CN1286319A - Ordinary-temp phosphonating liquid - Google Patents

Ordinary-temp phosphonating liquid Download PDF

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Publication number
CN1286319A
CN1286319A CN 99117563 CN99117563A CN1286319A CN 1286319 A CN1286319 A CN 1286319A CN 99117563 CN99117563 CN 99117563 CN 99117563 A CN99117563 A CN 99117563A CN 1286319 A CN1286319 A CN 1286319A
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liquid
naf
phosphatization
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CN1163629C (en
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黄霓裳
郭良生
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Second Department Of Fujian Institute Of Material Structure Chinese Academy Of Sciences
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Second Department Of Fujian Institute Of Material Structure Chinese Academy Of Sciences
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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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Abstract

An ordinary-temp phosphonating liquid for treating steel surface before painting contains H3PO4 (12.6-50.7 g/l), (HOC2H4)3N (2.4-4.0 g/l), ZnO (1.88-11.5 g/l), C6H8O7 (0.5-1.5 g/l), Na2MoO4 (0.5-1.5 g/l), NaF (0.5-1.5 g/l), OP (0.1-0.2 g/l) and H2O (the rest). After the steel is phosphonated for 5-15 min, the phosphonated film is compact and anticorrosive. Its advantages are no content of NO2(-), NO3(-), ClO3(-), Ni(2+) and Mn(2+) ions, less environmental pollution, stable property of solution and low cost.

