CN104357825A - Tinned steel plate surface treatment solution and preparation method thereof - Google Patents
Tinned steel plate surface treatment solution and preparation method thereof Download PDFInfo
- Publication number
- CN104357825A CN104357825A CN201410650819.2A CN201410650819A CN104357825A CN 104357825 A CN104357825 A CN 104357825A CN 201410650819 A CN201410650819 A CN 201410650819A CN 104357825 A CN104357825 A CN 104357825A
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- China
- Prior art keywords
- surface treatment
- plate surface
- sodium
- tin plate
- treatment liquid
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- 238000004381 surface treatment Methods 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910000831 Steel Inorganic materials 0.000 title abstract description 4
- 239000010959 steel Substances 0.000 title abstract description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 57
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000003756 stirring Methods 0.000 claims abstract description 35
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 21
- 239000011591 potassium Substances 0.000 claims abstract description 21
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 20
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims abstract description 20
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 20
- 239000011734 sodium Substances 0.000 claims abstract description 20
- FENRSEGZMITUEF-ATTCVCFYSA-E [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].OP(=O)([O-])O[C@@H]1[C@@H](OP(=O)([O-])[O-])[C@H](OP(=O)(O)[O-])[C@H](OP(=O)([O-])[O-])[C@H](OP(=O)(O)[O-])[C@H]1OP(=O)([O-])[O-] Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].OP(=O)([O-])O[C@@H]1[C@@H](OP(=O)([O-])[O-])[C@H](OP(=O)(O)[O-])[C@H](OP(=O)([O-])[O-])[C@H](OP(=O)(O)[O-])[C@H]1OP(=O)([O-])[O-] FENRSEGZMITUEF-ATTCVCFYSA-E 0.000 claims abstract description 19
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 19
- 229940083982 sodium phytate Drugs 0.000 claims abstract description 19
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000005028 tinplate Substances 0.000 claims description 52
- 239000007788 liquid Substances 0.000 claims description 40
- 229910019142 PO4 Inorganic materials 0.000 claims description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 20
- 239000010452 phosphate Substances 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- GEIAQOFPUVMAGM-UHFFFAOYSA-N Oxozirconium Chemical compound [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 18
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 claims description 18
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 18
- 235000019800 disodium phosphate Nutrition 0.000 claims description 18
- 239000001488 sodium phosphate Substances 0.000 claims description 18
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 18
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 18
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 18
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 13
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 239000011572 manganese Substances 0.000 claims description 8
- 239000003973 paint Substances 0.000 abstract description 10
- 230000007797 corrosion Effects 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 8
- 238000002161 passivation Methods 0.000 abstract description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 abstract description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract 2
- NAAXGLXYRDSIRS-UHFFFAOYSA-L dihydrogen phosphate;manganese(2+) Chemical compound [Mn+2].OP(O)([O-])=O.OP(O)([O-])=O NAAXGLXYRDSIRS-UHFFFAOYSA-L 0.000 abstract 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 abstract 2
- 229940048086 sodium pyrophosphate Drugs 0.000 abstract 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 abstract 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 abstract 2
- 230000000593 degrading effect Effects 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 238000005987 sulfurization reaction Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- VLSOAXRVHARBEQ-UHFFFAOYSA-N [4-fluoro-2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(F)C=C1CO VLSOAXRVHARBEQ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- DGLRDKLJZLEJCY-UHFFFAOYSA-L disodium hydrogenphosphate dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].OP([O-])([O-])=O DGLRDKLJZLEJCY-UHFFFAOYSA-L 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- -1 phosphorus compound Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 238000009736 wetting Methods 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
- C23C22/46—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 oxalates
- C23C22/47—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 oxalates containing also phosphates
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 invention discloses a tinned steel plate surface treatment solution and a preparation method thereof. The surface treatment solution contains 2-25 g/L disodium hydrogen phosphate, 2-13 g/L sodium pyrophosphate, 1-15 g/L ammonium hydrofluotitanate, 1-10 g/L potassium fluosilicate, 2-14 g/L nickel nitrate, 1-12 g/L zirconium titanate, 1-10 g/L sodium metaaluminate, 5-12 g/L manganese dihydrogen phosphate, 2-5 g/L sodium phytate and 1-7 g/L oxalic acid. The preparation method comprises the following steps: a. adding the disodium hydrogen phosphate and sodium pyrophosphate into deionized water, and stirring; b. adding the ammonium hydrofluotitanate, potassium fluosilicate, nickel nitrate, zirconium titanate, sodium metaaluminate and manganese dihydrogen phosphate; and c. regulating the pH value of the solution to 3-5 with phosphoric acid. On the basis of chromium-free passivation, the surface treatment solution ensures the corrosion resistance of the tinned plate without degrading the sulfur resistance, and also has excellent paint adhesiveness.
