CN101476120A - Environment-friendly type metal surface finishing agent and preparation thereof - Google Patents
Environment-friendly type metal surface finishing agent and preparation thereof Download PDFInfo
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- CN101476120A CN101476120A CNA2009101161349A CN200910116134A CN101476120A CN 101476120 A CN101476120 A CN 101476120A CN A2009101161349 A CNA2009101161349 A CN A2009101161349A CN 200910116134 A CN200910116134 A CN 200910116134A CN 101476120 A CN101476120 A CN 101476120A
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Abstract
The invention discloses an environmental-friendly type metal surface treating agent and a preparing method thereof which has steps as follows: moistening a filmerformer by a solution containing dispersant, then adding a coupling agent, stirring and dispersing for obtaining a steady colloid, adding water-soluble Si or complex compound containing F of IV family element, then adding acid as stabilizing agent and excess water, adjusting PH value of the system 1.0-3.0 and obtaining the environmental-friendly type metal surface treating agent. The environmental-friendly type metal surface treating agent is diluted to a working liquid with PH value 3.0-6.0 by using water, a micro-crystalline ceramic compound conversion film is obtained by contacting the waited-treat clean metal surface with the environmental-friendly type metal surface using immerging or spraying method. The treating agent has performance index of the treating agent is superior or equal to prior zinc family, iron family phosphate liquid. The treating agent has advantages of environmental-friendly, innocuity, low temperature treating, no surface conditioning with low slag and simple operation, is a new type environmental-friendly type product that can replace traditional metal surface treating agent.
Description
Technical field
The invention belongs to the metal conditioner technical field, particularly iron and steel, zinc-plated iron-steel, zinc and zinc alloy and aluminium and aluminium alloy are carried out surface-treated treatment agent and preparation method thereof before application.
Background technology
According to the relevant regulations among GB GB/T6807-2001 " phosphorization treatment technology before the iron and steel parts application " and " aviation industry standard " HB/25080-1996, the standard method that the coated metal front surface is handled is the method based on phosphoric acid salt, be commonly referred to bonderizing, promptly treating that coating metal surface generates the protective film of one deck phosphate crystal.Can obtain the favorable protection effect behind the coating metal surfaces.The method that phosphorization technology generally adopts as metal finishing before the application now, its further improved space is very little; Because contain a large amount of phosphorus and nitrogen in the phosphorization agent, existing phosphorization technology can bring serious pollution to environment inevitably, can cause the eutrophication of water body, the ecosystem in river, lake is threatened; The heavy metal that contains in the phosphorization agent can cause possible permanent damage to human body; The conventional phosphatizing technology use of need heating simultaneously causes energy consumption and produces a large amount of sludges.So be badly in need of new environment-friendly type metal surface finishing agent to replace the product of existing phosphating process.
In recent years, the alternative techniques research that conventional phosphatizing is handled both at home and abroad is a lot, mainly concentrates on the technology and the prescription of environmental protection, harmless, low temperature, low slag are studied, and wherein reports more to the membrane-forming agent technology of silane series; But owing to be difficult to solve as the problems such as controllability water-soluble, hydrolysis of the silane coupling agent of main film forming component, the film of its film forming layer is heavy, integrated performance index is undesirable after compactness and the application, does not see the report that maturation process is arranged so far.
The silane coupling agent class membrane-forming agent that Chinese patent application 200510127048.X proposes, form by moisture and/or pure siliceous binder solution as solvent, the weight percent concentration of its silica component is 8-25%, comprise by what the organoalkoxysilane hydrolysis condensation reaction obtained and have a metal conditioner that weight-average molecular weight is the alkoxysilane oligomer alcoholic solution of 1000-10000, appearance that can the long term inhibition white rust.But because this silane coupled technology is made solvent by alcohols and is needed the hydrolysis of control silane and difficult realization industrial application, and the corrosion-resistant test performance of formed ultra-thin organic membrane empirical tests 500h after application is relatively poor, so this metal conditioner still is difficult to substitute traditional phosphating agent.
Chinese patent application numbers 200710066786.7 is disclosed, and a kind of to be used for the metallic surface pretreated be the metal conditioner of main component with the silane coupling agent, at the container that injects 100 parts of deionized waters, stirring velocity is that per minute 2000～2200 changes, successively add first toughener, stablizer, second toughener, silane coupling agent and dispersion agent, obtain to be used for the preceding silane coupled prefilming agent of coated metal.But the corrosion-resistant test performance of ultra-thin organic membrane empirical tests 500h after application that this silane coupled technology forms is relatively poor, so this metal conditioner also is difficult to substitute traditional phosphating agent.
