CN107740168A - A kind of efficient corrosion resisting Zinc phosphating solution and preparation method thereof - Google Patents
A kind of efficient corrosion resisting Zinc phosphating solution and preparation method thereof Download PDFInfo
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- CN107740168A CN107740168A CN201710919434.5A CN201710919434A CN107740168A CN 107740168 A CN107740168 A CN 107740168A CN 201710919434 A CN201710919434 A CN 201710919434A CN 107740168 A CN107740168 A CN 107740168A
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- phosphating
- zinc
- phosphating solution
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/36—Phosphatising
Abstract
The invention discloses a kind of efficient corrosion resisting Zinc phosphating solution and preparation method thereof.In terms of mass fraction, the Zinc phosphating solution composition of raw materials component includes：Zn2+1 15 parts, PO4 3‑10 40 parts, 0.01 1 parts of graphene oxide, 1 15 parts of GO dispersants, 1 15 parts of stabilizer, 5 15 parts of pH adjusting agent, 1000 parts of water；The phosphatization electrolyte prepared according to the present invention, it is not only safe and non-toxic, and it can quickly and efficiently prepare phosphating coat, when carrying out electrolytic phosphating as negative electrode in phosphating solution especially for metal works, it can assign workpiece smooth surface, scratch-resistant, many excellent performances such as ageing-resistant, graphene oxide of the present invention can be evenly distributed in the coating of phosphating coat, efficiently it is filled with the Micro porosity on phosphate layer surface, form isolation layer, provide physical shielding effect, block the approach of the direct contacting metal workpiece of corrosive medium, it further suppress the generation of electrochemical corrosion, largely reduce corrosion rate.
Description
Technical field
The present invention relates to a kind of phosphating solution, more particularly to a kind of efficient corrosion resisting Zinc phosphating solution and preparation method thereof, tool
Body is related to the phosphating solution containing graphene oxide (GO)；The phosphating solution is used for Treatment of Metal Surface, belongs to phosphatization aseptic technic neck
Domain.
Background technology
Metal erosion refers to that metal material surface and environment occur chemistry and electrochemical reaction and make the hydraulic performance decline of material.
Metal erosion can cause huge loss, and China is every year because loss caused by corrosion accounts for hundred million yuan or so.For a long time, people
Multiple technologies are used always, slow down the speed that corrosion occurs.
At present, most important anti-corrosion means are exactly that metal surface is handled, make passivation of metal surfaces or isolation it is outer
Boundary's environment reaches corrosion-resistant purpose.Phosphorating treatment is exactly a kind of common and practical method, metal material through phosphorating treatment it
One layer of fine and close phosphate coating can be formed on surface afterwards, the decay resistance and postorder of metal material can be effectively improved
Adhesive force and adhesion between outer layer organic coating.Traditional phosphating process is：Degreasing-washing-derusting-washing-surface
Adjustment-phosphatization-washing-drying, process very complicated, and also the film forming mechanism of phosphating coat is determined in traditional phosphating solutions processing procedure
There can be handling process trouble, the speed for generating phosphate layer is relatively even unable to film forming slowly.Application No.
CN201610397553.4 Chinese invention patent application discloses a kind of formula of carbon steel pipe normal-temperature phosphorizing liquid, this application formula
It is middle to add a large amount of poisonous natrium nitrosum phosphatization stabilizers, environmental requirement is unsatisfactory for, also strongly limit its application field.
Application No. CN201310066354.1 Chinese invention patent discloses one kind and is used for steel tower corrosion-resistant phosphating solution and its preparation
Method, its PH are 0.43, and acidity is high, and waste liquid is difficult to also result in secondary pollution.
The content of the invention
It is an object of the invention to provide a kind of environmentally friendly efficient corrosion resisting Zinc phosphating solution, it is prepared into using this kind of phosphating solution
Not only surface is smooth for the metal works arrived, scratch-resistant, ageing-resistant, the excellent properties such as corrosion-resistant, high adhesion force, and preparation process
Nontoxic, technique is simple, facilitate it is controllable, beneficial to realize industrialize.
It is another object of the present invention to provide the preparation method of the new and effective anti-corrosion Zinc phosphating solution.
