CN109321908A - A kind of metal surface multifunction environment-protection type nanometer vitrification liquid and preparation method thereof and application method - Google Patents
A kind of metal surface multifunction environment-protection type nanometer vitrification liquid and preparation method thereof and application method Download PDFInfo
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- CN109321908A CN109321908A CN201811259480.8A CN201811259480A CN109321908A CN 109321908 A CN109321908 A CN 109321908A CN 201811259480 A CN201811259480 A CN 201811259480A CN 109321908 A CN109321908 A CN 109321908A
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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
- C23C22/05—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
- C23C22/40—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 molybdates, tungstates or vanadates
- C23C22/44—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 molybdates, tungstates or vanadates containing also 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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
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Abstract
The invention discloses a kind of metal surface multifunction environment-protection type nanometer vitrification liquid and preparation method thereof and application methods, metal surface multifunction environment-protection type nanometer vitrification liquid, by weight percentage, component is as follows: main film forming agent 3-10%, auxiliary film former 1-10%, aqueous organic resin 1-10%, Nano sol 0.1-3%, complexing agent 0.1-1%, coupling agent 0.1-1%, inhibition wetting agent 0.05-1%, surplus are water；And the method for preparing the preparation method of above-mentioned vitrification liquid and vitrification processing being carried out to metal component using above-mentioned vitrification liquid.The present invention provide it is a kind of there is good heat-resisting quantity, corrosion resistance, hydrophobicity and electric conductivity, suitable for the stable metal surface multifunction environment-protection type nanometer vitrification liquid of all metal components, and preparation method thereof and application method.
Description
Technical field
The invention belongs to field of metal surface treatment technology, specially a kind of metal surface multifunction environment-protection type nanometer vitrification
Liquid and preparation method thereof and application method.
Background technique
To prevent the metal components such as steel surface in storage, production process to be oxidized and get rusty, it is necessary in coating process
It is surface-treated before processing.Traditional process of surface treatment includes chromate conversion (abbreviation chromaking), phosphate conversion (abbreviation
Phosphatization) processing.It can generate Cr VI in chromaking treatment process, pollute environment and seriously endanger human health and being strictly limited makes
With；And contain the heavy metals such as phosphorus and nickel, manganese in etching waste liquor, phenomena such as causing red tide, wawter bloom is easy after discharging of waste liquid.Cause
This, develops process of surface treatment of new generation, i.e. vitrification treatment process.
Vitrification processing can metal surface formed nanometer vitrification film, it is different from traditional crystal type phosphatization protective layer, just by
Gradually substitute traditional phosphating process.The primary raw material of vitrification liquid is fluozirconate, and silane coupling agent etc., common system has zirconium
System, zirconium titanium system, silane system, silane zirconium system vitrification liquid.
Chinese invention patent " a kind of nanometer of vitrified agent and preparation method thereof (application number: 201610238833.0) ", " without phosphorus
Nanometer vitrified agent, preparation method and applications (application number: 201410166953.5) ", a kind of " novel, environmental protection macromolecule vitrification
Liquid and preparation method thereof (application number: all discloses a kind of vitrification liquid composition, and the vitrification liquid can in 201210530451.7) "
It is operated under room temperature, short processing time, simple process, but has a defect that in vitrification liquid and all contain chloride ion, be easy to adsorb
Cause metal component that spot corrosion phenomenon occurs in metal surface.
Chinese invention patent " a kind of heat zinc coating plate vitrified agent and preparation method thereof (application number: 201410178117.9) ",
" a kind of phosphate-free metal surface treating agent and its application method (application number: contain in vitrification liquid disclosed in 201210021650.5) "
Rare-earth salts and other heavy metal ion, and the former disclosed vitrified agent is only applicable to heat zinc coating plate, it is impossible to be used in carbon steel, casting
Other steel components such as iron, cold-rolled steel sheet.
Chinese invention patent " Metal surface vitrification agent and its application method (application number: 201210263316.0) " although public
Opened it is a kind of can produce a kind of inline type heterozygosis indissoluble nanometer scale ceramics conversion film in metal surface, have excellent impact resistance
Energy.But it is not introduced into stabilizer in the vitrification liquid, causes the corrosion resisting property of film layer poor, vitrification liquid service life is short.
In conclusion vitrification film prepared by existing vitrification method is not fine and close, corrosion resisting property and its attachment with paint layer
Power is poor, and the vitrification film formed is relatively thin, does not have the functional characteristics such as heat-resisting quantity, hydrophobicity, electric conductivity, while cannot apply
In all metal components.
Summary of the invention
In view of the above shortcomings of the prior art, the object of the invention is that providing a kind of with good high temperature resistant
Property, corrosion resistance, hydrophobicity and electric conductivity, the stable metal surface multifunction environment-protection type nanometer vitrification suitable for all metal components
Liquid and preparation method thereof and application method.