Description
Technical field
The present invention relates to the technical field of surface of steel plate, particularly a kind of tin plate surface treatment liquid and preparation method thereof.
Background technology
Tin plate is zinc-plated on steel sheet and product that is that make, and tin plate has good performance as a kind of metal packing material, and its feature comprises 1, nontoxic, and tin layers itself is harmless, and it is very safe to make food product pack; 2, appearance is beautiful, is easy to appearance and covers with paint, lacquer, colour wash, etc. and printing; 3, tin itself has good solidity to corrosion, and protection matrix prevents from being corroded; 4, tin-welding is good, is easily made into container; 5, tin has good ductility, oilness, can stand harsh processing; 6, tin layers is soft, and tin coating can not split, and also can not come off.
But tin plate does not carry out special chemical treatment, in atmosphere easy oxidation discoloration, and in special food, due to the raw black change of the sulphur sell of one's property.Therefore need to process tin plate, current process is the tunicle carrying out flooding or electrolysis treatment generates in chromic acid or chromate treating solution mostly, effectively can prevent the growth of tin-oxide, thus impart the excellent erosion resistance of tin plate, sulfuration resistant spot, also there are excellent coating wettability, paint film tack and processing characteristics etc. simultaneously.But containing to the disadvantageous chromium of environment in this treatment solution, and in production process, chromate waste water handling procedure is complicated and cost is higher, therefore, from environmental safety angle, should be replaced.
More and more higher for the requirement of tin plate chromium-free treating liquid at present, only can not require it not containing the chromium be harmful to environment and human body, and need to ensure that the tin plate after using this treatment solution Passivation Treatment has excellent corrosion resistance nature, sulfuration resistant performance and Paint Adhesion energy.
Application number be 200810035058.4 patent discloses a kind of surface treatment liquid for tin plate, be wherein selected from one or more compounds in molybdenum, zirconium, titanium, manganese or tungsten metallization compound containing the phosphorus compound of 1-50g/L, the vanadium compound of 1-20g/L, 1-30g/L, one or more compounds that 1-10g/L has at least one functional group in hydroxyl, carbonyl, carboxyl or phosphate.Although not containing chromium in its moiety, the corrosion resistance nature of tin plate after treatment, sulfuration resistant performance and Paint Adhesion can also improve further again.
Summary of the invention
The object of the invention is in order to overcome above the deficiencies in the prior art provide a kind of not containing chromium and tin plate corrosion resistance nature, sulfuration resistant performance and Paint Adhesion after treated liquid process can be excellent tin plate surface treatment liquid and preparation method thereof.
A kind of tin plate surface treatment liquid of the present invention contains: 2-25g/L Sodium phosphate dibasic, 2-13g/L trisodium phosphate, 1-15g/L ammonium titanium fluoride, 1-10g/L potassium silicofluoride, 2-14g/L nickelous nitrate, 1-12g/L metatitanic acid oxygen zirconium, 1-10g/L sodium metaaluminate, 5-12g/L phosphate dihydrogen manganese, 2-5g/L sodium phytate and 1-7g/L oxalic acid.
Preferably, a kind of tin plate surface treatment liquid contains: 5-15g/L Sodium phosphate dibasic, 4-10g/L trisodium phosphate, 3-10g/L ammonium titanium fluoride, 5-7g/L potassium silicofluoride, 5-10g/L nickelous nitrate, 4-8g/L metatitanic acid oxygen zirconium, 2-8g/L sodium metaaluminate, 7-9g/L phosphate dihydrogen manganese, 3-4g/L sodium phytate and 2-5g/L oxalic acid.
Preferred, a kind of tin plate surface treatment liquid contains: 10g/L Sodium phosphate dibasic, 9g/L trisodium phosphate, 7g/L ammonium titanium fluoride, 6g/L potassium silicofluoride, 7g/L nickelous nitrate, 5g/L metatitanic acid oxygen zirconium, 6.5g/L sodium metaaluminate, 8g/L phosphate dihydrogen manganese, 3.5g/L sodium phytate and 4g/L oxalic acid.
A preparation method for tin plate surface treatment liquid, comprises the following steps:
A, take moiety respectively, first Sodium phosphate dibasic, trisodium phosphate are joined in deionized water and stirred, controlling stirring velocity is that 60-80 turns/min, to dissolving completely;
Add ammonium titanium fluoride, potassium silicofluoride, nickelous nitrate, metatitanic acid oxygen zirconium, sodium metaaluminate and phosphate dihydrogen manganese in b, the solution that obtains to step a again, then stir, controlling stirring velocity is that 40-50 turns/min, to dissolving completely;
C, finally add sodium phytate and oxalic acid, stirring and dissolving evenly uses phosphoric acid regulator solution pH value to 3-5 afterwards, obtains tin plate surface treatment liquid.
Preferably, the control stirring velocity described in step a is that 65-75 turns/min.
Preferably, the control stirring velocity described in step a is 70 turns/min.
Preferably, the control stirring velocity described in step b is 45 turns/min.
Preferably, the use phosphoric acid regulator solution pH value to 4 described in step c.
Beneficial effect: the present invention, on the basis of chromium-free deactivation, both ensure that the solidity to corrosion of tin plate, made again resistance to SO_2 not decline, and Paint Adhesion can be also very excellent.
Tin plate surface treatment liquid provided by the invention is compared with the treatment solution of prior art, specific as follows:
1, containing the oxide compound such as nickel, manganese, there is passivation in the tin plate surface tunicle in the present invention, the phosphorus contained in tunicle has the effect improving solidity to corrosion and paint film adhesion, therefore give tin plate excellent sulfuration resistant spot, coating wettability and coating adhesion, material wets parameter contact angle of the present invention is minimum is 74.1 degree, and existing treatment solution material wets parameter contact angle is 80.2 degree, the treatment effect for the treatment of solution of the present invention is good.
2, do not contain the disadvantageous chromium of environment in surface treatment liquid of the present invention and use procedure thereof, free from environmental pollution, have significant meaning, in the present invention, process of surface treatment is simple in addition, and easy to implement, cost is lower.
Embodiment
Embodiment 1
A kind of tin plate surface treatment liquid contains: 2g/L Sodium phosphate dibasic, 2g/L trisodium phosphate, 1g/L ammonium titanium fluoride, 1g/L potassium silicofluoride, 2g/L nickelous nitrate, 1g/L metatitanic acid oxygen zirconium, 1g/L sodium metaaluminate, 5g/L phosphate dihydrogen manganese, 2g/L sodium phytate and 1g/L oxalic acid.
A preparation method for tin plate surface treatment liquid, comprises the following steps:
A, take moiety respectively, first Sodium phosphate dibasic, trisodium phosphate are joined in deionized water and stirred, controlling stirring velocity is 60 turns/min, to dissolving completely;
Add ammonium titanium fluoride, potassium silicofluoride, nickelous nitrate, metatitanic acid oxygen zirconium, sodium metaaluminate and phosphate dihydrogen manganese in b, the solution that obtains to step a again, then stir, controlling stirring velocity is 40 turns/min, to dissolving completely;
C, finally add sodium phytate and oxalic acid, stirring and dissolving evenly uses phosphoric acid regulator solution pH value to 3 afterwards, obtains tin plate surface treatment liquid.
Embodiment 2
A kind of tin plate surface treatment liquid contains: 25g/L Sodium phosphate dibasic, 13g/L trisodium phosphate, 15g/L ammonium titanium fluoride, 10g/L potassium silicofluoride, 14g/L nickelous nitrate, 12g/L metatitanic acid oxygen zirconium, 10g/L sodium metaaluminate, 12g/L phosphate dihydrogen manganese, 5g/L sodium phytate and 7g/L oxalic acid.
A preparation method for tin plate surface treatment liquid, comprises the following steps:
A, take moiety respectively, first Sodium phosphate dibasic, trisodium phosphate are joined in deionized water and stirred, controlling stirring velocity is 65 turns/min, to dissolving completely;
Add ammonium titanium fluoride, potassium silicofluoride, nickelous nitrate, metatitanic acid oxygen zirconium, sodium metaaluminate and phosphate dihydrogen manganese in b, the solution that obtains to step a again, then stir, controlling stirring velocity is 42 turns/min, to dissolving completely;
C, finally add sodium phytate and oxalic acid, stirring and dissolving evenly uses phosphoric acid regulator solution pH value to 3 afterwards, obtains tin plate surface treatment liquid.
