CN114318320A - Passivation process for phosphate film - Google Patents
Passivation process for phosphate film Download PDFInfo
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- CN114318320A CN114318320A CN202111382726.2A CN202111382726A CN114318320A CN 114318320 A CN114318320 A CN 114318320A CN 202111382726 A CN202111382726 A CN 202111382726A CN 114318320 A CN114318320 A CN 114318320A
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- phosphating
- passivating
- degreasing
- passivation
- oil
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- 238000002161 passivation Methods 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 58
- 229910019142 PO4 Inorganic materials 0.000 title description 10
- 239000010452 phosphate Substances 0.000 title description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 55
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000005406 washing Methods 0.000 claims abstract description 28
- 238000005260 corrosion Methods 0.000 claims abstract description 27
- 230000007797 corrosion Effects 0.000 claims abstract description 27
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 14
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 14
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004327 boric acid Substances 0.000 claims abstract description 14
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 12
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 11
- 239000010959 steel Substances 0.000 claims abstract description 11
- 238000003618 dip coating Methods 0.000 claims abstract description 5
- 238000005238 degreasing Methods 0.000 claims description 81
- 239000010408 film Substances 0.000 claims description 74
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 44
- 230000003750 conditioning effect Effects 0.000 claims description 43
- 238000001035 drying Methods 0.000 claims description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 238000005554 pickling Methods 0.000 claims description 31
- 238000007598 dipping method Methods 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 22
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 19
- 239000011701 zinc Substances 0.000 claims description 19
- 229910052725 zinc Inorganic materials 0.000 claims description 19
- 150000003751 zinc Chemical class 0.000 claims description 16
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 11
- 239000003112 inhibitor Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 239000011572 manganese Substances 0.000 claims description 8
- 150000002696 manganese Chemical class 0.000 claims description 6
- 239000010409 thin film Substances 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 abstract description 23
- 239000007921 spray Substances 0.000 abstract description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 15
- 230000007935 neutral effect Effects 0.000 abstract description 12
- 229910052742 iron Inorganic materials 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 230000003449 preventive effect Effects 0.000 description 16
- 238000003556 assay Methods 0.000 description 9
- 238000002791 soaking Methods 0.000 description 9
- 238000004448 titration Methods 0.000 description 9
- 238000005237 degreasing agent Methods 0.000 description 8
- 239000013527 degreasing agent Substances 0.000 description 8
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000004383 yellowing Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000002173 cutting fluid Substances 0.000 description 3
- 229910001437 manganese ion Inorganic materials 0.000 description 3
- 230000002087 whitening effect Effects 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- LPTIRUACFKQDHZ-UHFFFAOYSA-N hexadecyl sulfate;hydron Chemical compound CCCCCCCCCCCCCCCCOS(O)(=O)=O LPTIRUACFKQDHZ-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
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- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
A process for passivating the surface of iron or steel products and members includes such steps as pre-removing oil, washing with water, removing oxide skin by acid washing, regulating surface and phosphorizing. Passivating after the last said water wash; the mass percentage of each component in the passivating agent is 17-20% of boric acid, 13-17% of monoethanolamine, 25-27% of triethanolamine, 8-10% of sodium silicate and the balance of antirust components; the passivating agent and pure water are prepared into passivating solution according to the proportion of 4-6%, and meanwhile, the passivating bath solution is heated to 60-80 ℃, is centrifugally dried after being passivated for 20-30s, is dipped in anti-rust oil, and is finally centrifugally dried again. The invention adopts the passivation solution with low concentration of 4-6%, the passivation temperature is 60-80 ℃, and the production cost is saved; the combined action of passivation and dip-coating of anti-rust oil ensures that a neutral salt spray test (NSS) meets the requirement of no red rust for 72 hours, does not rust for 1 year in a natural environment, and improves the corrosion resistance effect by 3-4.5 times.
Description
Technical Field
The invention belongs to the field of phosphating corrosion prevention of steel parts, and particularly relates to a phosphating film passivation process.
Background
Phosphating of steel is a common surface treatment process and is a chemical conversion coating of phosphate formed chemically and electrochemically. The phosphorization has corrosion resistance and friction reduction performance and can effectively enhance the binding force between the coating film and a workpiece, so the phosphorization is widely used for fasteners in engine gearboxes and basement films for paint. But only depending on the phosphate coating, the corrosion resistance of work piece is still relatively poor, can rust soon when meeting water vapour, consequently can select rust-resistant oil to improve corrosion resistance in the production reality, but the oil mass too much will cause the inconvenience of transportation and assembly, and the oil mass is too little then rust-resistant effect will be not good again. The traditional manganese series phosphorization neutral salt spray test (NSS) can only reach 16-24h without red embroidery.
