CN100383281C - Rapid zinc series, zinc-calcium series or iron series clean phosphatizing liquid under room-temperature with multiple styles - Google Patents
Rapid zinc series, zinc-calcium series or iron series clean phosphatizing liquid under room-temperature with multiple styles Download PDFInfo
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- CN100383281C CN100383281C CNB200410023096XA CN200410023096A CN100383281C CN 100383281 C CN100383281 C CN 100383281C CN B200410023096X A CNB200410023096X A CN B200410023096XA CN 200410023096 A CN200410023096 A CN 200410023096A CN 100383281 C CN100383281 C CN 100383281C
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- zinc
- phosphatization
- phosphorizing
- liquid
- nitrate
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Classifications
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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
- C23C22/42—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 phosphates
Abstract
The present invention relates to a multimode, rapid, and room temperature zinc, or zinc calcium, or iron cleanness type phosphorizing liquid. The component of the phosphorizing liquid is completely composed of components which can form phosphorizing films, or settlement components, or molecules or ions which can be volatilized in the process of drying of the phosphorizing films, and therefore, the accumulation of byproducts and some components can not be produced not to affect the adjustment of the phosphorizing liquid. The components in the phosphorizing liquid comprise phosphoric acid, nitrate, zinc phosphate, zinc nitrate, calcium phosphate, calcium nitrate, manganese phosphate, manganese nitrate, nickel phosphate, nickel nitrate, ammonium molybdate, ammonium tungstate, phytic acid, H2O2 and non-ionic surface active agents, and the pH value of the phosphorizing liquid is from 2.0 to 5.8. The phosphorizing liquid does not contain toxic Cr and nitrite, the phosphorizing speed is high, and the phosphorizing liquid can be phosphorized in a soaking way, or a spraying way, or a brushing way, or a combined way of soaking, spraying and brushing in a temperature of 1 to 50 degrees. The present invention has the advantages of stable phosphorizing liquid, continuous, uniform and compact phosphorizing films, less settlement, and no waste water discharge after the phosphorization is carried out. Besides, the weight of each film is from 0.3 to 2.1 g. m <2>, and the adhesive force reaches one stage after the paint spraying is carried out.
Description
Technical field
The invention belongs to the preceding phosphorization treatment technology field of steel surface spraying, relating to a kind of multimode, quick room temperature zinc system or zinc calcium system or iron is clean phosphatization liquid.
Background technology
Bonderizing, the history surplus in the of existing 100 year is metal works handles and forms in processed metallic surface the process of phosphatize phosphate coat in the dihydrogen phosphate of metal or ammonium, solution that promotor is main component.Phosphatize phosphate coat has increases adhesive force of coatings, solidity to corrosion and protection, antifriction, effect such as lubricated.Phosphatization liquid can be divided into types such as zinc system, manganese system, iron system by the film forming positively charged ion.
Following reaction, take place in phosphatization when steel surface contact phosphatization liquid:
Fe+[O]+H
2O → Fe
2++ 2OH
-([O] represents oxygenant and the dissolved oxygen in the phosphatization liquid)
2Fe
2++[O]+H
2O→2Fe
3++2OH
-
Fe
3++PO
4 3-→FePO
4↓
After this, [the OH of generation
-] the pH value of steel surface is raise, react:
Fe
3++3OH
-→Fe(OH)
3↓
Simultaneously, in phosphatization liquid, there is metal ions M
2+(as Zn
2+, Mn
2+, Ca
2+, Ni
2+Deng) time:
3M
2++2PO
4 3-→M
3(PO
4)
2↓
In the drying process of phosphatize phosphate coat:
2Fe(OH)
3→Fe
2O
3+3H
2O↑
2(NH
4)
2HPO
4+6Fe+9[O]→2FePO
4+2Fe
2O
3+4NH
3↑+3H
2O↑
So, be in the phosphatization at iron, the phosphatize phosphate coat main component is FePO
4, 2Fe
2O
3In Zinc phosphating, the phosphatize phosphate coat main component is FePO
4, Zn
3(PO
4)
2And 2Fe
2O
3
The steel surface that any needs spray all needs to carry out phosphatization.Phosphatization is automobile, household electrical appliances and the necessary process of most machinery production.Present domestic phosphorization technology ubiquity: cost height, phosphatization temperature height, phosphatization liquid life-span short (have even high frequency hour just scrap surplus using 100), cause waste water, the waste residue of body eutrophication many (this waste residue belongs to dangerous refuse), most phosphating solution at room temperature contain toxic substances such as nitrite and chromium.Therefore, etching solution is badly in need of updating.Phosphorized waste water is crucial source of pollution that cause body eutrophication.Body eutrophication, the phosphorus, nitrogen that promptly are thrown into water body surpass the environmental problem that ability to bear caused of physical environment, are one of at present serious environmental problem of China.The whole nation has surplus the phosphatization production line 20,000, and the enterprise that wherein has produces every day needs discharging phosphorus exceed standard more than tens of times tens tons of phosphorized waste waters even ton up to a hundred.Grease-removing agent can fundamentally be eliminated nitrogen with agent of non-phosphate degreasing, phosphorus pollutes, and phosphatization also can't not used phosphoric acid salt with present scientific and technological level.
