CN110016659A - It is used to prepare the preparation method of the treatment fluid of the compound conversion film of fluorine zirconic acid, preparation method and conversion film - Google Patents
It is used to prepare the preparation method of the treatment fluid of the compound conversion film of fluorine zirconic acid, preparation method and conversion film Download PDFInfo
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- CN110016659A CN110016659A CN201910282813.7A CN201910282813A CN110016659A CN 110016659 A CN110016659 A CN 110016659A CN 201910282813 A CN201910282813 A CN 201910282813A CN 110016659 A CN110016659 A CN 110016659A
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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
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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
- C23C22/78—Pretreatment of the material to be coated
Abstract
The present invention relates to the preparation methods for being used to prepare the treatment fluid of the compound conversion film of fluorine zirconic acid, preparation method and conversion film.First prepare comprising fluozirconate, ammonium hydroxide, auxiliary oxidizing agent, amino acid polymer, promotor and complex compound treatment fluid, then the metal plate after surface preparation is placed in treatment fluid and dilutes progress chemical conversion film process in manufactured working solution, handle time 1min ~ 5min, 10 DEG C ~ 30 DEG C for the treatment of temperature, most afterwards through washing, drying, it is cooling to obtain the final product.The present invention has the advantages that low in the pollution of the environment, treatment temperature is low, short processing time, simple process, forms colourless conversion film in aluminum alloy surface, cold rolling steel surface forms blue conversion film；Conversion film is fine and close, strong with powdery paints binding force, and anti-impact force is strong, can effectively replace metal surface chromic acid salt treatment process, and prospect of the application is wide.
Description
Technical field
The treatment fluid that the present invention relates to a kind of for preparing the compound conversion film of fluozirconate in metal surface, preparation method and
In the method for the metal surface preparation compound conversion film of fluorine zirconic acid, this method is replaced mainly as metal surface chromic acid salt treatment process
Generation.
Background technique
Aluminium alloy and steel are that yield and dosage occupy the first metal in the world, and people are in process of production in order to improve
The mechanical characteristics such as the structure of metal and hardness strength can destroy metal lattice structural intergrity, so that these alloys are in wet environment
Middle surface is easy to be caused production safety hidden danger and property loss by electrochemical corrosion, limit it in actual production and life
Extensive use.
The chemical method for treating surface of aluminium alloy and steel is mainly chromate and phosphate conversion embrane method, six in chromate
Valence chromium environmental pollution is serious, very big to human health damage, and application is restricted, and WEES and ROHS instruction strictly limit
The use of chromate；Phosphate causes red tide or wawter bloom, breaks words ecological environment, European Union is due to that can cause water eutrophication
Legislation limits its use；National governments are just actively attempting the green metal surface conversion coating system for handling with environment compatibility
Exploitation and development.
Currently, metal Chrome-free process for treating surface emerges one after another, such as the ceramic treatment of fluotitanic acid fluorine zirconic acid, rare earth metal
Salt conversion film, manganese salt conversion film and silane treatment etc..The processing of titanium zirconium is that rare realization is industrialized in chromium-free treatment system
Technology, the technique can form very thin metal oxide film on aluminum profile, and Masahiko Matsuka has been invented for owning
The preprocess method (US 20040144451A1) of the metal such as coatings such as iron, zinc and aluminium, but this method uses silane coupling agent
It is hydrolyzed complicated at, preparation method；Joseph D.Pemberto has invented the preprocess method (US of processing non-ferrous metal
007815751B2), which contains zirconates, vanadic acid root, fluorine ion, but can contain a small amount of phosphorus in conversion fluid；Guo Rui light hair
A kind of processing method (CN1683590A) containing titanium salt, silicate and fluoride for aluminum alloy surface is illustrated, but converts temperature
Spend higher, the film layer of generation is colourless, is unfavorable for observing, and chromium-free deactivation is surface-treated before Qu Fengzuo has invented a kind of coatings of the aluminium profiles
Agent (CN102787312A), one of the inorganic agent fluorine zirconic acid, fluotitanic acid, fluorine hafnium acid, fluosilicic acid or a variety of, water-soluble phenolic
Urea formaldehyde or phenol-formaldehyde resin modified, chitosan, rare earth addition pH value be 4 it is inferior obtain high corrosion-resistant corrosion-inhibiting coating, but by
It is matched in the addition for using phenolic resin etc., required step is complicated, and it is longer to prepare the time.Bear gold equality has invented a kind of aluminium alloy
Chemical surface treatment liquid (CN 101122017A), is made of, the invention titanium sulfate, potassium permanganate, neopelex etc.
