CN108660448B - Normal-temperature environment-friendly phosphating solution with nano titanium dioxide participating in film formation and preparation method thereof - Google Patents
Normal-temperature environment-friendly phosphating solution with nano titanium dioxide participating in film formation and preparation method thereof Download PDFInfo
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- CN108660448B CN108660448B CN201810612545.6A CN201810612545A CN108660448B CN 108660448 B CN108660448 B CN 108660448B CN 201810612545 A CN201810612545 A CN 201810612545A CN 108660448 B CN108660448 B CN 108660448B
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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
The invention discloses a normal-temperature environment-friendly phosphating solution with nanometer titanium dioxide participating in film formation and a preparation method thereof, wherein 5.0-7.0 g of analytically pure zinc oxide is added with a small amount of deionized water and stirred into paste; adding 15-25 mL of analytically pure phosphoric acid, and violently stirring until the solution is clear; adding 3.8-4.2 g of the dissolved citric acid, and fully stirring; respectively dissolving 1.8-2.2 g of potassium chlorate, 0.4-0.6 g of ammonium molybdate and 0.55-0.65 g of sodium m-nitrobenzenesulfonate in deionized water, adding the obtained solution into the obtained solution, and fully stirring the obtained solution; weighing 0.25-0.35 g of 2-hydroxypropionic acid, and slowly dropwise adding the 2-hydroxypropionic acid into the solution under stirring; adding 0.5-0.8 g of sodium fluosilicate, fully stirring, and adding 50-150 ml of nano TiO under the stirring state2Suspending the solution to obtain a phosphating solution with the pH value of 2.8-3.2. The invention develops the nanometer TiO from the energy-saving and environment-friendly perspective2The phosphating solution is added in the form of suspension to prepare the phosphating solution, and the phosphating solution can obtain a nickel-free phosphating film of composite nano titanium dioxide on the surface of cold-rolled low-carbon steel, thereby reducing the pollution to the environment.
Description
Technical Field
The invention belongs to the technical field of surface treatment of cold-rolled low-carbon steel parts, and particularly relates to a normal-temperature environment-friendly phosphating solution with nano titanium dioxide participating in film formation and a preparation method thereof.
Background
Because of its good physical and mechanical properties, cold rolled steel is widely used in the manufacture of automobiles, household electrical appliances, industrial equipment and engineering machinery, and is still the mainstream of steel for automobile plates at present, and in steel plates for automobiles, hot rolled plates account for about 20% and cold rolled plates account for about 80%. However, cold rolled steel has a severe corrosion phenomenon as other metal materials. According to the statistics of developed countries, the loss caused by metal corrosion accounts for more than 4% of the total value of national production every year, and in order to reduce loss and save resources, different methods are adopted by various countries in the world to prevent corrosion, wherein the most important means is a surface engineering method, and the currently industrially more common cold-rolled steel surface treatment method comprises chromizing treatment and phosphating treatment technologies. The phosphating plays an important role in a plurality of surface treatment technologies, and the chromizing treatment is caused by Cr generated in the preparation process6+The compound is a carcinogenic substance, can cause serious harm to human bodies and environment, is forbidden by a plurality of countries such as European Union for a long time, and is forbidden in China at present along with the development of environment-friendly economic society and the enhancement of the enforcement of environment. Furthermore, along with the improvement of the requirements of automobile users on the performance of the automobile, higher automobile coating quality is providedIt is required that the automobile plate is also subjected to phosphating treatment before coating in order to improve the coating quality of the automobile plate and improve the bonding force between a substrate and a coating. At present, the phosphating treatment of automobile steel plates on automobile production lines at home and abroad still generally adopts Zn-containing2+、Mn2+、Ni2+The intermediate-temperature phosphating mode contains heavy metal ions, and has higher treatment temperature, large energy consumption and large slag deposition; although the normal temperature phosphating is popularized and applied in a large scale, the accelerator still mainly uses nitrite and nickel ions, generates toxic gas, pollutes the environment, and has the defects of more sediments, poor corrosion resistance and the like. Therefore, in order to reduce the environmental pollution caused by the traditional phosphating process, reduce the temperature of the phosphating process, save energy and improve the comprehensive performance of a phosphating film, the phosphating solution which is low in temperature, energy-saving, nontoxic, pollution-free, rapid in film forming and high in corrosion resistance is urgently needed to be developed.