The technical scheme of the present invention is realized as follows:
A kind of metal surface multifunction environment-protection type nanometer vitrification liquid, by weight percentage, component is as follows: main film forming agent 3-
10%, auxiliary film former 1-10%, aqueous organic resin 1-10%, Nano sol 0.1-3%, complexing agent 0.1-1%, coupling agent 0.1-
1%, inhibition wetting agent 0.05-1%, surplus are water.
Further, the main film forming agent is one or both of fluorine zirconic acid, ammonium fluozirconate.
Further, the main film forming agent further includes one of fluotitanic acid, ammonium titanium fluoride, fluosilicic acid, ammonium fluosilicate or more
Kind.
Further, the auxiliary film former is nitrate, borate, one of molybdate, aluminate, vanadate or more
Kind, the nitrate, borate, molybdate, aluminate, vanadate, specially ammonium nitrate, manganese nitrate, aluminum nitrate, Boratex,
One of sodium perborate, sodium fluoborate, ammonium molybdate, sodium molybdate, sodium metaaluminate, ammonium vanadate are a variety of.
Further, the aqueous organic resin is organic siliconresin, organic silicon emulsion, polyacrylic resin, acrylic acid tree
One of rouge, styrene-acrylic emulsion, polyethylene wax are a variety of.
Further, the Nano sol is nanometer polytetrafluoroethylcomposite dispersion liquid, nanometer Graphite fluoride Composite Deposition liquid, nanometer fluorination
Graphene dispersing solution, nano carbon sol, nano zirconium dioxide colloidal sol, nano silicon dioxide sol, nano-aluminium oxide colloidal sol,
One of nano titanic oxide sol is a variety of.
Further, the complexing agent be tannic acid and its salt, maleic acid and its salt, fumaric acid and its salt, phytic acid and its salt,
One of tartaric acid and its salt, citric acid and its salt, EDTA and its salt are a variety of；The coupling agent is silane coupling agent, titanium
One or both of acid esters coupling agent.
Further, the inhibition wetting agent is diethanol amine, triethanolamine, contraposition toluene thiocarbamide, ortho position toluene thiocarbamide, ten
One of dialkyl sulfonates, neopelex, lauryl sodium sulfate, ethylene glycol, polyethylene glycol are a variety of.
The method for preparing a kind of above-mentioned metal surface multifunction environment-protection type nanometer vitrification liquid, specifically includes the following steps:
(1) various raw materials are weighed in proportion；
(2) weighed main film forming agent, stirring to dissolution are added in its 2/3 water requirement；
(3) auxiliary film former, stirring to dissolution are added in the solution made from step (2)；
(4) aqueous organic resin, stirring to dissolution are added in the solution made from step (3)；
(5) Nano sol, stirring to dissolution are added in the solution made from step (4)；
(6) complexing agent, coupling agent, inhibition wetting agent, stirring to dissolution are added in the solution made from step (5)；
(7) in the solution made from step (6), remaining water is supplied, obtains colorless and transparent vitrification liquid.
Using a kind of above-mentioned method that metal surface multifunction environment-protection type nanometer vitrification liquid carries out vitrification processing, specifically include
Following steps:
(1) it pre-processes: the metal components such as steel is successively carried out to alkali cleaning oil removing, washing, overflow washing；
(2) vitrification is handled: matched vitrification liquid being diluted with deionized water by 25-50mL/L concentration, adjusting pH value is 4.5-
5.5, vitrification point 4-8.0, then carry out vitrification processing, vitrification processing has room temperature spray, immersion treatment technique and roller coating technology this
Three kinds of techniques: the vitrification liquid after dilution is placed in spray equipment, to metal structure under 0.08-0.12MPa pressure by room temperature spray
Part sprays 60-100s；Immersion treatment technique, by metal component be placed in dilution after vitrification liquid in impregnate 3-10min；Roller coating work
Vitrification liquid after dilution is coated on metal component, using transfer roller as carrier to obtain certain thickness vitrification film by skill；
(3) it post-processes: and then will be first washed with water by the metal component of vitrification processing, then overflow washing is carried out, then deionization
Metal component is finally placed in heat preservation 50-70 s under the conditions of 90-100 DEG C of temperature and dried by water or pure water rinsing, obtain through
Cross the metal component of vitrification processing.