Film forming is golden yellow, but conversion temperature is higher, and treatment fluid is due to deep containing potassium permanganate color, and technique is cumbersome, and corrosion resistance also has
Wait improve.Furthermore above method cannot be surface-treated steel and iron parts mostly just for aluminum alloy materials.
Summary of the invention
In view of the deficiencies of the prior art, one of the objects of the present invention is to provide a kind of Chrome-free and various metals are applicable to
Material surface processing is used to prepare the treatment fluid of the compound conversion film of fluozirconate in metal surface；The second object of the present invention exists
In the preparation method of the offer treatment fluid；The third object of the present invention, which is to provide, prepares the compound conversion of fluorine zirconic acid in metal surface
The method of film.
In order to solve the above-mentioned technical problem, technical scheme is as follows:
It is used to prepare the treatment fluid of the compound conversion film of fluorine zirconic acid, the treatment fluid is aqueous solution, contains in every liter for the treatment of fluid:
Wherein, the amino acid polymer is one or more of polyglutamic acid sodium, polyglycine sodium.
Further, contain in every liter for the treatment of fluid:
Further, the mass concentration of the ammonium hydroxide is 20%~35%.
Further, the fluozirconate is one of potassium fluorozirconate, sodium fluozirconate, fluorine zirconic acid or a variety of.
Further, the auxiliary oxidizing agent be potassium fluoborate, sodium fluoborate, fluoboric acid, boric acid, Boratex, potassium borate,
One or more of m-nitrobenzene sodium sulfonate, sodium tungstate, sodium molybdate.
Further, the complexing agent be one of triethylamine, ethylenediamine, ethanol amine, diethanol amine, triethanolamine or
It is several.
Further, the promotor is lithium acetate, sodium acetate, potassium acetate, calcium acetate, magnesium acetate, one in zinc acetate
Kind is several.
Optionally, in use, being reused after obtaining the working solution that pH value is 3.5~5.5 after treatment fluid is diluted 10~20 times.
Based on the same inventive concept, the present invention provides the preparation method for the treatment of fluid as described above, includes the following steps:
Fluozirconate, auxiliary oxidizing agent, complexing agent, ammonium hydroxide deionized water dissolving are obtained into component according to prescription for the treatment of liquid
a；
Amino acid polymer, promotor deionized water dissolving are obtained into component b according to prescription for the treatment of liquid；
Component a and component b is uniformly mixed to obtain treatment fluid.
Based on the same inventive concept, the present invention also provides a kind of preparation method of conversion film, include the following steps:
Metal surface is pre-processed；
The treatment fluid obtained to treatment fluid as described above or preparation method as described above is diluted processing, adjusts pH,
Obtain the working solution that pH value is 3.5-5.5；
Pretreated metal is placed in the working solution, chemical conversion film process is carried out；Period controls the reaction time
For 1-5min, treatment fluid temperature is 10-30 DEG C.
As one embodiment of the present invention, fluozirconate is prepared in cold-rolled steel/aluminum alloy surface with the treatment fluid
The method of compound conversion film, includes the following steps:
A) cold-rolled steel/aluminium alloy is polishing to surface is smooth；
B) cold-rolled steel/aluminum alloy surface is pre-processed；
C) work that pH value is 3.5~5.5 cold-rolled steel/aluminum alloy conversion processing: is obtained after treatment fluid is diluted 10~20 times
Respective metal is placed in progress chemical conversion film process in working solution by liquid, and the processing time is 1min~5min, treatment temperature 10
~30 DEG C；
D) metal of inverted processing is washed, naturally dry to obtain the final product.
Step a) the pretreatment are as follows: metal surface dirt, washing are cleaned using organic solvent, deionization is washed again
Pickling carries out metal surface light, finally washing removal metal surface raffinate is activated.
Further, when pre-processing to metal, metal surface dirt first is cleaned with organic solvent, successively washing, acid
After washing, then wash.
Further, when pre-processing to metal, metal surface dirt is first cleaned using organic solvent, after washing, is used
Deionization washing, then pickling carry out metal surface light is activated, finally washing removal metal surface raffinate.
Further, the metal is cold-rolled steel or aluminium alloy.