Disclosure of Invention
The invention aims to solve the technical problem of providing a normal-temperature environment-friendly phosphating solution with nanometer titanium dioxide participating in film formation and a preparation method thereof.
In order to solve the above technical problems, the present invention comprises:
zinc oxide: 5.0 to 7.0g/L
Phosphoric acid: 15 to 25mL/L
2-hydroxypropionic acid: 0.25 to 0.35g/L
Sodium m-nitrobenzenesulfonate: 0.55-0.65 g/L
And (3) potassium chlorate: 1.8-2.2 g/L
Sodium fluosilicate: 0.5 to 0.8g/L
Ammonium molybdate: 0.4 to 0.6g/L
Citric acid: 3.8-4.2 g/L
TiO2： 0.2～0.6g/L
Water: and (4) the balance.
Preferably, the method comprises the following steps:
zinc oxide: 6.0g/L
Phosphoric acid: 20mL/L
2-hydroxypropionic acid: 0.3g/L
Sodium m-nitrobenzenesulfonate: 0.6g/L
And (3) potassium chlorate: 2.0 g/L
Sodium fluosilicate: 0.75g/L
Ammonium molybdate: 0.5g/L
Citric acid: 4.0 g/L
TiO2： 0.4g/L
Water: and (4) the balance.
The pH value of the phosphating solution is 2.8-3.2.
The preparation method comprises the following steps:
(1) weighing 5.0-7.0 g of analytically pure zinc oxide, placing the analytically pure zinc oxide in a stirring container, adding a small amount of deionized water, and stirring the mixture into paste;
(2) weighing 15-25 mL of analytically pure phosphoric acid, adding into the stirring container, and violently stirring until the solution is clear, namely a No. two solution;
(3) weighing 3.8-4.2 g of citric acid, fully dissolving with deionized water, adding into No. two solution, and fully stirring to obtain No. three solution;
(4) respectively weighing 1.8-2.2 g of potassium chlorate, 0.4-0.6 g of ammonium molybdate and 0.55-0.65 g of sodium m-nitrobenzenesulfonate, completely dissolving the potassium chlorate, the ammonium molybdate and the sodium m-nitrobenzenesulfonate by using deionized water, then adding the potassium chlorate, the ammonium molybdate and the sodium m-nitrobenzenesulfonate into the solution No. III, and fully stirring the solution to obtain a solution No. IV;
(5) weighing 0.25-0.35 g of 2-hydroxypropionic acid, and slowly dropwise adding the weighed 2-hydroxypropionic acid into No. IV solution under stirring to obtain No. V solution;
(6) weighing 0.5-0.8 g of sodium fluosilicate, adding the sodium fluosilicate into the solution III, and fully stirring to obtain a solution III;
(7) accurately weighing 0.05g of sodium alginate, and dissolving in 1L of deionized water under magnetic stirring to obtain nano TiO2Wetting agent, 0.2-0.6 g of nano TiO is weighed2Adding the powder into a wetting agent, and continuously stirring by magnetic force to obtain the nano TiO2A suspension;
(8) taking 50-150 ml of nano TiO2The suspension is mixed with solution No. ⑥ under stirring to obtain phosphating solution.
The pH value of the phosphating solution is 2.8-3.2.
The pH value of the phosphating solution is adjusted by a pH value adjusting agent, the pH value adjusting agent is analytically pure sodium hydroxide, the content of the analytically pure sodium hydroxide in the pH value adjusting agent is 90-110g/L, the pH value adjusting agent is slowly dripped into the phosphating solution, the phosphating solution is stirred vigorously, and a precise pH meter is adopted to monitor the pH value of the phosphating solution in real time until the pH value is between 2.8 and 3.2.
