CN103255464A - Film-forming solution for forming electrochemical oxide film on surface of steel, application method thereof and film formed therefrom - Google Patents
Film-forming solution for forming electrochemical oxide film on surface of steel, application method thereof and film formed therefrom Download PDFInfo
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- CN103255464A CN103255464A CN2013101965267A CN201310196526A CN103255464A CN 103255464 A CN103255464 A CN 103255464A CN 2013101965267 A CN2013101965267 A CN 2013101965267A CN 201310196526 A CN201310196526 A CN 201310196526A CN 103255464 A CN103255464 A CN 103255464A
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- forming liquid
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Abstract
The invention discloses a film-forming solution for forming an electrochemical oxide film on the surface of steel, an application method thereof and a film formed therefrom. The film-forming solution comprises the following components: manganese dihydrogen phosphate, fluorosilicate and nitrate used as main salts, ascorbic acid and dodecyl sulfonate used as additives and phosphoric acid used as a pH regulator. The invention is characterized in that the film-forming solution comprises the following components: 50-100g/l of manganese dihydrogen phosphate, 5-20g/l of fluoroborate, 50-80g/l of nitrate, 1-10g/l of ascorbic acid, 0.5-1g/l of dodecyl sulfonate; the pH value is regulated with the phosphoric acid to 1-3; a plain steel plate, titanium plate or graphite plate is used as a cathode material; and the process conditions are as follows: the temperature is 10-30 DEG C, the current density is 0.1-1.5A/dm<2>, the voltage is 50-200V, and the oxidation time is 30-60 minutes. According to the invention, an electrochemical oxide film of which the corrosion resistance exceeds 200h and the microhardness is up to 500HV0.2 can be formed on the surface of steel.
Description
Technical field
The invention belongs to field of metal surface treatment, specifically relate to a kind of steel surface electrochemical oxidation film film forming liquid and using method thereof.
Background technology
Common iron and steel is applied to the every field in the industrial production, yet because it very easily is corroded, make many application have to adopt other precious materials, special steel or complicated secondary treatment is carried out on its surface, as plating, application, plasma spraying etc., these special processings have improved its application cost greatly, and may cause severe contamination to environment.Electrochemical oxidation is as the process of surface treatment of a kind of effective raising metal material surface solidity to corrosion, hardness, current metal and the alloy surface treatment industry thereof such as titanium, aluminium of being widely used in, though it is quite ripe that this processing mode has developed at present, but because the restriction of range of application, be considered to especially to directly apply to steel surface, seriously limited the promotion prospect of this technology at steel surface.
At present in the industrial production, most iron and steel parts that solidity to corrosion is had relatively high expectations adopt the high temperature technology of turning blue, this processing method not only consumes energy greatly, and Working environment extreme difference, influence to human body and environment is bigger, and the employing micro-arc oxidation process is also arranged, but since this technology to power supply and equipment require high, energy consumption is excessive, and certain restriction is arranged in the use.
Summary of the invention
First purpose of the present invention be for electrochemical oxidation can not be on steel surface be handled direct applied deficiency, and provide a kind of steel surface that is applicable to, and technology is simple, environmental protection, the membranous layer corrosion resistance excellence that obtains, the steel surface electrochemical oxidation film film forming liquid that bonding force is good, hardness is high, wear resistance is strong.
Second purpose of the present invention provides a kind of using method of steel surface electrochemical oxidation film film forming liquid.
The 3rd purpose of the present invention provides the formed rete of above-mentioned using method.
For realizing first purpose of the present invention, its technical scheme is to comprise following component:
Phosphate dihydrogen manganese 50 ~ 100 grams per liters;
Fluoroborate 5 ~ 20 grams per liters;
Nitrate 50～80 grams per liters;
The pH value is 1 ~ 3;
Solute is water.
Further arranging is also to include additive, and this additive comprises having:
Xitix 1 ~ 10 grams per liter;
Dodecane sulfonate 0.5 ~ 1 grams per liter;
The pH regulator agent.
Further arranging is that described dodecyl sulfate is dodecyl sulphate potassium, sodium lauryl sulphate or its compound.
Further arranging is that described nitrate is SODIUMNITRATE, saltpetre, nitrocalcite or its compound.
Further arranging is that described silicofluoride is Sodium Silicofluoride, potassium silicofluoride or its compound.