The Chinese patent application number 200810020748.2 a kind of treatment agents that propose, comprise silane coupling agent (SA), water-dispersible silica, fluorine cpd, acetate and water, by major ingredient such as surface conditioner, secondary film formers screening and composite, with final formation silane tunicle.But find that by checking the component of Zirconium tetrafluoride, titanium fluoride can't form rete, be difficult to form composite membrane with silane film to the example; This treatment agent exists rete single, and corrosion-resistant test performance is relatively poor, is difficult to reach the phosphorization agent substitution effect.
Summary of the invention
The object of the invention provides a kind of environment-friendly type metal surface finishing agent that is used for the coating metal surfaces pre-treatment and preparation method thereof, to substitute the conventional phosphatizing agent, overcomes defectives such as existing silane technology rete is single, solidity to corrosion difference.
Environment-friendly type metal surface finishing agent of the present invention is characterized in that containing by mass percentage following component:
0.01～10.0% membrane-forming agent is selected from nano level TiO
2, ZrO
2And/or SiO
2
0.01～10.0% dispersion agent is selected from polyacrylic acid, vinylformic acid and/or maleic acid-acrylic acid copolymer;
0.01～10.0% coupling agent is selected from copolymeric siloxane oligopolymer, titanium crosslinkers and/or aluminium zirconium crosslink agent solution;
0.1～15.0% water miscible Si or IV family element contain the F complex compound, be selected from H
2TiF
6, H
2ZrF
6, H
2HfF
6And/or H
2SiF
6, and/or their salt;
0.01～2.0% the acid as stablizer is selected from H
2SO
4, HF, HCl, HNO
3, citric acid and/or tartrate;
The water that adds surplus again mixes.
The preparation method of environment-friendly type metal surface finishing agent of the present invention, it is characterized in that: the membrane-forming agent that will account for system quality 0.01～10.0%, with contain the mass percent concentration that accounts for system quality 0.01～10.0% dispersion agent be 30% the aqueous solution wetting after, add the coupling agent that accounts for system quality 0.01～10.0%, with 2000～2200 rev/mins speed dispersed with stirring to obtaining stable colloid, what add the water miscible Si account for system quality 0.1～15.0% or IV family element again contains the F complex compound, adding what account for system quality 0.01～2.0% again is 1.0～3.0 as the water of the acid of stablizer and surplus and the pH value that is adjusted to system, promptly obtains environment-friendly type metal surface finishing agent of the present invention.
During use, environment-friendly type metal surface finishing agent of the present invention can be diluted with water to pH value and be 3.0～6.0 working fluid, adopt immersion or pending clean metallic surfaces is contacted with environment-friendly type metal surface finishing agent of the present invention at the normal temperature state, make pending metallic surface generate the protective conversion film in the spray mode; The preferred pH value that uses is adjusted to 3.8～5.5 working fluid.
Environment-friendly type metal surface finishing agent of the present invention is when contacting with the metallic surface, owing to contain H in its component
2TiF
6, H
2ZrF
6, H
2HfF
6, H
2SiF
6And/or its esters, be in 1.0～6.0 the solution state at pH value, can provide the H ion and to the dissolving metal of interface contact, the interface of dissolving metal then be a micro anode, the while produces corresponding micro cathode at metal interface, and the pH value of micro cathode can rise H
2TiF
6, H
2ZrF
6, H
2HfF
6, H
2SiF
6And its esters can to form under the alkaline condition that becomes with the oxide compound of Ti, Zr, Hf and/or Si be the precipitation rete of agent structure.Simultaneously because the effect of component membrane-forming agent and linking agent, can form intermolecular rete with intermetallic with covalent bonds power, it finally is the precipitation rete filling of agent structure to oxide compound with Ti, Zr, Hf and/or Si, improved the compactness of rete, form a kind of nano level fine and closely woven and compound conversion rete of micro-crystalline ceramic that porosity is low in the metallic surface, this rete has fabulous unreactiveness, acid-and base-resisting and resistance to oxidation, have the performance index that are better than or are equal to existing zinc system, phosphating liquor of iron series, can obtain the favorable protection effect; Especially the processing film that adopts surface treatment agent of the present invention to obtain before coated metal can be combined closely with the organic membrane of coating after the application, forms the protection layer system with excellent barrier propterty, thereby can reach the effect that substitutes phosphorization agent.
