiter be ethylene glycol, glycerol and sorbitol one or more；Chelating agen is one or more in triethanolamine, ethylenediaminetetraacetic acid, sodium tripolyphosphate, sodium pyrophosphate, Polymeric sodium metaphosphate., ATMP and phosphonobutane tricarboxylic acid；Hole sealing agent operating temperature is 20-30 DEG C, and hole sealing agent pH value is 3.0-4.0.
The present invention selects fluotitanic acid as main sealing of hole composition, and its ionization, hydrolysis are reacted with sealing of hole and is:
H2TiF6=2H++TiF6 2-(fluotitanic acid ionization) (1)
3TiF6 2-+6H2O=Ti(OH)3F3 2-+Ti(OH)2F4 2-+Ti(OH)F5 2-+6H++6F- (2)
(fluotitanic acid hydrolysis)
By (2) formula, the aqueous solution of fluotitanic acid is unstable, and facile hydrolysis becomes monohydroxy, dihydroxy and trihydroxy fluotitanic acid root, discharges H simultaneously+And F-, make tank liquor pH value decline, F-Concentration increases；If raising pH value, by (2) formula, reaction is moved to the right, and when pH value is more than 4.5, trihydroxy fluotitanic acid hydrolyzes further, turbidity and precipitation occurs:
Ti(OH)3F3 2-+H2O=Ti(OH)4↓+H++3F-(fluotitanic acid decomposes, separates out titanium hydroxide) (3)
When tank liquor is put into the aluminium alloy containing oxide-film, F-React with oxide-film:
Al2O3+12F-+3H2O=2AlF6 3-+6OH-(oxide-film is dissolved, and pH value raises) (4)
2AlF6 3-+Al2O3+3H2O=2Al2(OH)3F3↓+6F-(powder on aluminium) (5)
Formula (1)-(5) the display dynamic (dynamical) overall process of sealing of hole.Formula (1) shows that fluotitanic acid is ionized into 2H in tank liquor++TiF6 2-；Formula (2) shows that fluotitanic acid root is hydrolyzed into Ti (OH) in tank liquor3F3 2-+Ti(OH)2F4 2-+Ti(OH)F5 2-, and discharge 6H++6F-；Formula (4) shows F-React at oxide-film micropore, discharge OH-, improve the pH value in micropore；Formula (3) surface in oxide-film micropore, the rising of pH value, Ti (OH)3F3 2-Hydrolysis further, generates sealing of hole goods and materials Ti (OH)4, complete sealing of hole.
(1), the sealing of hole time impact on sealing quality
The sealing of hole time directly determines sealing quality.Time is the shortest, and sealing of hole is incomplete, and the time is oversize, easily caused sealing of hole, aluminum alloy surface to play ash serious, and affected the presentation quality of aluminium；Anodic oxidation film thickness is the biggest, and sealing of hole is more difficult to, and oxide-film weightlessness is the biggest, and sealing quality is the poorest, it is noted that the thickness of conservative control oxide-film during production.The sealing of hole time is the embodiment of hole sealing agent sealing of hole ability, is affected bigger by temperature, pH value, hole sealing agent composition and concentration, additive component and concentration.Under equal conditions, compared with Nickel difluoride, the sealing of hole ability of fluotitanic acid is at about three times.The i.e. sealing of hole time of fluotitanic acid is the 1/3 of Nickel difluoride.If the thickness of oxide-film is 15 μm, Nickel difluoride needs sealing of hole 15 minutes, and fluotitanic acid needs about 5 minutes.
(2), the sealing of hole temperature impact on sealing quality
Temperature affects chemical reaction velocity, is usually and often raises 10 DEG C of chemical reaction velocities raisings l times, and the sealing of hole time can shorten 1 half.Test according to the sealing of hole under different temperatures, available fluotitanic acid sealing quality and the Changing Pattern of temperature.When temperature is in 15-20 DEG C, sealing quality is preferable；When the temperature increases, ion diffusion velocity is accelerated, and hydrolysis rate is accelerated, Ti (OH) in oxide-film micropore3F3 2-+Ti(OH)2F4 2-+Ti(OH)F5 2-Concentration increase, F-Concentration improves, and reacts quickening with oxide-film, the Ti (OH) of generation4Many, sealing of hole speed improves；When temperature is the lowest, F-Concentration is low, reacts weak with oxide-film, the Ti (OH) of generation4Few, sealing of hole effect is the most poor.Experiment shows, when other Con trolling index are in working range, the sealing of hole temperature of fluotitanic acid with the relation of sealing of hole speed is: temperature when 15-20 DEG C, sealing of hole speed about 1 μm/min；Temperature when 20-25 DEG C, sealing of hole speed about 2 μm/min；Temperature when 25-30 DEG C, sealing of hole speed about 3 μm/min.Now, the sealing of hole time can be determined according to oxide-film character, thickness, sealing of hole temperature etc..
