CN104357825B - Tinned steel plate surface treatment solution and preparation method thereof - Google Patents
Tinned steel plate surface treatment solution and preparation method thereof Download PDFInfo
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- CN104357825B CN104357825B CN201410650819.2A CN201410650819A CN104357825B CN 104357825 B CN104357825 B CN 104357825B CN 201410650819 A CN201410650819 A CN 201410650819A CN 104357825 B CN104357825 B CN 104357825B
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- surface treatment
- sodium
- plate surface
- tin plate
- preparation
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- 238000004381 surface treatment Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910000831 Steel Inorganic materials 0.000 title abstract description 11
- 239000010959 steel Substances 0.000 title abstract description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 51
- 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 19
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 19
- 239000011734 sodium Substances 0.000 claims abstract description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 18
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 18
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims abstract description 18
- 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 18
- 239000011591 potassium Substances 0.000 claims abstract description 18
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 18
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims abstract description 18
- 229940048086 sodium pyrophosphate Drugs 0.000 claims abstract description 18
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims abstract description 18
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims abstract description 18
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 17
- 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 15
- 229940083982 sodium phytate Drugs 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000005028 tinplate Substances 0.000 claims description 38
- 239000007788 liquid Substances 0.000 claims description 27
- 239000002253 acid Substances 0.000 claims description 19
- 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 17
- 238000002156 mixing Methods 0.000 claims description 17
- GEIAQOFPUVMAGM-UHFFFAOYSA-N Oxozirconium Chemical compound [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 claims description 16
- 239000012530 fluid Substances 0.000 claims description 15
- 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 14
- 239000000470 constituent Substances 0.000 claims description 8
- 239000012467 final product Substances 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims 1
- 239000003973 paint Substances 0.000 abstract description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 abstract description 7
- 239000011593 sulfur Substances 0.000 abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 4
- 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
- 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
- 230000000593 degrading effect Effects 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 15
- 229910019142 PO4 Inorganic materials 0.000 description 14
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 14
- 239000010452 phosphate Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- 208000010201 Exanthema Diseases 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 201000005884 exanthem Diseases 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 206010037844 rash Diseases 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
- 150000001875 compounds Chemical class 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 238000005987 sulfurization reaction Methods 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-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
- KETSPIPODMGOEJ-UHFFFAOYSA-B dodecasodium;(2,3,4,5,6-pentaphosphonatooxycyclohexyl) phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OC1C(OP([O-])([O-])=O)C(OP([O-])([O-])=O)C(OP([O-])([O-])=O)C(OP([O-])([O-])=O)C1OP([O-])([O-])=O KETSPIPODMGOEJ-UHFFFAOYSA-B 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- KVCWSJZUKMSPLM-UHFFFAOYSA-N O.O[PH2]=O Chemical compound O.O[PH2]=O KVCWSJZUKMSPLM-UHFFFAOYSA-N 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
- 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
- 238000005868 electrolysis reaction Methods 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
- 238000011156 evaluation Methods 0.000 description 1
- 235000013305 food Nutrition 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
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 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
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material 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
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 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
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- -1 phosphorus compound Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate 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
- 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 to a kind of tin plate surface treatment liquid and its system
Preparation Method.
Background technology
Tin plate is product that is tin plating on sheet metal and making, and tin plate has as a kind of metal packing material
Good performance, its feature includes 1, nontoxic, and tin layers itself are harmless, make packaging for foodstuff very safe；2nd, appearance is beautiful,
It is easy to appearance to cover with paint, lacquer, colour wash, etc. and print；3rd, stannum has good corrosion resistance in itself, and protect the substrate prevents from being corroded；4th, tin-welding is good,
Easily it is fabricated to container；5th, stannum has good ductility, lubricity, is amenable to the processing of harshness；6th, tin layers are soft, tin coating
Will not split, also will not fall off.
But, tin plate does not carry out special chemical treatment, easy oxidation discoloration in atmosphere, and in special food
In, produce blacking because sulfur becomes.It is thus desirable to processing to tin plate, current process is in chromic acid or chromate mostly
Being impregnated in treatment fluid or be electrolysed and processed the envelope generating, the growth of tin-oxide being effectively prevented, thus imparting plating
The excellent corrosion resistance of tin steel plate, sulfur resistive dissipating rashes, also have excellent coating wettability, paint film tack and processability simultaneously
Can etc..But, contain to environmentally undesirable chromium in this treatment fluid, and in production process chromate waste water processing routine complicated and
Relatively costly, therefore, it should be replaced from the point of view of Environmental security angle.