The present invention makes Zn under conditions of electrochemical phosphating2+、PO43-Efficiently, the surface of metal works is rapidly deposited on,
The phosphate layer of one layer of isolation external environment condition of generation, but the phosphating coat surface obtained under the conditions of traditional phosphating solutions can be big in the presence of some
The small Micro porosity to differ, the direct contact of corrosive medium and bare metal can be caused to cause the generation of corrosion.In order to solve this
Individual problem, present invention adds graphene oxide, while it has also been found that the addition of graphene oxide can greatly improve gold
The corrosion resistant degree of corrosion of metal work-pieces, probably due to graphene oxide can not only be evenly distributed in phosphating coat, and is efficiently filled
The Micro porosity on phosphate layer surface, the approach of corrosive medium direct contacting metal workpiece is blocked, further suppress electrification
Learn the generation of corrosion.
Application No. CN201710206943.3 Chinese invention patent application discloses a kind of green low temperature and quickly prepared
The method of fast phosphating coat, the addition of this method graphene oxide can be used as accelerator, promote the generation of phosphating coat, avoid using
Poisonous accelerator such as natrium nitrosum, sodium nitrate etc..Simultaneously herein on basis, present invention discover that graphene oxide is not only
It is as accelerator, but anti-corrosion material can be used as, there is very big raising to antiseptic effect.The present invention is from simple chemistry
Deposit phosphatization and arrive cathodic polarization electrochemical phosphating, can it is more efficient, rapidly prepare phosphating coat, and obtained phosphating coat is more
Add densification, more corrosion-resistant, effect highly significant.
Graphene oxide is the oxidation state of graphene, and it not only remains the excellent performance of graphene, and is aoxidizing
The hydrophilic oxygen-containing functional group such as its abundant hydroxyl, carboxyl, epoxy radicals is imparted in journey, ensure that and preferably divide in aqueous phase
Performance is dissipated, and then forms stable dispersion.Graphene oxide is dispersed in phosphating solution by the present invention first, makes itself and phosphorus
Hydrochlorate co-deposition is covered in the phosphate layer on the surface of metal works, being prepared obtaining and not only possessed into phosphating coat
Outside the premium properties such as the smooth, ageing-resistant of conventional phosphate film, scratch-resistant, high adhesion force, and graphene oxide can also be equal
It is even to be distributed in the phosphating coat of deposition, the Micro porosity on phosphate layer surface is efficiently filled with, forms one layer of isolation layer
Physical shielding effect is provided, the approach of corrosive medium contacting metal workpiece is blocked, substantially increases corrosion resistant degree of corrosion.
Add graphene oxide into phosphating solution, phosphating coat and oxidation are prepared under the conditions of cathodic polarization electrochemical phosphating
The method for the anti-corrosion phosphate coating that graphene is co-deposited has not been reported.
The object of the invention is realized by using following technical scheme：
A kind of efficient corrosion resisting Zinc phosphating solution, in terms of mass fraction, its composition of raw materials component is：
Described GO dispersants be triethyl group hexyl phosphoric acid, lauryl sodium sulfate, methyl anyl alcohol, cellulose derivative,
One or more in polyacrylamide, guar gum, fatty acid polyethylene glycol ester.
Further to realize the object of the invention, it is preferable that described Zn2+Come from zinc oxide, zinc sulphide, zinc chloride and phosphorus
One or more in the sour zinc of hydrogen two.
Preferably, described PO4 3-Come from a kind of or more in phosphoric acid, trbasic zinc phosphate, potassium dihydrogen phosphate and sodium phosphate
Kind.
Preferably, described stabilizer is polyoxethylene octylphenyl phenol ether -10, poly-methyl pyrrole alkanone, gelatin, carboxymethyl
One or more in sodium cellulosate (CMCNa), sodium alginate, carragheen and APES.
Preferably, described pH adjusting agent is one kind in monoethanolamine, ammoniacal liquor, sodium hydroxide, sodium acid carbonate and sodium carbonate
It is either a variety of.
Preferably, described graphene oxide is that Hummers methods prepare the powdered oxidation obtained by being freeze-dried excessively
Graphene or 0.1~4.0wt% graphene oxide water solutions.
Preferably, described water derives from running water or deionized water；Mass fraction meter, dosage are 1000 parts.