Description

A kind of normal-temperature phosphorizing liquid
The invention belongs to chemical field, especially relate to the parkerized new technology of steel surface.
Along with the progress of phosphorization technology, Modern Phosphating handles mainly towards low temperature, form the direction thin and phosphate layer that barrier propterty is good fast develops.Traditional normal temperature phosphating adopts NO usually 2 -, NO 3 -, ClO 3 -And Ni 2+, Mn 2+Deng as promotor, need table to transfer before the phosphatization, need passivation after the phosphatization, otherwise film forming speed is slow, membrane crystallization is coarse, and solidity to corrosion is poor.As " " normal temperature phosphating technology " that electroplating technology handbook (China Machine Press's in August, 1997 second edition) is the 431st page (1--4), not only using dosage is big, stability of solution is poor, and life cycle is short, complex process, production efficiency is low, and can produce toxic gas or a large amount of sediment in process of production, cause environmental pollution, and make the phosphatize phosphate coat dust, influence coating quality, frequent clear groove increases working strength of workers again.Therefore from reducing sediment, protection environment and easy to use, should adopt no NO as far as possible 2 -, NO 3 -, ClO 3 -And Ni 2+, Mn 2+The phosphatization of component.At present domestic advanced normal temperature phosphating technology have " electroplating and environmental protection " (1997. the 17th volume. the 4th phase. the 18-20 page or leaf) report beam just, the Quick Phosphating Agent under Room Temperature of people's development such as Shu Wanliang.Though this phosphorization agent does not contain NO 2 -, NO 3 -, ClO 3 -, F -, but still contain Ni 2+, Mn 2+Etc. environmentally harmful heavy metal ion, and adopt the reductive agent azanol to promote that the acidity of technology is unstable, processing range is narrower, and pharmacy variety is many, and price is more expensive.
The objective of the invention is to develop and a kind ofly can form thin and anti-corrosion phosphatize phosphate coat, and solution property is stable, processing range is wideer, and film forming speed is quick, and comprehensive cost is cheap, the novel normal-temperature phosphatization liquid of nontoxic pollution-free.
For realizing purpose of the present invention, technological line and action principle that we adopted are as follows: constitute main salt system by zinc oxide and phosphatase reaction, and utilize the characterization of adsorption of organo-functional group in acidic medium, organic compound and mineral compound that selection has multi-function action carry out the science compatibility, promptly by Sodium orthomolybdate, trolamine, citric acid, Sodium Fluoride and an amount of OP emulsifying agent are formed compound accelerant, make it to form the multiple macromolecular organic compound that has machine functional group, give full play to the synergistic effect between each functional group, have complementary advantages, make film process quicken phosphatization fs generation unformed layer, and guiding is sealed the active centre earlier and is finished phosphatization crystalline subordinate phase earlier, thereby form the phosphatize phosphate coat of absorption and deposition coexistence, make the phosphatize phosphate coat attenuate, chemical consumption and sediment weight reduce, to reach the acceleration parkerizing process, strengthen the purpose of phosphatize phosphate coat solidity to corrosion and raising stability of solution.
1. phosphatization liquid basic recipe: by the H of technical grade 3PO 4, ZnO, (HOC 2H 4) 3N, Na 2MoO 4, C 6H 8O 7, NaF, OP and water forms, each component concentration (g/L) is:
H 3PO 4(85％) 12.6～50.7 (HOC 2H 4)3N(90％) 2.4～4.0
ZnO(99.5％) 1.88～11.5 C 6H 8O 7(99.5％) 0.5～1.5
Na 2MoO 4(98.8％)0.5～1.5 NaF(99.5％) 0.5～1.5
OP 0.1～0.2 H 2The O surplus
2. phosphatization liquid processing parameter: solution proterties: the limpid transparent liquid of colorless and odorless; Total acidity TA (point): 22～86; Free acid FA (point): 2.5～10.5; PH value: 2.5～3.5; Proportion d 23 ℃: 1.010～1.036; Temperature: normal temperature; Treatment time: 5～15min.
3. phosphating process flow process: degreasing and rust removal (2 close 1)--washing--phosphatization--washing (or water not
Wash)--dry (or oven dry).
4. the mechanism of action of each component:
4-1. the effect of main salt: the present invention adopts good comprehensive properties phosphoric acid zinc salt system.Promptly by H 3PO 4Reaction constitutes the main body of phosphating reaction, excessive H with ZnO 3PO 4In order to keep the acidity of phosphatization liquid, promote the dissolving of matrix in the parkerizing process, accelerate phosphatization speed, make it promptly to form phosphating protective film.
4-2. the effect of compound accelerant: iron and steel is in phosphating reaction, along with Zn 3PO 4, Zn 2Fe (PO 4) 2And Fe 3(PO 4) 2Separate out, can constantly produce new H 3PO 4, PH is constantly reduced, and H 3PO 4Have only sub-fraction and iron and steel direct reaction to consume, so normal temperature phosphating needs often to adjust PH or FA.The present invention is by Na 2MoO 4, (HOC 2H 4) 3N, C 6H 8O 7And the compound accelerant formed of NaF, pH value that can cushioning balance solution can quicken parkerizing process again and strengthen the solidity to corrosion of phosphatize phosphate coat.