Phosphatization by its treatment temp, can be divided into high temperature phosphorization, middle temperature phosphating, normal (low, chamber) warm phosphatization (15-45 ℃); By its film forming positively charged ion, can be divided into zinc system, manganese system, iron system etc.The phosphatization liquid that spraying pre-treatment is at present used generally needs washing after the phosphatization, otherwise the degradation production of the accelerator in the phosphatize phosphate coat dust, phosphatization liquid is (as the reacted Cl of sodium chlorate
-, Na
+Ion, auxiliary agent are (as F
-Ion or fluorochemical) obviously influence the quality of phosphatize phosphate coat; 15 ℃ or more, generally will heat basically by winter for phosphatization temperature; Phosphating solution at room temperature promotor is generally contained deleterious Ni (nickel) and Cr (chromium) and carcinogenic and decomposition generation toxic gas oxynitride (NO
x) nitrite, phosphatization is of poor quality etc.; Sediment in the parkerizing process is more, phosphatization 1m
2Produce several grams even more sediment.
The research of phosphatization, developing direction are asepsis environment-protecting, low temperature low cost, high-performance at present, and along with the high and scientific and technological progress of the day of environmental protection cry, (finally) will be the cleaning phosphatization soon.
Summary of the invention
Technical problem to be solved by this invention is at above-mentioned weak point of the prior art, and it is clean phosphatization liquid that a kind of multimode, quick room temperature zinc system or zinc calcium system or iron are provided.Make: (1) phosphatization liquid life-span is long, no waste water.Each component of phosphatization liquid all enters phosphatize phosphate coat to be become the integral part of phosphatize phosphate coat and sediment or volatilizees in the phosphatize phosphate coat drying process, parkerizing process is not exerted an influence byproduct or the accumulation of certain component that phosphatization liquid adjusts, therefore, the phosphatization liquid life-span is long, and the film after the phosphatization needn't be washed or wash water can reclaim and adds in the phosphatization liquid and do not have waste water.(2) quality is good.Synergy by an amount of ammonium molybdate and nitrate etc. is controlled the ratio that passive film accounts for phosphatize phosphate coat, the concentration of control phosphatization liquid and pH value and make the film after the phosphatization not wash defectives such as also not producing dust, phosphatize phosphate coat has good solidity to corrosion and makes coating that comparatively ideal sticking power be arranged, and quality index such as its corrosion resisting property surpass existing normal-temperature zinc series and iron is phosphatization.(3) save energy.Adopt 10～40 ℃ of (minimum 1 ℃) phosphatization, farthest save energy of room temperature.(4) economical with materials.Heavy (the 1g/m of suitable membrane
2About), sediment is few, accomplished that really phosphatization needn't heat, constitute the molecule of phosphatization liquid or ion all enters phosphatize phosphate coat or in the phosphatize phosphate coat drying process volatilization and the wash water of the phosphatization liquid life-span is long, workpiece is taken away phosphatization liquid or phosphatize phosphate coat can reclaim to join and use in the phosphatization liquid, consume obviously and reduce.(5) environmental protection and safe in utilization.Do not contain deleterious Cr, nitrite in the phosphatization liquid, phosphorization at room temperature needn't be adjusted on the surface, can not wash after the phosphatization; Recyclable again less the raw material of no waste water, waste residue as production phosphatization liquid, iron oxide red etc.(6) simple to operate.The phosphating process controlled variable is wide, mode is many: phosphatization liquid is stable, simple to operate, phosphating time 30 seconds to tens hours all can (though the long phosphorization film quality that does not influence workpiece of phosphating time, but influence the life-span of phosphatization liquid and produce sediment), do not wash direct oven dry or dried certainly after the phosphatization.Can adopt all phosphatization modes: brush, soak, spray or its combination.