(3), the pH value impact on sealing quality
According to pH value, the impact of sealing quality is tested, the pH value affecting laws to sealing quality can be obtained.With the rising of tank liquor pH value, by (2) formula, fluotitanic acid hydrolysis increases, and sealing quality improves；But pH value is the highest, Surface of profile easily produces white lime, and this is primarily due to fluotitanic acid loss of stability, hydrolyzes in a large number；PH value is the lowest, is not enough to cause fluotitanic acid to hydrolyze, does not reaches sealing of hole effect.PH value is the chemical reaction by (2) (3) (4) formula to the action principle of sealing of hole, the hydrolysis of fluotitanic acid, fluorine and the reaction of oxide-film, the rising of pH value in micropore, the Ti (OH) generated in fenestra4Deposition reaches the purpose of sealing of hole, and hydrolysate deposition number directly affect the effect of sealing of hole.PH value deposition of fluotitanic acid hydrolysis between 2.5-4.5 is more, can reach the purpose of sealing of hole, and pH value sealing of hole effect when about 3.0-4.0 is best, and the best control of acidity at this moment, just the hydrolysising balance at fluotitanic acid is interval, and pH value is sufficiently stable.
(4) the fluotitanic acid concentration impact on sealing quality
The present invention selects fluotitanic acid as primary seal hole material, and fluotitanic acid root is one of topmost ion in liquor of hole-sealing tank.Sealing of hole enters oxidation fenestra carrying out hydrolyzing and precipitating by fluotitanic acid root and is achieved, and fluotitanic acid system is the reaction of hydrolysis-dissolution-deposition without the mechanism of nickel rapid hole sealing, and its sealing of hole material is mainly by Ti (OH)4And Al2(OH)3F3Composition, is the synthesis result by the reaction of (1)-(5) formula.Ti(OH)4Filling speed directly affects sealing of hole speed, and fluotitanic acid content is the biggest on sealing quality impact.Test result indicate that fluotitanic acid (50wt.%) concentration controls between 6.0-9.0g/L.
(5), the density of corrosion inhibitor impact on sealing quality
Low molecular polylol class selected by corrosion inhibiter of the present invention, such as ethylene glycol, glycerol and sorbitol etc., by the absorption of electronegative hydroxyl in positively charged aluminum alloy surface, isolates tank liquor, slows down corrosion.Under fluotitanic acid sealing of hole system, pH value operation interval 2.5-4.5, slant acidity, by (4) (5) formula, low ph value is conducive to Al2O3With F-Reaction, generates AlF6 3-, Al (OH) F5 3-, Al (OH)2F4 3-, when its content reaches certain value, interionic associates, hydrolyzes and concentrates, and is finally translated into stable phase complexation aluminium fluoride Al2(OH)3F3, in oxide-film micropore, Al2(OH)3F3It is sealing of hole goods and materials, at aluminum alloy surface, Al2(OH)3F3It is Refined Mercurous chloride, in tank liquor, Al2(OH)3F3It it is muddy thing.So, the molten aluminum amount of tank liquor is too big, and powder easily gone up by aluminium alloy, tank liquor easily muddy dead groove.The interpolation of corrosion inhibiter, precisely in order to protection oxide-film not go up powder, reduces molten aluminum amount, prolongation tank liquor service life.Empirically result, the concentration ranges of Organic Alcohol corrosion inhibiter is 1-3g/L.