The new technology for rust-removing and passivating iron and steel disclosed in CN85104742B is characterized by that after the surfaces of iron and steel products and components are pretreated, the iron and steel products and components are placed in an acid rust-removing solution containing sodium dodecyl sulfate or hexadecyl sulfate and polyoxyethylene ether alkylphenol to be soaked for rust-removing for about 3-5 min, then the iron and steel products and components are quickly placed in a passivating solution containing quicklime to be passivated for 3-5 min after being soaked and cleaned in a clean water tank, and then the steel and steel products and components are naturally dried in the air after being cleaned in water. The compact passive film can be formed in 3-5 minutes, the rust can be avoided within one month, the raw materials are cheap, the goods source is wide, and the construction efficiency is high. But the passivation process and the liquid medicine can not meet the phosphating standard of the automobile industry.
Disclosure of Invention
The invention aims to solve the technical problem of providing a phosphating film passivation process which saves the production cost and improves the corrosion-resistant effect.
In order to solve the technical problems, the invention provides a phosphating film passivation process which sequentially comprises the following operation steps according to the operation sequence: the method comprises the following steps of loading, pre-removing oil, hot washing, pickling, washing, neutralizing, washing, surface conditioning, phosphating, washing, passivating, centrifugally drying, dip-coating antirust oil, centrifuging and blanking.
After the final washing, carrying out a passivation step, wherein the mass percent of various components in the passivator is 17-20% of boric acid, 13-17% of monoethanolamine, 25-27% of triethanolamine, 8-10% of sodium silicate and the balance of antirust components; the passivating agent and pure water are prepared into passivating solution according to the proportion of 4-6%, meanwhile, the passivating bath solution is heated to 60-80 ℃ to fully react, centrifugal drying is carried out after passivation is carried out for 20-30s, anti-rust oil is dip-coated, and the final centrifugal drying is carried out.
By adopting the passivating agent, a dry film can be formed after drying to protect the phosphating film from rusting and has no influence on machining, welding, assembly and the like in subsequent processes.
Further, hot dipping degreasing is adopted for pre-degreasing and degreasing, and the hot dipping degreasing adopts the following steps: 2 mass ratio of the degreasing powder to the sodium hydroxide mixed water, wherein the concentration of the degreasing powder is required to be 80 +/-20 g/L, the degreasing temperature is 60-80 ℃, and the degreasing time is 40 +/-10 min.
By adopting the oil removing process, the rust-proof oil and the cutting fluid of the blank can be completely removed, and the influence on phosphating and film forming can be prevented.
Further, removing oxide skin by acid washing, namely preparing hydrochloric acid in an acid washing tank, and adding a corrosion inhibitor with 5 per mill of total solution; hydrochloric acid, compared with water, the concentration requirement is 475 plus or minus 125 ml/L; the pickling time is 180-300s at normal temperature.
By adopting the acid washing process, the oxide skin on the surface of the blank can be removed, and the uniformity of a phosphating film and higher binding force are ensured.
Further, the surface conditioning agent for surface conditioning is a thin film zinc series phosphating surface conditioning agent, a thick film zinc series phosphating surface conditioning agent or a manganese series phosphating surface conditioning agent, the surface conditioning agent has the water concentration of 3-5 per mill, the surface conditioning agent is carried out at normal temperature, and the processing time is 20 s.
Further, phosphating adopts film zinc phosphating solution, the phosphating temperature is 30-45 ℃, and the phosphating time is 8-15 min; or thick film zinc phosphating solution is adopted for phosphating, the phosphating temperature is 70-90 ℃, and the phosphating time is 10-20 min; or phosphating with manganese phosphating solution at a temperature of 90 deg.C or more for 10-20 min.
Further, centrifugal drying is carried out, wherein the centrifugal rotation speed is 200r/s, the drying temperature is 100 +/-10 ℃, and the centrifugal drying time is 5-10 min.
Furthermore, the coating is dip-coated with anti-rust oil, solvent type anti-rust oil RPS 6203 is selected as the anti-rust oil, an extremely thin oil film can be formed, and the water draining property is good. Soaking at normal temperature for 20-30 s. And finally, carrying out centrifugal drying for 20-40s at a centrifugal rotation speed of 200 r/s.
By the process for dipping and throwing the anti-rust oil, the parts can be uniformly coated with the anti-rust oil, the phosphating film crystal grains can be filled with the anti-rust oil, and the transportation and assembly cannot be influenced by excessive anti-rust oil on the surfaces of the parts.
