CN102747356A - Normal temperature calcium-manganese phosphorizing liquid - Google Patents
Normal temperature calcium-manganese phosphorizing liquid Download PDFInfo
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- CN102747356A CN102747356A CN2012102657057A CN201210265705A CN102747356A CN 102747356 A CN102747356 A CN 102747356A CN 2012102657057 A CN2012102657057 A CN 2012102657057A CN 201210265705 A CN201210265705 A CN 201210265705A CN 102747356 A CN102747356 A CN 102747356A
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Abstract
The invention discloses normal temperature calcium-manganese phosphorizing liquid, which comprises Mn<2+>, Ca<2+> and sodium benzoate or benzoic acid or nickel nitrate. The environment-friendly calcium-manganese phosphorizing liquid provided by the invention can be used at normal temperature, and has the advantages of no surface adjusting process before phosphorizing and no washing process after phosphorizing, simple operation, long service life and excellent effect, when the generated phosphorizing membrane is taken as a coating basement, the coating has good adhesive force, thereby overcoming the problems of complicated conventional phosphorizing process, higher phosphorizing liquid temperature, large consumption of water and phosphate, much harmful wastewater and the like. The phosphorizing liquid is suitable for surface treatment before coating the surface of black metal steel, and the generated phosphorizing film is used as a basement of the coating.
Description
Technical field
The invention belongs to the environment-friendly phosphating field of ferrous metal steel surface pre-treatment, be specifically related to a kind of normal temperature manganese calcium series phosphatating liquid.
Background technology
Bonderizing, the history surplus in the of existing 160 year is metal works handles and generates in the metallic surface that is processed the process of the conversion film that is called phosphatize phosphate coat in dihydrogen phosphate, accelerator are the solution of staple.Phosphatize phosphate coat can obviously improve adhesive force of coatings, solidity to corrosion and barrier propterty as the bottom of coating, is widely used in industries such as automobile, household electrical appliances, machinery, military project.Phosphatization can be divided into types such as zinc system, manganese system, iron system, zinc calcium system by the film forming positively charged ion; Press the bonderizing temperature, can roughly be divided into high temperature phosphorization, middle temperature phosphating, low temperature, normal (chamber) warm phosphatization etc.
After iron and steel immersed phosphatization liquid, steel surface had formed many micro anodes district and micro cathode district.Dissolving metal takes place in the micro anode district; Hydrogen is separated out in hydrogen ion in solution discharge in the micro cathode district simultaneously, and near the pH value in micro cathode district is raise, as the PO of phosphoric acid or dihydrogen phosphate ionization generation
4 3-With the positively charged ion Fe in the solution
2+, Mn
2+, Ca
2+, Ba
2+Deng ionic product form insoluble phosphate when surpassing solubility product constant, be deposited on the metallic surface and form phosphatize phosphate coat.The deposition that does not become phosphatize phosphate coat becomes the phosphatization sediment.
SO in the phosphatization liquid
4 2 –Can be attracted to phosphatize phosphate coat inside, influence the corrosion resisting property of phosphatize phosphate coat.Therefore, in phosphatization liquid, add nitrate of baryta, can remove SO automatically
4 2 –:
Remove SO with respect to conventional phosphatizing technology
4 2 –Method for washing, be employed in the phosphatization liquid and add barium salt and remove SO
4 2 –Technology is simple; All to participate in film formation reaction and product be phosphatize phosphate coat, sediment and volatile matter to main raw in this phosphatization liquid simultaneously; And the evaporation rates such as water in the residual liquid of phosphatization caudacoria surface are adapted with continuing film forming speed, and eliminate the getting rusty of phosphatize phosphate coat, dust, realize exempting from washing after the workpiece phosphatization.
The steel surface that any needs spray all should carry out phosphatization.Present domestic phosphorization technology ubiquity: phosphatization temperature is higher, phosphatization liquid work-ing life short (have even high frequency hour just scrap surplus using 100), need after the phosphatization together or the multiple tracks washing to remove the NO that contains on the workpiece surface
2 –, NO
3 –, F
–, SO
4 2 –And the remaining phosphatization liquid of the salt of higher concentration, to avoid phosphatize phosphate coat corrosion, serious dust.Leaching requirement is big, contains the material that P, N, Zn, COD, BOD etc. are harmful, can cause body eutrophication in the wash water, must handle before the discharging, not only increases the burden of environmental improvement but also consumed resources such as water, phosphoric acid salt.