In particular, existing cold-rolled steel, aluminium alloy non-chromium process for treating surface there are aiming at the problem that, as treatment temperature is high,
The problems such as treatment fluid color is deep, corrosion resisting property is low, treatment fluid stability is poor, treatment fluid of the invention can be not only used for cold-rolled steel also
It can be used for the preparation method of the compound conversion film of the various metals material surface fluozirconate such as aluminum alloy surface.Side through the invention
Method can form uniform, continuous fluozirconate conversion film in cold-rolled steel and aluminum alloy surface, and the preparation method of conversion fluid is simple, and
Short processing time, treatment temperature is low, without being post-processed.With good corrosion resistance and with the binding force of coating, can be used as chromium
A kind of effective substitute of hydrochlorate conversion film.
The present invention will be further explained below:
In the present invention, the pH value of working solution used in cold-rolled steel/compound conversion film of aluminum alloy surface two-component fluozirconate is
3.5~5.5, optimum value is 4.0~4.5, because development person of the invention has found through a large number of experiments, as pH >=5.5, and film forming speed
Spend fast, cause conversion fluid muddy, film layer crystalline particle is coarse, and as pH≤3.5, solution to metal base seriously corroded,
Film layer film forming is uneven, anti-corrosion capability decline.
When the present invention converts film process, the temperature for the treatment of fluid is preferably controlled in 10 DEG C~30 DEG C, and excessively high temperature can make
Conversion film film forming speed is too fast, and film layer is caused to crack, and corrosion resistance declines instead.
In the present invention, the processing time of the compound conversion film of metal surface two-component fluozirconate is 1~5min, and optimum value is
2~3min, transformation time is too long, and conversion film understands oneself dissolution, and corrosion resistance is deteriorated.
In the present invention, the mass ratio of fluozirconate and promotor is 2~5:1, and optimum value 5:1, promotor is too many, film forming
Reaction is hindered, and cannot completely be formed a film.
Compared with prior art, beneficial effects of the present invention are as follows:
(1) the effective solution of the present invention method system of existing metal surface chromium-free chemical conversion product and its conversion film
Standby complicated, technique is cumbersome, the problem of practical application effect difference.
(2) the compound conversion film preparation process flow of fluozirconate of the invention is simple, at low cost, can handle in room temperature, turns
Changing film has preferable corrosion resistance and the binding force with coating, and treatment fluid is of light color, and wastewater treatment is convenient.
(3) applied widely, it is suitable for fine aluminium and aluminium alloy and cold-rolled steel, at the chromate conversion of alternative metal surface
Reason.
(4) contain amino acid polymer in treatment fluid of the invention, the stability for the treatment of fluid can be enhanced, can also further mention
Rise the corrosion resistance of the compound conversion film of fluozirconate.
(5) conversion film that the present invention obtains is fine and close, strong with powdery paints binding force, and anti-impact force is strong, can effectively replace gold
Metal surface chromic acid salt treatment process, prospect of the application are wide.
Detailed description of the invention
Fig. 1 is the scanning electron microscope sem figure of the 1 compound conversion film of aluminum alloy surface fluorine zirconic acid of the embodiment of the present invention；
Fig. 2 is 2 cold-rolled steel surface scan Electronic Speculum SEM of present example figure；
Fig. 3 is the scanning electron microscope sem figure that 1 aluminum alloy surface of comparative example of the present invention converts film process through titanium zirconium system；
Fig. 4 is the scanning electron microscope sem figure that 2 cold rolling steel surface of comparative example of the present invention converts film process through titanium zirconium system；
Fig. 5 is that the embodiment of the present invention 1 and comparative example 1 are made in the compound conversion film 3.5%NaCl of aluminum alloy surface fluorine zirconic acid
Electrochemical tests comparison diagram；
Fig. 6 is that the compound conversion film of aluminum alloy surface fluorine zirconic acid is made in 3.5%NaCl in the embodiment of the present invention 1 and comparative example 1
Middle electrochemical AC impedance comparison diagram；
Fig. 7 is that the embodiment of the present invention 2 and comparative example 2 are made in the compound conversion film 3.5%NaCl of aluminum alloy surface fluorine zirconic acid
Electrochemical tests comparison diagram；
Fig. 8 is that the compound conversion film of aluminum alloy surface fluorine zirconic acid is made in 3.5%NaCl in the embodiment of the present invention 2 and comparative example 2
Middle electrochemical AC impedance comparison diagram.
Fig. 9 is that four pieces of box methods survey throwing power schematic diagram.
