CN116607138A - Normal-temperature zinc phosphating solution, preparation method thereof and phosphating method - Google Patents
Normal-temperature zinc phosphating solution, preparation method thereof and phosphating method Download PDFInfo
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- CN116607138A CN116607138A CN202310513312.1A CN202310513312A CN116607138A CN 116607138 A CN116607138 A CN 116607138A CN 202310513312 A CN202310513312 A CN 202310513312A CN 116607138 A CN116607138 A CN 116607138A
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- Prior art keywords
- phosphating
- normal
- zinc
- film
- temperature
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000011701 zinc Substances 0.000 title claims abstract description 29
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims description 19
- 238000002360 preparation method Methods 0.000 title claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 22
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims abstract description 20
- 239000000654 additive Substances 0.000 claims abstract description 13
- 230000000996 additive effect Effects 0.000 claims abstract description 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 11
- 239000011787 zinc oxide Substances 0.000 claims abstract description 11
- 239000011775 sodium fluoride Substances 0.000 claims abstract description 10
- 235000013024 sodium fluoride Nutrition 0.000 claims abstract description 10
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 9
- 235000015393 sodium molybdate Nutrition 0.000 claims abstract description 9
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000001737 promoting effect Effects 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 238000013329 compounding Methods 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 abstract description 17
- 238000005260 corrosion Methods 0.000 abstract description 17
- 230000002829 reductive effect Effects 0.000 abstract description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000002411 adverse Effects 0.000 abstract description 3
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 3
- 230000004630 mental health Effects 0.000 abstract description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- 230000001988 toxicity Effects 0.000 abstract description 3
- 231100000419 toxicity Toxicity 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 48
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 23
- 229910019142 PO4 Inorganic materials 0.000 description 11
- 235000021317 phosphate Nutrition 0.000 description 11
- 229910052742 iron Inorganic materials 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 10
- 239000010452 phosphate Substances 0.000 description 10
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 7
- 239000003973 paint Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000009472 formulation Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910000365 copper sulfate Inorganic materials 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 4
- 229910000165 zinc phosphate Inorganic materials 0.000 description 4
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 229910001437 manganese ion Inorganic materials 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229910001453 nickel ion Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- SCYYUUINVKYGRP-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Zn+2].[Mn+2] Chemical compound P(=O)([O-])([O-])[O-].[Zn+2].[Mn+2] SCYYUUINVKYGRP-UHFFFAOYSA-K 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- MFXMOUUKFMDYLM-UHFFFAOYSA-L zinc;dihydrogen phosphate Chemical compound [Zn+2].OP(O)([O-])=O.OP(O)([O-])=O MFXMOUUKFMDYLM-UHFFFAOYSA-L 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- JBMRMLLHFBHFDV-UHFFFAOYSA-N [Ni].[Mn].[Zn] Chemical compound [Ni].[Mn].[Zn] JBMRMLLHFBHFDV-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- LZMCUTZPLPUFMB-UHFFFAOYSA-L dihydroxy(oxo)manganese Chemical compound O[Mn](O)=O LZMCUTZPLPUFMB-UHFFFAOYSA-L 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 1
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 description 1
- 230000028161 membrane depolarization Effects 0.000 description 1
- 150000007522 mineralic acids Chemical group 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 235000012736 patent blue V Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- AIBXSHVSHIGKQQ-UHFFFAOYSA-K zinc;nickel(2+);phosphate Chemical compound [Ni+2].[Zn+2].[O-]P([O-])([O-])=O AIBXSHVSHIGKQQ-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The embodiment of the invention discloses a normal-temperature zinc phosphating solution, which is characterized by comprising the following components in per liter: 15-25g of zinc oxide; 40-60g of phosphoric acid; 0.8-1.2g of sodium fluoride; 0.6-1.2g of sodium molybdate; 30-40g of a composite promoting additive HN; also comprises clean water. The normal temperature zinc phosphating liquid film layer is equal to the high temperature phosphating film layer in the aspects of appearance, corrosion resistance and the like, and can completely ensure the product technical index requirements in the mine production process. Can be directly applied to the part processing of various army and civil products; the normal-temperature zinc phosphating solution is a water-soluble system, does not contain formaldehyde, benzene, heavy metals and other harmful substances, and is beneficial to environmental protection and physical and mental health of operators; the wastewater treatment cost and consumption are reduced, the emission and toxicity of wastes are reduced, and the adverse effect of the whole life cycle of parts on the environment is reduced; the obtained phosphating film has the advantages of uniformity, strong corrosion resistance and good application prospect in the field of military and civil products.
Description
Technical Field
The invention relates to the field of metal phosphating, in particular to a normal-temperature zinc phosphating solution, a preparation method thereof and a phosphating method.
Background
The metal is immersed in the phosphating salt solution, and after chemical reaction, a phosphate conversion film which is difficult to dissolve in water is obtained on the surface of the metal part, and the process is called phosphating treatment. The purpose of phosphating is to prevent rust between working procedures before coating, and simultaneously enhance the adhesive force between a metal workpiece substrate and a paint film and improve the corrosion resistance of the metal workpiece.
The traditional phosphating process adopts high-temperature and medium-temperature phosphating processes, and the phosphating processes have the problems of long treatment process route, narrow process technical parameter range, complicated tank liquor maintenance, and often containing harmful substances such as chromium, nitrite and the like, thereby being unfavorable for environmental protection.
In view of the above problems in the prior art, no effective solution exists at present.
Disclosure of Invention
In order to solve the problems, the invention provides a normal-temperature zinc phosphating solution, a preparation method thereof and a phosphating method, wherein phosphating is carried out under normal-temperature conditions, so that the power consumption is reduced, the maintenance of bath solution is simple, and the environment is protected.
The invention provides a normal-temperature zinc phosphating solution, which comprises the following components in per liter:
also comprises clean water.
Further optionally, the compounding promoting additive HN comprises per liter:
also comprises clean water.
Further alternatively, the temperature value of the phosphating solution is 18-30 ℃.
On the other hand, the invention also provides a phosphating method, which adopts the normal-temperature zinc phosphating solution to carry out phosphating on metal, wherein the phosphating time is 18-25min.
A preparation method of a normal-temperature zinc phosphating solution comprises the following steps: injecting clean water into the phosphating tank to 60% of the volume of the phosphating tank; mixing 8% zinc oxide with deionized water to form paste, and slowly adding the paste into the phosphating tank under continuous stirring; 10% of nitric acid, 12% of phosphoric acid, 3% of sodium fluoride, 3% of sodium molybdate and 6% of composite accelerator additive HN are sequentially added under continuous stirring, and after all chemical reagents are dissolved, clear water is added to a preset volume and stirred uniformly.
The technical scheme has the following beneficial effects: the normal temperature zinc phosphating liquid film layer is equal to the high temperature phosphating film layer in the aspects of appearance, corrosion resistance and the like, and can completely ensure the product technical index requirements in the mine production process. Can be directly applied to the part processing of various army and civil products;
the normal-temperature zinc phosphating solution is a water-soluble system, does not contain formaldehyde, benzene, heavy metals and other harmful substances, and is beneficial to environmental protection and physical and mental health of operators;
the wastewater treatment cost and consumption are reduced, the emission and toxicity of wastes are reduced, and the adverse effect of the whole life cycle of parts on the environment is reduced;
the obtained phosphating film has the advantages of uniformity, strong corrosion resistance and good application prospect in the field of military and civil products.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a preparation method of a normal temperature zinc-based phosphating solution provided by an embodiment of the invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The current prior art is: normal temperature iron phosphating solution, medium temperature zinc phosphating solution, ternary phosphating, multi-metal iron phosphating solution, corrosion-resistant zinc-manganese phosphating solution, medium temperature drawing phosphating solution, zinc-calcium phosphating solution, four-in-one phosphating solution, nitrate phosphating solution and the like.
In the traditional phosphating solution formula, the accelerator such as nitrite and nitrate is usually added, the accelerator can accelerate the film forming speed of the phosphating solution, but the accelerator can not be completely consumed in the oxidation-reduction process, and the rest nitrite and nitrate are reduced to nitric oxide and nitrogen dioxide to enter the air, so that the environment is polluted.
The phosphate solution of low acidity alkali metal or ammonia containing various accelerators in the iron-based phosphating solution forms a phosphating film by the dissolved metal ions themselves, which is basically an amorphous film, which we call iron-based phosphating. This type of phosphating film is generally a very good substrate for painting steel parts. The film is plastic, and as a coil pipe paint pretreatment, the paint film will not crack when formed. However, iron-based phosphating films have low corrosion resistance compared to other types of phosphating films. Therefore, such a phosphate film is not used in an outdoor environment or under heavy load application conditions.
Another type of phosphating is salts containing divalent metal ions and forming insoluble phosphates on the metal surface, and is widely used in the production of zinc phosphate, manganese phosphate, zinc-nickel, zinc-calcium, zinc-manganese-nickel, and the like. The amount of manganese ions and nickel ions added into the zinc-based phosphating solution is small at the beginning, so as to improve the protection performance of the phosphating film, but in order to improve the alkali resistance of the phosphating film, particularly in cathode electrophoretic painting and coating used under severe conditions, the content of manganese ions and nickel ions in the modern zinc-based phosphating solution exceeds the content of zinc ions, namely the content of manganese ions, nickel ions and the like in the zinc-based phosphating solution is improved from the original second cations to first cations, namely ternary phosphating or polycrystal phosphating. The film of manganous acid and zinc-manganese phosphate has high hardness and is used as a carrier of lubricant for lubrication friction. Zinc phosphate, manganate, zinc-nickel phosphate and zinc-manganese phosphate films are all more or less coarse crystalline structures, and while coarse crystals may absorb more lubricant or rust inhibitive oil is advantageous in some lubrication and protection applications, it is often disadvantageous for most other applications, particularly as a base layer for paints. In this case, this will result in a greater amount of paint than is used on the iron-based phosphating film. A further problem is that the coated metal parts cannot be bent and deformed more. Because bending or deforming it will result in a loss of paint film cohesion, due to the coarser crystallization of the second type of phosphating film than the iron-based phosphating film.
In order to solve the problems, the invention provides a normal-temperature zinc phosphating solution, which comprises the following components in per liter:
also comprises clean water.
The film forming agent is one or more of zinc phosphate, calcium phosphate salt, light zinc carbonate and light calcium carbonate, and zinc is used as the main film forming agent, so that the crystalline structure of the film can be improved, the adhesive force of the film can be improved, and the film is compact, uniform and high in corrosion resistance. Zinc oxide is used as a main film forming substance and forms zinc dihydrogen phosphate with phosphoric acid, so that a zinc phosphate type phosphating film is formed, and meanwhile, the crystallization of the phosphating film can be fine.
The accelerator has the function of oxidizing substance H 2 Oxidation to H 2 O, accelerating the depolarization of the cathode, improving the current density of the micro-cell and accelerating the phosphating; fe of 2+ Oxidation to Fe 3+ The accumulation of byproducts is prevented, the progress of phosphating is prevented, and the quality of a phosphating film is improved; the metal ion accelerator is a metal salt with potential more positive than that of iron, can not perform displacement reaction with the iron, is deposited on the surface of the iron under the chemical action of the solution to form an iron-noble metal primary cell, plays a role of a cathode, generates a large number of new crystal nuclei and improves the corrosion resistance. The accelerator needs to have a certain dosage, if the dosage is insufficient, the phosphating reaction is slow, the crystallization is coarse, and the film is incomplete; excessive use of Fe in the solution 2+ All oxidized to Fe 3+ A large amount of precipitation is generated, even the metal surface is passivated, and a phosphating film is difficult to generate. Sodium fluoride is one of the accelerators, and citric acid has better composite addition effect as the accelerator.
The activator is an inorganic acid or salt such as one or more of sodium phosphate, phosphoric acid, and oleate. The activator accelerates phosphating speed, refines grains and forms a compact low-pore film. Phosphoric acid is an indispensable component for normal-temperature phosphating, and plays a role in reacting with zinc oxide to generate zinc dihydrogen phosphate, reducing the pH value of phosphating solution, increasing the pH value of a solid/liquid interface, promoting the hydrolysis or rearrangement of dihydrogen phosphate to generate insoluble phosphate to deposit on the cathode surface of a battery to form a phosphate film.
The passivating agent (calcium agent) is at least one of molybdate, acetate and phosphate. The effect is to effectively seal micropores in the formed phosphating film, make the film layer compact and improve the corrosion resistance.
The complex promoting additive is a metal salt, typically a nitrate, added to the phosphating solution. The effect of the composite addition of ions of various technologies is to keep proper concentration of ions of the technologies, accelerate phosphating and facilitate crystal nucleus generation and grain refinement.
Further optionally, the compounding promoting additive HN comprises per liter:
also comprises clean water.
Further alternatively, the temperature value of the phosphating solution is 18-30 ℃.
The phosphating temperature is also one of the only factors affecting the surface quality and corrosion resistance of the phosphating film. When the temperature is raised to 18-30 ℃, the copper sulfate drip resistant time of the phosphating film is obviously increased, and when the temperature reaches 30 ℃, the corrosion resistance is reduced. When the temperature is too low, the generation rate of the phosphating film is low, the phosphating film on the surface of the steel part is uneven, and the defects of partial exposure and the like are overcome; after the temperature is gradually increased, the mass concentration of film forming ions is increased, the growth rate of nucleation nuclei of the phosphate film is accelerated, the generation of the phosphate film is promoted, and when the temperature is too high, the film forming rate is accelerated, but residues are easy to generate in the phosphate solution, and the generated phosphate film becomes loose and porous, so that the corrosion resistance is reduced. Therefore, the temperature of the phosphating solution is suitably 18-30 ℃.
On the other hand, the invention also provides a phosphating method, which adopts the normal-temperature zinc phosphating solution to carry out phosphating on metal, wherein the phosphating time is 18-25min.
The phosphating time is too short, the film forming amount is insufficient, and a compact phosphating film reaching a specified film thickness cannot be formed. As the phosphating time increases, the phosphating film becomes thicker and the copper sulfate drip time increases. After phosphating for about 18min, the copper sulfate resistant drip time is stabilized at about 150s, and the film thickness tends to be stable; after phosphating for about 25min, the copper sulfate resistance drop time tends to decrease. This is because if the phosphating time is too long, continued crystallization on the film formed will result in a loose phosphating film, which directly affects the adhesion of the paint layer. The suitable phosphating time is thus determined to be 18 to 25 minutes.
The test method after phosphating comprises the following steps:
1. appearance test
After the phosphating film is washed and dried, whether the surface color of the phosphating film is uniform and smooth or not and whether the defects of metal white, rust, dust scraping and the like exist or not are observed by naked eyes.
2. Determination of Corrosion resistance
The process was carried out by the copper sulphate dropping method according to GB/T6807-1986. At 15-25 ℃,1 drop of the detection solution of the cupric sulfate pentahydrate is dripped on the phosphating surface, a stopwatch is started at the same time, and the time for the dripping liquid to turn from sky blue to light red is observed and recorded. The longer the time, the better the corrosion resistance.
In the first embodiment, the phosphating solution prepared by the above formula is subjected to orthogonal test experiments as shown in tables 1 and 2:
TABLE 1 orthogonal test factor-level table
TABLE 2 orthogonal experimental protocol
TABLE 3 Table of Performance parameters of phosphating films of each group
In Table 3, the appearance of the phosphated film was 10 minutes, and the appearance was classified into excellent (10 minutes), excellent (9 minutes), middle (8 minutes) and the rest (7 minutes) according to the visual effect after the phosphation.
And (5) comprehensive assessment: multiplying the data of each performance by the weight of each performance, and adding to obtain comprehensive evaluation scores. Here, the importance of the film weight is indicated by placing the result of the film weight of the phosphating layer at the most important position and the weight of the phosphating layer at 70%. Let the composite score be M i M is then i = (film weight) ×70++ (copper sulfate drip time) ×15++ (immersion time) ×15%. Wherein M is i The larger the number, the higher the score and the better the quality.
Table 4 table of analysis for orthogonal test
From the experimental results of Table 4, experiment 7 (A 3 B 1 C 3 D 2 ) The phosphating solution comprises 40g of zinc oxide and phosphoric acid, 3.6g of sodium fluoride and sodium molybdate, 35g of a compound accelerating additive, and the phosphating time is 25min, and specifically can be 10g of zinc oxide, 30g of phosphoric acid, 1.8g of sodium fluoride, 1.8g of sodium molybdate, 35g of a compound accelerating additive HN and 25min.
In addition, there are other phosphating solution formulation choices, base formulation one:
the weight of the phosphated film obtained according to the above formulation is shown in Table 5:
table 5 film weight of phosphated film at one base formulation two:
the weight of the phosphated film obtained according to the above formulation is shown in Table 6:
TABLE 6 film weight of phosphating film at base formulation two times
As an alternative implementation manner, the embodiment of the present invention further provides a method for preparing a normal-temperature zinc-based phosphating solution, and fig. 1 is a flowchart of the method for preparing a normal-temperature zinc-based phosphating solution provided by the embodiment of the present invention, as shown in fig. 1, where the method includes:
s1, injecting clear water into a phosphating tank to 60% of the volume of the phosphating tank;
s2, 8% of zinc oxide is mixed into paste by deionized water, and the paste is slowly added into a phosphating tank under continuous stirring; 10% of nitric acid, 12% of phosphoric acid, 3% of sodium fluoride, 3% of sodium molybdate and 6% of composite accelerator additive HN are sequentially added under continuous stirring, and after all chemical reagents are dissolved, clear water is added to a preset volume and stirred uniformly.
Wherein, the reference composite accelerator HN dosage of 20 kg solution is prepared: 100-120g at 0-5 ℃; 90g at 10 ℃; 80g at 20 ℃; 40-50g at 25-30 ℃.
Specific embodiment II:
injecting clean water into the phosphating tank to 60% of the volume of the phosphating tank; mixing 8% zinc oxide with deionized water to form paste, and slowly adding into a phosphating tank under continuous stirring; 10% of nitric acid, 12% of phosphoric acid, 3% of sodium fluoride, 3% of sodium molybdate and 6% of composite accelerator additive HN are sequentially added under continuous stirring, and after all chemical reagents are dissolved, clear water is added to a preset volume and stirred uniformly. Specifically, the amount of each component added is as follows, based on the amount of 1L solution:
the balance of clear water.
Third embodiment:
injecting clean water into the phosphating tank to 60% of the volume of the phosphating tank; mixing 8% zinc oxide with deionized water to form paste, and slowly adding into a phosphating tank under continuous stirring; 10% of nitric acid, 12% of phosphoric acid, 3% of sodium fluoride, 3% of sodium molybdate and 6% of composite accelerator additive HN are sequentially added under continuous stirring, and after all chemical reagents are dissolved, clear water is added to a preset volume and stirred uniformly. Specifically, the amount of each component added is as follows, based on the amount of 1L solution:
the balance of clear water.
Fourth embodiment:
injecting clean water into the phosphating tank to 60% of the volume of the phosphating tank; mixing 8% zinc oxide with deionized water to form paste, and slowly adding into a phosphating tank under continuous stirring; 10% of nitric acid, 12% of phosphoric acid, 3% of sodium fluoride, 3% of sodium molybdate and 6% of composite accelerator additive HN are sequentially added under continuous stirring, and after all chemical reagents are dissolved, clear water is added to a preset volume and stirred uniformly. Specifically, the amount of each component added is as follows, based on the amount of 1L solution:
the balance of clear water.
The technical scheme has the following beneficial effects: the normal temperature zinc phosphating liquid film layer is equal to the high temperature phosphating film layer in the aspects of appearance, corrosion resistance and the like, and can completely ensure the product technical index requirements in the mine production process. Can be directly applied to the part processing of various army and civil products;
the normal-temperature zinc phosphating solution is a water-soluble system, does not contain formaldehyde, benzene, heavy metals and other harmful substances, and is beneficial to environmental protection and physical and mental health of operators;
the wastewater treatment cost and consumption are reduced, the emission and toxicity of wastes are reduced, and the adverse effect of the whole life cycle of parts on the environment is reduced;
the obtained phosphating film has the advantages of uniformity, strong corrosion resistance and good application prospect in the field of military and civil products.
The foregoing description of the embodiments of the present invention further provides a detailed description of the objects, technical solutions and advantages of the present invention, and it should be understood that the foregoing description is only illustrative of the embodiments of the present invention and is not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements, etc. that fall within the spirit and principles of the present invention should be included in the scope of the present invention.
Claims (5)
1. The normal-temperature zinc phosphating solution is characterized by comprising the following components in per liter:
2. the normal temperature zinc-based phosphating solution according to claim 1, wherein the compounding promoting additive HN per liter includes:
3. the room temperature zinc-based phosphating solution according to claim 1, wherein:
the temperature value of the phosphating solution is 18-30 ℃.
4. A phosphating method, characterized in that the normal temperature zinc phosphating solution according to any one of claims 1 to 3 is adopted to carry out phosphating on metal, and the phosphating time is 18 to 25min.
5. The preparation method of the normal-temperature zinc phosphating solution is characterized by comprising the following steps:
injecting clean water into the phosphating tank to 60% of the volume of the phosphating tank;
mixing 8% zinc oxide with deionized water to form paste, and slowly adding the paste into the phosphating tank under continuous stirring;
10% of nitric acid, 12% of phosphoric acid, 3% of sodium fluoride, 3% of sodium molybdate and 6% of composite accelerator additive HN are sequentially added under continuous stirring, and after all chemical reagents are dissolved, clear water is added to a preset volume and stirred uniformly.
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| CN119243137A (en) * | 2024-12-03 | 2025-01-03 | 安徽华威铜箔科技有限公司 | Solution for preparing carrier copper foil peeling layer and method for preparing carrier copper foil peeling layer |
| CN119243137B (en) * | 2024-12-03 | 2025-04-15 | 安徽华威铜箔科技有限公司 | Solution for preparing carrier copper foil peeling layer and method for preparing carrier copper foil peeling layer |
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| CN119243137A (en) * | 2024-12-03 | 2025-01-03 | 安徽华威铜箔科技有限公司 | Solution for preparing carrier copper foil peeling layer and method for preparing carrier copper foil peeling layer |
| CN119243137B (en) * | 2024-12-03 | 2025-04-15 | 安徽华威铜箔科技有限公司 | Solution for preparing carrier copper foil peeling layer and method for preparing carrier copper foil peeling layer |
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