In addition, also do not see at present special in Mn
2+, Ca
2+Be combined as the cationic manganese calcium series phosphatating liquid report of main film forming metal, disclosing a kind of multimode, quick room temperature zinc system or zinc calcium system or iron among the patent documentation CN1680623A is clean phosphatization liquid, can contain Zn in its phosphatization fluid component
2+, Mn
2+, Ca
2+But its original meaning remains the combination of conventional phosphatizing positively charged ion; Promptly form Zn system, Zn-Ca system, Mn system, Zn-Mn or Mn-Zn system, ternary Zn-Ca-Mn based phosphatization liquid; The phosphatize phosphate coat that uses these phosphatization liquid to form exists alkali resistance not so good, paint film impact resistance or the strong or not relatively poor problem of sticking power sometimes after spraying paint.
Summary of the invention
The present invention is intended to overcome the deficiency of prior art, and a kind of normal temperature manganese calcium series phosphatating liquid is provided.
In order to achieve the above object, technical scheme provided by the invention is:
Said each component of normal temperature manganese calcium series phosphatating liquid and content are:
Phosphoric acid and phosphoric acid salt are with PO
4 3-Meter 8.5～21.0 g/L;
Nitric acid and nitrate salt are with NO
3 -Meter 0.3～4.0 g/L;
Molybdate is with MoO
4 2-Meter 0.2～1.5 g/L;
Mn
2+ 1.0～4.5?g/L；
Ca
2+ 0.2～2.1?g/L；
Ba
2+ 0～1.5?g/L；
Sodium Benzoate 0.1～0.2 g/L or phenylformic acid 0.1～0.2 g/L or nickelous nitrate 1.0～1.5 g/L; Tartrate 0.1～1.5 g/L;
H
2O
2 0.1～2.0?g/L；
Hydrocerol A 0.0～1.5 g/L;
Sodium tetrafluoroborate 0.0～1.0 g/L;
Phytic acid 0.0～1.0 g/L;
Nonionogenic tenside (like TX-10, OP-10 or AEO-9) 0.0～1.0 g/L;
All the other are water;
Wherein, said phosphoric acid salt is manganese, calcium or the ammonium salt class of phosphoric acid; Said nitrate salt is manganese, calcium, barium or the ammonium salt class of nitric acid; Said molybdate is ammonium molybdate and Sodium orthomolybdate; The HLB value of said nonionogenic tenside is 8 ~ 16; The pH value of phosphatization liquid is 1.6～3.8 (generally adjusting with ammoniacal liquor).
Preferably, said each component of phosphatization liquid and content are:
Phosphoric acid and phosphoric acid salt are with PO
4 3-Meter 13.5～16.5 g/L;
Nitric acid and nitrate salt are with NO
3 -Meter 1.8～3.6 g/L;
Molybdate is with MoO
4 2-Meter 0.4～1.2 g/L;
Mn
2+ 2.5～3.5?g/L；
Ca
2+ 0.25～1.0?g/L；
Ba
2+ 0～1.2?g/L；
Sodium Benzoate 0.1～0.15 g/L;
Tartrate 0.1～0.2 g/L;
The H of mass percentage concentration 30%
2O
20～0.1 g/L;
Hydrocerol A 0.0～0.2 g/L;
Sodium tetrafluoroborate 0.0～0.1 g/L;
Phytic acid 0.0～0.3 g/L of mass percentage concentration 70%;
All the other are water;
The pH value is 2.4～2.9.
Production of products method of the present invention is: the above acid is dissolved in the tap water; The Industrial Salt of adding except that barium salt, Sodium Benzoate is like phosphoric acid salt, nitrate salt and molybdate etc., after the stirring and dissolving; Add residue reagent, adjust the pH value to requiring with ammoniacal liquor or industrial phosphoric acid after the stirring and dissolving.