Specific embodiment
With reference to embodiment, the present invention will be further explained and invention, but the present invention is not limited to realities
Apply range described in example.
The present invention includes: to cold-rolled steel/Conversion Coatings on Aluminum Alloys film layer related detecting method
1. electro-chemical test: electrochemical apparatus be Shanghai Chen Hua equipment company production electrochemical workstation and its
CHI660D software kit measures the electrochemical tests of different conversion films respectively, judges its corrosion resistance with this.
2. the XL-30 field emission scanning electron microscope (SEM) using PHILIPS company, Japan carries out metal surface conversion
Film Morphology analysis.
3. boiling water adhesion test: being coated with the conversion film layer of powder coating referring to GB/T5237.4-2008 standard test
The adhesion performance of resistance to boiling water.
4. cupping performance: being coated with the cup drawing resistance energy of the conversion film layer of powder coating referring to GB5237.4-2008 measurement.
5. salt water immersion test: after using 3.5%NaCl solution, observation conversion film film layer to impregnate three days in the solution
Whether there is or not fall off and color change etc. conversion film.
6. throwing power is tested: throwing power means during electrophoretic painting, the different coated surface electrophoresis of electric field shielding degree
The upper film ability of coating generally makes to be applied by the hidden cavity inner surface swimming of electric field and (cover on vehicle body by aperture, gap penetration
Lid) ability coated, it is tested using four pieces of box methods.
Four pieces of box methods (Fig. 9) illustrate the structure at each position of vehicle body: the face A vehicle body door exterior surface；The face H is back (or remote) from electricity
The surface (such as car body top cover outer surface) of pole；B, the face C be back (or remote) from surface (vehicle body inner surface, floor)；D, E indicates vehicle
Body door inner cavity, column；F, G indicates to need guiding through the hole of 3 Ф 8mm, table in the intraformational bed for overcoming screen effect to get to, cavity
Face.
Embodiment 1: the preparation of the compound conversion film of aluminum alloy surface fluozirconate
Fluorine zirconic acid (mass concentration is 40%~45%) 8g is taken, fluoboric acid 5g, boric acid 2g is added when being stirred with glass bar
Deionized water is added to be configured to 1L solution with ammonium hydroxide (mass concentration is 25%~28%) 3g, triethanolamine 12g；Separately 500g is taken to go
Above-mentioned two component is uniformly mixed and obtains light yellow fluorine zirconic acid conversion processing by deionized water solution calcium acetate 1g, polyglutamic acid sodium 10g
Liquid, specific gravity 1.04g/cm3。
It is working solution that above-mentioned treatment fluid, which is diluted with water 20 times, adjusts pH value to 4.3；Prepare the examination of AA1070 line aluminium alloy
Aluminium alloy test piece is immersed and handles 7min in commercially available RS-228 acid degreasing agent (60g/L) by piece, immerses above-mentioned match after washing completely
3min in the treatment fluid for the metal surface fluorine zirconic acid composite membrane that the temperature made is 25 DEG C is dried up after test piece washing with cold wind, cold
But up to the compound conversion film of 1 fluorine zirconic acid of embodiment, spraying polyester powder coating is tested for cupping experiment and boiling water adhesive force.
The embodiment of the present invention 1 converts membrane structure and performance detection is analyzed as follows:
Scanning electron microscope result (Fig. 1) shows the 1 compound conversion film of aluminium alloy fluozirconate of embodiment in cloud cluster shape knot
Structure, film layer is fine and close continuous, is simulated (such as Fig. 6) with Zsimpwin software to electrochemical impedance spectroscopy circuit, and activation polarization is bent
Line test result (such as Fig. 5): the result shows that 1 conversion film of embodiment corrosion potential in 3.5%NaCl solution is -0.73V, it is rotten
Erosion electric current is 1.225*10-7A/cm2, AC impedance 1.39*104Ω/cm2, on conversion film after coating polyester powder coating, resist
Impact property test is 50cm2, powder coating is without falling off and cracking phenomena.