The preparation method of the efficient corrosion resisting Zinc phosphating solution：Add graphene oxide into water, it is equal to carry out ultrasonic disperse
Zn is added after even2+、PO4 3-, GO dispersants, stabilizer, and continue ultrasonic disperse to being completely dissolved, add pH adjusting agent extremely
PH is 4-5, and the normal temperature preservation that stirs.
Compared with prior art, the present invention has following outstanding advantages：
(1) it is of the present invention to be dispersed in first using graphene oxide as anti-corrosion material in phosphating solution, make itself and phosphoric acid
Salt co-deposition is covered on the surface of metal works into the phosphating coat of densification, is efficiently filled with conventional phosphate film surface
Micro porosity, form isolation layer, there is provided physical shielding act on, block the direct contacting metal workpiece of corrosive medium way
Footpath, the generation of electrochemical corrosion is further suppress, substantially increases antiseptic property.
(2) heretofore described graphene oxide reduces making for later stage poisonous anticorrosion material as anti-corrosion material
With, cost has been greatly reduced on the post-processing three wastes, and the metal ions such as harmful nickel and chromium are free of in phosphating solution,
Ecological environment is not detrimental to health and destroys during use and using rear.
(3) efficient corrosion resisting Zinc phosphating solution electrochemical phosphating method of the present invention is using electrochemical cathode pole
Chemical industry skill, i.e., enter to be about in the presence of electric field workpiece as negative electrode carry out electrochemical phosphating be co-deposited to obtain graphene oxide and
Phosphatic corrosion-inhibiting coating, using electrochemical phosphating mode not only rapidly and efficiently, and obtained phosphating coat densification is smooth, resistance to
The premium properties such as aging, scratch-resistant, high adhesion force.
4) the preparation process step of graphene oxide of the present invention and phosphate complex phosphate coating is few, easy to operate,
Technological process is simple, requires low, generally conventional container and electro-deposition production equipment to pressure and no requirement (NR), therefore to instrument and equipment
The requirement is can reach, is adapted to large-scale production.
Brief description of the drawings
Fig. 1 is the electron microscope of the gained phosphating coat of embodiment 1.
Fig. 2 is the electrochemical tests figure that the gained phosphating coat of embodiment 1 is determined using electrochemical workstation.
Embodiment
For a better understanding of the present invention, the invention will be further described with reference to the accompanying drawings and examples, it is necessary to say
Bright, embodiment does not form the limitation to the claimed scope of the invention.
Embodiment 1：
A kind of efficient corrosion resisting Zinc phosphating solution, its composition of raw materials group are grouped into：
A kind of efficient corrosion resisting Zinc phosphating solution is made by the steps：
Graphene oxide (GO) 1g is taken in 1L water, carries out ultrasonic disperse, zinc oxide 5g, sodium phosphate are added after being uniformly dispersed
10g, fatty acid polyethylene glycol ester 1g, and continue ultrasonic disperse to being completely dissolved；PH with monoethanolamine regulation solution is left for 4
The right side, stir storage at room temperature, obtains efficient corrosion resisting Zinc phosphating solution.
The efficient corrosion resisting Zinc phosphating solution of preparation is put into three electrode phosphating ponds, metal works carry out electrification as negative electrode
Phosphatization is learned, phosphating time is 1 minute, and in parkerizing process, workpiece surface is with the presence of substantial amounts of negatron, the Zn in phosphating solution2+
And PO4 3-Plasma is under current field condition, and fast deposition is in workpiece surface, generation metallic zinc, trbasic zinc phosphate, ferric phosphate zinc, oxidation stone
The co-precipitation composite coating of black alkene, then the workpiece obtained after phosphatization is washed down to the phosphatization dried after can obtain phosphatization with water
Film.
In order to preferably study the structure of phosphating coat, by phosphating coat carry out metal spraying processing, then again with model FE-SEM,
The phosphating coat that ZEISS ULTRA 55 SEM obtains to the electrochemistry of embodiment 1 amplifies 10000 times and observed,
As shown in figure 1, it can be clearly seen that the graphene oxide of lamellar structure is evenly distributed in phosphating coat in circle, effectively
Ground is filled with the Micro porosity between phosphate crystal grain, and this is graphene oxide and metallic zinc, trbasic zinc phosphate, phosphorus in parkerizing process
The product that sour iron zinc is co-deposited.