Nanometer vitrification film is inhaled by main film-former, Nano sol particle and the coupling agent hydrolysis-condensation in vitrification liquid
Attached formation.When metal component and vitrification liquid contact, redox reaction occurs for component surface and auxiliary film former, causes piece table
Face regional area pH value sharply increases, and deposition is precipitated the main film-former, Nano sol particle in vitrification liquid forms nanometer pottery
Change film.Meanwhile hydrolysis-condensation reaction will occur for coupling agent, modified Nano particle simultaneously promotes to form a film, to obtain compact nanometer pottery
Change film.And the other metal ions added in the present invention, such as manganese, aluminium, zirconium metal ion, accelerate deposition velocity, and combine network
The effect of mixture, inhibition wetting agent and aqueous organic resin etc., can quickly be formed it is fine and close it is anti-corrosion, with high steady of paint layer adhesive force
Fixed nanometer vitrification film.Meanwhile being formed according to selected vitrification liquid, it is special to assign the functions such as conductive, the hydrophobic, high temperature resistant of vitrification film
Property.
Compared with prior art, the invention has the following beneficial effects:
1, vitrification liquid stability of the invention is good, and the nanometer vitrification film for the more uniform densification that can be formed on the metal surface has
Beneficial to enhancing corrosion resistance and with the adhesive force of paint film.
2, Nano sol particle is added in the present invention, these high-activity nano particles are not only able into the micropore of vitrification film
Improve film layer compactness, moreover it is possible to assign that vitrification film is conductive, the functional characteristics such as hydrophobic.
3, aqueous organic resin is added in the present invention, and a nanometer adhesive force for vitrification film and paint film not only can be improved；And it is organic
Silicone resin, organic silicon emulsion can also assign vitrification film characteristic resistant to high temperature；Simultaneously except suitable for room temperature spray, immersion treatment technique
Outside, the thickness that nanometer vitrification film can be also improved by roller coating technology, further increases the corrosion-proof wear performance of film layer.
4, the beneficiating ingredients such as aluminate, manganese salt, molybdate, titanate coupling agent greatly improve nanometer vitrification film composition
Inorganic characteristic and its deposition efficiency and performance.
Detailed description of the invention
Photo in Fig. 1-embodiment 1 after 180 DEG C of the common vitrification film (5min) of cold rolling plate surface heat preservation 1h.
Photo in Fig. 2-embodiment 1 after 180 DEG C of cold-reduced sheet surface refractory vitrification film (5min) heat preservation 1h.
Cold-reduced sheet surface high-corrosion-resistance vitrification film (3min) surface microscopic topographic figure in Fig. 3-embodiment 2.
Cold-reduced sheet surface high-corrosion-resistance vitrification film (10min) surface microscopic topographic figure in Fig. 4-embodiment 2.
Photo after Fig. 5-embodiment 2 cold-reduced sheet surface high-corrosion-resistance vitrification film (10min) anti-corrosion 48h.
Photo after the 2 anti-corrosion 48h of blank cold-reduced sheet of Fig. 6-embodiment.
Photo after the japanning of 2 cold-reduced sheet surface high-corrosion-resistance vitrification film (10min) of Fig. 7-embodiment after anti-corrosion 1000h.
High anti-corrosion and hydrophobic vitrification film (5min) the surface microscopic topographic figure of aluminum alloy surface in Fig. 8-embodiment 3.
High anti-corrosion and hydrophobic vitrification film (5min) the surface microscopic topographic figure of Mg alloy surface in Fig. 9-embodiment 3.
Figure 10-embodiment 4 intermediate carbon steel sheet surface high-corrosion-resistance thickness vitrification film (roller coating 5) surface microscopic topographic figure.
The conduction vitrification of cold-reduced sheet surface high-corrosion-resistance film (5min) surface microscopic topographic figure in Figure 11-embodiment 5.
Specific embodiment
Invention is further described in detail with reference to the accompanying drawings and detailed description.
Embodiment 1
A kind of metal surface multifunction environment-protection type nanometer vitrification liquid, by weight percentage, raw material composition are as follows:
| Material name | Dosage % |
| Fluorine zirconic acid | 4 |
| Ammonium fluosilicate | 1.6 |
| Ammonium nitrate | 4.5 |
| Aluminum nitrate | 4.8 |
| Organic silicon emulsion | 3 |
| Nano silicon dioxide sol | 1 |
| Tannic acid | 0.3 |
| Silane coupling agent | 0.2 |
| Triethanolamine | 0.1 |
| Water | Surplus |
Following steps are seen according to the preparation method of the composition of raw materials of above-mentioned offer, the vitrification liquid:
(1) various raw materials are weighed in proportion；
(2) weighed main film forming agent fluorine zirconic acid and ammonium fluosilicate, stirring to dissolution are added in its 2/3 water requirement；
(3) auxiliary film former ammonium nitrate and aluminum nitrate, stirring to dissolution are added dropwise in the solution made from step (2)；
(4) organic silicon emulsion, stirring to dissolution are slowly added in the solution made from step (3)；
(5) nano silicon dioxide sol, stirring to dissolution are slowly added in the solution made from step (4)；
(6) tannic acid, silane coupling agent, triethanolamine, stirring to dissolution are slowly added in the solution made from step (5)；
(7) in the solution made from step (6), remaining water is supplied, obtains colorless and transparent vitrification liquid.
