CN108330480B - Single-component nickel-free medium-temperature black phosphating solution - Google Patents
Single-component nickel-free medium-temperature black phosphating solution Download PDFInfo
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- CN108330480B CN108330480B CN201810158582.4A CN201810158582A CN108330480B CN 108330480 B CN108330480 B CN 108330480B CN 201810158582 A CN201810158582 A CN 201810158582A CN 108330480 B CN108330480 B CN 108330480B
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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 single-component nickel-free medium-temperature black phosphating solution, which relates to the field of metal surface treatment, and each liter of the phosphating solution is prepared from the following components: 30-50g/L of ferromanganese phosphate, 25-35g/L of 50% manganese nitrate, 20-25g/L of zinc nitrate, 0.5-1g/L of potassium fluoride, 1-2g/L of sodium fluoborate, 1-1.5g/L of ammonium citrate, 15-25g/L of calcium nitrate, 0.5-1g/L of antimony potassium tartrate, 5mL of mixed liquid of sodium tungstate and bismuth nitrate, and the balance of water; the invention can generate a compact and uniform black phosphating film on the surface of steel, has high corrosion resistance, greatly reduces energy consumption compared with pure manganese high-temperature black phosphating, does not contain nickel and nitrite, is environment-friendly, has high blackness after phosphating, and accords with the green development trend.
Description
Technical Field
The invention relates to the field of metal surface treatment, in particular to a single-component nickel-free medium-temperature black phosphating solution.
Background
The metal surface phosphating treatment is widely used for matching treatment of metal paint spraying and electrophoresis, and with the development of technology and the improvement of requirements, common zinc series phosphating can not meet the industrial requirements more and more. The black phosphorization is higher than zinc series phosphorization due to the comprehensive properties such as corrosion resistance, wear resistance and the like, and the cost is lower than that of galvanizing, so that the black phosphorization becomes the key point of the research of the majority of manufacturers. The normal temperature selenide blackening is that a layer of black cuprous selenide is attached to the surface of metal, and the black cuprous selenide is easy to fall off after a period of time, and the selenide is toxic and expensive, so the application and further development of the selenide are limited. The oxide film obtained by high-temperature alkaline cooking is thin, black in color but insufficient in corrosion resistance, and huge in energy waste. The high-temperature phosphating temperature of pure manganese is slightly lower than that of high-temperature alkaline boiling, but is about 95 ℃, so that energy waste is large, and the requirement on a production line is high. Thus, medium and low temperature black phosphating is of particular interest.
Disclosure of Invention
The invention aims to overcome the defect of insufficient medium temperature phosphating blackness in the prior art and provides a single-component medium temperature black phosphating solution containing no nickel.
The invention is realized by the following technical scheme:
a single-component nickel-free medium-temperature black phosphating solution is prepared from the following components in each liter: 30-50g/L of manganese ferric phosphate, 25-35g/L of 50% manganese nitrate, 20-25g/L of zinc nitrate, 0.5-1g/L of potassium fluoride, 1-2g/L of sodium fluoborate, 1-1.5g/L of ammonium citrate, 15-25g/L of calcium nitrate, 0.5-1g/L of antimony potassium tartrate, 5mL of mixed liquid of sodium tungstate and bismuth nitrate and the balance of water.
Further, the mixed solution is prepared by mixing sodium tungstate and bismuth nitrate 2:1, dissolving 5g of the mixture in 20mL of 65% nitric acid, and adding water to dilute the mixture to 50mL for later use.
Further, the invention provides a use method of the phosphating solution, which comprises the following steps: the method comprises the steps of degreasing and cleaning a workpiece, washing with water, washing with acid, washing with water, performing surface conditioning, immersing into phosphating solution, controlling the ratio of total acid to free acid of the phosphating solution to be 12-15, phosphating time to be 12-16 minutes, treating temperature to be 70-80 ℃, washing the phosphated workpiece with cold water, and scalding with hot water to obtain the dry phosphating film.
