CN1127800A - Cold black coslettising liquid - Google Patents
Cold black coslettising liquid Download PDFInfo
- Publication number
- CN1127800A CN1127800A CN95111453A CN95111453A CN1127800A CN 1127800 A CN1127800 A CN 1127800A CN 95111453 A CN95111453 A CN 95111453A CN 95111453 A CN95111453 A CN 95111453A CN 1127800 A CN1127800 A CN 1127800A
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- CN
- China
- Prior art keywords
- phosphate
- salt
- film
- phosphating solution
- phosphating
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- C23C22/42—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also phosphates
Abstract
The black phosphonating liquor for surface treatment of metal is prepared from phosphoric acid, Cu salt, Se salt, ZnO, calcium hypophosphite, ammonium molybdate, EDTA, compound containing polyhydroxyl phosphate and water, and features low blackening temp, stable performances, and uniform phosphonated film having compact crystalline, high corrosion resistance and high adhesion to substrate.
Description
The invention belongs to the field of metal-to-surface chemistry, and particularly relates to a black phosphating solution for phosphating and blackening the surface of steel.
The traditional phosphating solution has high temperature, large energy consumption, long time, high cost and serious pollution. The normal temperature phosphating and blackening treatment can overcome the defects, so that the method is emphasized by people and is developed rapidly in recent years. However, in the prior art, the phosphorization and blackening are carried out step by step, and Chinese patents CN1076225 and CN1077757 disclose 2 black phosphorization liquids and processes thereof for step by step treatment. Although black phosphating films can be obtained through step-by-step treatment, the formed films are loose, the corrosion resistance is poor, the process is long, and the cost is high. Chinese patent CN1085606 introduces a normal temperature rapid blackening agent for steel, which can form a phosphating blackening film in one step. At present, researches show that the phosphorus content of a phosphating film is low, and the performance of the phosphating film is poor, but only phosphate in the CN1085606 patent component can provide a certain phosphorus content, so that the phosphorus content of the generated film is not high, and the performance is not good enough; secondly, it reduces the reaction temperature by sacrificing free acidity in a conventional manner, so that its free acidity is small (4-6 points) and needs to be continuously adjusted during the treatment of the workpiece to ensure the ability to treat the workpiece.
Aiming at the problems in the prior art, the invention aims to provide the normal-temperature black phosphating solution for simultaneously carrying out phosphating and blackening, which has the advantages of high phosphorus content of a formed film, quick film forming time (2-10 minutes), black color, uniformity, compactness, plate-shaped crystallization, good sealing effect on a base material, strong adhesive force, good corrosion resistance, higher free acidity and strong workpiece processing capacity.
The invention is composed of 60-100 g/L phosphoric acid, 40-40 g/L ZnO10, 1-8 g/L copper salt selenium salt, 2-15 g/L ammonium molybdate, 0.05-0.5 g/L calcium hypophosphite, 1-10 g/L EDTA, 0.1-3.0 g/L polyhydroxy compound and the balance of water. The copper salt can be copper sulfate or copper carbonate, and the selenium salt can be sodium selenite or selenium dioxide; the polyhydroxy phosphate ester compound contains polyhydroxy characteristics such as tannin, polyvinyl alcohol phosphate ester or oxidized polyvinyl alcohol phosphate ester, oxidized starch phosphate ester or grafted starch phosphate ester. The preparation and use method of the invention is as follows: the components are respectively diluted and dissolved according to the proportion, then are added successively, and are stirred uniformly, so that the liquid can be obtained. The workpiece after oil-removing, rust-removing and cleaning treatment is sprayed or soaked with said invented liquid at 10-40 deg.C for 2-10 min, so that the phosphorization and blackening process can be completed.