Embodiment 2: the preparation of the compound conversion film of cold rolling steel surface fluozirconate
Sodium fluozirconate solution (mass concentration is 40%~45%) 10g is taken, fluoboric acid is added when being stirred with glass bar
20g, boric acid 9g and ammonium hydroxide (mass concentration is 25%~28%) 5g, triethanolamine 14g, sodium tungstate 7g, sodium molybdate 6g/L add
Ionized water is configured to 1L solution；Separately 500g deionized water solution magnesium acetate 1g, polyglycine sodium 5g is taken to mix above-mentioned two component
Uniformly obtain colourless fluozirconate conversion treating solution, specific gravity 1.073g/cm3。
It is working solution that above-mentioned treatment fluid, which is diluted with water 10 times, adjusts pH value to 4.1, lower pH value advantageously forms
The more excellent throwing power of adhesive force more preferably converts film layer.Prepare cold-rolled steel test piece, commercially available RS-228 acidity is immersed into cold-rolled steel test piece and is taken off
7min is handled in rouge agent (60g/L), washes the clean rear metal surface fluozirconate for immersing above-mentioned prepared temperature and being 25 DEG C
2min in the treatment fluid of composite membrane is dried up after test piece washing with cold wind, the cooling compound conversion film of 2 fluozirconate of embodiment to obtain the final product,
It is mating with subsequent electrophoretic coating, adhesive force, throwing power are surveyed after the toasted film forming of film layer.
The embodiment of the present invention 2 converts membrane structure and performance detection is analyzed as follows:
Scanning electron microscope result (Fig. 2) shows that the 2 compound conversion film of cold-rolled steel fluozirconate of embodiment is in cluster structure,
Film layer is fine and close continuous, is simulated (such as Fig. 8) with Zsimpwin software to electrochemical impedance spectroscopy circuit, and electrochemical tests are surveyed
Test result (such as Fig. 7): the result shows that 1 conversion film of embodiment corrosion potential in 3.5%NaCl solution is -0.79V, corrosion electricity
Stream is 6.726*10-7A/cm2, AC impedance is 947 Ω/cm2, adhesive force uses cross-hatching test for 0 grade, and throwing power is
0.57。。
In order to compare the difference of the present invention and the existing chromium-free treatment technique for main agents that uses fluotitanic acid fluorine zirconic acid,
Invention uses following comparative example.
Comparative example 1
Weigh fluotitanic acid (mass concentration is 40%~50%) 5g, fluorine zirconic acid (mass concentration is 40%~50%) 3g, side
It stirs side and fluoboric acid 5g, boric acid 2g and nitric acid (mass concentration is 65%~68%) 6g is added, add a small amount of deionized water dissolving mixed
Close, ammonium hydroxide (mass concentration be 25%~28%) 2g be then added, is uniformly mixed, with deionized water be diluted to 1L obtain it is colourless
Transparent titanium zirconium system treatment fluid.
Weighing above-mentioned treatment fluid 50mL and being diluted to 1000mL is working solution, adjusts pH value to 5.0.First A1070 aluminium is closed
Golden test piece handles 7min in section's richness RS-228 60g/L acidic degreasing liquid, and washing is clean, immerses above-mentioned prepared temperature and is
4min in 20 DEG C for the treatment of fluid is dried up after the washing of test piece deionization with cold wind.Gained conversion film is titanium zirconium conversion film.
The conversion film analysis of comparative example 1:
Scanning electron microscope result (Fig. 3) shows: 1 aluminum alloy surface titanium zirconium conversion film of comparative example shows microcosmic part
Deposition locally has chap；Electrochemical impedance is simulated with Zsimpwin software, compound turn of 1 fluozirconate of comparative example
Changing film corrosion potential in 3.5%NaCl solution is -1.28V, corrosion current 6.325*10-6A/cm2, impedance value is
2.72*103Ω/cm2, there is no have very high corrosion resistance as fluozirconate composite membrane.To the titanium zirconium conversion film of comparative example 1, spraying
Polyester powder coating is for cupping experiment and boiling water adhesion test.
Comparative example 2
Comparative example 1 is repeated, A1070 aluminium alloy test piece is changed to cold-rolled steel, prepares titanium zirconium conversion film in cold rolling steel surface.
The conversion film analysis of comparative example 2:
Scanning electron microscope result (Fig. 4) shows: 2 cold rolling steel surface titanium zirconium conversion film of comparative example shows spherical particle
Aggregation, film layer are relatively thin；Electrochemical impedance is simulated with Zsimpwin software, the compound conversion film of 1 fluozirconate of comparative example exists
Corrosion potential is -0.91V, corrosion current 7.525*10 in 3.5%NaCl solution-6A/cm2, impedance value is 423 Ω/cm2,
There is no corrosion resistances with higher as fluozirconate composite membrane.To the titanium zirconium conversion film of comparative example 2, polyester powder is sprayed
Coating is for cupping experiment and boiling water adhesion test.