The ear detection method for free acid and total acid comprises the following steps:
the detection method of the free acidity comprises the following steps: putting 10mL of tank liquor into a 10mL triangular flask, diluting the tank liquor to 30-40mL by using distilled water, dripping 3-4 drops of bromophenol blue indicator, titrating the solution by using 0.1mol/LNaOH standard solution, changing the solution in the triangular flask from light yellow to light blue, keeping the solution from fading for 30 seconds, namely the end point of titration, and reading the descending indication number of a burette, namely the number of free acid points.
The total acidity detection method comprises the following steps: sucking 10mL of tank liquor by a pipette, putting the tank liquor into a 100mL triangular flask, adding water (distilled water) to 30-40mL of scale mark, dripping 3-4 drops of phenolphthalein indicator, titrating by using 0.1mol/L NaOH standard solution, changing the solution in the triangular flask from colorless to light red, not fading in 30 seconds, and reading the reduced indication of a burette to obtain the total acidity of the phosphating solution.
The treatment time of the phosphating solution is 12-16 minutes.
Compared with the prior art, the invention has the following advantages: the single-component nickel-free medium-temperature black phosphating solution provided by the invention can generate a compact and uniform black phosphating film on the surface of steel, has high corrosion resistance, greatly reduces energy consumption compared with pure manganese high-temperature black phosphating, does not contain nickel and nitrite, is environment-friendly, and accords with the green development trend; compared with the phosphating solution in the prior art, the black degree of the phosphating solution is higher.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
The invention provides a single-component nickel-free medium-temperature black phosphating solution, wherein each liter of the phosphating solution is prepared from the following components: 30-50g/L of manganese ferric phosphate, 25-35g/L of 50% manganese nitrate, 20-25g/L of zinc nitrate, 0.5-1g/L of potassium fluoride, 1-2g/L of sodium fluoborate, 1-1.5g/L of ammonium citrate, 15-25g/L of calcium nitrate, 0.5-1g/L of antimony potassium tartrate, 5mL of mixed liquid of sodium tungstate and bismuth nitrate and the balance of water.
Further, the mixed solution is prepared by mixing sodium tungstate and bismuth nitrate 2:1, dissolving 5g of the mixture in 20mL of 65% nitric acid, and adding water to dilute the mixture to 50mL for later use.
The invention also provides a using method of the phosphating solution, which comprises the following steps: the method comprises the steps of degreasing and cleaning a workpiece, washing with water, washing with acid, washing with water, performing surface conditioning, immersing into phosphating solution, controlling the ratio of total acid to free acid of the phosphating solution to be 12-15, phosphating time to be 12-16 minutes, treating temperature to be 70-80 ℃, washing the phosphated workpiece with cold water, and scalding with hot water to obtain the dry phosphating film.
The detection method of the free acid and the total acid comprises the following steps:
the detection method of the free acidity comprises the following steps: putting 10mL of tank liquor into a 10mL triangular flask, diluting the tank liquor to 30-40mL by using distilled water, dripping 3-4 drops of bromophenol blue indicator, titrating the solution by using 0.1mol/LNaOH standard solution, changing the solution in the triangular flask from light yellow to light blue, keeping the solution from fading for 30 seconds, namely the end point of titration, and reading the descending indication number of a burette, namely the number of free acid points.
The total acidity detection method comprises the following steps: sucking 10mL of tank liquor by a pipette, putting the tank liquor into a 100mL triangular flask, adding water (distilled water) to 30-40mL of scale mark, dripping 3-4 drops of phenolphthalein indicator, titrating by using 0.1mol/L NaOH standard solution, changing the solution in the triangular flask from colorless to light red, not fading in 30 seconds, and reading the reduced indication of a burette to obtain the total acidity of the phosphating solution.
Examples
1. The phosphating solution is selected, and the workpiece is immersed in the phosphating solution for 12-16 minutes after oil and rust removal. And washing the phosphated workpiece with cold water and scalding with hot water to obtain the dry phosphating film.
