CN109338347A - A kind of chromium-free deactivation composition, chromium-free passivation liquid and preparation method thereof - Google Patents
A kind of chromium-free deactivation composition, chromium-free passivation liquid and preparation method thereof Download PDFInfo
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- CN109338347A CN109338347A CN201811158590.5A CN201811158590A CN109338347A CN 109338347 A CN109338347 A CN 109338347A CN 201811158590 A CN201811158590 A CN 201811158590A CN 109338347 A CN109338347 A CN 109338347A
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- chromium
- free
- water
- passivation liquid
- aluminum profile
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
Abstract
The invention discloses a kind of chromium-free deactivation composition, chromium-free passivation liquid and its application methods, the chromium-free deactivation composition is by weight percentage, including following components: hydrofluoric acid 20-40%, nitric acid 20-30%, fluorine zirconic acid 15-25%, phytic acid 5-10%, nitrogen-containing hetero cyclics 5-10%, diethylene glycol dimethyl ether 5-15%.The chromium-free passivation liquid is the mixture of the chromium-free deactivation composition and water, wherein the concentration of the chromium-free deactivation composition is 8-10g/L.Chromium-free passivation liquid proposed by the present invention can be used for the surface passivating treatment of aluminium alloy extrusions, aluminium sheet, aluminium alloy castings and Al-alloy products, the chemical composition coating of passivated treated aluminium base Surface Creation dense uniform, can effectively promote paint film adhesion and corrosion resistance of the aluminum alloy surface in conjunction with coating.Since the passivating solution in the present invention does not contain crome metal and other heavy metals, meet environment protection requirement, traditional agent containing chromium passivating can be substituted completely.
Description
Technical field
The present invention relates to technical field of chrome-free passivation, and in particular to a kind of chromium-free deactivation composition, chromium-free passivation liquid and its
Preparation method.
Background technique
With flourishing for national economy, currently, China is aluminium consumption big country.Because traditional Cr VI passivation technology has
Very high corrosion resistance, processing before aluminum profile is carried out before electrophoretic painting frequently with chromate chemical deactivation method, however, due to sexavalence
Chromium compound is easily absorbed by the body, human body can be invaded by digestive system, respiratory tract, skin and mucous membrane, therefore endanger to human body
Evil is larger, and serious pollution can also be caused to environment by dealing with improperly, therefore chromating technique is greatly paid close attention to, some
Country has limited its use.The content for reducing Cr VI becomes passivating solution Future Development even with not chromyl passivating solution
One of direction.Recent domestic has conducted extensive research non-chromium inactivating technique, develops rare earth, cobalt salt, silicate, molybdenum
A variety of passivating solution system for handling such as acid, titanium/zirconates have certain corrosion resistance.But passivation effect still can exist blunt
Change film is not uniform enough, and compactness is inadequate, poor adhesive force, and the not ideal enough disadvantage of corrosion resistance needs to improve.
Summary of the invention
The object of the invention is to one of in order to solve the defects of prior art, provide a kind of chromium-free deactivation composition, nothing
Chromium passivating liquid and preparation method thereof.
The present invention provides a kind of chromium-free deactivation compositions, and by weight percentage, the chromium-free deactivation composition includes
Following components:
Preferably, the nitrogen-containing hetero cyclics are benzotriazole and/or methyl phenylpropyl triazole and/or 3- ammonia
Base -1,2,4- triazole.
In addition, also providing a kind of chromium-free passivation liquid, the chromium-free passivation liquid includes the chromium-free deactivation composition and water, institute
State the preferred tap water of water.
Preferably, the chromium-free deactivation composition is 8-10g/L with the mixed concentration of water in deactivation slot.
Preferably, the pH value of the chromium-free passivation liquid is 2.8-3.8.
Preferably, the temperature when chromium-free passivation liquid uses is 15-45 DEG C.