(6), the chelating agent concentrations impact on sealing quality
Chelating agen of the present invention selects acetic acid system (such as triethanolamine; ethylenediaminetetraacetic acid etc.); phosphoric acid system (such as sodium tripolyphosphate, sodium pyrophosphate, Polymeric sodium metaphosphate., ATMP (ATMP) etc.); with phosphate carboxylic serials (such as phosphonobutane tricarboxylic acid (PBTCA) etc.); with its powerful chelating bond energy, stablize Ti4+And Al3+, it is ensured that tank liquor is the most muddy, and powder do not gone up by aluminium alloy.By (2) (5) formula, when pH raises, easily generate Ti (OH)4And Al2(OH)3F3.These goods and materials, if generating at oxide-film micropore, are sealing of hole goods and materials；If generating in aluminum alloy surface, it is powder；If generating in tank liquor, it is muddy thing.The addition of chelating agen, improves Ti (OH)4And Al2(OH)3F3Generation threshold.By (4) formula, in micropore, F-With Al2O3The OH that reaction produces-Being difficult to the tank liquor being diffused into outside aluminum alloy surface, in hole, pH rises higher, and chelate bonds is opened, Ti4+And Al3+It is released, generates Ti (OH)4And Al2(OH)3F3, it is achieved sealing of hole；And at aluminum alloy surface, OH-Rapidly diffusing in tank liquor, surface p H rises limited, it is impossible to open chelate bonds, it is impossible to generate Ti (OH)4And Al2(OH)3F3, aluminium alloy is difficult to powder, and tank liquor is difficult to muddiness.Additionally, the acidic group in chelating agen is electronegative, can be adsorbed on positively charged oxide-film, play corrosion inhibiter effect, reduce the meltage of aluminium alloy.The consumption of chelating agen to be paid special attention to, and concentration is the highest, and chelate bonds is bad to be opened, and sealing of hole ability drastically declines；Chelating agent concentrations is the lowest, though sealing of hole is good, but powder on aluminium alloy, tank liquor is muddy.Experiment shows, appropriate chelating agent concentrations is 1-3g/L.
(7), the foreign ion impact on sealing quality
The most constantly bring foreign ion into, cause the accumulation of impurity, such as NH4 +、Na+、K+、Ca2+、Mg2+Increasing etc. cation, chelating agen consumption is accelerated.Therefore, hold cleaning and close most important.During it addition, tank liquor pH is too low, available ammonia regulation pH value, to about 3.5, does not regulate with sodium hydroxide, so can effectively stop Na+Addition, consume chelating agen.Selecting fluotitanic acid rather than potassium fluotitanate is K as main sealing of hole composition, key reason+Consumption to chelating agen.
Affecting aluminium alloy a lot of without the factor of nickel sealing quality, mainly have fluotitanic acid concentration, density of corrosion inhibitor and chelating agent concentrations, these 3 factors are the keys determining aluminium alloy sealing quality；The pH value of tank liquor, temperature and sealing of hole time are the key factors affecting aluminium alloy sealing quality；And improve the cleanliness factor of tank liquor, the content that reduces impurity is the important guarantee of aluminium alloy sealing quality.Test shows, aluminium alloy should be without the manufacturing condition of nickel hole sealing agent:
Fluotitanic acid (50wt.%) concentration ranges is 6.0-9.0g/L
The concentration ranges of corrosion inhibiter is 1-3g/L
Chelating agent concentrations interval is 1-3g/L
Sealing of hole speed 1-3um/min
Temperature 15-35 DEG C
Time 5-15min
PH value 2.5-4.5
Fluting: use tap water preparation tank liquor, but it should be noted that reduce and bring other tank liquor in the course of processing, reduce the extra consumption to chelating agen.
Embodiment 1
Select fluotitanic acid (50wt.%) 7.5g/L as sealing of hole composition；Ethylene glycol 2.0g/L is as corrosion inhibiter, and sodium tripolyphosphate 2.0g/L is as chelating components, and using operating temperature is 25 DEG C, and pH value is 3.5, and sealing of hole speed 1 μm/minute.
Embodiment 2
Select fluotitanic acid (50wt.%) 7.5g/L as sealing of hole composition；Glycerol 2.0g/L is as corrosion inhibiter, and sodium tripolyphosphate 2.0g/L is as chelating components, and operating temperature is 25 DEG C, and pH value is 3.5, and sealing of hole speed 1 μm/minute.
Embodiment 3
Select fluotitanic acid (50wt.%) 7.5g/L as sealing of hole composition；Sorbitol 2.0g/L is as corrosion inhibiter, and sodium tripolyphosphate 2.0g/L is as chelating components, and operating temperature is 25 DEG C, and pH value is 3.5, and sealing of hole speed 1 μm/minute；
Embodiment 4
Select fluotitanic acid (50wt.%) 7.5g/L as sealing of hole composition；Glycerol 2.0g/L is as corrosion inhibiter, and triethanolamine 2.0g/L is as chelating components, and operating temperature is 25 DEG C, and pH value is 3.5, and sealing of hole speed 1 μm/minute.
Embodiment 5
Select fluotitanic acid (50wt.%) 7.5g/L as sealing of hole composition；Glycerol 2.0g/L is as corrosion inhibiter, and ethylenediaminetetraacetic acid 2.0g/L is as chelating components, and operating temperature is 25 DEG C, and pH value is 3.5, and sealing of hole speed 1 μm/minute.