The main reaction process and mechanism of the invention are as follows: the phosphating film and the blackening film in the phosphating solution are simultaneously formed, insoluble phosphate converted from dihydric phosphate is separated out from CuSe in a double salt form to form a conversion film, and the film has the properties of both the phosphating film and the blackening film and is compact in film quality. However, under the condition of larger free acidity, the CuSe generation speed is higher than that of phosphate, and the formed film is easy to loose and porous, so that the EDTA is used as a complexing agent to regulate the relative speed of the CuSe and the phosphate. More importantly, the invention adds polyhydroxy phosphate compound as an accelerator, accelerates the formation of a phosphating film and inhibits the generation speed of CuSe, changes the deposition ratio of two salts, thereby obtaining a perfect conversion film; meanwhile, the compound is a film-forming substance, has the property of composite deposition with phosphate, and is converted into insoluble salt on the metal surface, and the formula is as follows:
The working temperature of the invention is 10-40 ℃, the time for processing the workpiece is 2-10 minutes, the PH value is 2.0-2.4, and the potential of the working liquid is 0.200-0.240. The solution has stable performance, and the obtained film is black, uniform and compact, is plate-shaped crystal (see attached figures and analysis materials), has good sealing performance on a base material, strong corrosion resistance, strong adhesive force on steel and strong paint film binding force.
Example (b):
phosphoric acid (85%) 90g/L, ammonium molybdate 5g/L
ZnO 30g/L EDTA sodium salt 1.0g/L
Na2SeO 33 g/L calcium hypophosphite 0.1g/L
Cuso 4.5H 2O 12g/L tannin 1.0g/L
Balance of water
Diluting phosphoric acid with 300ml water, slowly adding zinc oxide, stirring to dissolve completely, and sequentially adding Na2SeO3Copper sulfate, ammonium molybdate, calcium hypophosphite and EDTA are added into the mixture, and the tannin solution is added into the mixture and mixed evenly to obtain the liquid. Wherein the tannin solution is prepared by adding tannin into 100ml water, boiling, filtering to remove the dissolved matter, and diluting with water to desired volume.
And (3) immersing the workpiece subjected to oil removal, rust removal and cleaning treatment into the phosphating solution at room temperature for 3 minutes to finish phosphating and blackening the workpiece, wherein the treated workpiece can be washed or not washed by water.
Performance indexes are as follows:
completely conforms to the GB 8607-86 and WJ 535-28 standards.
With 3% CuSO4The dripping experiment shows that the color of the product is not changed when the product is dried for 120 seconds at 15-20 ℃.
The stainless steel sheet has no rust after being soaked in 3% neutral NaCl water solution at 15-20 deg.c for 3 hr.
The phosphatized blackened workpiece is repeatedly bent for 80 times after being painted, and the paint film has no phenomena of cracks, bubbles and falling off.
The attached figure is an electron microscope image of the black phosphating solution coating prepared in the embodiment, (an analysis report sheet is attached).
Chongqing building university test analysis center
Analysis report sheet
Sample sending unit: SJ scientific research group
2. in the case of sufficient sample, the sample was kept for one month for future examination. And (4) an analysis department: human analysis: qinlietan center governs the main role:20/3/1995
| Analysis item | SEM electron microscope image | Sample feeding and sample feeding time | Axe clock 1995.3.5 | ||
| Sample name | Normal temperature black phosphating solution | Sample quantity and State | Liquid coating | ||
| And (3) analysis results: first, picture (100 x): the coating and the surface of the base material are in a staggered shape. Due to the existence of the eraser on the surface of the substrate Marks, along which the coating penetrated like hair, were visible. Undissolved matter with the thickness of 10-60 mu m exists in the coating Particle distribution of the solution. II, picture (750 x)): the coating is crystalline particles which are distributed in a brain-shaped aggregate in a tight mosaic manner, the grain boundary of the particles is clear and is uniformly distributed on the basal plane. Thirdly, the method comprises the following steps: picture (850 x): the coating is uniformly covered on the base surface in the form of plate-shaped coating, and two groups of cleavage hairs The cleavage included angle is approximately equal to 90 degrees, and the trace of the circular particles which are not completely dissolved can be seen. Fourth, picture (2500 x): the coating is in a crystal plate shape and uniformly covers the base surface. Is coated with Is air-tight and has no air holes. Two groups of cleavage development, the wafer particle size is 10 × 10 to 10 × 30 μm (length x width). | |||||
| Remarking: | |||||
Claims (5)
1. The black phosphating solution for metal surface treatment is characterized by comprising the following components: 60-100 g/L of phosphoric acid, 40-40 g/L of ZnO10, 1-8 g/L of copper salt, 1-8 g/L of selenium salt, 2-15 g/L of ammonium molybdate, 0.05-0.5 g/L of calcium hypophosphite, 10g/L of EDTAl, 0.1-3.0 g/L of polyhydroxy phosphate compound and the balance of water.