In addition, also providing a kind of application method of chromium-free passivation liquid, comprising the following steps:
(1) after hydrofluoric acid, fluorine zirconic acid being added in a certain amount of water, it is stirred 5-8min, nitric acid and phytic acid is then added,
Continue to stir 5-10min, forms acidic mixed solution；
(2) the acidic mixed solution in step (1) is warming up to 35-45 DEG C, then sequentially adds and contains into the mixed solution
Heterocyclic nitrogen compound and diethylene glycol dimethyl ether continue to stir 3-6min, are down to room temperature later, surplus is finally added thereto
Water, be stirred 1-3min, obtain the chromium-free passivation liquid, it is spare；
(3) aluminum profile to be processed is put into after bridging washed, wash after put the profile into free acid point be 20-40,
In the tank liquor of aluminium ion concentration < 3.5g/L, degreasing degreasing 2-3min is carried out under room temperature；It is washed later, places into free acid
Pickling 1-3min is carried out in the tank liquor of point 20-50, aluminium ion < 3g/L；Aluminum profile is subjected to the series connection cleaning of three water later, directly
Conductivity≤100us/cm of water after to washing aluminum profile, wherein first three road washing time is 1-3min；By the aluminium after washing
Profile is slowly put into the deactivation slot tank liquor being formulated by step (1), it is ensured that the aluminum profile is completely by the deactivation slot slot
Liquid submergence after the completion of passivation of the aluminum profile in the deactivation slot tank liquor, is slowly withdrawn, is connected and cleaned with twice water,
Middle per pass water scavenging period is 1-2min, after washing, after aluminum profile taking-up is drained the water, is put into 80-120 DEG C of baking oven
10-20min is toasted, the aluminum profile that surface forms one layer of dense uniform passivating film can be obtained in drying.
The beneficial effects of the present invention are: chromium-free passivation liquid proposed by the present invention is that a kind of colorless and transparent environment-friendly type is acid
Inorganic agent can effectively promote aluminum alloy surface using composite salt in the chemical composition coating of aluminum substrate Surface Creation dense uniform
Paint film adhesion and corrosion resistance in conjunction with coating.Tank liquor preparation is simple, technology controlling and process is convenient, stable working performance.
This product is free of crome metal, is free of any heavy metal, meets environment protection requirement, can substitute traditional agent containing chromium passivating completely and use
In aluminum alloy surface Coating Pretreatment, can be used for spraying or impregnating.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Embodiment 1
A kind of chromium-free deactivation composition, by weight percentage, the chromium-free deactivation composition includes following components:
The nitrogen-containing hetero cyclics are benzotriazole and/or methyl phenylpropyl triazole and/or 3- amino -1,2,4-
Triazole；The nitrogen-containing hetero cyclics and metallic atom are coordinated, and form one layer of molecule protective film, play protection aluminum profile base
The effect of body, and then play the role of being passivated inhibition, so that the passivating film of aluminum profile matrix surface is fine and close, adhesive force is strong.
The addition of the diethylene glycol dimethyl ether plays wetting action to the aluminum profile matrix being passivated, and is conducive at passivation
Reason and raising passivation effect.
In addition, also providing a kind of chromium-free passivation liquid, the chromium-free passivation liquid includes the chromium-free deactivation composition and water, institute
State the preferred tap water of water.
Wherein, the passivation effect for the chromium-free passivation liquid being prepared by tap water and chromium-free deactivation composition, it is same to make
With slot identical as the passivation effect for the chromium-free passivation liquid that chromium-free deactivation composition is prepared by pure water, and being prepared by tap water
Liquid without having to worry about bring inconvenience when need to use pure water, while also saving the production cost of entire production technology.
The chromium-free deactivation composition is 8-10g/L, the i.e. chromium-free passivation liquid with the mixed concentration of water in deactivation slot
For water solubility, solution is not stratified, can be with water with any ratio dilution, optium concentration 8-10g/L.
The pH value of the chromium-free passivation liquid is 2.8-3.8.
The temperature when chromium-free passivation liquid uses is 15-45 DEG C, and temperature applicable range is broad.