Embodiment 6
Select fluotitanic acid (50wt.%) 7.5g/L as sealing of hole composition；Glycerol 2.0g/L is as corrosion inhibiter, and sodium pyrophosphate 2.0g/L is as chelating components, and operating temperature is 25 DEG C, and pH value is 3.5, and sealing of hole speed 1 μm/minute.
Embodiment 7
Select fluotitanic acid (50wt.%) 7.5g/L as sealing of hole composition；Glycerol 2.0g/L is as corrosion inhibiter, and Polymeric sodium metaphosphate. 2.0g/L is as chelating components, and operating temperature is 25 DEG C, and pH value is 3.5, and sealing of hole speed 1 μm/minute.
Embodiment 8
Select fluotitanic acid (50wt.%) 7.5g/L as sealing of hole composition；Glycerol 2.0g/L is as corrosion inhibiter, and ATMP 2.0g/L is as chelating components, and operating temperature is 25 DEG C, and pH value is 3.5, and sealing of hole speed 1 μm/minute.
Embodiment 9
Select fluotitanic acid (50wt.%) 7.5g/L as sealing of hole composition；Glycerol 2.0g/L is as corrosion inhibiter, and phosphonobutane tricarboxylic acid 2.0g/L is as chelating components, and operating temperature is 25 DEG C, and pH value is 3.5, and sealing of hole speed 1 μm/minute.
Embodiment 10
Select fluotitanic acid (50wt.%) 6.0g/L as sealing of hole composition；Glycerol 2.0g/L is as corrosion inhibiter, and phosphonobutane tricarboxylic acid 2.0g/L is as chelating components, and operating temperature is 25 DEG C, and pH value is 3.5, and sealing of hole speed 1 μm/minute.
Embodiment 11
Select fluotitanic acid (50wt.%) 9.0g/L as sealing of hole composition；Glycerol 2.0g/L is as corrosion inhibiter, and phosphonobutane tricarboxylic acid 2.0g/L is as chelating components, and operating temperature is 25 DEG C, and pH value is 3.5, and sealing of hole speed 1 μm/minute.
Embodiment 12
Select fluotitanic acid (50wt.%) 7.5g/L as sealing of hole composition；Glycerol 1.0g/L is as corrosion inhibiter, and phosphonobutane tricarboxylic acid 2.0g/L is as chelating components, and operating temperature is 25 DEG C, and pH value is 3.5, and sealing of hole speed 1 μm/minute.
Embodiment 13
Select fluotitanic acid (50wt.%) 7.5g/L as sealing of hole composition；Glycerol 3.0g/L is as corrosion inhibiter, and phosphonobutane tricarboxylic acid 2.0g/L is as chelating components, and operating temperature is 25 DEG C, and pH value is 3.5, and sealing of hole speed 1 μm/minute.
Embodiment 14
Select fluotitanic acid (50wt.%) 7.5g/L as sealing of hole composition；Glycerol 2.0g/L is as corrosion inhibiter, and phosphonobutane tricarboxylic acid 1.0g/L is as chelating components, and operating temperature is 25 DEG C, and pH value is 3.5, and sealing of hole speed 1 μm/minute.
Embodiment 15
Select fluotitanic acid (50wt.%) 7.5g/L as sealing of hole composition；Glycerol 2.0g/L is as corrosion inhibiter, and phosphonobutane tricarboxylic acid 3.0g/L is as chelating components, and operating temperature is 25 DEG C, and pH value is 3.5, and sealing of hole speed 1 μm/minute.
Embodiment 16
Select fluotitanic acid (50wt.%) 7.5g/L as sealing of hole composition；Glycerol 2.0g/L is as corrosion inhibiter, and phosphonobutane tricarboxylic acid 2.0g/L is as chelating components, and operating temperature is 15 DEG C, and pH value is 3.5, and sealing of hole speed 1 μm/minute.
Embodiment 17
Select fluotitanic acid (50wt.%) 7.5g/L as sealing of hole composition；Glycerol 2.0g/L is as corrosion inhibiter, and phosphonobutane tricarboxylic acid 2.0g/L is as chelating components, and operating temperature is 25 DEG C, and pH value is 3.5, and sealing of hole speed 2 μm/minute.
Embodiment 18
Select fluotitanic acid (50wt.%) 7.5g/L as sealing of hole composition；Glycerol 2.0g/L is as corrosion inhibiter, and phosphonobutane tricarboxylic acid 2.0g/L is as chelating components, and operating temperature is 35 DEG C, and pH value is 3.5, and sealing of hole speed 3 μm/minute.