The invention takes the cold rolled steel for modern automobiles as a research object, develops the nano TiO from the energy-saving and environment-friendly angle2Cold-rolled low-carbon steel nickel-free nitrite-free normal-temperature phosphating solution participating in film forming. Mixing nanometer TiO2Adding the prepared phosphating solution in the form of suspension, wherein the phosphating solution can obtain a nickel-free phosphating film of composite nano titanium dioxide on the surface of cold-rolled low-carbon steel. When nano TiO2When the content in the phosphating solution reaches 0.4 g/L, the obtained phosphating film has the strongest corrosion resistance and moderate film thickness, and the film thickness of the phosphating film can be greatly increased by continuously increasing the concentration. The composite nano TiO is subjected to SEM (scanning Electron microscope), EDS (energy Spectroscopy), XRD (X-ray diffraction) analysis, electrochemical Tafel polarization curve, EIS (electronic article system) impedance spectrum test and the like2The representation of the phosphating film shows that the composite film is uniform and compact, has excellent corrosion resistance and can effectively prevent the corrosion of the medium to the film. At the same time, nano TiO is added2The composite phosphating film sample plate participating in film forming is used as an electrophoresis substrate, and the adhesion and salt spray experiment tests are carried out on the paint film coating after electrophoresis, and the results show that all performances of the paint film after electrophoresis can reach the national and industrial standards.
Detailed Description
Preparing a pH value regulator for later use: weighing 18-22 g of analytically pure sodium hydroxide, dissolving in about 200ml of deionized water, and then using a 500ml volumetric flask to fix the volume to obtain the pH value regulator, wherein the content of the analytically pure sodium hydroxide in the pH value regulator is 90-110 g/L.
Preparation of nano TiO2The suspension is ready for use:accurately weighing 0.05g of sodium alginate, and dissolving in 1L of deionized water under magnetic stirring to obtain nano TiO2Wetting agent, 0.2-0.6 g of nano TiO is weighed2Adding the powder into a wetting agent, and continuously stirring by magnetic force to obtain the nano TiO2And (3) suspension.
Example 1
Weighing 6.0g of analytically pure zinc oxide in a stirring container, adding a small amount of deionized water, stirring into paste, weighing 20mL of analytically pure phosphoric acid, adding the analytically pure phosphoric acid into the stirring container, stirring vigorously until the solution is clear, named as ② # solution, weighing 4.0 g of citric acid, dissolving the citric acid in deionized water completely, adding the solution into ② # solution, stirring fully to obtain ③ # solution, weighing 2.0g of potassium chlorate, 0.5g of ammonium molybdate and 0.6g of sodium m-nitrobenzenesulfonate, dissolving the potassium chlorate in deionized water completely, adding the solution into ③ # solution, stirring fully to obtain ④ # solution, weighing 0.3g of 2-hydroxypropionic acid, slowly dropping the solution into ④ # solution under stirring to obtain ⑤ # solution, weighing 0.75g of sodium fluosilicate, adding the solution into ⑤ # solution, stirring fully to obtain ⑥ # solution, weighing 100mL of nano TiO2And slowly dripping a pH value regulator into the composite phosphating solution, violently stirring until the pH value is 3.112, placing a cold-rolled low-carbon steel workpiece or sample into the composite phosphating solution for 7min, and then testing the formed phosphating film for 167s by using a copper sulfate drip test.
Example 2
Weighing 5.0g of analytically pure zinc oxide in a stirring container, adding a small amount of deionized water, stirring into paste, weighing 20mL of analytically pure phosphoric acid, adding the analytically pure phosphoric acid into the stirring container, stirring vigorously until the solution is clear, named as ② solution, weighing 4.2g of citric acid, dissolving the citric acid in deionized water completely, adding the solution into ② solution, stirring completely to obtain ③ solution, weighing 2.0g of potassium chlorate, 0.4g of ammonium molybdate and 0.65g of sodium m-nitrobenzenesulfonate, dissolving the solutions in deionized water completely, adding the solutions into ③ solution, stirring completely to obtain ④ solution, weighing 0.25g of 2-hydroxypropionic acid, slowly dripping the solution into ④ solution under stirring to obtain ⑤ solution, weighing 0.8g of sodium fluosilicate, adding the solution into ⑤ solution,stirring thoroughly to obtain ⑥ # solution, collecting 50ml nanometer TiO2And slowly dripping a pH value regulator into the composite phosphating solution, violently stirring until the pH value is 2.877, placing a cold-rolled low-carbon steel workpiece or sample into the phosphating solution for 10min, and then testing the formed phosphating film for 129s by using a copper sulfate drip test.