2. The phosphating solution of claim 1 wherein the copper salt is copper sulfate or copper carbonate.
3. The phosphating solution of claim 1 wherein the selenium salt is sodium selenite or selenium dioxide.
4. The phosphating solution according to claim 1, wherein the structure of the polyhydroxy phosphate compound contains polyhydroxy characteristics, such as tannin, polyvinyl alcohol phosphate or oxidized polyvinyl alcohol phosphate, oxidized starch phosphate or grafted starch phosphate.
5. The phosphating solution of claim 1, which can be sprayed or soaked for 2-10 min at 10-40 deg.C, pH of the working solution 2.0-2.4, total acid 20-60, free acid 10-30, and acid ratio 1.5-4.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95111453A CN1127800A (en) | 1995-08-01 | 1995-08-01 | Cold black coslettising liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95111453A CN1127800A (en) | 1995-08-01 | 1995-08-01 | Cold black coslettising liquid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1127800A true CN1127800A (en) | 1996-07-31 |
Family
ID=5078744
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95111453A Pending CN1127800A (en) | 1995-08-01 | 1995-08-01 | Cold black coslettising liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1127800A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103726040A (en) * | 2013-12-17 | 2014-04-16 | 沈阳帕卡濑精有限总公司 | Phosphorizing agent for improving surface brightness of electro-galvanized steel plate and preparation method for phosphorizing agent |
| CN104962898A (en) * | 2015-06-30 | 2015-10-07 | 大连碧城环保科技股份有限公司 | Manganese-bearing phosphating solution additive and using method thereof |
| CN105177547A (en) * | 2015-09-17 | 2015-12-23 | 宝钢集团南通线材制品有限公司 | Blueing method for improving abrasive resistance of surface of spring steel |
| CN108085667A (en) * | 2017-12-25 | 2018-05-29 | 三达奥克化学股份有限公司 | Suitable for the corrosion-resistant black phosphating inorganic agent of medium temperature and preparation method of cast iron, carbon steel work-piece |
| CN115522191A (en) * | 2022-10-11 | 2022-12-27 | 山东商业职业技术学院 | Phosphating solution for metal surface treatment and preparation method and application thereof |
-
1995
- 1995-08-01 CN CN95111453A patent/CN1127800A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103726040A (en) * | 2013-12-17 | 2014-04-16 | 沈阳帕卡濑精有限总公司 | Phosphorizing agent for improving surface brightness of electro-galvanized steel plate and preparation method for phosphorizing agent |
| CN104962898A (en) * | 2015-06-30 | 2015-10-07 | 大连碧城环保科技股份有限公司 | Manganese-bearing phosphating solution additive and using method thereof |
| CN104962898B (en) * | 2015-06-30 | 2017-09-26 | 大连碧城环保科技股份有限公司 | A kind of manganese-series phosphorized solution additive and its application method |
| CN105177547A (en) * | 2015-09-17 | 2015-12-23 | 宝钢集团南通线材制品有限公司 | Blueing method for improving abrasive resistance of surface of spring steel |
| CN108085667A (en) * | 2017-12-25 | 2018-05-29 | 三达奥克化学股份有限公司 | Suitable for the corrosion-resistant black phosphating inorganic agent of medium temperature and preparation method of cast iron, carbon steel work-piece |
| CN115522191A (en) * | 2022-10-11 | 2022-12-27 | 山东商业职业技术学院 | Phosphating solution for metal surface treatment and preparation method and application thereof |
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| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |