CN107012453B - A kind of method that green low temperature quickly prepares phosphating coat - Google Patents

A kind of method that green low temperature quickly prepares phosphating coat Download PDF

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CN107012453B
CN107012453B CN201710206943.3A CN201710206943A CN107012453B CN 107012453 B CN107012453 B CN 107012453B CN 201710206943 A CN201710206943 A CN 201710206943A CN 107012453 B CN107012453 B CN 107012453B
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phosphating
parts
graphene oxide
phosphating coat
low temperature
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CN107012453A (en
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张心亚
黄浩炜
谢于辉
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South China University of Technology SCUT
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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
    • C23C22/06Chemical 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
    • C23C22/07Chemical 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 phosphates
    • C23C22/08Orthophosphates
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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
    • C23C22/06Chemical 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
    • C23C22/07Chemical 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 phosphates
    • C23C22/08Orthophosphates
    • C23C22/12Orthophosphates containing zinc cations
    • C23C22/13Orthophosphates containing zinc cations containing also nitrate or nitrite anions
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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
    • C23C22/06Chemical 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
    • C23C22/07Chemical 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 phosphates
    • C23C22/08Orthophosphates
    • C23C22/18Orthophosphates containing manganese cations
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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
    • C23C22/06Chemical 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
    • C23C22/07Chemical 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 phosphates
    • C23C22/08Orthophosphates
    • C23C22/18Orthophosphates containing manganese cations
    • C23C22/182Orthophosphates containing manganese cations containing also zinc cations
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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
    • C23C22/06Chemical 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
    • C23C22/07Chemical 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 phosphates
    • C23C22/08Orthophosphates
    • C23C22/22Orthophosphates containing alkaline earth metal cations

Abstract

The invention discloses a kind of methods that green low temperature quickly prepares phosphating coat.This method comprises: 1) in terms of mass fraction, it will be in the raw material components investment reaction kettle of 5~8 parts of dihydric phosphate, 6~9 parts of nitrate, 0.5~3 part of phosphoric acid, 0.05~0.5 part of graphene oxide, 0.1~1 part of stabilizer, 6~10 parts of pH buffer, 100~120 parts of water, 20~40 DEG C are warming up to, stirring 20~go out kettle after sixty minutes;2) etching solution of preparation is put into phosphating pond, parkerized temperature is made to rise to 15~40 DEG C, be then immersed steel test specimen, handled 2~20 minutes, dry, obtain phosphating coat.The phosphatization film outward appearance ash that the present invention obtains is bright, has preferable corrosion resistance, strong with the adhesive force of paint.Method for bonderizing phosphatization speed of the invention is fast, and phosphatization temperature is low, and film layer crystallization is thin, and phosphating solution is stable, sediment is few, nontoxic to human and environment, low in cost.