Normal temperature manganese calcium series phosphatating liquid of the present invention is with PO
4 3-, Mn
2+, Ca
2+And from steel surface dissolved Fe
2+Be main film forming substance, with NO
3 -, molybdate is main accelerator, is SO in filmogen and the phosphatization liquid with the barium salt
4 2-The deposition remover, be fungistat with Sodium Benzoate or phenylformic acid or nickelous nitrate, other reagent (containing nickelous nitrate) mainly are the film forming properties that improves phosphatization liquid, the quality that improves phosphatize phosphate coat, realize that the workpiece after the phosphatization is exempted from washing.Phosphatization liquid contains manganese, calcium, the barium salt class of phosphoric acid, nitric acid or phosphoric acid and nitric acid; Molybdate; And tartrate, Hydrocerol A, ydrogen peroxide 50, phytic acid, Sodium Benzoate or phenylformic acid or nickelous nitrate, nonionogenic tenside (its HLB value is 8 ~ 16) etc., do not contain carcinogenic and decomposition generation toxic gas NO
xNitrite, do not contain deleterious Cr salt, also can not contain Zn, Ni salt.
Manganese calcium series phosphatating film, with traditional Zn system, Zn-Ca system, Zn-Mn system, ternary Zn-Ca-Mn be phosphatization (if carrying out phosphatization under Mn owner's medium and high temperature) ratio, have the good characteristics of alkali resistance.Zn is an amphoteric metal, promptly is dissolved in acid and also is dissolved in alkali, and its compound is acid and alkali-resistance not generally, and Mn, Ca all are insoluble to alkali, and its compound alkali resistance is better, and manganese calcium series phosphatating film alkali resistance is good.Electrocoating paint is alkalescence, and the phosphatize phosphate coat that is used for its bottom all requires alkali resistance good, otherwise in the process of electrophoresis japanning, phosphatize phosphate coat can be dissolved in paint film, the electrocoating paint, influences the performance of paint film, electrocoating paint.
Yet; Length has fungi in the phosphatization liquid of in research, industry process on probation, finding to put for a long time; This possibly be because under the specific multiple factor affecting of pH value, solution composition and weather; From some fungi in the environment in phosphatization liquid fast the breeding, forms transparent or colored flocculence be suspended in the phosphatization liquid or be deposited on bottom.Eubacteriales in the phosphatization liquid detects and shows and can see after, and when workpiece came out from phosphatization liquid, feel was like the phosphatize phosphate coat surface that the fungi crowd of oil can adhere to, and causes on it paint film property poor, even bubbles immediately, comes off, and is off quality.Though fungi can remove by filter, the speed of filtering the back breeding can be very fast.The present invention has produced beyond thought effect after in phosphatization liquid, having added fungistat,, no longer goes out to estimate the visible fungi in the phosphatization liquid that is, and the workpiece after the phosphatization can be realized spraying paint preferably, and paint film adhesion, impact resistance strengthen greatly.
At present, do not see that also appearance obviously influences the fungi of phosphatization quality and the report of removing method in the phosphatization liquid.
Product of the present invention handle to be recommended technical process to steel surface: steel surface degreasing → washing → degreasing is eliminated rust when rustless (surperficial can omit) → washing → phosphatization → drying.
Phosphorization film quality effect after phosphatization liquid of the present invention is handled on the workpiece is following:
1. phosphatize phosphate coat is continuous, even, fine and close, and alkali resistant erosion performance is good, and it is colored that the mass defect that allows invariably, outward appearance are;
2. the anti-corrosion time of phosphatize phosphate coat (the anti-3% sodium chloride solution corrosive time is by regulation obtain solution and the detection of GB/T 6807-2001) be 1.5 h (hour) above (GB/T 6807-2001 regulations should greater than 1 h).
3. checking the film of phosphatize phosphate coat by the regulation of GB/T 9792-1988 heavily is 0.7～1.8 g/m
2
4. with the matching performance of paint film: the regulation of pressing GB 1720-79 " paint film adhesion assay method " is measured the sticking power of iron red epoxy primer, all reaches 1 grade; The regulation of pressing GB/T 1732-1993 " the shock-resistant assay method of paint film " is measured the impact resistance behind the spraying iron red epoxy primer, reaches 50 kgcm (paint film is not broken through).