Compared with the prior art, the invention has the following beneficial effects:
1. the components comprise, by mass, 17-20% of boric acid, 13-17% of monoethanolamine, 25-27% of triethanolamine, 8-10% of sodium silicate and the balance of a passivator of an antirust component, and a dry film can be formed after drying to protect a phosphating film from rusting and have no influence on machining, welding, assembly and the like in subsequent processes.
2. The invention adopts the passivation solution with low concentration (4-6%), the passivation temperature is 60-80 ℃, the corrosion resistance effect of parts is improved, and the production cost is saved.
3. The invention has combined action of passivation and dip-coating of anti-rust oil, simultaneously meets the requirements of salt spray and hand-touch drying, ensures that a neutral salt spray test (NSS) meets the requirement of no red rust for 72 hours, keeps no rust for 1 year in a natural environment, improves the corrosion resistance effect by 3-4.5 times, and prolongs the service life of a product.
Drawings
FIG. 1 is a comparison of salt spray effects before and after the process of the present invention is improved.
Detailed Description
The invention relates to a phosphating film passivation process which sequentially comprises the following operation steps in the operation sequence: the method comprises the following steps of loading, pre-removing oil, hot washing, pickling, washing, neutralizing, washing, surface conditioning, phosphating, washing, passivating, centrifugally drying, dip-coating antirust oil, centrifuging and blanking on the surfaces of steel products and components. The mass percentage of each component in the passivating agent in the passivating step is 17-20% of boric acid, 13-17% of monoethanolamine, 25-27% of triethanolamine, 8-10% of sodium silicate and the balance of antirust components. As shown in figure 1, M6 x 1.25-6h inner plum bolt was selected as an embodiment, and various types of phosphating were verified respectively.
Example 1
The pre-degreasing and the degreasing adopt hot dipping degreasing, and the hot dipping degreasing adopts the following steps: the degreasing agent is prepared from degreasing powder and sodium hydroxide mixed water in a mass ratio of 2, wherein the concentration of the degreasing powder is required to be 60g/L, the degreasing temperature is 60 ℃, and the degreasing time is 30 min. The process can ensure that the rust-proof oil and the cutting fluid of the blank are removed completely, and prevent the rust-proof oil and the cutting fluid from influencing phosphating and film forming.
After oil removal, the workpiece is immersed into a pickling tank to remove oxide skin on the surface of the workpiece, hydrochloric acid is prepared in the pickling tank, 5 per mill of corrosion inhibitor in total solution is added, the concentration of the hydrochloric acid is 350ml/L, and the pickling time is 180s at normal temperature. The acid washing process can remove oxide skin on the surface of the blank and ensure that the phosphating film is uniform and has higher binding force.
The surface conditioning agent is a film zinc series phosphating surface conditioning agent, the concentration of the surface conditioning agent compared with water is 3 per mill, the surface conditioning is carried out at normal temperature, and the treatment time is 20 s.
The film zinc phosphating solution is used for phosphating, the main components of the film zinc phosphating solution are zinc ions and phosphate radicals, and the process requirements are that the total acidity is 37pt, the free acidity is 1.5pt and the accelerator is 1.5 g/L. pt is the unit of titration in the assay. The phosphorization temperature is 30 ℃, the phosphorization time is 8min, and the phosphorization is low-temperature phosphorization.
The passivating agent comprises, by mass, 17.1% of boric acid, 13% of monoethanolamine, 25.2% of triethanolamine, 8% of sodium silicate and the balance of an antirust component. The passivation is carried out by preparing passivation solution from the passivating agent and pure water according to a proportion of 4%, and heating the passivation tank solution to 60 ℃, namely the passivation reaction temperature, so that the passivation solution can fully react for 20 s.
And (4) after passivation and water washing, removing water by using a centrifugal machine, and drying at the centrifugal rotation speed of 200r/s and the drying temperature of 90 ℃ for 5 min.
The antirust oil is solvent type antirust oil RPS 6203, can form an extremely thin oil film, and has good drainage property. Soaking at normal temperature for 20s, centrifuging to remove excessive oil, centrifuging at 200r/s for 20 s. The immersion-throwing antirust oil process can ensure that parts are uniformly coated with antirust oil, the inside of crystal grains of a phosphating film can be filled with the antirust oil, and meanwhile, the surfaces of the parts cannot be influenced by excessive antirust oil to be transported and assembled.
After the passivation process treatment of the thin film zinc-based phosphating film, the surface of the bolt is observed to be uniform light gray, the bottom exposure and yellowing are avoided, and the part has a uniform antirust oil film but moderate oil quantity, so that the appearance requirement of a customer can be met. Through a neutral salt spray test (NSS), after the zinc phosphating of the film is subjected to a passivation process, the salt spray can meet 48-hour no-red embroidery, the passivation process is not added, the requirement of 24-hour no-red embroidery at most can be met, and the corrosion resistance effect is greatly improved.