Embodiment 19
Select fluotitanic acid (50wt.%) 7.5g/L as sealing of hole composition；Glycerol 2.0g/L is as corrosion inhibiter, and phosphonobutane tricarboxylic acid 2.0g/L is as chelating components, and operating temperature is 25 DEG C, and pH value is 2.5, and sealing of hole speed 1 μm/minute.
Embodiment 20
Select fluotitanic acid (50wt.%) 7.5g/L as sealing of hole composition；Glycerol 2.0g/L is as corrosion inhibiter, and phosphonobutane tricarboxylic acid 2.0g/L is as chelating components, and operating temperature is 25 DEG C, and pH value is 3.5, and sealing of hole speed 1 μm/minute.
Embodiment 21
Select fluotitanic acid (50wt.%) 7.5g/L as sealing of hole composition；Glycerol 2.0g/L is as corrosion inhibiter, and phosphonobutane tricarboxylic acid 2.0g/L is as chelating components, and operating temperature is 25 DEG C, and pH value is 4.5, and sealing of hole speed 1 μm/minute.
As seen from the above embodiment, in the present invention along with the increase of fluotitanic acid concentration, aluminium alloy strengthens without the sealing of hole ability of nickel hole sealing agent；The concentration ranges of fluotitanic acid is 6-9g/L；Along with the increase of glycerol concentration, aluminium alloy slightly reduces without the sealing of hole ability of nickel hole sealing agent；But aluminum alloy surface Refined Mercurous chloride reduces；Its concentration ranges is 1.0-3.0g/L；Along with the increase of phosphonobutane tricarboxylic acid's concentration, aluminium alloy reduces without the sealing of hole ability of nickel hole sealing agent；Liquor of hole-sealing tank contamination resistance strengthens, and aluminum alloy surface Refined Mercurous chloride reduces；Its concentration ranges is 1.0-3.0g/L；Along with operating temperature raises, aluminium alloy rises without the sealing of hole ability of nickel hole sealing agent, and sealing of hole temperature range is 15-35 DEG C；Temperature is the lowest, and sealing of hole ability is inadequate, and temperature is the highest, and oxide-film corrosion is too fast, powder on surface；Optimal interval is 20-30 DEG C；Along with work pH value raises, aluminium alloy first rises without the sealing of hole ability of nickel hole sealing agent, declines afterwards, and sealing of hole pH value interval is 2.5-4.5；PH value is the lowest, then sealing of hole ability is inadequate, powder on surface；PH value is the highest, then sealing of hole ability declines；Optimal interval is 3.0-4.0.
In order to ensure life-time service after alumilite process, it is necessary to carrying out sealing pores, the purpose of sealing of hole is that therefore sealing of hole is highly important sport technique segment in order to improve the corrosion resistance of aluminium, its surface anti-pollution ability and the color of coloring film thereof and fast light, weatherability.The present invention also provides for a kind of aluminium alloy without nickel hole-sealing treatment process, by aluminum alloy base material by processing without nickel process unit, comprises the steps:
(1) will be heated to 15-35 DEG C without nickel hole sealing agent, and be immersed in hole sealing agent without nickel by the aluminum alloy base material after anodic oxidation, sealing of hole speed is 1-3 μm/min；
(2) hole sealing agent of the aluminum alloy base material remained on surface through soaking without nickel hole sealing agent of step (1) gained is washed, dry up after flushing, pack.
Production system, heating system, gas agitating system, filtration system and Waste Water Treatment is included in the present invention without nickel process unit.This production system includes 1# sealing of hole groove, 2# rinsing bowl and 3# rinsing bowl, and 1# sealing of hole groove is main work nest, has been used for the sealing of hole of Process on Aluminum Alloy Oxidation Film, 2# rinsing bowl and the 3# rinsing bowl hole sealing agent of aluminum alloy surface residual after cleaning sealing of hole；Heating system includes steam-heating pipe and the 8# valve being arranged on described steam-heating pipe, and described steam-heating pipe is respectively arranged at the both sides of described 1# sealing of hole groove, for the heating of described 1# sealing of hole groove；Waste Water Treatment is made up of 2# rinsing bowl, 3# rinsing bowl, 4# stillpot, acid-proof pump, filter, 3# valve, 4# valve, 5# valve and pipeline, described Waste Water Treatment is for purifying the cleanout fluid in described 2# rinsing bowl and 3# rinsing bowl, it is achieved cycling utilization of wastewater；Gas agitating system includes air compressor machine, feed channel and the 6# valve being arranged in described feed channel and 7# valve, and described gas agitating system is the uniform stirring of solution in described 1# sealing of hole groove and 4# stillpot；Filtration system is connected by 1# sealing of hole groove, 2# rinsing bowl, 3# rinsing bowl, 4# stillpot, acid-proof pump, filter, 1# valve, 2# valve, 3# valve, 4# valve, 5# valve and pipeline and forms, and described filtration system is the filtration of water lotion in described 1# sealing of hole groove, described 2# rinsing bowl and 3# rinsing bowl.
Aluminium alloy sealing operates, open 8# valve, heating 1# sealing of hole groove, checks and confirms that indices is within the scope of following: between fluotitanic acid (50wt.%) concentration 6.0-9.0g/L, concentration 1-3g/L of corrosion inhibiter, chelating agent concentrations 1-3g/L, temperature 15-35 DEG C, pH value 2.5-4.5；Along with the increase of fluotitanic acid concentration, aluminium alloy strengthens without the sealing of hole ability of nickel hole sealing agent.
Open 3# valve, 4# valve, 5# valve, start acid-proof pump, confirm that the pH value of 4# stillpot, between 5-8, in the water lotion in circulation 4# stillpot to 2# rinsing bowl and 3# rinsing bowl, returns again to 4# stillpot.After sealing of hole completes, through 2# rinsing bowl and 3# rinsing bowl, cleaning aluminum alloy remained on surface hole sealing agent, then air-dry, pack, complete to produce overall process.
In the present invention, during the heating of 1# sealing of hole groove, 8# valve is opened, and 8# valve automatically controls sealing of hole temperature between 20-30 DEG C.After adding hole sealing agent in 1# sealing of hole groove, open 7# valve, gas agitating system stir, continue to produce；Close 3# valve, 4# valve, 5# valve, open gas agitating 6# valve, quick lime is added 4# stillpot, stirring while adding, to pH value be 8.0 time, stop adding quick lime and stirring.
The aluminium alloy of the present invention, without nickel hole-sealing technology, also includes: the hole sealing agent filter regeneration in 1# sealing of hole groove: close 3# valve and 4# valve, cleans acid-proof pump, filter and pipeline；Open 1# valve, 2# valve；Start acid-proof pump, circulating filtration 1# sealing of hole groove, to so clear that you can see the bottom, complete hole sealing agent regeneration；Water lotion filter regeneration in 2# rinsing bowl and 3# rinsing bowl: in water-washing process, hole sealing agent is constantly brought into rinsing bowl, reduces the pH value of rinsing bowl, starts Waste Water Treatment, to water lotion filter regeneration, recycles；Close 1# valve and 2# valve, open 3# valve, 4# valve and 5# valve；Start acid-proof pump, after being filtered by the water lotion of 4# stillpot, be evacuated to 3# rinsing bowl, then through 2# rinsing bowl, certainly flow back to 4# stillpot, complete the circulating filtration of rinsing bowl.When the pH value of water lotion is less than 5.0, stop acid-proof pump, close 3#, 4#, 5# valve, open gas agitating 6# valve, quick lime is added 4# stillpot, stirring while adding, pH value is surveyed on limit, during to pH value close to 8.0, stop adding quick lime and stirring, stand 1 hour, restart Waste Water Treatment, complete to clean the recycling of waste water.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all within the spirit and principles in the present invention, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.
Claims (8)
1. aluminium alloy is without nickel hole sealing agent, it is characterised in that include the water-soluble of fluotitanic acid, corrosion inhibiter and chelating agen
Liquid, on the basis of the volume of hole sealing agent, the concentration of described fluotitanic acid is 6.0-9.0g/L, described corrosion inhibiter
Concentration is 1.0-3.0g/L, and the concentration of described chelating agen is 1.0-3.0g/L；Described corrosion inhibiter be ethylene glycol,
Glycerol and sorbitol one or more；
Described chelating agen is triethanolamine, ethylenediaminetetraacetic acid, sodium tripolyphosphate, sodium pyrophosphate, Metaphosphoric acid
One or more in sodium, ATMP and phosphonobutane tricarboxylic acid；The pH value of described hole sealing agent
For 2.5-4.5.
Aluminium alloy the most according to claim 1 is without nickel hole sealing agent, it is characterised in that described hole sealing agent work
Being 20-30 DEG C as temperature, the pH value of described hole sealing agent is 3.0-4.0.
3. an aluminium alloy is without nickel hole-sealing treatment process, it is characterised in that by aluminum alloy base material by without nickel work
Process and equipment processes, and comprises the steps:
(1) aluminium alloy according to claim 1 is heated to 15-35 DEG C without nickel hole sealing agent, by anode
Aluminum alloy base material after oxidation immerses in above-mentioned hole sealing agent without nickel, and sealing of hole speed is 1-3 μm/min；
(2) by the sealing of hole of the aluminum alloy base material remained on surface through soaking without nickel hole sealing agent of step (1) gained
Agent is washed, and dries up, packs after flushing.