Compared with prior art, the beneficial effect of normal temperature manganese calcium series phosphatating liquid of the present invention is:
(l) the phosphatization liquid life-span long, fungus breeding can not take place and coating adhesion obviously reduces when causing phosphatize phosphate coat as the coating bottom problem in no waste water.
(2) the phosphatization quality is greatly improved, and the phosphatization mode is many, and phosphorization film quality surpasses the preceding phosphatization specification of quality of spraying of GB/T 6807-2001 regulations.Can adopt brush, soak, phosphatization mode such as spray carries out phosphatization.
(3) save energy adopts 5～45 ℃ (minimum 3 ℃) to soak phosphatization, farthest save energy and setup time.
(4) economical with materials.
(5) environmental protection and safe in utilization.
(6) simple to operate, the phosphating process controlled variable is wide, mode is many, and phosphatization liquid is stable; The phosphating time of spray phosphatization is 1 min～2 min more than 25 ℃, and the phosphating time that normal temperature soaks phosphatization down is that (phosphating time extends to 24 h to 5 min～15 min, and phosphorization film quality is also fine; Though the long phosphorization film quality that does not influence workpiece of phosphating time; But the life-span and the sediment that influence phosphatization liquid increase), phosphatization temperature is 3～45 ℃, the workpiece after the phosphatization is not washed and directly oven dry or seasoning.Can adopt the phosphatization mode for to brush, to soak, spray or its combination.
In a word; The invention provides a kind ofly can use at normal temperatures, not have before the phosphatization do not have the washing operation after surface adjustment operation, the phosphatization, easy and simple to handle, the life-span is long and effect is good, the manganese calcium of strong adhesion is environment-friendly phosphating solution,, water higher with the complex process, the phosphatization temperature that overcome conventional phosphatizing and phosphoric acid salt etc. consume problems such as big, that harmful waste water is many.The present invention is applicable to the preceding surface treatment of application of ferrous metal steel surface, and the phosphatize phosphate coat that is generated is used for the bottom as coating.
Embodiment
Be non-limiting examples of the present invention below, among the embodiment, test piece is the cold-reduced sheet of 100 mm * 70 mm * 1.0 mm, and phosphatization immediately after eliminating oil and clean with rust and with tap water with recommendation technology all obtains not having the colored phosphatize phosphate coat of mass defect.Anti-3% sodium chloride solution etching time is tested by 5.3 sections the regulation of GB/T 6807-2001.Measure behind the regulation spraying iron red epoxy primer of sticking power by GB 1720-79 " paint film adhesion assay method ".Measure behind the regulation spraying iron red epoxy primer of impact resistance by GB/T 1732-1993 " the shock-resistant assay method of paint film ".Percentage composition among the embodiment is the quality percentage composition.
(1) embodiment 1
Phosphoric acid (85%) 7.0 g/L, two hypophosphite monohydrate dihydro manganese, 14.5 g/L, manganese nitrate solution (50%) 5.0 g/L; Ammonium Molybdate Tetrahydrate 0.5 g/L, calcium nitrate tetrahydrate 1.5 g/L, Hydrocerol A 0.1 g/L; Sodium tetrafluoroborate 0.1 g/L, phytic acid (70%) 0.3 g/L, tartrate 0.1 g/L; Ydrogen peroxide 50 (30%) 0.1 g/L, Sodium Benzoate 0.1 g/L is with ammoniacal liquor adjustment pH value to 2.5 ~ 2.8.
Test piece is dipped in the phosphatization working fluid under above-mentioned 15 ℃; Take out behind 7 min at 120 ℃ and dry by the fire 10min down; The anti-3% sodium chloride solution etching time of colored phosphatize phosphate coat that generates is greater than 2 h, and iron red epoxy primer sticking power reaches 1 grade, and impulse withstand test reaches 50 kgcm (paint film is not broken through).