Fig. 2 is the corrosion polarization curve that gained phosphating coat in embodiment is determined using test function in electrochemical workstation,
As shown in Fig. 2 the corrosion polarization curve that the phosphating coat that 0 zero expressions obtain without addition graphene oxide is carried out, 1. -5. represent real
The polarization curve that a 1-5 adds different amounts of graphene oxide corrosion is applied, and figure upper curve shows to the addition of graphene oxide
The corrosion potential of polarization curve is substantially more much higher than the corrosion potential of no addition graphene oxide, shows corrosion rate significantly
Reduction, it was demonstrated that the corrosion resistance for the phosphating coat that the addition of graphene oxide obtains is greatly improved.
Phosphating coat service check
The performance of the gained phosphating coat of embodiment 1 is tested according to the pertinent regulations of national standard, the results are shown in Table 1
The service check result of the phosphating coat of table 1
The phosphatization obtained as can be seen from Table 1 under the conditions of new and effective anti-corrosion Zinc phosphating solution electrochemical phosphating of the invention
Film has the excellent performance such as corrosion-resistant, scratch-resistant, high adhesion force.Entitled " the special phosphorus of vehicle of Publication No. CN 104962894A
Change liquid and preparation method thereof " the Introduction To Cn Patent traditional phosphating solutions method of automobile-used part (each component is added to the water, adjusted
PH is 3.5, after stirring, part is immersed in phosphating solution, traditional phosphating solutions 15min, takes out and dries test corrosion resistance), its
Corrosive nature test shows：Corrosion resistance is 2.5h, and outward appearance table is the phosphating coat of black rough, and the present invention is in electrochemistry phosphorus
Under the conditions of turning to 1min, corrosion test is not corrode for 3 months；Salt mist experiment at least 36 hours, appearance are glossy
Silver-gray fine and closely woven phosphating coat, illustrate that the workpiece that phosphating solution of the present invention obtains under electrochemical phosphating is quick and convenient, outward appearance
Image is good, and efficient corrosion resisting, the features such as excellent combination property.
Embodiment 2：
A kind of efficient corrosion resisting Zinc phosphating solution, its composition of raw materials group are grouped into：
A kind of efficient corrosion resisting Zinc phosphating solution is made by the steps：
Take graphene oxide (GO)：0.01g carries out ultrasonic disperse in 1L water, added after being uniformly dispersed zinc chloride 20g,
Sodium phosphate 40g, triethyl group hexyl phosphoric acid 15g simultaneously continue ultrasonic disperse to being completely dissolved；With ammoniacal liquor regulation solution pH be
5 or so, stir enough storage at room temperature, can be to obtain this new and effective anti-corrosion Zinc phosphating solution.
The new and effective anti-corrosion Zinc phosphating solution of preparation is put into three electrode phosphating ponds, metal works are carried out as negative electrode
Electrochemical phosphating, phosphating time is 1 minute, and in parkerizing process, workpiece surface is with the presence of substantial amounts of negatron, in phosphating solution
Zn2+And PO4 3-Plasma is under current field condition, and fast deposition is in workpiece surface, generation metallic zinc, trbasic zinc phosphate, ferric phosphate zinc, oxygen
The co-precipitation composite coating of graphite alkene, then the workpiece obtained after phosphatization is washed down to the phosphorus dried after can obtain phosphatization with water
Change film.
For the method for testing of the corrosion polarization curve of phosphating coat with embodiment 1, test result is shown in Fig. 2, phosphatization film properties test
As a result with table 1.
Embodiment 3：
A kind of efficient corrosion resisting Zinc phosphating solution, its composition of raw materials group are grouped into：
A kind of efficient corrosion resisting Zinc phosphating solution is made by the steps：
Take graphene oxide (GO)：0.03g carries out ultrasonic disperse in 1L water, added after being uniformly dispersed zinc sulphide 10g,
Potassium hydrogen phosphate 26g, lauryl sodium sulfate 8g, and continue ultrasonic disperse to being completely dissolved；Use manganese hydrogen sodium regulating solution
PH be 4.5 or so, storage at room temperature after stirring, can be to obtain this new and effective anti-corrosion Zinc phosphating solution.