Embodiment 3
A kind of tin plate surface treatment liquid contains: 5g/L Sodium phosphate dibasic, 4g/L trisodium phosphate, 3g/L ammonium titanium fluoride, 5g/L potassium silicofluoride, 5g/L nickelous nitrate, 4g/L metatitanic acid oxygen zirconium, 2g/L sodium metaaluminate, 7g/L phosphate dihydrogen manganese, 3g/L sodium phytate and 2g/L oxalic acid.
A preparation method for tin plate surface treatment liquid, comprises the following steps:
A, take moiety respectively, first Sodium phosphate dibasic, trisodium phosphate are joined in deionized water and stirred, controlling stirring velocity is 75 turns/min, to dissolving completely;
Add ammonium titanium fluoride, potassium silicofluoride, nickelous nitrate, metatitanic acid oxygen zirconium, sodium metaaluminate and phosphate dihydrogen manganese in b, the solution that obtains to step a again, then stir, controlling stirring velocity is 48 turns/min, to dissolving completely;
C, finally add sodium phytate and oxalic acid, stirring and dissolving evenly uses phosphoric acid regulator solution pH value to 5 afterwards, obtains tin plate surface treatment liquid.
Embodiment 4
A kind of tin plate surface treatment liquid contains: 15g/L Sodium phosphate dibasic, 10g/L trisodium phosphate, 10g/L ammonium titanium fluoride, 7g/L potassium silicofluoride, 10g/L nickelous nitrate, 8g/L metatitanic acid oxygen zirconium, 8g/L sodium metaaluminate, 9g/L phosphate dihydrogen manganese, 4g/L sodium phytate and 5g/L oxalic acid.
A preparation method for tin plate surface treatment liquid, comprises the following steps:
A, take moiety respectively, first Sodium phosphate dibasic, trisodium phosphate are joined in deionized water and stirred, controlling stirring velocity is 80 turns/min, to dissolving completely;
Add ammonium titanium fluoride, potassium silicofluoride, nickelous nitrate, metatitanic acid oxygen zirconium, sodium metaaluminate and phosphate dihydrogen manganese in b, the solution that obtains to step a again, then stir, controlling stirring velocity is 50 turns/min, to dissolving completely;
C, finally add sodium phytate and oxalic acid, stirring and dissolving evenly uses phosphoric acid regulator solution pH value to 5 afterwards, obtains tin plate surface treatment liquid.
Embodiment 5
A kind of tin plate surface treatment liquid contains: 10g/L Sodium phosphate dibasic, 9g/L trisodium phosphate, 7g/L ammonium titanium fluoride, 6g/L potassium silicofluoride, 7g/L nickelous nitrate, 5g/L metatitanic acid oxygen zirconium, 6.5g/L sodium metaaluminate, 8g/L phosphate dihydrogen manganese, 3.5g/L sodium phytate and 4g/L oxalic acid.
A preparation method for tin plate surface treatment liquid, comprises the following steps:
A, take moiety respectively, first Sodium phosphate dibasic, trisodium phosphate are joined in deionized water and stirred, controlling stirring velocity is 70 turns/min, to dissolving completely;
Add ammonium titanium fluoride, potassium silicofluoride, nickelous nitrate, metatitanic acid oxygen zirconium, sodium metaaluminate and phosphate dihydrogen manganese in b, the solution that obtains to step a again, then stir, controlling stirring velocity is 45 turns/min, to dissolving completely;
C, finally add sodium phytate and oxalic acid, stirring and dissolving evenly uses phosphoric acid regulator solution pH value to 4 afterwards, obtains tin plate surface treatment liquid.
After the present invention adopts first direct-current plate electrolysis, the surface treatment mode of Cathode DC electrolysis processes, and current density is 5-10A/dm
2, the treatment time is 1-5 second.
The tin plate surface treatment liquid process tin plate prepared with above-described embodiment, then carries out performance evaluation to the tin plate after process.