Requirement more and more higher for tin plate chromium-free treating liquid does not contain to environment it is impossible to be only required to it at present
The chromium being harmful to human body, and need to ensure, using the tin plate after this treatment fluid Passivation Treatment, there is excellent corrosion resistance
Energy, sulfuration resistant performance and Paint Adhesion energy.
The patent of Application No. 200810035058.4 discloses a kind of surface treatment liquid for tin plate, wherein contains
The phosphorus compound of 1-50g/l, the vfanadium compound of 1-20g/l, 1-30g/l is had to be selected from molybdenum, zirconium, titanium, manganese or tungsten metallization compound
One or more compound, 1-10g/l have at least one of hydroxyl, carbonyl, carboxyl or phosphate functional group one kind or
Multiple compounds.Although not containing chromium in its constituent, the decay resistance of tin plate after treatment, sulfuration resistant
Performance and Paint Adhesion can also further improve.
Content of the invention
The invention aims to overcoming above the deficiencies in the prior art and providing one kind not contain chromium and treated liquid
Tin plate decay resistance after process, sulfuration resistant performance and Paint Adhesion 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 disodium hydrogen phosphate, 2-13g/l sodium pyrophosphate,
1-15g/l ammonium titanium fluoride, 1-10g/l potassium fluosilicate, 2-14g/l nickel nitrate, 1-12g/l metatitanic acid oxygen zirconium, 1-10g/l meta-aluminic acid
Sodium, 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 disodium hydrogen phosphate, 4-10g/l sodium pyrophosphate,
3-10g/l ammonium titanium fluoride, 5-7g/l potassium fluosilicate, 5-10g/l nickel 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.
It is furthermore preferred that a kind of tin plate surface treatment liquid contains: 10g/l disodium hydrogen phosphate, 9g/l sodium pyrophosphate, 7g/l
Ammonium titanium fluoride, 6g/l potassium fluosilicate, 7g/l nickel 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 kind of preparation method of tin plate surface treatment liquid, comprises the following steps:
A, weigh constituent respectively, first disodium hydrogen phosphate, sodium pyrophosphate are added in deionized water and are stirred, control
Mixing speed processed turns/min for 60-80, to being completely dissolved；
Ammonium titanium fluoride, potassium fluosilicate, nickel nitrate, metatitanic acid oxygen zirconium, sodium metaaluminate is added to step a in b, the solution obtaining again
And phosphate dihydrogen manganese, then it is stirred, control mixing speed to turn/min for 40-50, to being completely dissolved；
C, it is eventually adding sodium phytate and oxalic acid, adjust solution ph to 3-5 with phosphoric acid after stirring and dissolving is uniform, obtain final product tin plating
Surface of steel plate treatment fluid.
Preferably, the control mixing speed described in step a turns/min for 65-75.
Preferably, the control mixing speed described in step a is 70 turns/min.
Preferably, the control mixing speed described in step b is 45 turns/min.
Preferably, adjust solution ph to 4 with phosphoric acid described in step c.
Beneficial effect: the present invention, on the basis of chromium-free deactivation, both ensure that the corrosion resistance of tin plate, makes resistance to SO_2 again
Do not decline, and Paint Adhesion can be also very excellent.
The tin plate surface treatment liquid that the present invention provides is compared with the treatment fluid of prior art, specific as follows:
1st, containing the oxide such as nickel, manganese, there is passivation in the tin plate surface envelope in the present invention, contain in envelope
The phosphorus playing the role of has raising corrosion resistance and paint film adhesion, therefore gives the excellent sulfur resistive dissipating rashes of tin plate, coating
Wettability and coating adhesion, minimum 74.1 degree of coating wettability parameter contact angle of the present invention, and existing treatment fluid coating is wet
Lubricant nature parameter contact angle is 80.2 degree, the high treating effect for the treatment of fluid of the present invention.
2nd, do not contain to environmentally undesirable chromium during the surface treatment liquid of the present invention and its use, free from environmental pollution, tool
Have significant meaning, in addition in the present invention process of surface treatment simple it is easy to implement, cost is relatively low.