Description

A kind of method that green low temperature quickly prepares phosphating coat
Technical field
The invention discloses phosphating coats to belong to material more particularly to a kind of method that green low temperature quickly prepares phosphating coat Material science and field of surface technology.
Background technique
Metal all must carry out conversion processing to its surface before spraying, coating, it is made to generate conversion film.Conversion film includes Phosphating coat, passivating film, organic film, rare-earth conversion coatings and colloidal sol silane film etc..Wherein phosphatization film preparation is metal parts It enters containing Zn, Ni, Mn, in the salting liquid based on the specific acid phosphate such as Fe, while various compound additions is added Agent, by chemical treatment, in the phosphate conversion film that there is the Surface Creation of metal parts certain thickness to be insoluble in water.Phosphatization Purpose be mainly: give parent metal provide protection, prevent metal to be corroded to a certain extent;For preceding bottoming of painting, mention The adhesive force and anti-corrosion capability of high paint film layer;Play antifriction lubrication in metal cold processing.
Currently, both at home and abroad phosphorating treatment using it is more be medium temperature, high temperature phosphorization, not only energy consumption is high, the treatment process time Long and sediment is more, and needs to carry out Seal treatment after phosphatization, complicates phosphorization treatment process, directly affects painting Quality, yield or cost.
Currently, still having many defects for the parkerized phosphating solution of steel material, the various aspects of performance of phosphating solution still has It is to be modified.
Traditional phosphating process is quite time-consuming and operation temperature is relatively high.
The Chinese patent application of Publication No. CN101029386A discloses a kind of to be contained for what steel plate and galvanized sheet were handled Calcium zinc-manganese triple cationic phosphorizing fluid, although the phosphating solution has phosphating coat formation, speed is fast, good with electrophoretic coating matching, Be the phosphating solution concentration it is big, at high cost, operating temperature is not suitable with the requirement of low temperature phosphor at 40~60 DEG C.
Application No. is the patent applications of CN103469187A to disclose a kind for the treatment of fluid for steel surface phosphatization melanism, Although the temperature for the treatment of fluid operation is room temperature and treated that steel surface light is corrosion-resistant, film quality is good, should Phosphating solution phosphatization steel material speed is slow, long the time required to phosphatization.
Traditional promotor such as nitride, though nitrate and chlorate etc. can effectively improve the property of phosphate coating Can, but it is harmful to human health and environment.
Application No. is the Chinese invention patent applications of CN201610397553.4 to disclose a kind of carbon steel pipe normal-temperature phosphorizing liquid Formula, although the formula can use toxic in the phosphorating treatment for being carried out workpiece quickly close under room temperature Harmful sodium nitrite and sodium fluoride are as promotor, and ratio is higher, and the three-protection design difficulty of generation is big, are unsatisfactory for environmental protection Demand.
Application No. is the Chinese invention patent applications of CN201510387197.3, provide the organic and inorganic compounding of one kind Zinc phosphating solution promotor contains in used inorganic accelerator though effectively reducing the operating time of parkerizing process There is the strong go back original reagent of the Strong oxdiatives such as zinc nitrite, sodium chlorate and hydrogen peroxide, has certain corrosion and to people to operation equipment Body health is harmful, and higher cost, is not suitable for mass production needs.
In order to adapt to fast-developing market competition needs, the quality of phosphating solution is improved, realizes that room temperature quickly forms phosphatization Film, reduces energy consumption cost, and technical process simplification, functionalization etc. become current development trend.And according to current existing phosphorus Change in formula of liquid design, is not yet related to promoting the research of the related fields of phosphating coat film forming about graphene oxide.
Summary of the invention
The technical problem to be solved in the present invention is that a kind of method that green low temperature quickly prepares phosphating coat is provided, to solve The problem of energy consumption is high for certainly existing phosphorating treatment, processing time length, phosphating process complexity etc. lead to phosphatization increased costs, realization is low Cost prepares anti-corrosion, wear-resisting phosphating coat, and used phosphating solution is free of the metal ions such as harmful sodium nitrite and chromium, Operation temperature is room temperature, meets energy conservation and environmental protection consumption reduction and requires.
Graphene oxide (graphene oxide, GO) is a kind of important derivative of graphene, also referred to as functionalization Graphene, oxidation removing graphite is mainly prepared by Hummers method, GO is made.The structure of GO is substantially the same with graphene, only It is that some oxygen-containing functional groups (such as epoxy group, hydroxyl, carboxyl) is connected on two-dimentional basal plane.It is worth noting that, graphene exists It is easy to reunite in solution, and since GO contains more oxygen-containing functional group, hydrophily is especially excellent, so that it is easy to It is distributed in various solvents, greatly extends its application range.The oxygen-containing group on the surface GO can also live as reaction simultaneously Property site and solution in other ionic reactions or as nucleation adsorption site bear nucleus, therefore to a certain extent promote crystallization Generate and construct the nanocrystal with certain pattern.The graphite oxide of 0.02-0.5wt% is added in the present invention in phosphating solution Alkene is allowed to be co-deposited with phosphating coat on the surface of steel, forms nano graphene oxide complex phosphate coating, utilize graphene oxide With the characteristic of nano material, enhance resistance to corrosion, the wearability of phosphating coat, while reducing preparation time and the reduction of phosphating coat Reaction temperature.This is a kind of new quick, low temperature and environmental protection phosphatization membrane preparation method.
The object of the invention is to realize by technical solution:
A kind of green low temperature method for quickly preparing phosphating coat, it is characterised in that preparation steps including etching solution and Phosphorating treatment step:
1) preparation of etching solution: in terms of mass fraction, by 5~8 parts of dihydric phosphate, 6~9 parts of nitrate, phosphoric acid 0.5~3 part, 0.05~0.5 part of graphene oxide, 0.1~1 part of stabilizer, 6~10 parts of pH buffer, 100~120 parts of water Raw material components are put into reaction kettle, are warming up to 20~40 DEG C, and control mixing speed is at 200~300 revs/min, mechanical stirring 20 ~go out kettle after sixty minutes;
2) phosphorating treatment: the etching solution of preparation is put into phosphating pond, and parkerized temperature is made to rise to 15~40 DEG C, then steel test specimen is immersed, is handled the time 2~20 minutes, is washed down and dried with water, obtain phosphating coat.
To further realize the object of the invention, it is preferable that the dihydric phosphate is phosphate dihydrogen manganese, zinc dihydrogen phosphate It is one or more with calcium dihydrogen phosphate.