Using above-mentioned prepared vitrification liquid, vitrification processing is carried out to cold-reduced sheet, steps are as follows for specifically used method:
(1) it pre-processes: cold-reduced sheet successively being carried out to alkali cleaning oil removing, washing, pH value is finally used to wash for 7 overflow；
(2) vitrification is handled: matched vitrification liquid being diluted with deionized water by 25mL/L concentration, pH value 4.5-5.5, vitrification
Point 4-8.0, by cold-reduced sheet be placed in dilution after vitrification liquid in impregnate 5min；
(3) three washings: being first washed with water after cold-reduced sheet is taken out, and is then washed with the overflow that pH value is 7, finally uses deionized water
Or pure water rinsing；
(4) it dries: after 90 DEG C of drying box temperature of setting, processing sample being placed wherein, temperature keeps the temperature 60s after rising to 90 DEG C, so
It will be taken out afterwards by the cold-reduced sheet of vitrification processing.
Heat-resisting quantity experiment: using the identical vitrification step of above-mentioned vitrification method, using other existing vitrification liquid to cold
It rolls plate progress vitrification and obtains common vitrification sample, then put common vitrification sample and the vitrification sample of embodiment 1 respectively
It sets and is taken out after toasting 1h in 180 DEG C of baking ovens, observe the surface of two samples, Fig. 1 is common vitrification sample, and Fig. 2 is embodiment 1
Vitrification sample, compare discovery, common vitrification sample has got rusty discoloration, and the vitrification sample of embodiment 1 is not given birth to yet
Rust discoloration, it was demonstrated that the vitrification sample of embodiment 1 has good heat-resisting quantity.
Embodiment 2
A kind of metal surface multifunction environment-protection type nanometer vitrification liquid, by weight percentage, raw material composition are as follows:
| Material name | Dosage % |
| Ammonium fluozirconate | 3 |
| Ammonium titanium fluoride | 2 |
| Ammonium fluosilicate | 2 |
| Manganese nitrate | 1 |
| Sodium metaaluminate | 1 |
| Sodium molybdate | 4 |
| Water-based acrylic resin | 3 |
| Nano silicon dioxide sol | 1 |
| Nano titanic oxide sol | 0.5 |
| Nano-aluminium oxide colloidal sol | 0.5 |
| Tartaric acid | 0.2 |
| Tannic acid | 0.1 |
| Titanate coupling agent | 0.3 |
| Silane coupling agent | 0.1 |
| Dodecyl sodium sulfate | 0.1 |
| Water | Surplus |
Following steps are seen according to the preparation method of the composition of raw materials of above-mentioned offer, the vitrification liquid:
(1) various raw materials are weighed in proportion；
(2) weighed main film forming agent ammonium fluozirconate, ammonium titanium fluoride and ammonium fluosilicate are added in its 2/3 water requirement, stirs to molten
Solution；
(3) auxiliary film former manganese nitrate, sodium metaaluminate and sodium molybdate, stirring to dissolution are added dropwise in the solution made from step (2)；
(4) water-based acrylic resin, stirring to dissolution are slowly added in the solution made from step (3)；
(5) nano silicon dioxide sol, nano titanic oxide sol and nanometer three are slowly added in the solution made from step (4)
Al 2 O colloidal sol, stirring to dissolution；
(6) tartaric acid, tannic acid, titanate coupling agent, silane coupling agent and ten are slowly added in the solution made from step (5)
Dialkyl sulfonates, stirring to dissolution；
(7) in the solution made from step (6), remaining water is supplied, obtains colorless and transparent vitrification liquid.
Using above-mentioned prepared vitrification liquid, vitrification processing is carried out to cold-reduced sheet, steps are as follows for specifically used method:
(1) pre-process: by two pieces of cold-reduced sheets successively carry out alkali cleaning oil removing, washing, finally use pH value for 7 overflow washing；
(2) vitrification is handled: matched vitrification liquid being diluted with deionized water by by 50mL/L concentration, pH value 4.5-5.5, is made pottery
Change point 4-8.0, two pieces of cold-reduced sheets are respectively placed in the vitrification liquid after dilution and impregnate 3min and 10min；
(3) three washings: will two pieces of cold-reduced sheets take out after first be washed with water, then washed with the overflow that pH value is 7, finally spend from
Sub- water or pure water rinsing；
(4) dry: two drying box temperature of setting are to place processing sample wherein respectively, temperature rises to 100 DEG C after 100 DEG C
60s is kept the temperature afterwards, then will be taken out by two cold-reduced sheets of vitrification processing.
Cold rolling plate surface vitrification film microstructure through above-mentioned processing is as shown in Figure 3 and Figure 4, it is seen that vitrification film uniformly causes
It is close, no microfissure and apparent defect.