For realizing second purpose of the present invention, its technical scheme is to comprise following operation:
(1) with the workpiece of iron and steel material quality through oil removing, scale removal activates and cleans up;
(2) under the normal temperature condition, the metal material workpiece after step (1) is handled is put into plating bath as claimed in claim 1, carries out electrochemical oxidation according to following processing condition:
Its oxidizing process condition is: the workpiece with iron and steel material quality is anode, is electrode cathode with general steel plate, titanium plate or graphite cake, and temperature condition is 10 ~ 30 ℃, current density range 0.1 ~ 1.5A/dm
2, positive oxidation voltage scope 50 ~ 200V, negative oxidation power supply 0 ~ 20V, supply frequency 50 ~ 200Hz, oxidization time are 30 ~ 60 minutes;
(3) electroplate and to finish the back and take out cleaning and dry or dry.
Further arranging is that electric current is control stage by stage in the described step (2), and its stage control parameter is:
Initial current: 0.1 ~ 0.2 A/dm
2
5min：0.3~0.4A/dm
2
10min：0.5~0.7?A/dm
2
12min：0.8~1.1A/dm
2
15min：1.2~1.5A/dm
2
The front several stages is the coating growth time, according to the requirement of product, sets each stage time span;
Last 10min:0.8 ~ 1.0A/dm
2This stage is rete leveling, and repairing phase can improve corrosion resisting property and the planeness of rete greatly.
The 3rd purpose of the present invention is achieved through the following technical solutions, and membranous layer ingredient consists of:
Mn:15 ~ 30wt%; O:20 ~ 25 wt%; Fe:15 ~ 30 wt %; P:10 ~ 20 wt %; Si:2 ~ 5 wt %; F:2 ~ 5 wt %; N:10 ~ 15 wt %; Other trace elements :≤5 wt %.
Further arranging is that this thicknesses of layers is 20 ~ 50 μ m.
Further arranging is the hardness 〉=500HV of this rete
0.2
Principle of the present invention is in electrochemical oxidation process, by square topped pulse moment strong current density 50 ~ 100A/dm
2The surging force of effect is destroyed the chemical bond in phosphate ion, the fluoroboric acid ion, and ionization goes out Si
4+, F
-, N
5+, and P
5+, the while makes Si under the effect of its strong impact force effect, the effect of negative current oxide etch and electric field conversion
4+, F
-, N
5+, P
5+, and Mn
2+The Fe that obtains together with the anode etching oxidation
3+Form fine and close insoluble Mn-Fe-O-P-Si-N-F oxide film in the anode workpiece surface recombination.
The main reaction that takes place is as follows:
PO
5 3-+ 10H
+→ P
5++ 5H
2Under the O(strong current density impact condition)
SiF
4 4-→ B
3++ 4F
-(under the strong current density impact condition)
NO
3-+ 6H
+→ N
5++ 3H
2Under the O(strong current density impact condition)
Si
4++F
-+N
5++P
5+?+?Mn
2++Fe
3+→Mn-Fe-O-P-Si-N-F
Electrooxidation rete by prescription of the present invention and technology obtain detects it according to national standard, and each Performance Detection of rete is as follows:
Average hardness 523HV
0.2(examination criteria: the Vickers hardnes test of GB/T4340.4-2009 metallic substance)
With the bonding force of matrix be 1 grade; (examination criteria: the method for inspection of SJ 1282-1977 metal plating bonding force)
Anti-neutral salt spray test (NSS) can reach 200h.(examination criteria: GB/T 10125-1997 artificial atmosphere corrosion test salt-fog test)
Advantage of the present invention:
The invention discloses a kind of steel surface electrochemical oxidation film film forming liquid and using method thereof, adopt electrochemical oxidation technology in steel surface characteristics Mn-Fe-O-P-Si-N-F oxide film such as obtain having corrosion resistance excellent, bonding force is good, hardness is high, wear resistance is strong, this prescription has the following advantages:
(1) hypotoxicity.The starting material that adopt are nontoxic or low harmful toxic matter, have avoided the hexavalent chromium environmental pollution and to the able-bodied infringement of workman, have improved production environment.
(2) can carry out oxidation at normal temperatures, with minimum to the harm of human body in the operating process time, also reach purpose of energy saving.
Below in conjunction with specification drawings and specific embodiments the present invention is done further introduction.
Description of drawings
50 times of enlarged views of the formed rete of Fig. 1 the present invention;
500 times of enlarged views of the formed rete of Fig. 2 the present invention;
1000 times of enlarged views of the formed rete of Fig. 3 the present invention;
Fig. 4 using method schema of the present invention.