Solve technical scheme that the technology of the present invention problem adopted and be this multimode, fast room temperature cleaning zinc system or zinc calcium system or its phosphatization liquid of phosphating liquor of iron series component all by the integral part that can become phosphatize phosphate coat or sediment integral part can the evaporable molecule in the drying process of phosphatize phosphate coat or ion constitute, make the byproduct that the phosphatization liquid that do not exert an influence in the parkerizing process adjusts and the accumulation of certain component.Phosphatization liquid contains the salt of phosphoric acid, nitric acid or phosphoric acid and nitric acid (except that basic metal) ammonium, zinc, calcium, nickel, manganese and ammonium molybdate, ammonium tungstate, phytic acid, hydrogen peroxide, nonionogenic tenside etc., does not contain carcinogenic and decompose to produce toxic gas NO
xNitrite, do not contain poisonous Cr salt, also can not contain Zn, Mn and Ni salt, each components contents scope is:
Phosphoric acid salt and phosphoric acid are (with PO
4 3-Meter): 6.8～32.0gL
-1
Nitrate is (with NO
3 -Meter): 0.1～10.0gL
-1
Molybdate is (with MoO
4 2-Meter): 1.0～8.1gL
-1
Tungstate (WO
4 2-Meter): 0.0～4.1gL
-1
Zn
2+：0.0～12.5g·L
-1；
Ca
2+：0.0～6.5g·L
-1；
Mn
2+：0.0～4.5g·L
-1；
Ni
2+：0.0～3.5g·L
-1；
Phytic acid: 0.0～5.1gL
-1
H
2O
2：0.0～5.0g·L
-1
Nonionogenic tenside: 0.0～1.0gL
-1
PH value: 2.0～5.8;
Controlled variable: phosphating time: 30～900s (phosphating time extends to 72h, and phosphorization film quality is also fine) when phosphatization liquid is used; Phosphatization temperature: 1～50 ℃; Phosphatization mode: soak, spray, brush or its combination.
Alkali-free metallic salt in the phosphatization liquid.
Main drying treatment mode has following several after the workpiece phosphatization:
1. do not wash oven dry or seasoning;
2. washing back oven dry, seasoning or hot water are scalded the back seasoning.
The making method of product of the present invention is: with the above Industrial Salt such as phosphoric acid salt, nitrate and molybdate, or acid is dissolved in quantitative tap water, and the pH value is adjusted to requiring with industrial phosphoric acid or ammoniacal liquor in the dissolving back, adds nonionogenic tenside again.Phosphoric acid salt, nitrate and molybdate refer to ammonium salt, zinc salt, calcium salt, manganese salt and nickel salt.Nonionogenic tenside such as TX-10.
Arbitrary molecule of phosphatization liquid or ion or enter the integral part that phosphatize phosphate coat becomes phosphatize phosphate coat and sediment among the present invention, in the drying process of phosphatize phosphate coat, volatilize, so in parkerizing process, do not have the byproduct accumulation and the accumulation of certain phosphatization fluid component of film formation reaction.Therefore, add some material in the phosphatization liquid, just the actual composition behind the phosphatization liquid life-time service can be changed to the suitable composition or the design requirements of phosphatization liquid, also not have concentration height in the preparation of certain ratio of component because in parkerizing process, both increased irreversible novel substance.
The molecule or the ion that comprise in the general phosphatization liquid have:
(1) film forming maybe can become sediment (sediment all is a material of forming phosphatize phosphate coat): phosphate radical anion is (with PO
4 3-Meter), the metal sun is from M
2+(as zinc Zn
2+, manganese Mn
2+, calcium Ca
2+, nickel
2+, molybdenum ion etc.), their are in conjunction with becoming insoluble phosphoric acid salt (phosphatize phosphate coat that does not allow not wash contains the salt of solubility, influences the quality of phosphatize phosphate coat like this, and the phosphatize phosphate coat of cleaning phosphatization does not have the salt of solubility).
Phosphating liquor of iron series does not generally contain zinc, manganese plasma.Zinc phosphating solution must contain Zn
2+All phosphatization liquid must have the part (phosphate anion is absolutely necessary) in these ions, and cleaning phosphatization liquid is no exception.