Environment-friendly type metal surface finishing agent of the present invention has the following advantages with existing comparing based on the surface treatment agent of phosphoric acid salt:
1) environmentally friendly, do not contain heavy metal and phosphorus nitrogen, the discharging for the treatment of processes slag and effluent is few, only need do simple sewage discharge processing and get final product;
2) use economy, simple to operate, no sediment; Can be in room temperature treatment, the mode that adapts to spray or immersion is used;
3) application art of this product is suitable for traditional phosphating process production line.
Environment-friendly type metal surface finishing agent of the present invention is the ideal replacement type product of existing bonderite.
Embodiment
Get the 4 * 8cm that meets 08 II-P-GB13237-91 standard
215 of same cold-rolled steel sheets and 4 * 8cm
23 of Baosteel heat production galvanized sheet DD51D+Z steel plates are standby.Adopt commercially available pure polyester powder coating to carry out the application coating among the embodiment.
Embodiment 1:
Present embodiment prepares each component in the environment-friendly type metal surface finishing agent by following composition and quality proportioning:
Nano level TiO
29.0%,
Maleic acid-acrylic acid copolymer 0.8%,
2909 water soluble amino functional group copolymeric siloxane oligopolymers 3.0%,
H
2TiF
6 4.0％，
HF 0.02％，
Surplus is a deionized water.
The concrete operations step that present embodiment prepares environment-friendly type metal surface finishing agent is as follows:
Membrane-forming agent is added entry and coupling agent after with the solution-wet of dispersion agent again, be dispersed to 2000～2200 rev/mins of high-speed stirring and obtain stable colloid, whipped state adds down slowly sour HF and the balance of deionized water as stablizer, and resultant pH value is the environment-friendly type metal surface finishing agent that 1.0～3.0 liquid is the present embodiment preparation.Standby.
Get 4 * 8cm
2Three of standby cold-rolled steel sheets are got the environment-friendly type metal surface finishing agent liquid of the above-mentioned preparation of present embodiment, and adding deionized water, to adjust to pH value be 4.8 as treatment solution; Carry out metallic surface pre-treatment and application operation steps then successively: degreasing → water cleaning → film forming processing → water cleaning → washed with de-ionized water → 130 ℃ of dry 10min → powder coating → 185 ℃ curing 20min,
Prepare the 5wt% aqueous solution of commercially available Henkel PC-1523 grease-removing agent, heat, adopt immersion or spray degreasing oil removing to obtain clean surface through the clear water rinsing again 3 standby cold-rolled steel sheets respectively to 50 ℃; Standby cold-rolled steel sheet being immersed the above-mentioned pH value for preparing with the present embodiment environment-friendly type metal surface finishing agent again and be 4.8 treatment solution, maybe is the evenly standby cold-rolled steel sheet of spray of 4.8 treatment solution with this pH value; Treatment time is 120s; Again with clear water and rinsed with deionized water 2min; Then through 130 ℃ of dry 10min, get wherein 2 through commercially available Aksu pure polyester powder coating do electrostatic spraying, solidify 20min through 185 ℃ again, control coating thickness 60 μ m, wherein another piece does not enter application and curing process, it is heavy to give over to test rete outward appearance and film.
Test event at the prepared environment-friendly type metal surface finishing agent sample of the present invention has: (1) conversion film outward appearance; (2) film is heavy; (3) hundred lattice of the sticking power after application test, with reference to CNS GB1720-85, interval 2mm, the 3M special adhesive tape draws three times; (4) anti-corrosion test is carried out with reference to 500 hours neutral salt spray test modes of test listed among the CNS GB/T1771-91; (5) shock resistance is with reference to the anti-50Kg/cm test of CNS GB/T1732-93.
Environment-friendly type metal surface finishing agent film forming layer demoulding method for measuring weight of the present invention is: get the coated steel sheet of a 4x6 square inch, dry up the back and measure its weight A, be accurate to 0.1 milligram; In temperature is that 66 ℃, concentration are to soak 10 minutes in the KOH solution of 45wt%; Take out model, water flushing at least 1 minute is extremely rinsed after-blow dry sample plate fully well, and is measured its weight B, is accurate to 0.1 milligram.It is heavy to calculate total film according to following formula: (A-B)/and 2 * surface-area.