Example 2
The pre-degreasing and the degreasing adopt hot dipping degreasing, and the hot dipping degreasing adopts the following steps: the degreasing agent is prepared by mixing degreasing powder and sodium hydroxide with the mass ratio of 2, the concentration of the degreasing powder is required to be 100g/L, the degreasing temperature is 80 ℃, and the degreasing time is 50 min.
After oil removal, the workpiece is immersed into a pickling tank to remove oxide skin on the surface of the workpiece, hydrochloric acid is prepared in the pickling tank, 5 per mill of corrosion inhibitor in total solution is added, the concentration of the hydrochloric acid is 500ml/L, and the pickling time is 300s at normal temperature.
The surface conditioning agent is a film zinc series phosphating surface conditioning agent, the concentration of the surface conditioning agent is 5 per mill compared with that of water, the surface conditioning is carried out at normal temperature, and the treatment time is 20 s.
The zinc phosphating solution for film is used for phosphating, the main components of the zinc phosphating solution are zinc ions and phosphate radicals, and the process requirements are that the total acidity is 43pt, the free acidity is 3.5pt and the accelerator is 3.5 g/L. pt is the unit of titration in the assay. The phosphorization temperature is 45 ℃, the phosphorization is carried out at low temperature, and the phosphorization time is 15 min.
The mass percentage of each component in the passivating agent is 19.5 percent of boric acid, 16.8 percent of monoethanolamine, 27 percent of triethanolamine, 9.6 percent of sodium silicate and the balance of antirust components; the passivating agent and pure water are prepared into passivating solution according to the proportion of 6 percent for passivation, and meanwhile, the passivating bath solution is heated to 80 ℃, namely the passivating reaction temperature, so that the passivating solution can fully react for 30 s.
And after passivation and water washing, removing water by using a centrifugal machine, and drying at the centrifugal rotation speed of 200r/s and the drying temperature of 110 ℃ for 10 min.
The rust preventive oil is solvent type rust preventive oil RPS 6203. Soaking at normal temperature for 30s, centrifuging to remove excessive oil, centrifuging at 200r/s for 40 s. After the passivation process treatment of the thin film zinc-based phosphating film, the surface of the bolt is observed to be uniform light gray, the bottom exposure and yellowing are avoided, and the part has a uniform antirust oil film but moderate oil quantity, so that the appearance requirement of a customer can be met. Through a neutral salt spray test (NSS), after the zinc phosphating of the film is subjected to a passivation process, the salt spray can meet 48-hour no-red embroidery, the passivation process is not added, the requirement of 24-hour no-red embroidery at most can be met, and the corrosion resistance effect is greatly improved.
Example 3
The pre-degreasing and the degreasing adopt hot dipping degreasing, and the hot dipping degreasing adopts the following steps: the degreasing agent is prepared by mixing degreasing powder and sodium hydroxide in a mass ratio of 2, wherein the concentration of the degreasing powder is 80g/L, the degreasing temperature is 70 ℃, and the degreasing time is 40 min.
After oil removal, the workpiece is immersed into a pickling tank to remove oxide skin on the surface of the workpiece, hydrochloric acid is prepared in the pickling tank, 5 per mill of corrosion inhibitor in total solution is added, the concentration of the hydrochloric acid is 475ml/L, and the pickling time is 220s at normal temperature.
The surface conditioning agent is a film zinc series phosphating surface conditioning agent, the concentration of the surface conditioning agent is 4 per mill compared with that of water, the surface conditioning is carried out at normal temperature, and the treatment time is 20 s.
The zinc phosphating solution for film is used for phosphating, the main components of the zinc phosphating solution are zinc ions and phosphate radicals, and the process requirements are that the total acidity is 40pt, the free acidity is 2.5pt and the accelerator is 2.5 g/L. pt is the unit of titration in the assay. The phosphorization temperature is 40 ℃, the phosphorization time is 12min, and the phosphorization is low temperature phosphorization.
The mass percentage of each component in the passivating agent is 18 percent of boric acid, 16 percent of monoethanolamine, 26 percent of triethanolamine, 9 percent of sodium silicate and the balance of antirust components; the passivating agent and pure water are prepared into passivating solution according to the proportion of 5 percent for passivation, and meanwhile, the passivating bath solution is heated to 70 ℃ for full reaction, and the passivating time is 25 s.
And after passivation and water washing, removing water by using a centrifugal machine, and drying at the centrifugal rotation speed of 200r/s and the drying temperature of 100 ℃ for 8 min.