Comparative example 1, comparative example 2 and the metal surface conversion film properties of embodiment 1, embodiment 2 are shown in Table 1.
1 cold-rolled steel of table/aluminum alloy surface difference conversion film properties compare
By 1 result of table, it was found that, the compound conversion film film of fluozirconate in the embodiment of the present invention belongs to lightweight again,
Film weighs the lower binding force for being conducive to raising and coating and reduces cost, still further it can be seen that the conversion film film weight after composite modified is general
All over higher than the corrosion resistance of titanium zirconium conversion film, impact resistance test and salt water immersion test etc. illustrate that it is good with powder coating binding force
It is good, it is good with electrophoretic coating binding force and throwing power.
The embodiment of the above is only the preferred embodiments of the invention, and but not intended to limit the scope of the present invention,
Therefore all components according to the present invention, change made by principle, it should all be included within the scope of protection of the present invention.
Claims (10)
1. being used to prepare the treatment fluid of the compound conversion film of fluorine zirconic acid, which is characterized in that the treatment fluid is aqueous solution, every liter of processing
Contain in liquid:
5 ~ 30g of fluozirconate
1 ~ 5g of ammonium hydroxide
5 ~ 40g of auxiliary oxidizing agent
5 ~ 20g of complexing agent
1 ~ 10g of amino acid polymer
0.5 ~ 5g of promotor
Wherein, the amino acid polymer is one or more of polyglutamic acid sodium, polyglycine sodium.
2. treatment fluid according to claim 1, which is characterized in that contain in every liter for the treatment of fluid:
10 ~ 25g of fluozirconate
1.5 ~ 3.5g of ammonium hydroxide
10 ~ 35g of auxiliary oxidizing agent
10 ~ 15g of complexing agent
4 ~ 8g of amino acid polymer
1.5 ~ 3.5g of promotor.
3. treatment fluid according to claim 1, which is characterized in that the fluozirconate is potassium fluorozirconate, sodium fluozirconate, fluorine
One of zirconic acid is a variety of.
4. treatment fluid according to claim 1, which is characterized in that the auxiliary oxidizing agent be potassium fluoborate, sodium fluoborate,
One or more of fluoboric acid, boric acid, Boratex, potassium borate, m-nitrobenzene sodium sulfonate, sodium tungstate, sodium molybdate.
5. treatment fluid according to claim 1, which is characterized in that the complexing agent be triethylamine, ethylenediamine, ethanol amine,
One or more of diethanol amine, triethanolamine.
6. treatment fluid according to claim 1, which is characterized in that the promotor be lithium acetate, sodium acetate, potassium acetate,
One or more of calcium acetate, magnesium acetate, zinc acetate.
7. the preparation method for the treatment of fluid as claimed in any one of claims 1 to 6, which comprises the steps of:
Fluozirconate, auxiliary oxidizing agent, complexing agent, ammonium hydroxide deionized water dissolving are obtained into component a according to prescription for the treatment of liquid；
Amino acid polymer, promotor deionized water dissolving are obtained into component b according to prescription for the treatment of liquid；
Component a and component b is uniformly mixed to obtain treatment fluid.
8. the preparation method of the compound conversion film of fluorine zirconic acid, which comprises the steps of:
Metal surface is pre-processed；
The treatment fluid that treatment fluid as claimed in any one of claims 1 to 6 or preparation method as claimed in claim 7 are obtained into
Row dilution processing, adjusts pH value, obtains the working solution that pH value is 3.5-5.5；
Pretreated metal is placed in the working solution, chemical conversion film process is carried out；Period, control reaction time are 1-
5min, treatment fluid temperature are 10-30 DEG C.
9. preparation method according to claim 7, which is characterized in that when pre-processing to metal, first use organic solvent
Metal surface dirt is cleaned, successively after washing, pickling, then is washed.
10. preparation method according to claim 7, which is characterized in that the metal is cold-rolled steel or aluminium alloy.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110607522A (en) * | 2019-10-12 | 2019-12-24 | 佛山市湾厦新材料科技有限公司 | Vitrification agent and preparation method and application thereof |
| CN111733409A (en) * | 2020-06-04 | 2020-10-02 | 太仓托普斯特金属制品有限公司 | Vitrification process of automobile parts made of carbon steel material |
| CN113201731A (en) * | 2021-05-08 | 2021-08-03 | 东北大学 | Method for quickly forming zirconium film on surface of high-strength steel for automobile |
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