Corrosion resistance test: the vitrification of above-mentioned immersion 10min is handled into cold-reduced sheet and the blank without handling by vitrification is cold
Roll plate and be placed in 5%(weight percent) erosion experiment is carried out in NaCl solution, intermediate region is the region for carrying out erosion experiment, 48h
Afterwards, two cold rolling plate surfaces are as shown in Figure 5 and Figure 6, and Fig. 5 is vitrification treated cold-reduced sheet, and Fig. 6 is blank cold-reduced sheet, can by figure
Know, the naked film surface of vitrification film on vitrification treated cold-reduced sheet intermediate region surface it is smooth it is fine and smooth, do not change colour, illustrate without obviously
Corrosion, and blank cold-reduced sheet intermediate region has changed colour and corrodes, and forms rough surface；Using the side of embodiment 2
Method by impregnate 10min vitrification processing cold-reduced sheet japanning after in 5%(weight percent) NaCl solution impregnate 1000h after, cold-reduced sheet
The surface of sample is as shown in fig. 7, the paint film of cold rolling plate surface is intact, without obvious corrosion.It can be seen that the present invention obtained
Vitrification film has highly corrosion resistant, has stronger adhesive force with paint film.
Embodiment 3
A kind of metal surface multifunction environment-protection type nanometer vitrification liquid, by weight percentage, raw material composition are as follows:
| Material name | Dosage % |
| Fluorine zirconic acid | 2 |
| Fluotitanic acid | 1.5 |
| Ammonium fluosilicate | 2 |
| Sodium fluoborate | 1 |
| Sodium metaaluminate | 2 |
| Sodium molybdate | 2 |
| Styrene-acrylic emulsion | 3 |
| Polyethylene wax | 1 |
| Nanometer polytetrafluoroethylcomposite dispersion liquid | 0.5 |
| EDTA | 0.2 |
| Sodium citrate | 0.1 |
| Silane coupling agent | 0.1 |
| Ethylene glycol | 0.5 |
| Dodecyl sodium sulfate | 0.1 |
| Water | Surplus |
Following steps are seen according to the preparation method of the composition of raw materials of above-mentioned offer, the vitrification liquid:
(1) various raw materials are weighed in proportion；
(2) weighed main film forming agent fluorine zirconic acid, fluotitanic acid and ammonium fluosilicate, stirring to dissolution are added in its 2/3 water requirement；
(3) auxiliary film former sodium fluoborate, sodium metaaluminate and sodium molybdate are added dropwise in the solution made from step (2), stirs to molten
Solution；
(4) phenylpropyl alcohol lactic acid and polyethylene wax, stirring to dissolution are slowly added in the solution made from step (3)；
(5) nanometer polytetrafluoroethylcomposite dispersion liquid, stirring to dissolution are slowly added in the solution made from step (4)；
(6) EDTA, sodium citrate, ethylene glycol, silane coupling agent and dodecyl are slowly added in the solution made from step (5)
Sodium sulfonate, stirring to dissolution；
(7) in the solution made from step (6), remaining water is supplied, obtains colorless and transparent vitrification liquid.
Using above-mentioned prepared vitrification liquid, vitrification processing, specifically used method step are carried out to aluminium alloy and magnesium alloy
It is as follows:
(1) pre-process: aluminium alloy and magnesium alloy are successively carried out alkali cleaning oil removing, washing, finally use pH value for 7 overflow water
It washes；
(2) vitrification is handled: being by volume that the ratio of 50:1000 is diluted with deionized water by matched vitrification liquid, pH value is
Aluminium alloy and magnesium alloy are respectively placed in the vitrification liquid after dilution and impregnate 5min by 4.5-5.5, vitrification point 4-8.0；
(3) three washings: being first washed with water after aluminium alloy and magnesium alloy are taken out, and is then washed with the overflow that pH value is 7, is finally used
Deionized water or pure water rinsing；
(4) dry: two drying box temperature of setting are to place processing sample wherein respectively, after temperature rises to 95 DEG C after 95 DEG C
70s is kept the temperature, then takes out the aluminium alloy and magnesium alloy that handle by vitrification.
The microscopic appearance difference of aluminium alloy and magnesium alloy vitrification processing rear surface is as shown in Figure 8 and Figure 9, except because of alloy surface
Impurity causes the dispersion of vitrification liquid uneven, so that except in the case of having a small amount of nanoparticle agglomerates in Fig. 8 and Fig. 9, aluminium alloy and magnesium
Alloy vitrification treated vitrification film even compact, and the nano particle that there is protrusion in film is relatively uniform is dispersed in vitrification film table
Face, to provide the surface layer of nanostructure for vitrification film is hydrophobic.