Specific embodiment
Embodiment 1
A kind of tin plate surface treatment liquid contains: 2g/l disodium hydrogen phosphate, 2g/l sodium pyrophosphate, 1g/l ammonium titanium fluoride,
1g/l potassium fluosilicate, 2g/l nickel 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 kind of preparation method of tin plate surface treatment liquid, comprises the following steps:
A, weigh constituent respectively, first disodium hydrogen phosphate, sodium pyrophosphate are added in deionized water and are stirred, control
Mixing speed processed is 60 turns/min, to being completely dissolved；
Ammonium titanium fluoride, potassium fluosilicate, nickel nitrate, metatitanic acid oxygen zirconium, sodium metaaluminate is added to step a in b, the solution obtaining again
And phosphate dihydrogen manganese, then it is stirred, control mixing speed is 40 turns/min, to being completely dissolved；
C, it is eventually adding sodium phytate and oxalic acid, adjust solution ph to 3 with phosphoric acid after stirring and dissolving is uniform, obtain final product tin-coated steel
Plate surface treatment fluid.
Embodiment 2
A kind of tin plate surface treatment liquid contains: 25g/l disodium hydrogen phosphate, 13g/l sodium pyrophosphate, 15g/l fluotitanic acid
Ammonium, 10g/l potassium fluosilicate, 14g/l nickel 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 kind of preparation method of tin plate surface treatment liquid, comprises the following steps:
A, weigh constituent respectively, first disodium hydrogen phosphate, sodium pyrophosphate are added in deionized water and are stirred, control
Mixing speed processed is 65 turns/min, to being completely dissolved；
Ammonium titanium fluoride, potassium fluosilicate, nickel nitrate, metatitanic acid oxygen zirconium, sodium metaaluminate is added to step a in b, the solution obtaining again
And phosphate dihydrogen manganese, then it is stirred, control mixing speed is 42 turns/min, to being completely dissolved；
C, it is eventually adding sodium phytate and oxalic acid, adjust solution ph to 3 with phosphoric acid after stirring and dissolving is uniform, obtain final product tin-coated steel
Plate surface treatment fluid.
Embodiment 3
A kind of tin plate surface treatment liquid contains: 5g/l disodium hydrogen phosphate, 4g/l sodium pyrophosphate, 3g/l ammonium titanium fluoride,
5g/l potassium fluosilicate, 5g/l nickel 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 kind of preparation method of tin plate surface treatment liquid, comprises the following steps:
A, weigh constituent respectively, first disodium hydrogen phosphate, sodium pyrophosphate are added in deionized water and are stirred, control
Mixing speed processed is 75 turns/min, to being completely dissolved；
Ammonium titanium fluoride, potassium fluosilicate, nickel nitrate, metatitanic acid oxygen zirconium, sodium metaaluminate is added to step a in b, the solution obtaining again
And phosphate dihydrogen manganese, then it is stirred, control mixing speed is 48 turns/min, to being completely dissolved；
C, it is eventually adding sodium phytate and oxalic acid, adjust solution ph to 5 with phosphoric acid after stirring and dissolving is uniform, obtain final product tin-coated steel
Plate surface treatment fluid.
Embodiment 4
A kind of tin plate surface treatment liquid contains: 15g/l disodium hydrogen phosphate, 10g/l sodium pyrophosphate, 10g/l fluotitanic acid
Ammonium, 7g/l potassium fluosilicate, 10g/l nickel nitrate, 8g/l metatitanic acid oxygen zirconium, 8g/l sodium metaaluminate, 9g/l phosphate dihydrogen manganese, 4g/l phytic acid
Sodium and 5g/l oxalic acid.
A kind of preparation method of tin plate surface treatment liquid, comprises the following steps:
A, weigh constituent respectively, first disodium hydrogen phosphate, sodium pyrophosphate are added in deionized water and are stirred, control
Mixing speed processed is 80 turns/min, to being completely dissolved；
Ammonium titanium fluoride, potassium fluosilicate, nickel nitrate, metatitanic acid oxygen zirconium, sodium metaaluminate is added to step a in b, the solution obtaining again
And phosphate dihydrogen manganese, then it is stirred, control mixing speed is 50 turns/min, to being completely dissolved；
C, it is eventually adding sodium phytate and oxalic acid, adjust solution ph to 5 with phosphoric acid after stirring and dissolving is uniform, obtain final product tin-coated steel
Plate surface treatment fluid.