(2) embodiment 2
Phosphoric acid (85%) 5.5 g/L, two hypophosphite monohydrate dihydro manganese, 15.0 g/L, manganese nitrate solution (50%) 4.0 g/L; Ammonium Molybdate Tetrahydrate 0.9 g/L, calcium nitrate tetrahydrate 2.5 g/L, nitrate of baryta 1.2 g/L; Sodium tetrafluoroborate 0.1 g/L, Hydrocerol A 0.2 g/L, tartrate 0.1 g/L; Sodium Benzoate 0.1 g/L is with ammoniacal liquor adjustment pH value to 2.4 ~ 2.6.
Test piece is dipped in the phosphatization working fluid under above-mentioned 10 ℃, takes out seasoning 8 h behind 8 min, its effect is with embodiment 1.
(3) embodiment 3
Phosphoric acid (85%) 9.0 g/L, two hypophosphite monohydrate dihydro manganese, 11.3 g/L, calcium nitrate tetrahydrate 5.0 g/L; Ammonium Molybdate Tetrahydrate 1.2 g/L; Tartrate 0.2 g/L, phytic acid (70%) 0.2 g/L, ydrogen peroxide 50 (30%) 0.1 g/L; Sodium Benzoate 0.1 g/L is with ammoniacal liquor adjustment pH value to 2.6 ~ 2.9.
Test piece is dipped in the phosphatization working fluid under above-mentioned 20 ℃, takes out seasoning 8 h behind 6 min, its effect is with embodiment 1.
Claims (4)
1. a normal temperature manganese calcium series phosphatating liquid is characterized in that, said each component of phosphatization liquid and content are:
Phosphoric acid and phosphoric acid salt are with PO
4 3-Meter 8.5～21.0 g/L;
Nitric acid and nitrate salt are with NO
3 -Meter 0.3～4.0 g/L;
Molybdate is with MoO
4 2-Meter 0.2～1.5 g/L;
Mn
2+ 1.0～4.5?g/L；
Ca
2+ 0.2～2.1?g/L；
Ba
2+ 0～1.5?g/L；
Sodium Benzoate 0.1～0.2 g/L or phenylformic acid 0.1～0.2 g/L or nickelous nitrate 1.0～1.5 g/L;
Tartrate 0.1～1.5 g/L;
H
2O
2 0～2.0?g/L；
Hydrocerol A 0.0～1.5 g/L;
Sodium tetrafluoroborate 0.0～1.0 g/L;
Phytic acid 0.0～1.0 g/L;
Nonionogenic tenside 0.0～1.0 g/L;
All the other are water;
Wherein, said phosphoric acid salt is manganese, calcium or the ammonium salt class of phosphoric acid; Said nitrate salt is manganese, calcium, barium or the ammonium salt class of nitric acid; Said molybdate is ammonium molybdate and Sodium orthomolybdate; The HLB value of said nonionogenic tenside is 8 ~ 16.
2. manganese calcium series phosphatating liquid as claimed in claim 1 is characterized in that, said nonionogenic tenside is TX-10, OP-10 or AEO-9.
3. manganese calcium series phosphatating liquid as claimed in claim 1 is characterized in that, the pH value of said phosphatization liquid is 1.6～3.8.
4. manganese calcium series phosphatating liquid as claimed in claim 3 is characterized in that, said each component of phosphatization liquid and content are:
Phosphoric acid and phosphoric acid salt are with PO
4 3-Meter 13.5～16.5 g/L;
Nitric acid and nitrate salt are with NO
3 -Meter 1.8～3.6 g/L;
Molybdate is with MoO
4 2-Meter 0.4～1.2 g/L;
Mn
2+ 2.5～3.5?g/L；
Ca
2+ 0.25～1.0?g/L；
Ba
2+ 0～1.2?g/L；
Sodium Benzoate 0.1～0.15 g/L;
Tartrate 0.1～0.2 g/L;
The H of mass percentage concentration 30%
2O
20～0.1 g/L;
Hydrocerol A 0.0～0.2 g/L;
Sodium tetrafluoroborate 0.0～0.1 g/L;
Phytic acid 0.0～0.3 g/L of mass percentage concentration 70%;
All the other are water;
The pH value is 2.4～2.9.