Embodiment 2:
Present embodiment prepares each component in the environment-friendly type metal surface finishing agent by following composition and quality proportioning:
Nano level SiO
28.0%,
Polyacrylic acid 2.0%,
2909 water soluble aminos/alkyl functional group copolymeric siloxane oligopolymer 10.0%,
H
2SiF
6 12.0％，
H
2SO
4 0.2％，
Surplus is a deionized water.
The concrete operations step that present embodiment prepares environment-friendly type metal surface finishing agent is as follows:
Membrane-forming agent is added entry and coupling agent after with the solution-wet of dispersion agent again, be dispersed to 2000～2200 rev/mins of high-speed stirring and obtain stable colloid, whipped state slowly adds the H as stablizer down
2SO
4And balance of deionized water, resulting pH value is the environment-friendly type metal surface finishing agent that 1.0～3.0 liquid is the present embodiment preparation.
Get 4 * 8cm
2Three of standby cold-rolled steel sheets are got the environment-friendly type metal surface finishing agent liquid of above-mentioned present embodiment preparation, and adding deionized water, to adjust to pH value be 4.5 as treatment solution; Carry out metallic surface pre-treatment and application operation steps then successively: degreasing → water cleaning → film forming processing → water cleaning → washed with de-ionized water → 130 ℃ of dry 10min → powder coating → 185 ℃ curing 20min,
Prepare the 5wt% aqueous solution of commercially available Henkel PC-1523 grease-removing agent, heat, adopt immersion or spray degreasing oil removing to obtain clean surface through the clear water rinsing again 3 standby cold-rolled steel sheets respectively to 50 ℃; Again standby cold-rolled steel sheet is immersed the above-mentioned pH value for preparing with the present embodiment environment-friendly type metal surface finishing agent and be 4.5 treatment solution, or to adopt the pH value for preparing with the present embodiment environment-friendly type metal surface finishing agent be the evenly standby cold-rolled steel sheet of spray of 4.5 treatment solution; Treatment time is 120s; Again with clear water and rinsed with deionized water 2min; Then through 130 ℃ of dry 10min; Get wherein 2 through commercially available Aksu pure polyester powder coating do electrostatic spraying, solidify 20min, control coating thickness 60 μ m through 185 ℃ again; Wherein another piece does not enter application and curing process, and it is heavy to give over to test rete outward appearance and film.
Test event and operation are with embodiment 1.
Embodiment 3:
Present embodiment prepares each component in the environment-friendly type metal surface finishing agent by following composition and quality proportioning:
Nano level TiO
29.0%,
Vinylformic acid 3.0%,
2926 soluble epoxide base functional group siloxanes oligopolymers 2.0%,
H
2ZrF
6 6.0％，
H
2SiF
6 3.0％，
HCl 0.05％，
Surplus is a deionized water.
The concrete operations step that present embodiment prepares environment-friendly type metal surface finishing agent is as follows:
Membrane-forming agent is added entry and coupling agent after with the solution-wet of dispersion agent again, be dispersed to 2000～2200 rev/mins of high-speed stirring and obtain stable colloid, whipped state adds down slowly HCl and the balance of deionized water as stablizer, obtains pH value and be the environment-friendly type metal surface finishing agent that 1.0～3.0 liquid is the present embodiment preparation.
Get 4 * 8cm
2Three of standby cold-rolled steel sheets, the environment-friendly type metal surface finishing agent liquid of getting the preparation of above-mentioned present embodiment add deionized water, and to be adjusted to pH value be 5.1 to deal with liquid; Carry out metallic surface pre-treatment and application operation steps then successively: degreasing → water cleaning → film forming processing → water cleaning → washed with de-ionized water → 130 ℃ of dry 10min → powder coating → 185 ℃ curing 20min,
Prepare the 5%wt aqueous solution of commercially available Henkel PC-1523 grease-removing agent, heat, adopt immersion or spray degreasing oil removing to obtain clean surface through the clear water rinsing again 3 standby cold-rolled steel sheets respectively to 50 ℃; Again standby cold-rolled steel sheet is immersed the above-mentioned pH value for preparing with the present embodiment environment-friendly type metal surface finishing agent and be 5.1 treatment solution, or to adopt the above-mentioned pH value for preparing with the present embodiment environment-friendly type metal surface finishing agent be the evenly standby cold-rolled steel sheet of spray of 5.1 treatment solution; Treatment time is 120s; Again through clear water and rinsed with deionized water 2min; Then through 130 ℃ of dry 10min, get wherein 2 through commercially available Aksu pure polyester powder coating do electrostatic spraying, solidify 20min, control coating thickness 60 μ m through 185 ℃ again; Wherein another piece does not enter application and curing process, and it is heavy to give over to test rete outward appearance and film.