Embodiment
Carry out concrete description below by the present invention of embodiment; only be used for the present invention is further specified; can not be interpreted as the restriction to protection domain of the present invention, the technician in this field can make some nonessential improvement and adjustment to the present invention according to the content of foregoing invention.
Embodiment 1
The present invention adopts the following step to obtain 1 grade of sticking power at the 45# steel workpiece successively, and the neutral salt spray test (NSS) that the 10125-1997 of anti-GB/T standard is carried out can reach 223 hours Mn-Fe-O-P-Si-N-F oxide film:
(a) with the workpiece of 45# steel matter through oil removing, scale removal activates and cleans up;
(b) configure and contain phosphate dihydrogen manganese 50 ~ 100 grams per liters, fluoroborate 5 ~ 20 grams per liters, nitrate 50～80 grams per liters, xitix 1 ~ 10 grams per liter, dodecane sulfonate 0.5 ~ 1 grams per liter, phosphoric acid is regulated between pH to 1 ~ 3; Cathode material is general steel plate, titanium plate or graphite cake; Processing condition: temperature condition is 10 ~ 30 ℃, current density range 0.1 ~ 1.5A/dm
2, voltage range 50 ~ 200V, power frequency is selected 100Hz, and oxidization time is 60 minutes.
(c) take out to clean after oxidation is finished and dry.
Embodiment 2
The present invention adopts the following step to obtain 1 grade of sticking power at the Zl101 workpiece successively, and the neutral salt spray test (NSS) that the 10125-1997 of anti-GB/T standard is carried out can reach 206 hours Mn-Fe-O-P-Si-N-F oxide film:
(a) with the workpiece of HT300 through oil removing, scale removal activates and cleans up;
(b) configure and contain phosphate dihydrogen manganese 50 ~ 100 grams per liters, fluoroborate 5 ~ 20 grams per liters, nitrate 50～80 grams per liters, xitix 1 ~ 10 grams per liter, dodecane sulfonate 0.5 ~ 1 grams per liter, phosphoric acid is regulated between pH to 1 ~ 3; Cathode material is general steel plate, titanium plate or graphite cake; Processing condition: temperature condition is 10 ~ 30 ℃, current density range 0.1 ~ 1.5A/dm
2, voltage range 50 ~ 200V, power frequency is selected 100Hz, and oxidization time is 60 minutes.
(c) take out after oxidation is finished and clean and oven dry.
Experimental example
The present invention is through testing through German Brooker wavelength scattering fluorescence spectrophotometer, and its composition is as following table.
Table 1 zone of oxidation component content
Claims (10)
1. steel surface electrochemical oxidation film film forming liquid is characterized in that comprising following component:
Phosphate dihydrogen manganese 50 ~ 100 grams per liters;
Fluoroborate 5 ~ 20 grams per liters;
Nitrate 50～80 grams per liters;
The pH value is 1 ~ 3;
Solute is water.
2. a kind of steel surface electrochemical oxidation film film forming liquid according to claim 1, it is characterized in that: also include additive, this additive comprises having:
Xitix 1 ~ 10 grams per liter;
Dodecane sulfonate 0.5 ~ 1 grams per liter;
The pH regulator agent.
3. a kind of steel surface electrochemical oxidation film film forming liquid according to claim 2, it is characterized in that: described dodecyl sulfate is dodecyl sulphate potassium, sodium lauryl sulphate or its compound.
4. a kind of steel surface electrochemical oxidation film film forming liquid according to claim 1, it is characterized in that: described nitrate is SODIUMNITRATE, saltpetre, nitrocalcite or its compound.
5. a kind of steel surface electrochemical oxidation film film forming liquid according to claim 1, it is characterized in that: described silicofluoride is Sodium Silicofluoride, potassium silicofluoride or its compound.
6. the using method of a steel surface electrochemical oxidation film film forming liquid is characterized in that comprising following operation:
(1) with the workpiece of iron and steel material quality through oil removing, scale removal activates and cleans up;
(2) under the normal temperature condition, the metal material workpiece after step (1) is handled is put into plating bath as claimed in claim 1, electroplate oxidation according to following processing condition;
Its oxidizing process condition is: the workpiece with iron and steel material quality is anode, is electrode cathode with general steel plate, titanium plate or graphite cake, and temperature condition is 10 ~ 30 ℃, current density range 0.1 ~ 1.5A/dm
2, positive oxidation voltage scope 50 ~ 200V, negative oxidation power supply 0 ~ 20V, supply frequency 50 ~ 200Hz, oxidization time are 30 ~ 60 minutes;
Take out to clean after plating is finished and dry or dry.