The rust preventive oil is solvent type rust preventive oil RPS 6203. Soaking at normal temperature for 25s, centrifuging to remove excessive oil, centrifuging at 200r/s for 30 s.
After the passivation process treatment of the thin film zinc-based phosphating film, the surface of the bolt is observed to be uniform light gray, the bottom exposure and yellowing are avoided, and the part has a uniform antirust oil film but moderate oil quantity, so that the appearance requirement of a customer can be met. Through a neutral salt spray test (NSS), after the zinc phosphating of the film is subjected to a passivation process, the salt spray can meet 48-hour no-red embroidery, the passivation process is not added, the requirement of 24-hour no-red embroidery at most can be met, and the corrosion resistance effect is greatly improved.
Example 4
The pre-degreasing and the degreasing adopt hot dipping degreasing, and the hot dipping degreasing adopts the following steps: the degreasing agent is prepared by mixing degreasing powder and sodium hydroxide in a mass ratio of 2, wherein the concentration of the degreasing powder is 60g/L, the degreasing temperature is 60 ℃, and the degreasing time is 30 min.
After oil removal, the workpiece is immersed into a pickling tank to remove oxide skin on the surface of the workpiece, hydrochloric acid is prepared in the pickling tank, 5 per mill of corrosion inhibitor in total solution is added, the concentration of the hydrochloric acid is 350ml/L, and the pickling time is 180s at normal temperature.
The surface conditioner is thick film zinc series phosphorization surface conditioner, the concentration of the surface conditioner is 3 per mill compared with water, the surface conditioner is surface-conditioned at normal temperature, and the processing time is 20 s.
The thick film zinc phosphating solution is mainly composed of zinc ions and phosphate radicals, and has the process requirements that the total acidity is 12pt, pt is a titration unit in an analysis assay, the iron content is 1g/L, the phosphating temperature is 70 ℃, the medium-temperature phosphating is adopted, and the phosphating time is 10 min.
The passivation is passivation solution prepared by a passivating agent and pure water according to a proportion of 4%, wherein the passivating agent comprises, by mass, 17% of boric acid, 13% of monoethanolamine, 25% of triethanolamine, 8% of sodium silicate and the balance of an antirust component. Meanwhile, the temperature of the passivation bath solution is raised to 60 ℃ to ensure that the passivation bath solution fully reacts, and the passivation time is 20 s.
And (4) after passivation and water washing, removing water by using a centrifugal machine, and drying at the centrifugal rotation speed of 200r/s and the drying temperature of 90 ℃ for 5 min.
The rust preventive oil is solvent type rust preventive oil RPS 6203. Soaking at normal temperature for 20s, centrifuging to remove excessive oil, centrifuging at 200r/s for 20 s. After the thick film zinc series phosphating film is treated by the passivating process, the surface of the bolt is observed to be uniform dark gray, no whitening or yellowing, and the part has a uniform antirust oil film but moderate oil quantity, so that the appearance requirement of a customer can be met. Through a neutral salt spray test (NSS), after the thick film zinc series phosphorization is subjected to a passivation process, the salt spray can meet 72-hour red embroidery-free performance, the passivation process is not added, the requirement of 36-hour red embroidery-free performance can be met at most, and the corrosion resistance effect is greatly improved.
Example 5
The pre-degreasing and the degreasing adopt hot dipping degreasing, and the hot dipping degreasing adopts the following steps: the degreasing agent is prepared by mixing degreasing powder and sodium hydroxide in a mass ratio of 2, wherein the concentration of the degreasing powder is 100g/L, the degreasing temperature is 80 ℃, and the degreasing time is 50 min.
After oil removal, the workpiece is immersed into a pickling tank to remove oxide skin on the surface of the workpiece, hydrochloric acid is prepared in the pickling tank, 5 per mill of corrosion inhibitor in total solution is added, the concentration of the hydrochloric acid is 500ml/L, and the pickling time is 300s at normal temperature.
The surface conditioner is thick film zinc series phosphorization surface conditioner, the concentration of the surface conditioner is 5 per mill compared with water, the surface conditioner is surface-conditioned at normal temperature, and the processing time is 20 s.
The thick film zinc phosphating solution is mainly composed of zinc ions and phosphate radicals, and has the process requirements that the total acidity is 26pt, pt is a titration unit in an analysis assay, the iron content is 11g/L, the phosphating temperature is 90 ℃, the medium-temperature phosphating is adopted, and the phosphating time is 20 min.