Embodiment 4
A kind of metal surface multifunction environment-protection type nanometer vitrification liquid, by weight percentage, raw material composition are as follows:
| Material name | Dosage % |
| Fluorine zirconic acid | 6 |
| Manganese nitrate | 0.5 |
| Sodium molybdate | 2 |
| Acrylic resin | 1 |
| Styrene-acrylic emulsion | 4 |
| Polyethylene wax | 1 |
| Nano zirconium dioxide colloidal sol | 0.5 |
| Nano titanic oxide sol | 0.5 |
| Tannic acid | 0.2 |
| Phytic acid | 0.1 |
| Titanate coupling agent | 0.1 |
| Triethanolamine | 0.1 |
| Neopelex | 0.1 |
| Water | Surplus |
Following steps are seen according to the preparation method of the composition of raw materials of above-mentioned offer, the vitrification liquid:
(1) various raw materials are weighed in proportion；
(2) weighed main film forming agent fluorine zirconic acid, stirring to dissolution are added in its 2/3 water requirement；
(3) auxiliary film former manganese nitrate and sodium molybdate, stirring to dissolution are added dropwise in the solution made from step (2)；
(4) acrylic resin, styrene-acrylic emulsion and polyethylene wax, stirring to dissolution are slowly added in the solution made from step (3)；
(5) nano zirconium dioxide colloidal sol and nano titanic oxide sol are slowly added in the solution made from step (4), stirring is extremely
Dissolution；
(6) tannic acid, phytic acid, titanate coupling agent, triethanolamine and dodecane are slowly added in the solution made from step (5)
Base benzene sulfonic acid sodium salt, stirring to dissolution；
(7) in the solution made from step (6), remaining water is supplied, obtains colorless and transparent vitrification liquid.
Using above-mentioned prepared vitrification liquid, vitrification processing is carried out to cold-reduced sheet, steps are as follows for specifically used method:
(1) it pre-processes: carbon steel sheet successively being carried out to alkali cleaning oil removing, washing, pH value is finally used to wash for 7 overflow；
(2) vitrification is handled: matched vitrification liquid being diluted with deionized water by 45mL/L concentration, pH value 4.5-5.5, vitrification
Point 4-8.0, using transfer roller as carrier, by the vitrification liquid after dilution coated in carbon steel sheet 5, to obtain certain thickness vitrification
Film；
(3) three washings: being first washed with water after carbon steel sheet is taken out, and is then washed with the overflow that pH value is 7, finally uses deionized water
Or pure water rinsing；
(4) dry: two drying box temperature of setting are to place processing sample wherein respectively, after temperature rises to 95 DEG C after 95 DEG C
50s is kept the temperature, then will be taken out by the carbon steel sheet of vitrification processing.
The microscopic appearance for the carbon steel sheet vitrification sample surfaces that the present embodiment obtains is as shown in Figure 10, what carbon steel plate surface was formed
Vitrification film even compact, is well combined with carbon steel sheet substrate, and microcosmic gully present in figure is carbon steel sheet matrix bruting process
In scratch in itself that leave.
Embodiment 5
A kind of metal surface multifunction environment-protection type nanometer vitrification liquid, by weight percentage, raw material composition are as follows:
| Material name | Dosage % |
| Fluorine zirconic acid | 6 |
| Ammonium fluosilicate | 1 |
| Boratex | 5 |
| Sodium molybdate | 1 |
| Water-based acrylic resin | 3 |
| Waterborne organic silicon resin | 2 |
| Nano carbon sol | 1 |
| Tannic acid | 0.1 |
| Silane coupling agent | 0.1 |
| Lauryl sodium sulfate | 0.1 |
| EDTA | 0.1 |
| Water | Surplus |
Following steps are seen according to the preparation method of the composition of raw materials of above-mentioned offer, the vitrification liquid:
(1) various raw materials are weighed in proportion；
(2) weighed main film forming agent fluorine zirconic acid and ammonium fluosilicate, stirring to dissolution are added in its 2/3 water requirement；
(3) auxiliary film former Boratex and sodium molybdate, stirring to dissolution are added dropwise in the solution made from step (2)；
(4) it is slowly added to water-based acrylic resin and waterborne organic silicon resin in the solution made from step (3), stirs to molten
Solution；
(5) nano carbon sol, stirring to dissolution are slowly added in the solution made from step (4)；
(6) it is slowly added to tannic acid, silane coupling agent, EDTA and lauryl sodium sulfate in the solution made from step (5), stirred
It mixes to dissolution；
(7) in the solution made from step (6), remaining water is supplied, obtains colorless and transparent vitrification liquid.