4-2-1.Na 2MoO 4Effect: Na 2MoO 4In parkerizing process, can play oxygenant, inhibiter, complexing agent and reduction rete weight simultaneously.Its electropotential can be deposited on steel surface by electrochemical reaction than iron height, thereby increases cathode and anode area ratio, quickens the forming process of phosphatize phosphate coat under the normal temperature.
Na 2MoO 4Another key property be: MoO 2- 4Can form diversified condensation polyacid radical ion by the polyhedral concurrent or the common rib condensation of oxygen.In the polyacid root anion structure of molybdenum, basic structural unit is the MoO of the octahedral bodily form 6, the orthophosphoric acid salt reaction in it and phosphatization liquid, PO 3- 4Positive tetrahedron is immediately by MoO 6The octahedra encirclement promptly inserted heteroatoms P (V) and formed the heteropolyacid radical ion at polyacid radical ion center.Heteropolyacid has very strong oxidation capacity and than the stronger acidity of they each components oxygen acid alone, helps promoting some element in the solution, particularly reductibility compound generation chemical conversion, and can rapidly metal/solution interface be reacted the Fe that is dissolved out 2+Be oxidized to Fe 3+, make it and PO 3- 4Reaction forms stable phosphatoptosis film, and self becomes reduced state, and reduzate is the molybdenum orchid
Figure 9911756300051
The molybdenum orchid is a negatively charged ion that volume is bigger, still keeps the condensation structure under reduced state, and the heteropolyacid that airborne oxygen is easy to be reduced reoxidizes, and makes its active recovery.So molybdate helps not only as oxidation promotor that the spontaneous of phosphating reaction carries out under the normal temperature, and more help the stable of solution than other oxygenants.When the heteropolyacid radical ion is adsorbed on the phosphatoptosis film, strengthened the cation selective of film, with Fe 3+Act on, be formed with the molybdate complex compound of provide protection, the imperfection and the leakiness of having replenished the phosphatoptosis film have stoped Fe 2+To the migration of solution, reduce the corrosion of matrix metal, promote the passivation of film process and iron and steel.
4-2-2.NaF and C 6H 8O 7Effect: NaF and C 6H 8O 7Normal temperature phosphating accelerator, activator and complexing agent have been widely used as.Because the F-electronegativity is very big, electronics there is bigger avidity, easily form HF (associated complex of 1-6), thus the pH value of stabilizing solution, the phosphatize phosphate coat that forms uniform and smooth and have the alkali resistant corrosive nature.C 6H 8O 7With H 3PO 4Synergistic effect the active site of nucleation also can be provided for the crystallisation process of phosphatization, thereby improve phosphatization speed, reduce thickness, the bonding force of reinforcing membrane and matrix.C 6H 8O 7And Fe 3+, Fe 2+And MoO 2- 4Reaction generates stable chelate, can also prevent to separate out in the acidic solution H 2MoO 4Or MoO 32H 2The O precipitation plays stable tank liquor.
Though NaF and C 6H 8O 7Etch to iron is very capable, but consumption too much can make film formation reaction stop, and consumption does not reach the purpose of acceleration and complexing very little again, thereby is not easy to grasp.Maximum defective also is C 6H 8O 7Crystallization is attenuated, do not increase the crystal number, cover not exclusively to cause film.The present invention introduces has collaborative complexing, and (the HOC of inhibition synergism is arranged again 2H 4) 3N has remedied NaF and C 6H 8O 7Deficiency.
4-2-3. (HOC 2H 4) 3The synergy mechanism of N can be explained by following several respects:
(HOC 2H 4) 3N is the stronger ligand of a kind of coordination ability, central atom N and the active H by pure amine groups at first in phosphatization liquid +Coordination forms ion (HOC 2H 4) 3NH +, and do partial physical adsorption in the cathodic area of steel surface, hinder H +To steel surface near and suppress H +Reduction reaction, and then with having not the central atom N and the O of share electron pair carry out comprehensive chemisorption to steel surface Me atom or ion, form in the hole that stable five-ring inner complex is adsorbed on the top layer of phosphatize phosphate coat or film, original exposed part is covered by chelating indissoluble film, suppress thereby make the iron and steel dissolution process be subjected to intensive, stop anode dissolution product Fe 2+To solution diffusion.Positively charged ion (HOC 2H 4) 3NH +Adsorbed the PO in the solution 3- 4, MoO 2- 4After, again further with Fe (H 2PO 4) 2And Zn (H 2PO 4) 2Effect generates the composite phosphate film that has the machine group at steel surface.
Alcohol amine groups and oxygen acid root negatively charged ion form the macromolecular organic compound of polynary weak acid and weak base, and with simple ligand compound deposits yields synergistic effect, after the ligancy inorganic ligand F-more less than higher central ion and volume ratio forms the unsaturation complex compound on solution or the steel surface, again with organic complex C 6H 8O 7(HOC 2H 4) 3The N combination forms simple coordination compound and multicomponent complex, and space or the unlapped zone between bulky organic compound molecule can be filled up or occupy to the mineral compound that volume is little, makes free H +Mobile being suppressed, after the reaction of steel surface and free acid, surperficial pH value rises rapidly, forms numerous phosphoric acid salt nucleus, makes film forming speed also be subjected to certain restriction, thus formation even compact and thin and anti-corrosion phosphatize phosphate coat.