Aluminium alloy the most according to claim 3 is without nickel hole-sealing treatment process, it is characterised in that described nothing
Nickel process unit includes production system, heating system, gas agitating system, filtration system and Waste Water Treatment；
Described production system includes 1# sealing of hole groove, 2# rinsing bowl and 3# rinsing bowl, and described 1# sealing of hole groove is main work
Making groove, be used for the sealing of hole of Process on Aluminum Alloy Oxidation Film, described 2# rinsing bowl and 3# rinsing bowl are used for cleaning sealing of hole
The hole sealing agent of rear aluminum alloy surface residual；
Described heating system includes steam-heating pipe and the 8# valve being arranged on described steam-heating pipe, described
Steam-heating pipe is respectively arranged at the both sides of described 1# sealing of hole groove, for the heating of described 1# sealing of hole groove；
Described Waste Water Treatment by 2# rinsing bowl, 3# rinsing bowl, 4# stillpot, acid-proof pump, filter,
3# valve, 4# valve, 5# valve and pipeline composition, described Waste Water Treatment is used for purifying described 2# rinsing bowl and 3#
Cleanout fluid in rinsing bowl, it is achieved cycling utilization of wastewater；
Described gas agitating system include air compressor machine, feed channel and the 6# valve being arranged in described feed channel and
7# valve, described gas agitating system is the uniform stirring of solution in described 1# sealing of hole groove and 4# stillpot；
Described filtration system is by 1# sealing of hole groove, 2# rinsing bowl, 3# rinsing bowl, 4# stillpot, acid-proof pump, mistake
Filter, 1# valve, 2# valve, 3# valve, 4# valve, 5# valve and pipeline connect composition, and described filtration system is used for
The filtration of water lotion in described 1# sealing of hole groove, described 2# rinsing bowl and 3# rinsing bowl.
Aluminium alloy the most according to claim 4 is without nickel hole-sealing treatment process, it is characterised in that open 8#
Valve, heats described 1# sealing of hole groove, opens 3# valve, 4# valve, 5# valve, starts acid-proof pump, in 4# stillpot
Water lotion in 2# rinsing bowl and 3# rinsing bowl, return again to 4# stillpot；
After oxidized aluminum alloy, in 1# sealing of hole groove, sealing of hole speed is 1-3 μm/min, after sealing of hole completes, warp
2# rinsing bowl and 3# rinsing bowl, cleaning aluminum alloy remained on surface hole sealing agent, then air-dry, pack.
Aluminium alloy the most according to claim 5 is without nickel hole-sealing treatment process, it is characterised in that described 1#
During the heating of sealing of hole groove, described 8# valve automatically controls hole sealing agent temperature between 20-30 DEG C.
Aluminium alloy the most according to claim 4 is without nickel hole-sealing treatment process, it is characterised in that described
After 1# sealing of hole groove adds without nickel hole sealing agent, open 7# valve, described gas agitating system in being stirred by 1# sealing of hole groove
Hole sealing agent mix uniformly, continue produce；Close 3# valve, 4# valve, 5# valve, open gas agitating 6# valve, will be raw
Calx adds 4# stillpot, stirring while adding, to pH value be 8.0 time, stop adding quick lime and stirring.
Aluminium alloy the most according to claim 4 is without nickel hole-sealing treatment process, it is characterised in that also include
The water lotion filter regeneration of hole sealing agent filter regeneration, 2# rinsing bowl and 3# rinsing bowl in 1# sealing of hole groove；
Hole sealing agent filter regeneration in described 1# sealing of hole groove, closes 3# valve and 4# valve, cleans acid-proof pump, filtration
Device and pipeline；Open 1# valve, 2# valve；Startup acid-proof pump, circulating filtration sealing of hole groove, to so clear that you can see the bottom,
Complete hole sealing agent regeneration；
Described 2# rinsing bowl and the water lotion filter regeneration of 3# rinsing bowl, close 1# valve and 2# valve, open
Open 3# valve, 4# valve and 5# valve；Start acid-proof pump, after the water lotion of 4# stillpot is filtered, take out
To 3# rinsing bowl, then through 2# rinsing bowl, certainly flow back into 4# stillpot, complete the circulating filtration of rinsing bowl；
When the pH value of water lotion is less than 5.0, stop acid-proof pump, close 3# valve, 4# valve and 5# valve, open
Gas agitating 6# valve, adds 4# stillpot by quick lime, stirring while adding, and pH value is surveyed on limit, close to pH value
When 8.0, stop adding quick lime and stirring, stand 1 hour, restart Waste Water Treatment, complete clear
Wash the recycling of waste water.