Test event and operation thereof are with embodiment 1.
Embodiment 4:
Present embodiment prepares each component in the environment-friendly type metal surface finishing agent by following composition and quality proportioning:
Nano level SiO2 6.8%,
Vinylformic acid 1.0%,
371 water-based titanium crosslinkers (coupling agent) 6.0%,
H
2TiF
6 10.0％，
Citric acid 1.5%,
Surplus is an amount of deionized water.
The concrete operations step that present embodiment prepares environment-friendly type metal surface finishing agent is as follows:
Membrane-forming agent is added entry and coupling agent after with the solution-wet of dispersion agent again, be dispersed to 2000～2200 rev/mins of high-speed stirring and obtain stable colloid, whipped state adds down slowly citric acid and balance of deionized water, obtains pH value and be the environment-friendly type metal surface finishing agent that 1.0～3.0 liquid is the present embodiment preparation.
Get 4 * 8cm
2Three of heat zinc coating plate DD51D+Z (Baosteel), the environment-friendly type metal surface finishing agent liquid of getting the preparation of above-mentioned present embodiment add deionized water, and to adjust to pH value be 4.0 to deal with liquid; Carry out metallic surface pre-treatment and application operation steps then successively: weak base degreasing → water cleaning → film forming processing → water cleaning → washed with de-ionized water → 130 ℃ of dry 10min → powder coating → 185 ℃ curing 20min,
Prepare the 3wt% aqueous solution of commercially available Henkel PC-1523 grease-removing agent, heat, adopt immersion or spray degreasing oil removing to obtain clean surface through the clear water rinsing again 3 standby cold-rolled steel sheets respectively to 45 ℃; Again standby cold-rolled steel sheet is immersed the above-mentioned pH value for preparing with the present embodiment environment-friendly type metal surface finishing agent and be 4.0 treatment solution, or to adopt the above-mentioned pH value for preparing with the present embodiment environment-friendly type metal surface finishing agent be the evenly standby cold-rolled steel sheet of spray of 4.0 treatment solution; Treatment time is 180s; Again through clear water and rinsed with deionized water 2min; Then through 130 ℃ of dry 10min, get wherein 2 through commercially available Aksu pure polyester powder coating do electrostatic spraying, solidify 20min, control coating thickness 60 μ m through 185 ℃ again; Wherein another piece does not enter application and curing process, and it is heavy to give over to test rete outward appearance and film.
Test event and operation thereof are with embodiment 1.
Comparative example 1:
Get the Henkel 6001 Zinc phosphatings work of treatment liquid of selling on the market,, and add yellow soda ash modulation total acidity 22.0, free acidity 1.2 with the deionized water dilution of 30 times of volumes; Add Sodium Nitrite and do promotor, transferring to the gas point is 2.6, is warming up to 45 ℃, is the treatment solution of the phosphating agent that this comparative example of preparing uses, standby.
Get 4 * 8cm
2Three of standby cold-rolled steel sheets, carry out metallic surface pre-treatment and application operation steps: degreasing → water cleaning → film forming processing → water cleaning → washed with de-ionized water → 130 ℃ of dry 10min → powder coating → 185 ℃ curing 20min,
Prepare the aqueous solution of the 5wt% of commercially available Henkel PC-1523 grease-removing agent, heat, adopt immersion or spray degreasing oil removing to obtain clean surface through the clear water rinsing again 3 standby cold-rolled steel sheets respectively to 50 ℃; Again standby cold-rolled steel sheet is immersed the treatment solution of the phosphating agent that above-mentioned this comparative example for preparing uses, or the even standby cold-rolled steel sheet of spray of the treatment solution that adopts the above-mentioned phosphating agent for preparing; Treatment time is 120s; Again through clear water and rinsed with deionized water 2min; Then through 130 ℃ of dry 10min, get wherein 2 through commercially available Aksu pure polyester powder coating do electrostatic spraying, solidify 20min, control coating thickness 60 μ m through 185 ℃ again; Wherein another piece does not enter application and curing process, and it is heavy to give over to test rete outward appearance and film.