7. the using method of a kind of steel surface electrochemical oxidation film film forming liquid according to claim 6 is characterized in that: current phase control parameter is in the described step (2):
Initial current: 0.1 ~ 0.2 A/dm
2
5min：0.3~0.4A/dm
2
10min：0.5~0.7?A/dm
2
12min：0.8~1.1A/dm
2
15min：1.2~1.5A/dm
2
Last 10min:0.8 ~ 1.0 A/dm
2
8. the formed rete of using method of a steel surface electrochemical oxidation film film forming liquid as claimed in claim 6, it is characterized in that: membranous layer ingredient consists of:
Mn:15 ~ 30wt%; O:20 ~ 25 wt%; Fe:15 ~ 30 wt %; P:10 ~ 20 wt %; Si:2 ~ 5 wt %; F:2 ~ 5 wt %; N:10 ~ 15 wt %; Other trace elements :≤5 wt%.
9. the formed rete of using method of steel surface electrochemical oxidation film film forming liquid according to claim 8, it is characterized in that: this thicknesses of layers is 20 ~ 50 μ m.
10. the formed rete of using method of steel surface electrochemical oxidation film film forming liquid according to claim 8 is characterized in that: the hardness 〉=500HV of this rete
0.2
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|---|---|---|---|
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| CN201310196526.7A CN103255464B (en) | 2013-05-23 | 2013-05-23 | The rete of a kind of steel surface electrochemical oxidation film film forming liquid, using method and formation thereof |
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| CN103255464B CN103255464B (en) | 2016-04-13 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106350854A (en) * | 2016-09-14 | 2017-01-25 | 东南大学 | Passivating method of chrome -containing reinforcing steel bar |
| CN110552044A (en) * | 2019-10-14 | 2019-12-10 | 四川轻化工大学 | Steel anodic oxidation electrolyte and anodic oxidation method thereof |
Citations (6)
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|---|---|---|---|---|
| US4639295A (en) * | 1984-08-14 | 1987-01-27 | Amchem Products, Inc. | Zinc phosphating method |
| CN1069077A (en) * | 1991-07-29 | 1993-02-17 | 亨凯尔公司 | Zinc phosphate conversion coatings and coating process |
| US5503733A (en) * | 1992-09-28 | 1996-04-02 | Henkel Kommanditgesellschaft Auf Aktien | Process for phosphating galvanized steel surfaces |
| CN1132801A (en) * | 1994-08-05 | 1996-10-09 | Itb有限公司 | Acid aqueous phosphatic solution and process using same for phosphating metal surface |
| CN1737211A (en) * | 2005-07-04 | 2006-02-22 | 江门市福斯特金属表面处理技术发展有限公司 | Differential arc oxidization abrasive polishing method for stainless steel surface |
| CN102719819A (en) * | 2011-03-30 | 2012-10-10 | 重庆市荣时金属表面处理剂有限公司 | General phosphating agent |
-
2013
- 2013-05-23 CN CN201310196526.7A patent/CN103255464B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4639295A (en) * | 1984-08-14 | 1987-01-27 | Amchem Products, Inc. | Zinc phosphating method |
| CN1069077A (en) * | 1991-07-29 | 1993-02-17 | 亨凯尔公司 | Zinc phosphate conversion coatings and coating process |
| US5503733A (en) * | 1992-09-28 | 1996-04-02 | Henkel Kommanditgesellschaft Auf Aktien | Process for phosphating galvanized steel surfaces |
| CN1132801A (en) * | 1994-08-05 | 1996-10-09 | Itb有限公司 | Acid aqueous phosphatic solution and process using same for phosphating metal surface |
| CN1737211A (en) * | 2005-07-04 | 2006-02-22 | 江门市福斯特金属表面处理技术发展有限公司 | Differential arc oxidization abrasive polishing method for stainless steel surface |
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|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106350854A (en) * | 2016-09-14 | 2017-01-25 | 东南大学 | Passivating method of chrome -containing reinforcing steel bar |
| CN106350854B (en) * | 2016-09-14 | 2019-01-29 | 东南大学 | A kind of passivating method of chrome-bearing steel muscle |
| CN110552044A (en) * | 2019-10-14 | 2019-12-10 | 四川轻化工大学 | Steel anodic oxidation electrolyte and anodic oxidation method thereof |
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| Publication number | Publication date |
|---|---|
| CN103255464B (en) | 2016-04-13 |
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