In addition, also providing a kind of application method of chromium-free passivation liquid, comprising the following steps:
(1) after hydrofluoric acid, fluorine zirconic acid being added in a certain amount of water, it is stirred 5-8min, nitric acid and phytic acid is then added,
Continue to stir 5-10min, forms acidic mixed solution；
(2) the acidic mixed solution in step (1) is warming up to 35-45 DEG C, then sequentially adds and contains into the mixed solution
Heterocyclic nitrogen compound and diethylene glycol dimethyl ether continue to stir 3-6min, are down to room temperature later, surplus is finally added thereto
Water, be stirred 1-3min, obtain the chromium-free passivation liquid, it is spare；
(3) aluminum profile to be processed is put into after bridging washed, wash after put the profile into free acid point be 20-40,
In the tank liquor of aluminium ion concentration < 3.5g/L, degreasing degreasing 2-3min is carried out under room temperature；It is washed later, places into free acid
Pickling 1-3min is carried out in the tank liquor of point 20-50, aluminium ion < 3g/L；Aluminum profile is subjected to the series connection cleaning of three water later, directly
Conductivity≤100us/cm of water after to washing aluminum profile, wherein first three road washing time is 1-3min；By the aluminium after washing
Profile is slowly put into the deactivation slot tank liquor being formulated by step (1), it is ensured that the aluminum profile is completely by the deactivation slot slot
Liquid submergence after the completion of passivation of the aluminum profile in the deactivation slot tank liquor, is slowly withdrawn, is connected and cleaned with three water,
Middle per pass water scavenging period is 1-2min, after washing, after aluminum profile taking-up is drained the water, is put into 80-120 DEG C of baking oven
10-20min is toasted, the aluminum profile that surface forms one layer of dense uniform passivating film can be obtained in drying.
The time that the aluminum profile is passivated processing in deactivation slot is 60-300s；This simple process, wide in range, convenience
Control, it is only necessary to control between deactivation slot tank liquor pH value 2.8-3.8；Passivating solution is stablized in deactivation slot, and epithelium is transparent without color, together
Sample is suitble to the pre-treatment of golden electrophoresis painting dressing technique.
Embodiment 2
On the basis of embodiment 1, the present embodiment 2 is as a preferred embodiment, wherein the chromium-free deactivation composition is pressed
Weight percent meter, including following components:
In the deactivation slot, the concentration of chromium-free deactivation composition described in the passivation tank liquor is 9g/L.
The pH value of the deactivation slot tank liquor is 3.0.
The temperature when chromium-free passivation liquid uses is 25 DEG C.
The Passivation Treatment time is 120s.
Embodiment 3
On the basis of embodiment 1, the present embodiment 3 is as a preferred embodiment, wherein the chromium-free deactivation composition is pressed
Weight percent meter, including following components:
In the deactivation slot, the concentration of chromium-free deactivation composition described in the passivation tank liquor is 8g/L.
The pH value of the deactivation slot tank liquor is 3.2.
The temperature when chromium-free passivation liquid uses is 20 DEG C.
The Passivation Treatment time is 180s.
Embodiment 4
On the basis of embodiment 1, the present embodiment 4 is as a preferred embodiment, wherein the chromium-free deactivation composition is pressed
Weight percent meter, including following components:
In the deactivation slot, the concentration of chromium-free deactivation composition described in the passivation tank liquor is 10g/L.
The pH value of the deactivation slot tank liquor is 2.8.
The temperature when chromium-free passivation liquid uses is 45 DEG C.
The Passivation Treatment time is 60s.
The performance test of the aluminum profile obtained after embodiment 2-4 Passivation Treatment in the present invention is compareed such as one institute of following table
Show:
Table one
Wherein, anti-finger printing: with vaseline for human sweat's simulation medium, it is uniform that a small amount of vaseline is dipped with clean soft cloth
It is applied to specimen surface, the color value that measurement sample smears front and back is poor.
Corrosion resistance: evaluation method is galvanized sheet that is processed by the invention but not painting, carries out salt mist experiment by erosional surface
Time of the product less than 5%.
The high-temperature baking performance: the sample of 70mm × 70mm is put into 350 DEG C of baking oven and toasts 30 minutes, observes sample
Surface △ E value is qualification less than 1.
The resistance to neutral salt spray time for the profile that embodiment 2-4 is handled it can be seen from above-mentioned table one is more than 160 small
When, far better than traditional chromating liquid (resistance to neutral salt spray time average out to 120 hours), the aluminum profile handled
Adhesive force reaches 1 grade, meanwhile, also there is water boiling resistance, anti-finger printing, resistance to copper accelerated corrosion, high-temperature baking resistant performance
Also especially excellent.