Test event is with embodiment 1, and film heavily adopts the chromic salt test, the phosphatize phosphate coat method for measuring weight: get 6 square inches of coated steel sheets of one 4 x, dry up back its weight of mensuration and be designated as m, be accurate to 0.1 milligram; When test fluid (the analytical pure chromic acid solution of 20% (w/v) concentration) is heated to after 80-95 ℃, test piece is dipped in the solution, 60 backs are taken out test piece and are washed in the mobile tap water, dry up, weigh once more, be designated as n (mg), be calculated as follows: heavy (milligram/square feet)=144 * (m-n) (milligram) of film/test piece surface-area (square inch).
Comparative example 2:
Getting Henkel 1090 iron of selling on the market is the bonderizing working fluid, with deionized water dilution, and modulation total acidity 12.0, free acidity 2.2 is warming up to 45 ℃, is the treatment solution of the phosphating agent that this comparative example of preparing uses, and is standby.
Get 4 * 8cm
2Three of standby cold-rolled steel sheets, carry out metallic surface pre-treatment and application operation steps: degreasing → water cleaning → film forming processing → water cleaning → washed with de-ionized water → 130 ℃ of dry 10min → powder coating → 185 ℃ curing 20min,
Prepare the aqueous solution of the 5wt% of commercially available Henkel PC-1523 grease-removing agent, heat, adopt immersion or spray degreasing oil removing to obtain clean surface through the clear water rinsing again 3 standby cold-rolled steel sheets respectively to 50 ℃; Again standby cold-rolled steel sheet is immersed the treatment solution of the phosphating agent that above-mentioned this comparative example for preparing uses, or the even standby cold-rolled steel sheet of spray of the treatment solution that adopts the above-mentioned phosphating agent for preparing; Treatment time is 120s; Again through clear water and rinsed with deionized water 2min; Then through 130 ℃ of dry 10min, get wherein 2 through commercially available Aksu pure polyester powder coating do electrostatic spraying, solidify 20min through 185 ℃ again, control coating thickness 60 μ m, wherein another piece does not enter application and curing process, it is heavy to give over to test rete outward appearance and film.
Test event is with embodiment 1, and film is resurveyed examination with comparative example 1.
Can prove the industrial utility value that this invention has by the parallel contrast test of above embodiment comparative example, checking the present invention is a kind of metal conditioner that can replace the novel environment-friendly of the promptly existing phosphatization liquid of conventional metals surface treatment agent.Test event at the prepared environment-friendly type metal surface finishing agent sample of the present invention has: (1) conversion film outward appearance; (2) film is heavy; (3) hundred lattice of the sticking power after application test, with reference to CNS GB1720-85, interval 2mm, the 3M special adhesive tape draws three times; (4) anti-corrosion test is carried out with reference to 500 hours neutral salt spray test modes of test listed among the CNS GB/T1771-91; (5) shock resistance is with reference to the anti-50Kg/cm test of CNS GB/T1732-93.
The performance test results is listed in following table 1 and table 2 respectively:
Table 1
| The conversion film outward appearance | The heavy mg/m of film 2 | |
| Embodiment 1 | Faint yellow | 55mg/m 2 |
| Embodiment 2 | Faint yellow | 67mg/m 2 |
| Embodiment 3 | Faint yellow | 58mg/m 2 |
| Embodiment 4 | Little yellow | 88mg/m 2 |
| Comparative example 1 | Dark grey | 1580mg/m 2 |
| Comparative example 2 | Blue color | 385mg/m 2 |
Table 2
| Adhesion performance | Anti-corrosion test mm/500h | Shock resistance 50Kg/cm | |
| Embodiment 1 | 100％ | 3.5mm | The coating flawless, come off |
| Embodiment 2 | 100％ | 3.0mm | The coating flawless, come off |
| Embodiment 3 | 100％ | 2.0mm | The coating flawless, come off |
| Embodiment 4 | 100％ | 2.0mm | The coating flawless, come off |
| Comparative example 1 | 100％ | 2.2mm | The coating flawless, come off |
| Comparative example 2 | 98％ | 4.0mm | The coating flawless, come off |
Analyzed more as can be seen by test data result listed in top table 1 and the table 2: the sticking power after its application of environment-friendly type metal surface finishing agent of the present invention, solidity to corrosion and shock resistance test all are better than or are equal at least existing zinc system, phosphating liquor of iron series performance index; Advantages such as environment-friendly type metal surface finishing agent of the present invention has environmental protection, harmless, subzero treatment, low slag be need not to do table and transfer, simple to operation; Prove that it can replace the i.e. new generation of environment protection product of existing phosphorization agent of conventional metals surface treatment agent, has industrial utility value.