Passivating by adopting passivating agent and pure water according to the proportion of 6% to prepare passivating solution, wherein the passivating agent comprises 20% of boric acid, 17% of monoethanolamine, 27% of triethanolamine, 10% of sodium silicate and the balance of antirust components in percentage by mass; meanwhile, the temperature of the passivation bath solution is raised to 80 ℃ to fully react, and the passivation time is 30 s.
And after passivation and water washing, removing water by using a centrifugal machine, and drying at the centrifugal rotation speed of 200r/s and the drying temperature of 110 ℃ for 10 min.
The rust preventive oil is solvent type rust preventive oil RPS 6203. Soaking at normal temperature for 30s, centrifuging at 200r/s for 0s to remove excessive oil, and centrifuging for 40 s.
After the thick film zinc series phosphating film is treated by the passivating process, the surface of the bolt is observed to be uniform dark gray, no whitening or yellowing, and the part has a uniform antirust oil film but moderate oil quantity, so that the appearance requirement of a customer can be met. Through a neutral salt spray test (NSS), after the thick film zinc series phosphorization is subjected to a passivation process, the salt spray can meet 72-hour red embroidery-free performance, the passivation process is not added, the requirement of 36-hour red embroidery-free performance can be met at most, and the corrosion resistance effect is greatly improved.
Example 6
The pre-degreasing and the degreasing adopt hot dipping degreasing, and the hot dipping degreasing adopts the following steps: the degreasing agent is prepared by mixing degreasing powder and sodium hydroxide with the mass ratio of 2, the concentration of the degreasing powder is 80g/L, the degreasing temperature is 65 ℃, and the degreasing time is 42 min.
After oil removal, the workpiece is immersed into a pickling tank to remove oxide skin on the surface of the workpiece, hydrochloric acid is prepared in the pickling tank, 5 per mill of corrosion inhibitor of the total solution is added, the concentration of the hydrochloric acid is 470ml/L, the temperature is normal, and the pickling time is 200 s.
The surface conditioner is thick film zinc series phosphorization surface conditioner, the concentration of the surface conditioner is 3.5 per mill compared with water, the surface conditioner is used at normal temperature, and the processing time is 20 s.
The thick film zinc phosphating solution is mainly composed of zinc ions and phosphate radicals, and has the process requirements that the total acidity is 20pt, pt is a titration unit in an analysis assay, the iron content is 5g/L, the phosphating temperature is 85 ℃, the phosphating time is medium-temperature phosphating and is 12 min.
Passivating by adopting passivating agent and pure water according to the proportion of 5 percent to prepare passivating solution, wherein the passivating agent comprises 18.7 percent of boric acid, 15.2 percent of monoethanolamine, 25.9 percent of triethanolamine, 9.2 percent of sodium silicate and the balance of antirust components in percentage by mass; meanwhile, the temperature of the passivation bath solution is raised to 75 ℃ to ensure that the passivation bath solution fully reacts, and the passivation time is 22 s.
And after passivation and water washing, removing water by using a centrifugal machine, and drying at the centrifugal rotation speed of 200r/s and the drying temperature of 104 ℃ for 8 min.
The rust preventive oil is solvent type rust preventive oil RPS 6203. Soaking at normal temperature for 24s, centrifuging to remove excessive oil, centrifuging at 200r/s for 32 s.
After the thick film zinc series phosphating film is treated by the passivating process, the surface of the bolt is observed to be uniform dark gray, no whitening or yellowing, and the part has a uniform antirust oil film but moderate oil quantity, so that the appearance requirement of a customer can be met. Through a neutral salt spray test (NSS), after the thick film zinc series phosphorization is subjected to a passivation process, the salt spray can meet 72-hour red embroidery-free performance, the passivation process is not added, the requirement of 36-hour red embroidery-free performance can be met at most, and the corrosion resistance effect is greatly improved.
Example 7
Hot dipping degreasing adopts the following steps: the degreasing agent is prepared from degreasing powder and sodium hydroxide mixed water in a mass ratio of 2, wherein the concentration of the degreasing powder is 61g/L, the degreasing temperature is 62 ℃, and the degreasing time is 32 min.
After oil removal, the workpiece is immersed into a pickling tank to remove oxide skin on the surface of the workpiece, hydrochloric acid is prepared in the pickling tank, 5 per mill of corrosion inhibitor in total solution is added, the concentration of the hydrochloric acid is 360ml/L, and the pickling time is 190s at normal temperature.
The surface conditioning agent is manganese series phosphating surface conditioning agent, the concentration of the surface conditioning agent is 6.2 per mill compared with water, the surface conditioning temperature is 42 ℃, and the surface conditioning treatment time is 20 s.
The main components of the manganese phosphating solution are manganese ions and phosphate ions, the process requirements are that the total acidity is 14pt, the free acid is 2.1pt, pt is a titration unit in an analysis and assay, the phosphating temperature is 92 ℃, and the phosphating time is 11 min.