(2) can not become the phosphatize phosphate coat integral part, comprise four classes: the first kind be can force that phosphatization liquid scraps by product appears in film formation reaction, as sodium chlorate during as accelerator, the sodium-chlor that sodium chlorate becomes behind film formation reaction (NaCl), along with constantly carrying out of phosphatization, sodium chlorate is constantly replenished, and the concentration of sodium-chlor constantly increases, after reaching finite concentration, just because chlorion (Cl
-) influence phosphatize phosphate coat and force phosphatization liquid to be scrapped; Second class is alkalimetal ion (sodium Na
+, potassium K
+), only influence the pH value of phosphatization liquid, can eliminate its influence by adding phosphoric acid; But if the phosphatize phosphate coat after the phosphatization is not washed, they will be adsorbed in the form of alkali or salt in the phosphatize phosphate coat, can influence the performance of phosphatize phosphate coat; The 3rd class is the artificial auxiliary agent that improves the phosphatize phosphate coat performance that adds, the Sodium Fluoride that adds as usual (NaF), EDTA, citric acid etc., majority is not participated in film formation reaction, and to eliminate the dissolving of deleterious aluminium plasma and iron and steel too fast and surpass the iron ion (Fe of film forming needs and be used for complexing
2+, Fe
3+) influence, constantly replenish along with constantly carrying out of phosphatization, reach finite concentration after, phosphatization liquid is scrapped, and the phosphatize phosphate coat after the phosphatization must be washed, otherwise phosphatize phosphate coat dust even get rusty; The 4th class is ammonia (NH
3) or ammonium (NH
4 +), can influence the pH value of phosphatization liquid, can eliminate its influence by adding phosphoric acid, if the phosphatize phosphate coat after the phosphatization is not washed, will in the drying process of phosphatize phosphate coat, volatilize, thereby not exert an influence.
Cleaning phosphatization liquid of the present invention, characteristics are " arbitrary molecule of phosphatization liquid or ion want one integral part that becomes phosphatize phosphate coat to want one to volatilize in the drying process of phosphatize phosphate coat; parkerizing process do not exert an influence byproduct that phosphatization liquid adjusts and the accumulation of certain component ", the above-mentioned first kind, two classes, three class ions promptly can not be arranged, only there is the 4th class ion, certainly, if phosphating process allows the phosphatize phosphate coat washing after the phosphatization then allows the second class ion.General phosphatization liquid all has two classes or the three class ions in the above-mentioned first kind, two classes, the three class ions.Therefore, phosphatization liquid of the present invention in theory work-ing life " endless ", and general phosphatization liquid in use itself just causes and scraps.
Cleaning phosphatization liquid proposed by the invention, the reason that the phosphatize phosphate coat after the phosphatization needn't be washed
One: do not contain the above-mentioned first kind, two classes, three class ions, only contain the 4th class ion in above-mentioned four classes, do not wash consistent with the component of the phosphatize phosphate coat of washing.
Its two: remain in the phosphatization liquid on phosphatize phosphate coat surface, in the phosphatize phosphate coat drying process, continue to continue film forming.Because above-mentioned reason, the kind of the component of its phosphatize phosphate coat do not increase because of the remaining phosphatization liquid in phosphatize phosphate coat surface.
Its three: remain in the composition (or concentration) of the phosphatization liquid on phosphatize phosphate coat surface, just adapt, do not cause the surperficial dust of phosphatize phosphate coat (its ash is solubility or insoluble phosphoric acid salt, oxide compound) with exsiccant speed.
Phosphorization film quality after phosphatization liquid of the present invention is handled on the product:
1. phosphatize phosphate coat is continuous, even, fine and close, no mass defect, and outward appearance is gray or colour slightly;
2. the anti-corrosion time of phosphatize phosphate coat (the anti-copper sulfate point dropping liquid time is by regulation dosing and the detection of GB 6807-86 appendix D) is 50～600s (second).
3. checking the film of phosphatize phosphate coat by the regulation of GB/T 9792-1988 heavily is 0.5～2.1gm
-2
4. with the matching performance of paint film: the regulation of pressing GB 1720-79 " paint film adhesion assay method " is measured, and all reaches 1 grade.