Claims (6)
1, a kind of environment-friendly type metal surface finishing agent is characterized in that containing by mass percentage following component:
Membrane-forming agent 0.01～10.0%;
Dispersion agent 0.01～10.0%;
Coupling agent 0.01～10.0%;
Water miscible Si and IV family element contain F complex compound 0.1～15.0%;
Acid 0.01～2.0% as stablizer;
The water of surplus.
2, environment-friendly type metal surface finishing agent as claimed in claim 1 is characterised in that described membrane-forming agent is selected from nano level TiO
2, ZrO
2And/or SiO
2
3, environment-friendly type metal surface finishing agent as claimed in claim 1 is characterised in that described dispersion agent is selected from polyacrylic acid, vinylformic acid and/or maleic acid-acrylic acid copolymer.
4, environment-friendly type metal surface finishing agent as claimed in claim 1 is characterised in that the F complex compound that contains of described water miscible Si and IV family element is selected from H
2TiF
6, H
2ZrF
6, H
2HfF
6And/or H
2SiF
6, and/or their salt.
5, environment-friendly type metal surface finishing agent as claimed in claim 1 is characterised in that described acid as stablizer is selected from H
2SO
4, HF, HCl, HNO
3, citric acid and/or tartrate.
6, the preparation method of the described environment-friendly type metal surface finishing agent of claim 1, it is characterized in that: the membrane-forming agent that will account for system quality 0.01～10.0%, with contain the mass percent concentration that accounts for system quality 0.01～10.0% dispersion agent be 30% the aqueous solution wetting after, add the coupling agent that accounts for system quality 0.01～10.0%, with 2000～2200 rev/mins speed dispersed with stirring to obtaining stable colloid, what add the water miscible Si account for system quality 0.1～15.0% or IV family element again contains the F complex compound, adding what account for system quality 0.01～2.0% again is 1.0～3.0 as the water of the acid of stablizer and surplus and the pH value that is adjusted to system, promptly obtains environment-friendly type metal surface finishing agent of the present invention.
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| CN104099593A (en) * | 2014-06-19 | 2014-10-15 | 锐展(铜陵)科技有限公司 | Surface treating agent for trace rare earth aluminum alloy |
| CN104313559A (en) * | 2014-11-11 | 2015-01-28 | 广州立铭环保科技有限公司 | Vitrifying agent, preparation method of vitrifying agent and vitrifying treatment method using vitrifying agent |
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| CN104099593A (en) * | 2014-06-19 | 2014-10-15 | 锐展(铜陵)科技有限公司 | Surface treating agent for trace rare earth aluminum alloy |
| CN104313559A (en) * | 2014-11-11 | 2015-01-28 | 广州立铭环保科技有限公司 | Vitrifying agent, preparation method of vitrifying agent and vitrifying treatment method using vitrifying agent |
| CN105970200A (en) * | 2016-05-30 | 2016-09-28 | 南京工程学院 | Train door protection layer and production method thereof |
| CN105970200B (en) * | 2016-05-30 | 2018-11-23 | 南京工程学院 | A kind of Train door protective layer and preparation method thereof |
| CN105907048A (en) * | 2016-05-31 | 2016-08-31 | 安徽开林新材料股份有限公司 | Steel surface water-based treatment agent carrier |
| CN106435548A (en) * | 2016-09-28 | 2017-02-22 | 广州凯耀资产管理有限公司 | Automotive window metal processing solution and preparation method and application method thereof |
| CN107099791A (en) * | 2017-07-07 | 2017-08-29 | 荆门市拓达科技有限公司 | Phosphateless environmentally friendly metal surface pretreatment liquid and its application method |
| CN113106434A (en) * | 2021-04-12 | 2021-07-13 | 南昌大学 | Environment-friendly aluminum alloy chemical oxidation liquid and chemical oxidation method |
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