Using above-mentioned prepared vitrification liquid, vitrification processing is carried out to cold-reduced sheet, steps are as follows for specifically used method:
(1) it pre-processes: cold-reduced sheet successively being carried out to alkali cleaning oil removing, washing, pH value is finally used to wash for 7 overflow；
(2) vitrification is handled: matched vitrification liquid being diluted with deionized water by 35mL/L concentration, pH value 4.5-5.5, vitrification
Point 4-8.0, by cold-reduced sheet be placed in dilution after vitrification liquid in impregnate 5min；
(3) three washings: being first washed with water after cold-reduced sheet is taken out, and is then washed with the overflow that pH value is 7, finally uses deionized water
Or pure water rinsing；
(4) dry: two drying box temperature of setting are to place processing sample wherein respectively, temperature rises to 100 DEG C after 100 DEG C
50s is kept the temperature afterwards, then will be taken out by the cold-reduced sheet of vitrification processing.
The present embodiment obtains cold-reduced sheet vitrification film with conductive characteristic, and the microscopic appearance on surface is as shown in figure 11, cold rolling
There is the nano particle of white for the particle in nano carbon sol in the vitrification film dense uniform formed after plate vitrification processing.
The present invention in provide it is a kind of there is good good heat-resisting quantity, stability, corrosion resistance, hydrophobicity and electric conductivity, fit
For the metal surface multifunction environment-protection type nanometer vitrification liquid of all metal components, and preparation method thereof and application method.It can be
The nanometer vitrification film of the more uniform densification formed on metal surface, it is high anti-corrosion and strong with paint film adhesion, it can be used for carbon steel, casting
The vitrification liquid and vitrification of the metal components such as iron, cold-rolled steel sheet, galvanized steel plain sheet, kirsite, aluminium alloy, magnesium alloy and environmental protection handle work
Skill.
Finally, it should be noted that the above embodiment of the present invention is only example to illustrate the invention, and it is not
It is the restriction to embodiment of the present invention.For those of ordinary skill in the art, on the basis of the above description also
Other various forms of variations and variation can be made.Here all embodiments can not be exhaustive.It is all to belong to this
The technical solution changes and variations that derived from of invention are still in the scope of protection of the present invention.
Claims (10)
1. a kind of metal surface multifunction environment-protection type nanometer vitrification liquid, which is characterized in that by weight percentage, component is such as
Under: main film forming agent 3-10%, auxiliary film former 1-10%, aqueous organic resin 1-10%, Nano sol 0.1-3%, complexing agent 0.1-
1%, coupling agent 0.1-1%, inhibition wetting agent 0.05-1%, surplus are water.
2. a kind of metal surface multifunction environment-protection type nanometer vitrification liquid according to claim 1, which is characterized in that the master
Film forming agent is one or both of fluorine zirconic acid, ammonium fluozirconate.
3. a kind of metal surface multifunction environment-protection type nanometer vitrification liquid according to claim 2, which is characterized in that the master
Film forming agent further includes one of fluotitanic acid, ammonium titanium fluoride, fluosilicic acid, ammonium fluosilicate or a variety of.
4. a kind of metal surface multifunction environment-protection type nanometer vitrification liquid according to claim 1, which is characterized in that described auxiliary
Furtherance film be nitrate, borate, one of molybdate, aluminate, vanadate or a variety of, the nitrate, borate,
Molybdate, aluminate, vanadate, specially ammonium nitrate, manganese nitrate, aluminum nitrate, Boratex, sodium perborate, sodium fluoborate, molybdic acid
One of ammonium, sodium molybdate, sodium metaaluminate, ammonium vanadate are a variety of.
5. a kind of metal surface multifunction environment-protection type nanometer vitrification liquid according to claim 1, which is characterized in that the water
Property organic resin be organic siliconresin, organic silicon emulsion, polyacrylic resin, acrylic resin, styrene-acrylic emulsion, in polyethylene wax
It is one or more.
6. a kind of metal surface multifunction environment-protection type nanometer vitrification liquid according to claim 1, which is characterized in that described to receive
Rice colloidal sol is that nanometer polytetrafluoroethylcomposite dispersion liquid, nanometer Graphite fluoride Composite Deposition liquid, nanometer fluorinated graphene dispersion liquid, nano-sized carbon are molten
Glue, nano zirconium dioxide colloidal sol, nano silicon dioxide sol, nano-aluminium oxide colloidal sol, in nano titanic oxide sol
It is one or more.
7. a kind of metal surface multifunction environment-protection type nanometer vitrification liquid according to claim 1, which is characterized in that the network
Mixture be tannic acid and its salt, maleic acid and its salt, fumaric acid and its salt, phytic acid and its salt, tartaric acid and its salt, citric acid and
One of its salt, EDTA and its salt are a variety of；The coupling agent is one of silane coupling agent, titanate coupling agent or two
Kind.