2. The commonly used SQ215, SQ235A, SQ235B, SQ255A and SPCC plates are selected as phosphorization objects.
3. The phosphating solution of the invention is used for carrying out a comparative test with common black phosphating solutions in the market, wherein:
NT-447 zinc-calcium series black phosphating solution is phosphated for 12-15 minutes at 70-80 ℃, washed by cold water and scalded by hot water to obtain a dry phosphating film;
HH315X manganese series black phosphating solution, phosphating at 75-85 deg.C for 12-15 min, washing with cold water, and hot water scalding to obtain dry phosphating film;
phosphating for 12-15 minutes by using pure manganese phosphating solution at the temperature of 90-95 ℃, washing by cold water, and scalding by hot water to obtain a dry phosphating film.
Other processing conditions such as degreasing and water washing are the same.
The average chromaticity value of the phosphating films treated by the four phosphating solutions detected by a WS70 spectrocolorimeter at three points is shown in a comparison table, and the data in the table show that under the same process conditions, the blackening degree of the phosphating solution is obviously higher than that of the other three phosphating solutions.
| Number plate | SQ215 | SQ235A | SQ235B | SQ255A | SPCC |
| NT-447 | 70 | 72 | 72 | 74 | 65 |
| FL-D03 | 72 | 72 | 72 | 74 | 67 |
| Pure manganese | 74 | 74 | 76 | 78 | 69 |
| The invention | 78 | 78 | 80 | 82 | 73 |
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (1)
1. The single-component nickel-free medium-temperature black phosphating solution is characterized by being prepared from the following components per liter: 30-50g/L of ferromanganese phosphate, 25-35g/L of 50% manganese nitrate, 20-25g/L of zinc nitrate, 0.5-1g/L of potassium fluoride, 1-2g/L of sodium fluoborate, 1-1.5g/L of ammonium citrate, 15-25g/L of calcium nitrate, 0.5-1g/L of antimony potassium tartrate, 5mL of mixed liquid of sodium tungstate and bismuth nitrate, and the balance of water;
the mixed solution is prepared by the following method, mixing sodium tungstate and bismuth nitrate by 2:1, dissolving 5g of the mixed solution in 20mL of 65% nitric acid, and adding water to dilute the solution to 50mL for later use;
the using method of the phosphating solution specifically comprises the following steps: the method comprises the steps of degreasing and cleaning a workpiece, washing with water, washing with acid, washing with water, performing surface conditioning, immersing into phosphating solution, controlling the ratio of total acid to free acid of the phosphating solution to be 12-15, phosphating time to be 12-16 minutes, treating temperature to be 70-80 ℃, washing the phosphated workpiece with cold water, and scalding with hot water to obtain the dry phosphating film.
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| CN201810158582.4A CN108330480B (en) | 2018-02-26 | 2018-02-26 | Single-component nickel-free medium-temperature black phosphating solution |
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| CN201810158582.4A CN108330480B (en) | 2018-02-26 | 2018-02-26 | Single-component nickel-free medium-temperature black phosphating solution |
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| CN108330480B true CN108330480B (en) | 2020-05-15 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101864564B (en) * | 2010-07-14 | 2012-06-06 | 西安北方光电有限公司 | High corrosion-resistance black phosphating process |
| CN102534591B (en) * | 2012-01-05 | 2013-12-18 | 安徽启明表面技术有限公司 | Thick film phosphating method |
| CN102605364B (en) * | 2012-04-17 | 2014-04-02 | 安徽启明表面技术有限公司 | Intermediate-temperature low-sediment and low-emission thick membrane phosphorizing liquid and phosphorizing method thereof |
| CN104630757A (en) * | 2013-11-11 | 2015-05-20 | 安徽未来表面技术有限公司 | Low temperature black phosphatization liquid with characteristics of high friction resistance and corrosion resistance |
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