Preferably, the nitrate be four nitric hydrate manganese, zinc nitrate hexahydrate and calcium nitrate tetrahydrate one kind or It is a variety of.
Preferably, the stabilizer be OP-10 emulsifier, PVP, APEO, SE-10 and TX-10 it is one or more.
Preferably, in terms of mass fraction, 0.05~0.5 part of graphene oxide of the dosage refers to graphene oxide Effective mass;The graphene oxide is 0.1~4.0wt% graphene oxide water solution or graphene oxide powder, oxidation Graphene is prepared by Hummers method.
Preferably, further include that lye is added in the feed in the preparation of step 1) etching solution, control etching solution PH value be 2-3.
The present invention tests the Corrosion Protection of phosphating coat using GB6458-86 neutral salt spray test.
The beneficial effects of the present invention are:
The present invention carries out phosphorating treatment to workpiece using the method that green low temperature quickly prepares phosphating coat, has used novel Graphene oxide has significantly speeded up the generating rate of phosphating coat as promotor, and phosphating time is short (2~20 minutes), phosphatization temperature Spend low (15~40 DEG C), can be carried out under room temperature, substantially without phosphating dregs in the phosphating pond after phosphatization, illustrate the phosphatization of test specimen at Power is high, and phosphatization film outward appearance ash is bright, and even film layer is fine and smooth, and corrosion resistance meets GB6458-86 regulation, and does not contain in phosphating solution The metal ions such as harmful sodium nitrite and chromium are not detrimental to health and destroy ecological ring in use and using rear Border, it is at low cost, it is easy to use, industrialization demand can be met.
Specific embodiment
For a better understanding of the invention, the present invention is further explained combined with specific embodiments below, but embodiment is not constituted Restriction to the claims in the present invention protection scope, is based on embodiment, and those skilled in the art are not making creative work Under the premise of other embodiments obtained, belong to protection scope of the present invention.
Embodiment 1
(1) according to parts by weight, following raw material components: 4 parts of zinc dihydrogen phosphate, 2 parts of phosphate dihydrogen manganese, zinc nitrate are weighed 6 parts, 2 parts of phosphoric acid, 6 parts of 3.5wt% graphene oxide water solution, 0.2 part of PVP, 100 parts of water.
(2) step (1) each component is put into reaction kettle, adjusting pH using lye is 2, then heats to 40 DEG C, stirring Uniformly.
(3) etching solution of preparation is put into phosphating pond, parkerized temperature is made to rise to 28 DEG C, then by steel Test specimen is immersed, and is handled the time 5 minutes, is washed down to dry with water parkerized test specimen can be obtained.
Substantially without phosphating dregs in phosphating pond after phosphatization, illustrate that the phosphatization success rate of test specimen is high.
The present invention tests the Corrosion Protection of phosphating coat using GB6458-86 neutral salt spray test.
The phosphatization film outward appearance ash that the present embodiment 1 obtains is bright, and film layer is fine and smooth, film thickness 2g/m2
Do not corrode within phosphating coat neutral salt spray test 20 hours, meets anti-corrosion standard as defined in GB6458-86.
Compared with 40~60 DEG C of technologies that traditional phosphating process such as Chinese patent CN101029386A are reported, this hair The bright method for quickly preparing phosphating coat using green low temperature carries out phosphorating treatment to workpiece, can greatly simplify phosphating process, phosphatization Temperature is low, can carry out under room temperature.
Compared with 30~60 minutes phosphorization treatment process that the prior art such as Chinese patent CN103469187A are reported, this The method that invention quickly prepares phosphating coat using green low temperature, the processing time is only 5 minutes, and phosphating reaction speed is fast, when phosphatization Between it is short.
With the prior art such as Chinese patent CN201610397553.4 report using environmentally harmful sodium nitrite and Sodium fluoride is compared as parkerized promotor, and the present invention is using biodegradable graphene oxide as promotor, nothing Poison is harmless, composite environmental-friendly requirement.
Embodiment 2
(1) following raw material components: 8 parts of zinc dihydrogen phosphate, 4 parts of zinc nitrate, 3 parts of calcium phosphate, phosphoric acid are taken by weight ratio 2.5 parts, 0.05 part of graphene oxide powder, 0.2 part of APEO, 100 parts of water.
(2) each component is put into reaction kettle, adjusting pH using lye is 3, then heats to 30 DEG C, stirs evenly.
(3) etching solution of preparation is put into phosphating pond, parkerized temperature is made to rise to 30 DEG C, then by steel Test specimen is immersed, and is handled the time 4 minutes, is washed down to dry with water parkerized test specimen can be obtained.
The present invention tests the Corrosion Protection of phosphating coat using GB6458-86 neutral salt spray test.
The phosphatization film outward appearance ash that the present embodiment 2 obtains is bright, and film layer is fine and smooth, film thickness 1.5g/m2
Do not corrode within phosphating coat neutral salt spray test 14 hours, meets anti-corrosion standard as defined in GB6458-86.
Embodiment 3
(1) following raw material components: 7 parts of zinc dihydrogen phosphate, 6 parts of zinc nitrate, phosphatase 11 part, 2.2wt% are taken by weight ratio 0.2 part of graphene oxide water solution, 0.2 part of OP-10 emulsifier, 0.3 part of TX-10,120 parts of water
(2) each component is put into reaction kettle, adjusting pH using lye is 3, then heats to 25 DEG C, stirs evenly.
(3) etching solution of preparation is put into phosphating pond, parkerized temperature is made to rise to 20 DEG C, then by steel Test specimen is immersed, and is handled the time 10 minutes, is washed down to dry with water parkerized test specimen can be obtained.
The present invention tests the Corrosion Protection of phosphating coat using GB6458-86 neutral salt spray test.
The phosphatization film outward appearance ash that the present embodiment 3 obtains is bright, and film layer is fine and smooth, film thickness 3.0g/m2
Do not corrode within phosphating coat neutral salt spray test 20 hours, meets anti-corrosion standard as defined in GB6458-86.
Embodiment 4
(1) following raw material components: 5 parts of phosphate dihydrogen manganese, 9 parts of zinc nitrate, 3 parts of phosphoric acid, oxidation stone are taken by weight ratio 0.5 part of black alkene powder, 1 part of OP-10 emulsifier, 100 parts of water
(2) each component is put into reaction kettle, is warming up to 30 DEG C, mixing speed is stirred evenly at 300 revs/min.
(3) etching solution of preparation is put into phosphating pond, parkerized temperature is made to rise to 40 DEG C, then by steel Test specimen is immersed, and is handled the time 2 minutes, is washed down to dry with water parkerized test specimen can be obtained.
The present invention tests the Corrosion Protection of phosphating coat using GB6458-86 neutral salt spray test.
The phosphatization film outward appearance ash that the present embodiment 4 obtains is bright, and film layer is fine and smooth, film thickness 2.2g/m2
Do not corrode within phosphating coat neutral salt spray test 10 hours, meets anti-corrosion standard as defined in GB6458-86.
The basic principles, main features and advantages of the present invention have been shown and described above.Industry technology people Member is it should be appreciated that the present invention is not limited to the above embodiments, without departing from the spirit and scope of the present invention, the present invention It will also have various changes and improvements, these changes and improvements all fall within the protetion scope of the claimed invention.