Parkerizing process comprises chemistry and electrochemical reaction, and under the condition that no inhibition membrane-forming agent exists, iron and steel is at H +Effect under produce chemistry and electrochemical dissolution simultaneously.Oxide catalyst Na 2MoO 4The electrochemical corrosion course that suppresses iron and steel, (HOC 2H 4) 3N suppresses the chemical corrosion process of iron and steel.Organo-functional group is in the absorption of steel surface, destroys not have the formation of surface crystallization layer of provide protection.While Na 2MoO 4Easily oxidizable also help pure amine groups and Me (Fe N+, Zn 2+) coordination forms insoluble chelate film and cover and deposit MoO 2- 4And PO 3- 4Steel surface, this screen layer has strengthened MoO 2- 4And PO 3- 4Corrosion inhibition.Both complement one another, and play the effect of repairing and passive film.Because (HOC 2H 4) 3N and inorganic acid radical are mutually promoted in the absorption of steel surface, (HOC 2H 4) 3The cation-adsorption of N increases its positive charge in steel surface, helps negatively charged ion to spread to steel surface.And the enrichment of inorganic acid radical has attracted (HOC again 2H 4) 3The positively charged ion of N.Interactive result makes the (HOC that is adsorbed 2H 4) 3What hydroxyl hydrocarbon chain and steel surface leaned in the N molecule is tightr, makes and adsorbs more stabilization.Therefore draw (HOC in the prescription 2H 4) 3N demonstrates bigger superiority.It had both played the normal temperature phosphating promoter action.Play the synergism of cushioning balance solution pH value again.Not only reduce the generation of sediment, reduce the consumption of pharmaceutical chemicals, also improved the compactness and the alkali-resistivity of film.
4-3.OP effect: the present invention adds a small amount of OP emulsifying agent.In order to improve the wettability of phosphatization liquid, reduce requirement to pre-treatment to workpiece surface.It can also improve the cathodic polarization effect simultaneously, helps obtaining the fine and closely woven phosphatize phosphate coat of crystallization.
The principal feature of novel normal-temperature phosphatization liquid is: with Na 2MoO 4As oxidization acceleration agent, NaF and C 6H 8O 7In the phosphoric acid zinc salt system as film forming accelerating, introduce (HOC 2H 4) 3N makes it to produce synergistic effect with the phosphatization fluid component; not only booster action is remarkable; solution property is stable, and the simple ligand compound or multicomponent complex, inner complex and the heteropolyacid complex compound that form, can also participate in forming thin and causes honey and the strong composite phosphate protective membrane of solidity to corrosion.Every index meets or is better than the GB6807 standard.This phosphatization liquid does not contain NO 2 -, NO 3 -, ClO 3 -And Ni 2+, Mn 2+Deng harmful ion, it integrates table accent, phosphatization, passivation, no special pre-process and post-process requirement, operation is simple, easy to operate, pharmacy variety only needs 7 kinds of starting material, has lacked 3 kinds than people's such as Liang Gang prescription, and cheap and easy to get, comprehensive cost be about people such as Liang Gang development Quick Phosphating Agent under Room Temperature 1/2nd.Its working range is wide, and the production efficiency height significantly reduces the clearing times and the wastewater treatment expense of phosphatization groove, reduces working strength of workers and environmental pollution.
Embodiment one: test solution adopts industrial raw material preparation as the aforementioned, and each component concentration (g/L) is: H 3PO 4(85%) 16.9, ZnO2.5, (HOC 2H 4) 3N3.2, Na 2MoO 41.0, C 6H 8O 71.0, NaF1.0, OP0.2, H 2The O surplus.
The compound method of phosphatization liquid: in container, add earlier less water, and add H by each component concentration 3PO 4(HOC 2H 4) 3N is stirred well to complete reaction, adds the ZnO of water furnishing pasty state again, is stirred to dissolving fully, adds Na then in the following order 2MoO 4, C 6H 8O 7, NaF, OP, supply the water yield at last.After should being stirred well to dissolving fully after every sample medicament adds, add the next item down again.
--(or oven dry) dried in washing--phosphatization--to phosphating process flow process: degreasing and rust removal (2 close 1).
Phosphating process parameter: TA:32 point, FA:3.4 point, PH:2.5, d 23 ℃: 1.011, T:20 ℃, t:15min
Phosphatization result: thickness: 1～2 μ m, cupric sulphate dropping test: 60s～90s, after 3%NaCl soaked 15min, 15～60 days were rustless, indoor lacing film: 2～4 months are rustless.Treatment capacity is 2M 2During/Kg, solution is still limpid transparent, does not have the precipitation of appearance.
Embodiment two: test solution adopts industrial raw material preparation as the aforementioned, and each component concentration (g/L) is: H 3PO 4(85%) 50.7, ZnO11.5, (HOC 2H 4) 3N3.2, Na 2MoO 41.0, C 6H 8O 71.0, NaF1.0, OP0.2, H 2The O surplus.
The compound method of phosphatization liquid and technical process are with embodiment one.
Phosphating process parameter: TA:83.5 point, FA:9.5 point, PH:2.6, d 23 ℃: 1.035, T:20 ℃, t:15min,
Phosphatization result: thickness: 2～3 μ m, cupric sulphate dropping test: 120s～180s, after 3%NaCl soaked 15min, 30～180 days rustless, indoor lacing film: 4～6 months rustless, preferably can reach 3 years rustless.Treatment capacity is 2.5M 2During/Kg, solution is still limpid transparent, does not have the precipitation of appearance.