In conclusion under the Passivation Treatment of the passivation technology parameter proposed in the present invention, in the nothing that Surface of profile is formed
The colloid of color passivating film, the passivating film is fine and close, and uniform film thickness has excellent corrosion resistance, can be with profile base and paint
There is good adhesive force between film；Meanwhile tank liquor preparation is simple, technology controlling and process is convenient, stable working performance.Due to the present invention
In passivating solution be chromium-free passivation liquid, be free of crome metal, also be free of other heavy metals, meet environmentally protective requirement, can be complete
Substituting traditional agent containing chromium passivating can be widely used for the surface of aluminium alloy extrusions, aluminium sheet, aluminium alloy castings and Al-alloy products
Coating Pretreatment can be used for spraying or impregnating.
It should be noted that embodiment described above for explaining only the invention, is not constituted to of the invention any
Limitation.If not departing from the spirit and scope of the present invention to various changes or modifications of the invention, if these modification and variations
Belong within the scope of claim and equivalent technologies of the invention, then the present invention is also intended to encompass these modification and variations.
Claims (7)
1. a kind of chromium-free deactivation composition, which is characterized in that by weight percentage, the chromium-free deactivation composition includes following
Component:
2. a kind of chromium-free deactivation composition according to claim 1, which is characterized in that the nitrogen-containing hetero cyclics are
Benzotriazole and/or methyl phenylpropyl triazole and/or 3- amino-1,2,4-triazol.
3. a kind of chromium-free passivation liquid, which is characterized in that the chromium-free passivation liquid includes the described in any item Chrome-frees of claim 1-2
It is passivated composition and water, the water is tap water.
4. a kind of chromium-free passivation liquid according to claim 3, which is characterized in that the chromium-free deactivation composition is in deactivation slot
The interior and mixed concentration of water is 8-10g/L.
5. a kind of chromium-free passivation liquid according to claim 3, which is characterized in that the pH value of the chromium-free passivation liquid is 2.8-
3.8。
6. a kind of chromium-free passivation liquid according to claim 3, which is characterized in that the temperature when chromium-free passivation liquid uses
It is 15-45 DEG C.
7. a kind of application method of such as described in any item chromium-free passivation liquids of claim 3-6, which is characterized in that including following step
It is rapid:
(1) after hydrofluoric acid, fluorine zirconic acid being added in a certain amount of water, it is stirred 5-8min, nitric acid and phytic acid is then added, is continued
5-10min is stirred, acidic mixed solution is formed；
(2) the acidic mixed solution in step (1) is warming up to 35-45 DEG C, then sequentially adds nitrogen-containing hetero into the mixed solution
Cyclics and diethylene glycol dimethyl ether continue to stir 3-6min, are down to room temperature later, surplus is finally added thereto
Water is stirred 1-3min, obtains the chromium-free passivation liquid, spare；
(3) aluminum profile to be processed is put into after bridging washed, wash after put the profile into free acid point be 20-40, aluminium from
In the tank liquor of sub- concentration < 3.5g/L, degreasing degreasing 2-3min is carried out under room temperature；It is washed later, places into free acid point
Pickling 1-3min is carried out in the tank liquor of 20-50, aluminium ion < 3g/L；Aluminum profile is subjected to the series connection cleaning of three water later, until
Conductivity≤100us/cm of water after washing aluminum profile, wherein three washing times are 1-3min；By the aluminum profile after washing
It is slowly put into the deactivation slot tank liquor being formulated by step (1), it is ensured that the aluminum profile is soaked by the deactivation slot tank liquor completely
Not yet, it after the completion of passivation of the aluminum profile in the deactivation slot tank liquor, is slowly withdrawn, is connected and cleaned with twice water, wherein often
Road water scavenging period is 1-2min, after washing, after aluminum profile taking-up is drained the water, is put into 80-120 DEG C of baking oven and toasts
The aluminum profile that surface forms one layer of dense uniform passivating film can be obtained in 10-20min, drying.
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Cited By (2)
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| CN111020549A (en) * | 2019-12-30 | 2020-04-17 | 奎克化学（中国）有限公司 | Chromium-free passivation solution for zinc-aluminum-magnesium coating plate |
| CN114774904A (en) * | 2022-04-24 | 2022-07-22 | 安徽光铧帝业化学有限公司 | Aluminum alloy chromium-free passivation agent containing fluorescent agent and preparation method and use method thereof |
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| CN111020549A (en) * | 2019-12-30 | 2020-04-17 | 奎克化学（中国）有限公司 | Chromium-free passivation solution for zinc-aluminum-magnesium coating plate |
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