8. a kind of metal surface multifunction environment-protection type nanometer vitrification liquid according to claim 1, which is characterized in that described slow
Erosion wetting agent is diethanol amine, triethanolamine, contraposition toluene thiocarbamide, ortho position toluene thiocarbamide, dodecyl sodium sulfate, dodecyl
One of benzene sulfonic acid sodium salt, lauryl sodium sulfate, ethylene glycol, polyethylene glycol are a variety of.
9. a kind of method for preparing a kind of metal surface multifunction environment-protection type nanometer vitrification liquid described in claim 1, feature
It is, specifically includes the following steps:
(1) various raw materials are weighed in proportion；
(2) weighed main film forming agent, stirring to dissolution are added in its 2/3 water requirement；
(3) auxiliary film former, stirring to dissolution are added in the solution made from step (2)；
(4) aqueous organic resin, stirring to dissolution are added in the solution made from step (3)；
(5) Nano sol, stirring to dissolution are added in the solution made from step (4)；
(6) complexing agent, coupling agent, inhibition wetting agent, stirring to dissolution are added in the solution made from step (5)；
(7) in the solution made from step (6), remaining water is supplied, obtains colorless and transparent vitrification liquid.
10. carrying out the side of vitrification processing using a kind of metal surface multifunction environment-protection type nanometer vitrification liquid described in claim 1
Method, which is characterized in that specifically includes the following steps:
(1) it pre-processes: the metal components such as steel is successively carried out to alkali cleaning oil removing, washing, overflow washing；
(2) vitrification is handled: matched vitrification liquid being diluted with deionized water by 25-50mL/L concentration, adjusting pH value is 4.5-
5.5, vitrification point 4-8.0, then carry out vitrification processing, vitrification processing has room temperature spray, immersion treatment technique and roller coating technology this
Three kinds of techniques: the vitrification liquid after dilution is placed in spray equipment, to metal structure under 0.08-0.12MPa pressure by room temperature spray
Part sprays 60-100s；Immersion treatment technique, by metal component be placed in dilution after vitrification liquid in impregnate 3-10min；Roller coating work
Vitrification liquid after dilution is coated on metal component, using transfer roller as carrier to obtain certain thickness vitrification film by skill；
(3) it post-processes: and then will be first washed with water by the metal component of vitrification processing, then overflow washing is carried out, then deionization
Metal component is finally placed in heat preservation 50-70 s under the conditions of 90-100 DEG C of temperature and dried by water or pure water rinsing, obtain through
Cross the metal component of vitrification processing.
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| CN111172524B (en) * | 2020-01-19 | 2021-07-06 | 东北大学 | Preparation method and use method of environment-friendly nano plating solution for tin plate |
| CN111893474A (en) * | 2020-08-20 | 2020-11-06 | 南京中车浦镇城轨车辆有限责任公司 | Metal piece treatment vitrification liquid and metal pretreatment method |
| CN112538294A (en) * | 2020-12-04 | 2021-03-23 | 攀钢集团攀枝花钢铁研究院有限公司 | Environment-friendly zinc-aluminum-magnesium coating surface treating agent and preparation method and use method thereof |
| CN112663037A (en) * | 2020-12-04 | 2021-04-16 | 佛山市顺德区美硕金属表面技术有限公司 | Vitrification agent, preparation method and application thereof |
| CN113215558A (en) * | 2021-05-18 | 2021-08-06 | 中山市壹桥环保科技有限公司 | Washing-free vitrification agent and use method thereof |
| CN114686866A (en) * | 2022-03-12 | 2022-07-01 | 浙江五源科技股份有限公司 | Non-phosphorus conversion film treatment process |
| CN114717543A (en) * | 2022-03-12 | 2022-07-08 | 浙江五源科技股份有限公司 | Preparation method of composition for improving salt spray resistance of coating after iron and steel non-phosphorus conversion treatment |
| CN114717543B (en) * | 2022-03-12 | 2023-06-09 | 浙江五源科技股份有限公司 | Preparation method of composition for improving salt spray resistance of coating after non-phosphorus conversion treatment of steel |
| CN114790545A (en) * | 2022-05-07 | 2022-07-26 | 安徽未来表面技术有限公司 | Corrosion-resistant and tarnish-resistant color-coating chromium-free coating liquid for galvanized sheet |
| CN114790545B (en) * | 2022-05-07 | 2023-11-21 | 安徽未来表面技术有限公司 | Corrosion-resistant and color-change-resistant color-coated chromium-free coating liquid for galvanized sheet |
| CN115558915A (en) * | 2022-10-08 | 2023-01-03 | 深圳市豪龙新材料技术有限公司 | Magnesium alloy high-corrosion-resistance hydrophobic sealant and preparation method thereof |
| CN115558915B (en) * | 2022-10-08 | 2023-06-09 | 深圳市豪龙新材料技术有限公司 | Magnesium alloy high corrosion-resistant hydrophobic sealing agent and preparation method thereof |
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