Passivation is carried out by adopting passivation solution prepared by a passivating agent and pure water according to the proportion of 4.1%, wherein the passivating agent comprises 17.2% of boric acid, 13.5% of monoethanolamine, 25.1% of triethanolamine, 8.2% of sodium silicate and the balance of antirust components by mass percent; meanwhile, the temperature of the passivation bath solution is raised to 62 ℃ to ensure that the passivation bath solution fully reacts, and the passivation time is 22 s.
And (4) after passivation and water washing, removing water by using a centrifugal machine, and drying at the centrifugal rotation speed of 200r/s and the drying temperature of 92 ℃ for 6 min.
The rust preventive oil is solvent type rust preventive oil RPS 6203. Immersing at normal temperature for 22s, centrifuging after immersion to remove excessive oil, centrifuging at a speed of 200r/s, and centrifuging for 21 s.
After the manganese phosphating film passivation process is used for treatment, the bolt surface is observed to be bright black, white and yellow, and parts have uniform antirust oil films but moderate oil amount, so that the appearance requirements of customers can be met. Through a neutral salt spray test (NSS), after the manganese series phosphorization is subjected to a passivation process, the salt spray can meet 96h no-red embroidery, the passivation procedure is not added, at most, 48h no-red embroidery can be met, and the corrosion resistance effect is greatly improved.
Example 8
The pre-degreasing and the degreasing adopt hot dipping degreasing, and the hot dipping degreasing adopts the following steps: 2 mass ratio of oil removing powder and sodium hydroxide mixed water, the concentration of the oil removing powder is 98g/L, the oil removing temperature is 77 ℃, and the oil removing time is 45 min.
After oil removal, the workpiece is immersed into a pickling tank to remove oxide skin on the surface of the workpiece, hydrochloric acid is prepared in the pickling tank, 5 per mill of corrosion inhibitor in total solution is added, the concentration of the hydrochloric acid is 490ml/L, the temperature is normal, and the pickling time is 280 s.
The surface conditioning agent is manganese series phosphating surface conditioning agent, the concentration of the surface conditioning agent is 7.8 per mill compared with water, the surface conditioning temperature is 60 ℃, and the surface conditioning treatment time is 20 s.
The main components of the manganese phosphating solution are manganese ions and phosphate ions, the process requirements are that the total acidity is 18pt, the free acid is 3pt, pt is a titration unit in an analysis assay, the phosphating temperature is 120 ℃, and the phosphating time is 18 min.
The passivation is passivation solution prepared by a passivating agent and pure water according to the proportion of 6%, wherein the passivating agent comprises 19.5% of boric acid, 16% of monoethanolamine, 26.5% of triethanolamine, 9.5% of sodium silicate and the balance of antirust components by mass percent; meanwhile, the temperature of the passivation bath solution is raised to 80 ℃ to fully react, and the passivation time is 30 s.
And after passivation and water washing, removing water by using a centrifugal machine, and drying at the centrifugal rotation speed of 200r/s and the drying temperature of 108 ℃ for 10 min.
The rust preventive oil is solvent type rust preventive oil RPS 6203. Soaking at normal temperature for 30s, centrifuging to remove excessive oil, centrifuging at 200r/s for 40 s.
After the manganese phosphating film passivation process is used for treatment, the bolt surface is observed to be bright black, white and yellow, and parts have uniform antirust oil films but moderate oil amount, so that the appearance requirements of customers can be met. Through a neutral salt spray test (NSS), after the manganese series phosphorization is subjected to a passivation process, the salt spray can meet 96h no-red embroidery, the passivation procedure is not added, at most, 48h no-red embroidery can be met, and the corrosion resistance effect is greatly improved.
Example 9
The pre-degreasing and the degreasing adopt hot dipping degreasing, and the hot dipping degreasing adopts the following steps: the degreasing agent is prepared from degreasing powder and sodium hydroxide mixed water in a mass ratio of 2, the concentration of the degreasing powder is 78g/L, the degreasing temperature is 75 ℃, and the degreasing time is 42 min.
After oil removal, the workpiece is immersed into a pickling tank to remove oxide skin on the surface of the workpiece, hydrochloric acid is prepared in the pickling tank, 5 per mill of corrosion inhibitor in total solution is added, the concentration of the hydrochloric acid is 400ml/L, and the pickling time is 270s at normal temperature.
The surface conditioning agent is manganese series phosphorization surface conditioning agent, the concentration of the surface conditioning agent is 7.2 per mill compared with water, the surface conditioning temperature is 52 ℃, and the surface conditioning treatment time is 20 s.