The design philosophy of phosphatization liquid formula of the present invention is presented as: any molecule of phosphatization liquid or ion all become the integral part of phosphatize phosphate coat and sediment or volatilize in the phosphatize phosphate coat drying process; Low consumption, easy to operate, phosphatization fast, high quality and environmental protection, can replace phosphatizations such as the zinc system that uses before the steel surface spraying, iron system.
Product of the present invention is handled with reference to technical process steel surface: to steel surface degreasing, washing, (degreasing rust cleaning, washing when rust is arranged), phosphatization, drying.
Product of the present invention has following technique effect:
(1) the phosphatization liquid life-span long, no waste water.
(2) the phosphatization quality is greatly improved, and the phosphatization mode is many: phosphorization at room temperature film corrosion resisting property and film heavily have breakthrough, and surpass the preceding phosphatization specification of quality of spraying of GB/T 6807-2001 regulation.All phosphatization modes of can adopt brush, soak, spraying are carried out phosphatization.
(3) save energy.Adopt 10～40 ℃ of (minimum 1 ℃) phosphatization, farthest save energy and setup times of room temperature.
(4) economical with materials.
(5) environmental protection and safe in utilization.
(6) simple to operate.The phosphating process controlled variable is wide, mode is many, and phosphatization liquid is stable, and phosphating time all can (though phosphating time length does not influence the phosphorization film quality of workpiece, influence the life-span of phosphatization liquid and produce sediment) in 30 seconds to tens hours, did not wash direct oven dry or dried certainly after the phosphatization.Can adopt all phosphatization modes: brush, soak, spray or its combination.
Embodiment
Be non-limiting examples of the present invention below, among the embodiment, test piece is the cold-reduced sheet of 70 * 80 * 2.0mm, by phosphatization immediately after recommending technology to eliminate oil and rust and tap water to clean, all obtains the phosphatize phosphate coat of ash-homogeneous color, no mass defect with strong acid and strong base.The anti-corrosion time, three times mean value is got in the regulation check of pressing GB 6807-86 appendix D.Sticking power is pressed the regulation spraying of GB 1720-79 " paint film adhesion assay method " and is measured.
(1) embodiment 1
Phosphatization liquid formula: primary ammonium phosphate [NH
4H
2PO
4]: 33.5gL
-1Ammonium Heptamolybdate [(NH
4)
6Mo
7O
244H
2O]: 8.5gL
-1Phytic acid (C
6H
18O
24P
6): 3.0gL
-1Nickelous nitrate [Ni (NO
3)
26H
2O]: 13.50gL
-1With ammoniacal liquor (NH
3H
2O) adjust pH value to 5.0.
Phosphatization situation and result: brushes in test piece one time with working fluid down for 10 ℃, at 120 ℃ of baking 10min, the anti-corrosion time of check is 220s behind the 30min then, 12h (hour) after be 320s; Sticking power reaches 1 grade.
(2) embodiment 2
Phosphatization liquid formula: primary zinc phosphate [Zn (H
2PO
4)
2]: 27.8gL
-1Ammonium Heptamolybdate: 8.1gL
-1Phytic acid: 1.0gL
-1Nitrocalcite [Ca (NO
3)
2]: 5.8gL
-1Ammonium nitrate [NH
4NO
3]: 2.1gL
-1Adjust pH value to 2.4 with ammoniacal liquor.
Phosphatization situation and result: 15 ℃, test piece is dipped in the phosphatization working fluid, take out behind the 5min at 120 ℃ and dry by the fire 8min down, detecting the anti-corrosion time behind the 30min is 120s, the heavy 1.25gm of film
-2, sticking power reaches 1 grade.
(3) embodiment 3
Phosphatization liquid formula: Secondary ammonium phosphate [(NH
4)
2HPO
4]: 16.0gL
-1Ammonium nitrate: 4.5gL
-1Ammonium Heptamolybdate: 8.0gL
-1With phosphoric acid (85% H
3PO
4) adjustment pH value to 3.5.
Phosphatization situation and result: under 10 ℃ test piece is dipped in 5min in the phosphatization working fluid, takes out at 120 ℃ and dry by the fire 10min down, detecting the anti-corrosion time behind the 30min is 138s, the heavy 0.81gm of film
-2, sticking power reaches 1 grade.