Claims (6)

1. a kind of method that green low temperature quickly prepares phosphating coat, it is characterised in that preparation steps and phosphorus including etching solution Change processing step:
1) preparation of etching solution: in terms of mass fraction, by 5~8 parts of dihydric phosphate, 6~9 parts of nitrate, phosphoric acid 0.5~ 3 parts, 0.05~0.5 part of graphene oxide, 0.1~1 part of stabilizer, 6~10 parts of pH buffer, the raw material group of 100~120 parts of water Divide in investment reaction kettle, be warming up to 20~40 DEG C, controls mixing speed at 200~300 revs/min, 20~60 points of mechanical stirring Go out kettle after clock;
2) phosphorating treatment: the etching solution of preparation is put into phosphating pond, so that parkerized temperature is risen to 15~40 DEG C, so Steel test specimen is immersed afterwards, is handled 2~20 minutes, is washed down and dried with water, obtain phosphating coat.
2. the method that green low temperature according to claim 1 quickly prepares phosphating coat, which is characterized in that the di(2-ethylhexyl)phosphate Hydrogen salt is the one or more of phosphate dihydrogen manganese, zinc dihydrogen phosphate and calcium dihydrogen phosphate.
3. the method that green low temperature according to claim 1 quickly prepares phosphating coat, which is characterized in that the nitrate For the one or more of four nitric hydrate manganese, zinc nitrate hexahydrate and calcium nitrate tetrahydrate.
4. the method that green low temperature according to claim 1 quickly prepares phosphating coat, which is characterized in that the stabilizer For OP-10 emulsifier, PVP, APEO, SE-10 and TX-10 it is one or more.
5. the method that green low temperature according to claim 1 quickly prepares phosphating coat, which is characterized in that with mass fraction Meter, 0.05~0.5 part of graphene oxide of the dosage refer to the effective mass of graphene oxide;The graphene oxide For 0.1~4.0wt% graphene oxide water solution or graphene oxide powder, graphene oxide is prepared by Hummers method.
6. the method that green low temperature according to claim 1 quickly prepares phosphating coat, which is characterized in that at step 1) phosphatization Managing in the preparation of liquid further includes that lye is added in the feed, and the pH value for controlling etching solution is 2-3.
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CN112391618A (en) * 2019-08-12 2021-02-23 东莞市颖兴金属表面处理材料有限公司 Environment-friendly phosphating solution containing graphene oxide and preparation method thereof
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CN105543826B (en) * 2015-12-29 2018-05-01 钢铁研究总院 A kind of normal-temperature phosphorizing liquid, preparation method and phosphating process for forming high anti-corrosion phosphating coat
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