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|---|---|---|---|
| CN201210265705.7A CN102747356B (en) | 2012-07-30 | 2012-07-30 | Normal temperature calcium-manganese phosphorizing liquid |
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|---|---|---|---|
| CN201210265705.7A CN102747356B (en) | 2012-07-30 | 2012-07-30 | Normal temperature calcium-manganese phosphorizing liquid |
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|---|---|---|---|---|
| CN103966588A (en) * | 2014-05-15 | 2014-08-06 | 清华大学 | Strip hot-rolling reinforcing steel bar pre-passivation liquid as well as using method and pre-passivated strip hot-rolling reinforcing steel bar |
| CN104294246A (en) * | 2014-10-29 | 2015-01-21 | 合肥市华阳工程机械有限公司 | High-temperature phosphating solution for surface treatment on rails |
| CN104313561A (en) * | 2014-10-29 | 2015-01-28 | 合肥市华阳工程机械有限公司 | Surface treatment phosphatizing agent for building sectional material |
| CN104451642A (en) * | 2014-12-23 | 2015-03-25 | 常熟市宏福塑料金属制品有限公司 | Surface treatment process for radiator shell metal stamping piece |
| CN107893224A (en) * | 2017-12-14 | 2018-04-10 | 马鞍山新徽铝业有限公司 | A kind of diel alramenting liquid |
| WO2018218436A1 (en) * | 2017-05-27 | 2018-12-06 | 深圳市恒兆智科技有限公司 | Modified phosphating agent, metal component, and surface phosphating treatment method therefor |
| CN111286728A (en) * | 2020-03-30 | 2020-06-16 | 沈阳理工大学 | Phosphating solution, phosphate coating, preparation method and application thereof |
| CN112795910A (en) * | 2020-12-25 | 2021-05-14 | 瑞声科技（南京）有限公司 | Temperature-equalizing plate manufacturing method and temperature-equalizing plate |
| CN113088946A (en) * | 2021-03-12 | 2021-07-09 | 浙江美力科技股份有限公司 | Pretreatment process for coating zinc-aluminum coating on non-shot-blasting workpiece |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103966588A (en) * | 2014-05-15 | 2014-08-06 | 清华大学 | Strip hot-rolling reinforcing steel bar pre-passivation liquid as well as using method and pre-passivated strip hot-rolling reinforcing steel bar |
| CN104294246A (en) * | 2014-10-29 | 2015-01-21 | 合肥市华阳工程机械有限公司 | High-temperature phosphating solution for surface treatment on rails |
| CN104313561A (en) * | 2014-10-29 | 2015-01-28 | 合肥市华阳工程机械有限公司 | Surface treatment phosphatizing agent for building sectional material |
| CN104451642A (en) * | 2014-12-23 | 2015-03-25 | 常熟市宏福塑料金属制品有限公司 | Surface treatment process for radiator shell metal stamping piece |
| WO2018218436A1 (en) * | 2017-05-27 | 2018-12-06 | 深圳市恒兆智科技有限公司 | Modified phosphating agent, metal component, and surface phosphating treatment method therefor |
| CN110691863A (en) * | 2017-05-27 | 2020-01-14 | 深圳市恒兆智科技有限公司 | Modified phosphating agent, metal piece and surface phosphating method thereof |
| CN107893224A (en) * | 2017-12-14 | 2018-04-10 | 马鞍山新徽铝业有限公司 | A kind of diel alramenting liquid |
| CN111286728A (en) * | 2020-03-30 | 2020-06-16 | 沈阳理工大学 | Phosphating solution, phosphate coating, preparation method and application thereof |
| CN112795910A (en) * | 2020-12-25 | 2021-05-14 | 瑞声科技（南京）有限公司 | Temperature-equalizing plate manufacturing method and temperature-equalizing plate |
| CN113088946A (en) * | 2021-03-12 | 2021-07-09 | 浙江美力科技股份有限公司 | Pretreatment process for coating zinc-aluminum coating on non-shot-blasting workpiece |
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