The present invention is applicable to the bonderizing before the steel surface sprayings such as cold-reduced sheet, hot-rolled sheet, angle steel.Phosphatization liquid is made of phosphoric acid, nitric acid or its ammonium, zinc, calcium, nickel, manganese salt and ammonium molybdate, ammonium tungstate, phytic acid, hydrogen peroxide etc., does not contain carcinogenic and decompose to produce toxic gas NO
xNitrite, do not contain deleterious Cr salt, can not contain harmful Zn, Mn and Ni salt.Phosphatization speed is fast, can be to soak, spray, to brush or its array mode phosphatization under 1～50 ℃.Phosphatization liquid is stable, and is simple to operate.Phosphatize phosphate coat is continuous, even, fine and close, no mass defect, and outward appearance gray or colour, the anti-copper sulfate point dropping liquid time can reach 50～600s, and film heavily is 0.3～2.1gm
-2, its sticking power of back that sprays paint reaches 1 grade.Sediment is few, but non-wastewater discharge after the phosphatization.
Claims (2)
- A multimode, room temperature zinc system or zinc calcium system or iron are clean phosphatization liquid fast, contain phosphoric acid and phosphoric acid salt, nitric acid and nitrate, molybdate, it is characterized in that described phosphoric acid salt and nitrate are one or more salt in ammonium except that basic metal, zinc, calcium, nickel, the manganese, molybdate is an ammonium molybdate, and each components contents scope is:Phosphoric acid and phosphoric acid salt are with PO 4 3-Meter: 6.8～32.0gL -1Nitric acid and nitrate are with NO 3 -Meter: 0.1～10.0gL -1Ammonium molybdate is with MoO 4 2-Meter: 1.0～8.1gL -1Zn 2+：0.0～12.5g·L -1；Ca 2+：0.0～6.5g·L -1；Mn 2+：0.0～4.5g·L -1；Ni 2+：0.0～3.5g·L -1；
- 2. multimode according to claim 1, quick room temperature zinc system or zinc calcium system or iron are clean phosphatization liquid, it is characterized in that also containing ammonium tungstate, phytic acid, hydrogen peroxide, and its component concentration scope is:Ammonium tungstate, WO 4 2-Meter: 0.0～4.1gL -1Phytic acid: 0.0～5.1gL -1H 2O 2：0.0～5.0g·L -1
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200410023096XA CN100383281C (en) | 2004-04-09 | 2004-04-09 | Rapid zinc series, zinc-calcium series or iron series clean phosphatizing liquid under room-temperature with multiple styles |
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|---|---|---|---|
| CNB200410023096XA CN100383281C (en) | 2004-04-09 | 2004-04-09 | Rapid zinc series, zinc-calcium series or iron series clean phosphatizing liquid under room-temperature with multiple styles |
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| CN100383281C true CN100383281C (en) | 2008-04-23 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101168840B (en) * | 2007-11-28 | 2010-06-16 | 东北大学 | Phosphor molybdenum heteropolyacid inactivating treatment liquid used for heat zinc coating plate |
| CN102121103B (en) * | 2010-01-11 | 2012-07-04 | 张华斌 | Low-temperature slag-free zinc bonderite as well as preparation method and applications thereof |
| CN102899651A (en) * | 2011-07-29 | 2013-01-30 | 史学斌 | Multi-function metal surface treatment agent |
| CN102747356B (en) * | 2012-07-30 | 2014-08-20 | 长沙学院 | Normal temperature calcium-manganese phosphorizing liquid |
| CN103769432B (en) * | 2014-01-28 | 2016-02-10 | 威海银兴预应力线材有限公司 | Electrolytic phosphating method |
| CN104313620A (en) * | 2014-10-14 | 2015-01-28 | 熊荣鑫 | Method for cleaning rust on surfaces of iron and iron alloy |
| CN106756926A (en) * | 2017-01-23 | 2017-05-31 | 江苏理工学院 | A kind of environment-friendly phosphating solution and its application for steel |
| CN108998787B (en) * | 2018-06-13 | 2021-01-26 | 河南北方红阳机电有限公司 | Phosphorus spraying film forming solution and phosphorus spraying process thereof |
| CN111286728A (en) * | 2020-03-30 | 2020-06-16 | 沈阳理工大学 | Phosphating solution, phosphate coating, preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1475603A (en) * | 2003-07-11 | 2004-02-18 | 余取民 | Environmental protection type multi mode, fast and enery saving iron series phosphatizing solution |
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|---|---|---|---|---|
| CN1475603A (en) * | 2003-07-11 | 2004-02-18 | 余取民 | Environmental protection type multi mode, fast and enery saving iron series phosphatizing solution |
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