The main components of the manganese phosphating solution are manganese ions and phosphate ions, the process requirements are that the total acidity is 15pt, the free acid is 2.5pt, pt is a titration unit in an analysis assay, the phosphating temperature is 150 ℃, and the phosphating time is 12 min.
Passivating by adopting passivating agent and pure water according to the proportion of 5% to prepare passivating solution, wherein the passivating agent comprises 18.5% of boric acid, 15% of monoethanolamine, 26% of triethanolamine, 9% of sodium silicate and the balance of antirust components in percentage by mass; meanwhile, the temperature of the passivation bath solution is raised to 75 ℃, and the passivation time is 28 s.
And after passivation and water washing, removing water by using a centrifugal machine, and drying at the centrifugal rotation speed of 200r/s and the drying temperature of 105 ℃ for 7 min.
The rust preventive oil is solvent type rust preventive oil RPS 6203. Soaking at normal temperature for 24s, centrifuging to remove excessive oil, centrifuging at 200r/s for 32 s.
After the manganese phosphating film passivation process is used for treatment, the bolt surface is observed to be bright black, white and yellow, and parts have uniform antirust oil films but moderate oil amount, so that the appearance requirements of customers can be met. Through a neutral salt spray test (NSS), after the manganese series phosphorization is subjected to a passivation process, the salt spray can meet 96h no-red embroidery, the passivation procedure is not added, at most, 48h no-red embroidery can be met, and the corrosion resistance effect is greatly improved.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and substitutions can be made without departing from the technical principle of the present invention, and these modifications and substitutions should also be regarded as the protection scope of the present invention.
Claims (8)
1. The passivation technology of the phosphating film comprises the steps of pre-removing oil, washing for multiple times, removing oxide skin by acid washing, adjusting the surface and phosphating the steel product and the component surface, and is characterized in that: passivating after the last said water wash; the mass percentage of each component in the passivating agent is 17-20% of boric acid, 13-17% of monoethanolamine, 25-27% of triethanolamine, 8-10% of sodium silicate and the balance of antirust components; the passivating agent and pure water are prepared into passivating solution according to the proportion of 4-6%, meanwhile, the passivating bath solution is heated to 60-80 ℃ to fully react, centrifugal drying is carried out after passivation is carried out for 20-30s, anti-rust oil is dip-coated, and finally centrifugal drying is carried out again.
2. A process for passivating a phosphating film according to claim 1, characterized in that: the pre-degreasing and degreasing adopt hot dipping degreasing, and the hot dipping degreasing adopts the following steps: 2 mass ratio of the degreasing powder to the sodium hydroxide mixed water, wherein the concentration of the degreasing powder is required to be 80 +/-20 g/L, the degreasing temperature is 60-80 ℃, and the degreasing time is 40 +/-10 min.
3. A process for passivating a phosphating film according to claim 1, characterized in that: the oxide skin is removed by acid washing, hydrochloric acid solution is prepared in an acid washing tank, and 5 per mill of corrosion inhibitor of the total solution is added; hydrochloric acid, compared with water, the concentration requirement is 475 plus or minus 125 ml/L; the pickling time is 180-300s at normal temperature.
4. A process for passivating a phosphating film according to claim 1, characterized in that: the surface conditioning agent for surface conditioning is a thin film zinc series phosphating surface conditioning agent, a thick film zinc series phosphating surface conditioning agent or a manganese series phosphating surface conditioning agent, the concentration of the surface conditioning agent is 3-5 per mill compared with water, the surface conditioning agent is carried out at normal temperature, and the processing time is 20 s.
5. A process for passivating a phosphating film according to claim 1, characterized in that: the phosphating adopts film zinc phosphating solution, the phosphating temperature is 30-45 ℃, and the phosphating time is 8-15 min; or thick film zinc phosphating solution is adopted for phosphating, the phosphating temperature is 70-90 ℃, and the phosphating time is 10-20 min; or phosphating with manganese phosphating solution at a temperature of 90 deg.C or more for 10-20 min.
6. A process for passivating a phosphating film according to claim 1, characterized in that: and (3) centrifugally drying at the centrifugal rotation speed of 200r/s and at the drying temperature of 100 +/-10 ℃ for 5-10 min.
7. A process for passivating a phosphating film according to claim 1, characterized in that: the dip-coating anti-rust oil is solvent type anti-rust oil RPS 6203, and is dipped at normal temperature for 20-30 s.
8. A process for passivating a phosphating film according to claim 1, characterized in that: and finally, carrying out centrifugal drying for the last time, wherein the centrifugal rotating speed is 200r/s, and the centrifugal time is 20-40 s.
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