The new and effective anti-corrosion Zinc phosphating solution of preparation is put into three electrode phosphating ponds, metal works are carried out as negative electrode
Electrochemical phosphating, phosphating time is 1 minute, and in parkerizing process, workpiece surface is with the presence of substantial amounts of negatron, in phosphating solution
Zn2+And PO4 3-Plasma is under current field condition, and fast deposition is in workpiece surface, generation metallic zinc, trbasic zinc phosphate, ferric phosphate zinc, oxygen
The co-precipitation composite coating of graphite alkene, then the workpiece obtained after phosphatization is washed down to the phosphorus dried after can obtain phosphatization with water
Change film.
For the method for testing of the corrosion polarization curve of phosphating coat with embodiment 1, test result is shown in Fig. 2, phosphatization film properties test
As a result with table 1.
Embodiment 4：
A kind of efficient corrosion resisting Zinc phosphating solution, its composition of raw materials group are grouped into：
A kind of efficient corrosion resisting Zinc phosphating solution is made by the steps：
Take graphene oxide (GO)：0.04g carries out ultrasonic disperse in 1L water, added after being uniformly dispersed zinc oxide 15g,
Phosphoric acid hydrogen zinc 18g, polyacrylamide 5g simultaneously carry out ultrasonic disperse to being completely dissolved；It is left for 4 with the pH of sodium hydrate regulator solution
The right side, storage at room temperature after stirring can be to obtain this new and effective anti-corrosion Zinc phosphating solution.
The new and effective anti-corrosion Zinc phosphating solution of preparation is put into three electrode phosphating ponds, metal works are carried out as negative electrode
Electrochemical phosphating, phosphating time is 1 minute, and in parkerizing process, workpiece surface is with the presence of substantial amounts of negatron, in phosphating solution
Zn2+And PO4 3-Plasma is under current field condition, and fast deposition is in workpiece surface, generation metallic zinc, trbasic zinc phosphate, ferric phosphate zinc, oxygen
The co-precipitation composite coating of graphite alkene, then the workpiece obtained after phosphatization is washed down to the phosphorus dried after can obtain phosphatization with water
Change film.
For the method for testing of the corrosion polarization curve of phosphating coat with embodiment 1, test result is shown in Fig. 2, phosphatization film properties test
As a result with table 1.
Embodiment 5：
A kind of efficient corrosion resisting Zinc phosphating solution, its composition of raw materials group are grouped into：
A kind of efficient corrosion resisting Zinc phosphating solution is made by the steps：
Take graphene oxide (GO)：0.05g carries out ultrasonic disperse in 1L water, added after being uniformly dispersed zinc oxide 16g,
Sodium phosphate 34g, polyacrylamide 5g, and continue ultrasonic disperse to being completely dissolved；It is 5 with the pH of sodium hydrate regulator solution
Left and right, storage at room temperature after stirring can be to obtain this new and effective anti-corrosion Zinc phosphating solution.
The new and effective anti-corrosion Zinc phosphating solution of preparation is put into three electrode phosphating ponds, metal works are carried out as negative electrode
Electrochemical phosphating, phosphating time is 1 minute, and in parkerizing process, workpiece surface is with the presence of substantial amounts of negatron, in phosphating solution
Zn2+And PO4 3-Plasma is under current field condition, and fast deposition is in workpiece surface, generation metallic zinc, trbasic zinc phosphate, ferric phosphate zinc, oxygen
The co-precipitation composite coating of graphite alkene, then the workpiece obtained after phosphatization is washed down to the phosphorus dried after can obtain phosphatization with water
Change film.
For the method for testing of the corrosion polarization curve of phosphating coat with embodiment 1, test result is shown in Fig. 2, phosphatization film properties test
As a result with table 1.
Above-described embodiment is visible, and the present invention is dispersed in graphene oxide as anti-corrosion material in phosphating solution, makes itself and phosphorus
Hydrochlorate co-deposition is covered on the surface of metal works into the phosphating coat of densification, is efficiently filled with conventional phosphate film table
The Micro porosity in face, forms isolation layer, there is provided physical shielding acts on, and blocks the way of the direct contacting metal workpiece of corrosive medium
Footpath, the generation of electrochemical corrosion is further suppress, substantially increases antiseptic property, far above prior art standard.
Graphene oxide reduces the use of later stage poisonous anticorrosion material, in the later stage as anti-corrosion material in the present invention
Cost has been greatly reduced on the processing three wastes, and process is being used without metal ions such as harmful nickel and chromium in phosphating solution
In and using rear be not detrimental to health and destroy ecological environment.