Example 3
Weighing 6.0g of analytically pure zinc oxide in a stirring container, adding a small amount of deionized water, stirring into paste, weighing 15mL of analytically pure phosphoric acid, adding the analytically pure phosphoric acid into the stirring container, violently stirring until the solution is clear, named as ② # solution, weighing 3.8g of citric acid, fully dissolving the citric acid in deionized water, adding the solution into ② # solution, fully stirring to obtain ③ # solution, respectively weighing 2.2 g of potassium chlorate, 0.6g of ammonium molybdate and 0.55g of sodium m-nitrobenzenesulfonate, fully dissolving the potassium chlorate in deionized water, adding the solution into ③ # solution, fully stirring to obtain ④ # solution, weighing 0.3g of 2-hydroxypropionic acid, slowly dripping the solution into ④ # solution under stirring to obtain ⑤ # solution, weighing 0.5g of sodium fluosilicate, adding the solution into ⑤ # solution, fully stirring to obtain ⑥ # solution, weighing 50mL of nano TiO2The suspension is mixed with No. ⑥ liquid under the stirring speed of 350 r/min to obtain composite phosphating solution, pH value regulator is slowly dripped into the phosphating solution and stirred vigorously until the pH value is 3.116, a sample or a workpiece is placed in the phosphating solution for 9min, and a formed phosphating film has the copper sulfate dripping test time of 151 s.
Example 4
Weighing 7.0g of analytically pure zinc oxide in a stirring container, adding a small amount of deionized water, stirring to form paste, weighing 25mL of analytically pure phosphoric acid, adding the paste into the stirring container, violently stirring until the solution is clear, named as ② # solution, weighing 4.0 g of citric acid, fully dissolving the citric acid in deionized water, adding the solution into ② # solution, fully stirring to obtain ③ # solution, respectively weighing 1.8g of potassium chlorate, 0.5g of ammonium molybdate and 0.6g of sodium m-nitrobenzenesulfonate, fully dissolving the potassium chlorate, the ammonium molybdate and the sodium m-nitrobenzenesulfonate in deionized water, adding the solution into the ③ # solution, fully stirring to obtain ④ # solution, weighing 0.35g of 2-hydroxypropionic acid, slowly dropwise adding the solution to ④ #④ to obtain ⑤ solution, weighing 0.75g sodium fluosilicate, adding into ⑤ solution, stirring to obtain ⑥ solution, and collecting 150ml nanometer TiO2And slowly dripping a pH value regulator into the phosphating solution, violently stirring until the pH value is 3.079, placing a cold-rolled low-carbon steel workpiece or sample into the phosphating solution for 7min, and then testing the formed phosphating film for 141s by using a copper sulfate drip test.
Claims (4)
1. The normal-temperature environment-friendly phosphating solution for the cold-rolled low-carbon steel plate for the automobile with the nano titanium dioxide participating in film forming is characterized by comprising the following components in parts by weight:
zinc oxide: 5.0 to 7.0g/L
Phosphoric acid: 15 to 25mL/L
2-hydroxypropionic acid: 0.25 to 0.35g/L
Sodium m-nitrobenzenesulfonate: 0.55-0.65 g/L
And (3) potassium chlorate: 1.8-2.2 g/L
Sodium fluosilicate: 0.5 to 0.8g/L
Ammonium molybdate: 0.4 to 0.6g/L
Citric acid: 3.8-4.2 g/L
TiO2： 0.2～0.6g/L
Water: balance of
The pH value of the obtained phosphating solution is between 2.8 and 3.2.