One, sulfuration resistant spot test
The testing liquid of sulfuration resistant spot consists of: the L-cysteine hydrochloride of the potassium primary phosphate of 2.8g/L, the disodium hydrogen phosphate dodecahydrate of 5.6g/L, 0.47g/L, and all the other are deionized water.In solution, pass into nitrogen be heated to boiling, solution is poured into rapidly sample is housed and is full of in the vial of nitrogen and seal, then at 121 DEG C, be incubated 2 hours, sample is contrasted.
Two, coating wettability test
The contact angle size formed when using contact angle instrument to measure drop and tin plate surface contact, liquid selects deionized water.According to existing theory, in the scope that Young's equation is suitable for, θ is less, and its wettability is better.Evaluate coating wettability by wetting angle to compare.
Three, coating adhesion test
Use the electronic Coating adhesion test instrument of QDF type to carry out lacquered film adhesion test to japanning sample, inspection paint film departs from the degree of sample surfaces, evaluates film adhesive performance compare by pull-away area.
The testing data of test one to three added up, test-results is in table 1.
Table 1
As shown in Table 1, material wets parameter contact angle of the present invention is minimum is 74.1 degree, and existing treatment solution material wets parameter contact angle is 80.2 degree, and the treatment effect for the treatment of solution of the present invention is good.Containing the oxide compound such as nickel, manganese, there is passivation in tin plate surface tunicle in the present invention, the phosphorus contained in tunicle has the effect improving solidity to corrosion and paint film adhesion, therefore gives tin plate excellent sulfuration resistant spot, coating wettability and coating adhesion.
Claims (8)
1. a tin plate surface treatment liquid, is characterized in that it contains: 2-25g/L Sodium phosphate dibasic, 2-13g/L trisodium phosphate, 1-15g/L ammonium titanium fluoride, 1-10g/L potassium silicofluoride, 2-14g/L nickelous nitrate, 1-12g/L metatitanic acid oxygen zirconium, 1-10g/L sodium metaaluminate, 5-12g/L phosphate dihydrogen manganese, 2-5g/L sodium phytate and 1-7g/L oxalic acid.
2. a kind of tin plate surface treatment liquid according to claim 1, is characterized in that it contains: 5-15g/L Sodium phosphate dibasic, 4-10g/L trisodium phosphate, 3-10g/L ammonium titanium fluoride, 5-7g/L potassium silicofluoride, 5-10g/L nickelous nitrate, 4-8g/L metatitanic acid oxygen zirconium, 2-8g/L sodium metaaluminate, 7-9g/L phosphate dihydrogen manganese, 3-4g/L sodium phytate and 2-5g/L oxalic acid.
3. a kind of tin plate surface treatment liquid according to claim 1, is characterized in that it contains: 10g/L Sodium phosphate dibasic, 9g/L trisodium phosphate, 7g/L ammonium titanium fluoride, 6g/L potassium silicofluoride, 7g/L nickelous nitrate, 5g/L metatitanic acid oxygen zirconium, 6.5g/L sodium metaaluminate, 8g/L phosphate dihydrogen manganese, 3.5g/L sodium phytate and 4g/L oxalic acid.
4. a preparation method for the tin plate surface treatment liquid as described in any one of claims 1 to 3, is characterized in that comprising the following steps:
A, take moiety respectively, first Sodium phosphate dibasic, trisodium phosphate are joined in deionized water and stirred, controlling stirring velocity is that 60-80 turns/min, to dissolving completely;
Add ammonium titanium fluoride, potassium silicofluoride, nickelous nitrate, metatitanic acid oxygen zirconium, sodium metaaluminate and phosphate dihydrogen manganese in b, the solution that obtains to step a again, then stir, controlling stirring velocity is that 40-50 turns/min, to dissolving completely;
C, finally add sodium phytate and oxalic acid, stirring and dissolving evenly uses phosphoric acid regulator solution pH value to 3-5 afterwards, obtains tin plate surface treatment liquid.
5. the preparation method of a kind of tin plate surface treatment liquid according to claim 4, is characterized in that the control stirring velocity described in step a is that 65-75 turns/min.
6. the preparation method of a kind of tin plate surface treatment liquid according to claim 5, is characterized in that the control stirring velocity described in step a is 70 turns/min.
7. the preparation method of a kind of tin plate surface treatment liquid according to claim 4, is characterized in that the control stirring velocity described in step b is 45 turns/min.
8. the preparation method of a kind of tin plate surface treatment liquid according to claim 4, is characterized in that the use phosphoric acid regulator solution pH value to 4 described in step c.
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