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| CN109778285A (en) * | 2019-02-20 | 2019-05-21 | 湖北叒成科技有限公司 | A kind of aluminium alloy high temperature is without nickel hole sealing agent and preparation method thereof |
| CN109972185A (en) * | 2019-04-17 | 2019-07-05 | 邓华斌 | A kind of aluminium alloy is without nickel environmental protection hole sealing agent and preparation method thereof |
| CN111020659A (en) * | 2019-12-07 | 2020-04-17 | 爱科科技有限公司 | Method for reducing porosity of coating on surface of neodymium iron boron permanent magnet material |
| CN111416139A (en) * | 2020-03-06 | 2020-07-14 | 中科院过程工程研究所南京绿色制造产业创新研究院 | Electrolyte corrosion inhibitor, aluminum-air battery, alkaline electrolyte and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4786336A (en) * | 1985-03-08 | 1988-11-22 | Amchem Products, Inc. | Low temperature seal for anodized aluminum surfaces |
| CN101191247A (en) * | 2006-11-28 | 2008-06-04 | 熊映明 | Aluminum alloy environment-friendly type nickel-free intermediate-temperature hole sealing agent |
| CN101717162A (en) * | 2009-12-02 | 2010-06-02 | 厦门世达膜科技有限公司 | Method for treating and recycling wastewater generated by processing surface of aluminum profile |
| CN101932447A (en) * | 2008-02-01 | 2010-12-29 | 富士胶片株式会社 | Hydrophilic members |
| CN202220201U (en) * | 2011-08-24 | 2012-05-16 | 曹健 | On-line water circulating and purifying device used in surface treatment process of fluorine-free, ammonia-free and four-in-one aluminum profile |
| CN103043818A (en) * | 2012-12-14 | 2013-04-17 | 苏州万科环境工程有限公司 | Waste water treating method in aluminum section bar oxidizing technology |
| CN103255462A (en) * | 2013-04-17 | 2013-08-21 | 佛山科学技术学院 | Environment-friendly hole sealing liquid for anodic aluminum oxide profiles and hole sealing method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0215192A (en) * | 1988-07-01 | 1990-01-18 | Nippon Senka Kogyo Kk | Method for sealing anodic oxide film of aluminum of aluminum alloy |
| JPH0320496A (en) * | 1989-06-15 | 1991-01-29 | Nippon Alum Mfg Co Ltd | Sealant for aluminum-based metal having oxide film and method for sealing oxide film of aluminum-based metal using the same |
| US8486203B2 (en) * | 2009-06-11 | 2013-07-16 | Metalast International, Inc. | Conversion coating and anodizing sealer with no chromium |
| CN202246946U (en) * | 2011-09-21 | 2012-05-30 | 梁守棋 | Intermediate temperature hole sealing slot heating system used in aluminum profile industry |
-
2013
- 2013-11-14 CN CN201310567738.1A patent/CN103590086B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4786336A (en) * | 1985-03-08 | 1988-11-22 | Amchem Products, Inc. | Low temperature seal for anodized aluminum surfaces |
| CN101191247A (en) * | 2006-11-28 | 2008-06-04 | 熊映明 | Aluminum alloy environment-friendly type nickel-free intermediate-temperature hole sealing agent |
| CN101932447A (en) * | 2008-02-01 | 2010-12-29 | 富士胶片株式会社 | Hydrophilic members |
| CN101717162A (en) * | 2009-12-02 | 2010-06-02 | 厦门世达膜科技有限公司 | Method for treating and recycling wastewater generated by processing surface of aluminum profile |
| CN202220201U (en) * | 2011-08-24 | 2012-05-16 | 曹健 | On-line water circulating and purifying device used in surface treatment process of fluorine-free, ammonia-free and four-in-one aluminum profile |
| CN103043818A (en) * | 2012-12-14 | 2013-04-17 | 苏州万科环境工程有限公司 | Waste water treating method in aluminum section bar oxidizing technology |
| CN103255462A (en) * | 2013-04-17 | 2013-08-21 | 佛山科学技术学院 | Environment-friendly hole sealing liquid for anodic aluminum oxide profiles and hole sealing method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Aging of Cold-sealed Aluminum Oxide Flims At Room Temperature and at 50℃;E.otero，V.Lopez.J.A.Gonzalez;《Plating&Surface Finishing》;19960831;第83卷(第8期);第50-54页 * |
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