Claims (4)

1. a novel normal-temperature phosphatization liquid is the H by technical grade 3PO 4, ZnO, (HOC 2H 4) 3N, Na 2MoO 4, C 6H 8O 7, NaF, OP and water is formulated, it is characterized in that each component concentration (g/L) is:
H 3PO 4(85％) 12.6～50.7 ZnO(99.5％) 1.88～11.5
(HOC 2H 4) 3N(90％) 2.4～4.0 Na 2MoO 4(98.8％) 0.5～1.5
C 6H 8O 7(99.5％) 0.5～1.5 NaF(99.5％) 0.5～1.5
OP 0.1～0.2 H 2The O surplus
2. the compound method of the novel normal-temperature phosphatization liquid of a claim 1 is characterized in that, adds earlier less water in container, and adds H by each component concentration 3PO 4(HOC 2H 4) 3N is stirred well to complete reaction; The ZnO that adds water furnishing pasty state again is stirred to dissolving fully; Add Na then in the following order 2MoO 4, C 6H 8O 7, NaF, OP; Supply the water yield at last, after every sample medicament adds, should be stirred well to dissolving fully, add the next item down again.
3. a kind of novel normal-temperature phosphatization liquid as claimed in claim 1 or 2 is characterized in that processing parameter is: the solution proterties is the limpid transparent liquid of colorless and odorless; PH2.5～3.5; Total acidity 22～86 points; Free acidity 2.5～10.5; Proportion d 23 ℃1.010～1.036; Soak time 5～15 minutes.
4. the using method of the novel normal-temperature phosphatization liquid of a claim 1 is characterized in that technical process is: degreasing and rust removal (2 close 1), and----phosphatization--washing (or not washing)--is dried (or oven dry) in washing.
CNB991175638A 1999-08-25 1999-08-25 Ordinary-temp phosphonating liquid Expired - Fee Related CN1163629C (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1314836C (en) * 2004-08-02 2007-05-09 吉林大学 Magnesium alloy phosphorization solution and its phosphorized technology
CN101629287B (en) * 2009-08-17 2011-03-23 浙江省缙云县三鼎实业有限公司 Magnesium alloy surface treatment process
CN102321883A (en) * 2011-09-29 2012-01-18 石敏 Normal-temperature phosphating solution
CN103374716A (en) * 2012-04-20 2013-10-30 郭良生 Normal-temperature efficient rust removing and melting treatment agent
CN103510081A (en) * 2012-06-19 2014-01-15 郭良生 Normal-temperature efficient pretreatment agent before painting
CN105414220A (en) * 2015-11-05 2016-03-23 贵州钢绳股份有限公司 Production technology of high strength galvanized steel wires
CN106086856A (en) * 2016-06-02 2016-11-09 重庆川东船舶重工有限责任公司 Carbon steel pipe normal-temperature phosphorizing liquid and parkerizing method thereof
CN109706440A (en) * 2019-01-10 2019-05-03 温州疆昊汽车部件有限公司 A kind of hinge for trunk of vehicle part and its production technology

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1314836C (en) * 2004-08-02 2007-05-09 吉林大学 Magnesium alloy phosphorization solution and its phosphorized technology
CN101629287B (en) * 2009-08-17 2011-03-23 浙江省缙云县三鼎实业有限公司 Magnesium alloy surface treatment process
CN102321883A (en) * 2011-09-29 2012-01-18 石敏 Normal-temperature phosphating solution
CN103374716A (en) * 2012-04-20 2013-10-30 郭良生 Normal-temperature efficient rust removing and melting treatment agent
CN103510081A (en) * 2012-06-19 2014-01-15 郭良生 Normal-temperature efficient pretreatment agent before painting
CN105414220A (en) * 2015-11-05 2016-03-23 贵州钢绳股份有限公司 Production technology of high strength galvanized steel wires
CN106086856A (en) * 2016-06-02 2016-11-09 重庆川东船舶重工有限责任公司 Carbon steel pipe normal-temperature phosphorizing liquid and parkerizing method thereof
CN109706440A (en) * 2019-01-10 2019-05-03 温州疆昊汽车部件有限公司 A kind of hinge for trunk of vehicle part and its production technology

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