2. The normal-temperature environment-friendly phosphating solution of the nano titanium dioxide participating in film forming for the cold-rolled low-carbon steel plate for the automobile as claimed in claim 1 is characterized by comprising the following components:
zinc oxide: 6.0g/L
Phosphoric acid: 20mL/L
2-hydroxypropionic acid: 0.3g/L
Sodium m-nitrobenzenesulfonate: 0.6g/L
And (3) potassium chlorate: 2.0 g/L
Sodium fluosilicate: 0.75g/L
Ammonium molybdate: 0.5g/L
Citric acid: 4.0 g/L
TiO2： 0.4g/L
Water: balance of
The pH value of the obtained phosphating solution is between 2.8 and 3.2.
3. A preparation method of a normal-temperature environment-friendly phosphating solution for an automobile cold-rolled low-carbon steel plate with nano titanium dioxide participating in film formation is characterized by comprising the following steps:
(1) weighing 5.0-7.0 g of analytically pure zinc oxide, placing the analytically pure zinc oxide in a stirring container, adding a small amount of deionized water, and stirring the mixture into paste;
(2) weighing 15-25 mL of analytically pure phosphoric acid, adding into the stirring container, and violently stirring until the solution is clear, namely a No. two solution;
(3) weighing 3.8-4.2 g of citric acid, fully dissolving with deionized water, adding into No. two solution, and fully stirring to obtain No. three solution;
(4) respectively weighing 1.8-2.2 g of potassium chlorate, 0.4-0.6 g of ammonium molybdate and 0.55-0.65 g of sodium m-nitrobenzenesulfonate, completely dissolving the potassium chlorate, the ammonium molybdate and the sodium m-nitrobenzenesulfonate by using deionized water, then adding the potassium chlorate, the ammonium molybdate and the sodium m-nitrobenzenesulfonate into the solution No. III, and fully stirring the solution to obtain a solution No. IV;
(5) weighing 0.25-0.35 g of 2-hydroxypropionic acid, and slowly dropwise adding the weighed 2-hydroxypropionic acid into No. IV solution under stirring to obtain No. V solution;
(6) weighing 0.5-0.8 g of sodium fluosilicate, adding into No. ⑤ solution, and fully stirring to obtain
Number solution;
(7) accurately weighing 0.05g of sodium alginate, and dissolving in 1L of deionized water under magnetic stirring to obtain nano TiO2Wetting agent, 0.2-0.6 g of nano TiO is weighed2Adding the powder into a wetting agent, and continuously stirring by magnetic force to obtain the nano TiO2Suspension liquid；
(8) Taking 50-150 mL of nano TiO2The suspension is stirred with
And mixing the solutions, and adjusting the pH value to 2.8-3.2 to obtain the phosphating solution.
4. The preparation method of the normal-temperature environment-friendly phosphating solution for the cold-rolled low-carbon steel plate for the automobile, which is formed by the participation of the nano-titanium dioxide in the film forming, according to the claim 3, is characterized in that the pH value of the phosphating solution is adjusted by a pH value regulator, the pH value regulator is analytically pure sodium hydroxide, the content of the analytically pure sodium hydroxide in an acidity regulator is 90-110g/L, the pH value regulator is slowly dripped into the phosphating solution, the phosphating solution is stirred vigorously, and a precision pH meter is adopted to monitor the pH value of the phosphating solution in real time until the pH value is between 2.8 and 3.2.
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| CN101629287A (en) * | 2009-08-17 | 2010-01-20 | 浙江省缙云县三鼎实业有限公司 | Magnesium alloy surface treatment process |
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| CN105951070A (en) * | 2016-05-31 | 2016-09-21 | 无锡伊佩克科技有限公司 | Phosphating solution for steel surface treatment and preparation method thereof |
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| CN101935832B (en) * | 2010-10-22 | 2011-12-21 | 南京有为化工有限公司 | Zinc-iron metal alramenting liquid capable of being recycled at normal temperature |
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| CN101629287A (en) * | 2009-08-17 | 2010-01-20 | 浙江省缙云县三鼎实业有限公司 | Magnesium alloy surface treatment process |
| CN102560461A (en) * | 2012-01-18 | 2012-07-11 | 河北科技大学 | Zirconium and zirconium alloy zinc-manganese composite phosphating solution and phosphating method thereof |
| CN105951070A (en) * | 2016-05-31 | 2016-09-21 | 无锡伊佩克科技有限公司 | Phosphating solution for steel surface treatment and preparation method thereof |
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