Using electrochemical cathode polarization process, i.e., efficient corrosion resisting Zinc phosphating solution electrochemical phosphating method of the present invention is
Enter to be about to workpiece in the presence of electric field and carry out electrochemical phosphating as negative electrode to be co-deposited to obtain graphene oxide and phosphatic
Corrosion-inhibiting coating, using electrochemical phosphating mode not only rapidly and efficiently, and obtained phosphating coat densification is smooth, ageing-resistant, resistance to
The premium properties such as scraping, high adhesion force.
The preparation process step of graphene oxide of the present invention and phosphate complex phosphate coating is few, easy to operate, technological process
Simply, to pressure and no requirement (NR), therefore low is required to instrument and equipment, generally conventional container and electro-deposition production equipment can reach
The requirement, it is adapted to large-scale production.
Claims (8)
1. a kind of efficient corrosion resisting Zinc phosphating solution, it is characterised in that in terms of mass fraction, its composition of raw materials component is：
Described GO dispersants are triethyl group hexyl phosphoric acid, lauryl sodium sulfate, methyl anyl alcohol, cellulose derivative, poly- third
One or more in acrylamide, guar gum, fatty acid polyethylene glycol ester.
2. efficient corrosion resisting Zinc phosphating solution according to claim 1, it is characterised in that described Zn2+Come from zinc oxide,
One or more in zinc sulphide, zinc chloride and zinc hydrogen phosphate.
3. efficient corrosion resisting Zinc phosphating solution according to claim 1, it is characterised in that described PO4 3-Come from phosphoric acid,
One or more in trbasic zinc phosphate, potassium dihydrogen phosphate and sodium phosphate.
4. efficient corrosion resisting Zinc phosphating solution according to claim 1, it is characterised in that described stabilizer is polyoxyethylene
Octyl phenol ether -10, poly-methyl pyrrole alkanone, gelatin, sodium carboxymethylcellulose (CMCNa), sodium alginate, carragheen and alkyl
One or more in phenol polyethenoxy ether.
5. efficient corrosion resisting Zinc phosphating solution according to claim 1, it is characterised in that described pH adjusting agent is ethanol
It is a kind of or a variety of in amine, ammoniacal liquor, sodium hydroxide, sodium acid carbonate and sodium carbonate.
6. efficient corrosion resisting Zinc phosphating solution according to claim 1, it is characterised in that described graphene oxide is
Hummers methods prepare powdered graphene oxide or 0.1~4.0wt% the graphene oxide water obtained by being freeze-dried excessively
Solution.
7. efficient corrosion resisting Zinc phosphating solution according to claim 1, it is characterised in that described water from running water or
Person's deionized water；Mass fraction meter, dosage are 1000 parts.
8. the preparation method of any one of the claim 1-7 efficient corrosion resisting Zinc phosphating solutions, it is characterised in that by graphite oxide
Alkene is added to the water, and carries out ultrasonic disperse and uniformly adds Zn afterwards2+、PO4 3-, GO dispersants, stabilizer, and continue ultrasonic disperse
To being completely dissolved, addition pH adjusting agent to pH is 4-5, and the normal temperature preservation that stirs.
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| CN109097809A (en) * | 2018-08-06 | 2018-12-28 | 佛山科学技术学院 | A kind of preparation process of high anti-corrosion thick phosphorization membrane |
| CN109252204A (en) * | 2018-08-29 | 2019-01-22 | 昆明理工大学 | A method of preparing magnesium phosphate/Super-P composite corrosion proof coating |
| CN109280910A (en) * | 2018-10-10 | 2019-01-29 | 安徽腾龙泵阀制造有限公司 | A kind of chemical pump surface granosealing technique |
| CN109853023A (en) * | 2019-03-26 | 2019-06-07 | 华南理工大学 | A kind of zinc system anti-corrosion electrolytic phosphating liquid and preparation method thereof |
| CN109898123A (en) * | 2019-03-11 | 2019-06-18 | 山东凤阳佰乐舒家居有限公司 | A kind of steel wire drawing electrolytic phosphating liquid and preparation method thereof |
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| CN109853023A (en) * | 2019-03-26 | 2019-06-07 | 华南理工大学 | A kind of zinc system anti-corrosion electrolytic phosphating liquid and preparation method thereof |
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