Embodiment 5
A kind of tin plate surface treatment liquid contains: 10g/l disodium hydrogen phosphate, 9g/l sodium pyrophosphate, 7g/l ammonium titanium fluoride,
6g/l potassium fluosilicate, 7g/l nickel nitrate, 5g/l metatitanic acid oxygen zirconium, 6.5g/l sodium metaaluminate, 8g/l phosphate dihydrogen manganese, 3.5g/l phytic acid
Sodium and 4g/l oxalic acid.
A kind of preparation method of tin plate surface treatment liquid, comprises the following steps:
A, weigh constituent respectively, first disodium hydrogen phosphate, sodium pyrophosphate are added in deionized water and are stirred, control
Mixing speed processed is 70 turns/min, to being completely dissolved；
Ammonium titanium fluoride, potassium fluosilicate, nickel nitrate, metatitanic acid oxygen zirconium, sodium metaaluminate is added to step a in b, the solution obtaining again
And phosphate dihydrogen manganese, then it is stirred, control mixing speed is 45 turns/min, to being completely dissolved；
C, it is eventually adding sodium phytate and oxalic acid, adjust solution ph to 4 with phosphoric acid after stirring and dissolving is uniform, obtain final product tin-coated steel
Plate surface treatment fluid.
The present invention be electrolysed using first direct-current plate after Cathode DC electrolysis surface treatment mode processed, electric current density
For 5-10a/dm2, process time be the 1-5 second.
Process tin plate with the tin plate surface treatment liquid of above-described embodiment preparation, then to the tin-coated steel after processing
Plate carries out performance evaluation.
First, sulfur resistive dissipating rashes test
The testing liquid of sulfur resistive dissipating rashes consists of: the potassium dihydrogen phosphate of 2.8g/l, the 12 hypophosphite monohydrate hydrogen two of 5.6g/l
Sodium, the l- cysteine hydrochloride of 0.47g/l, remaining is deionized water.It is passed through nitrogen to be heated to seething with excitement, by solution in solution
Pour into rapidly equipped with sample and seal full of in the vial of nitrogen, then at 121 DEG C, be incubated 2 hours, it is right that sample is carried out
Than.
2nd, coating wettability test
Measure the contact angle size being formed when drop is contacted with tin plate surface using contact angle instrument, liquid is selected and gone
Ionized water.Understand, in the scope that Young's equation is suitable for, θ is less, and its wettability is better according to existing theory.Use angle of wetting
It is compared to evaluate coating wettability.
3rd, coating adhesion test
Using qdf type electronic Coating adhesion test instrument, japanning sample is carried out with lacquered film adhesion test, inspection paint film takes off
From the degree of sample surfaces, evaluate film adhesive performance by pull-away area and be compared.
The test data of test one to three is counted, result of the test is shown in Table 1.
Table 1
As shown in Table 1, minimum 74.1 degree of coating wettability parameter contact angle of the present invention, and existing treatment fluid coating moistens
Property parameter contact angle be 80.2 degree, the high treating effect for the treatment of fluid of the present invention.Contain in tin plate surface envelope in the present invention
The oxides such as nickel, manganese are had to have passivation, the phosphorus containing in envelope has the effect improving corrosion resistance and paint film adhesion, because
This gives the excellent sulfur resistive dissipating rashes of tin plate, coating wettability and coating adhesion.
Claims (2)
1. a kind of tin plate surface treatment liquid is it is characterised in that it contains: 10g/l disodium hydrogen phosphate, 9g/l sodium pyrophosphate,
7g/l ammonium titanium fluoride, 6g/l potassium fluosilicate, 7g/l nickel nitrate, 5g/l metatitanic acid oxygen zirconium, 6.5g/l sodium metaaluminate, 8g/l biphosphate
Manganese, 3.5g/l sodium phytate and 4g/l oxalic acid.
2. a kind of preparation method of tin plate surface treatment liquid as claimed in claim 1 is it is characterised in that include following walking
Rapid:
A, weigh constituent respectively, first disodium hydrogen phosphate, sodium pyrophosphate are added in deionized water and are stirred, control is stirred
Mixing speed is 70 turns/min, to being completely dissolved；
Ammonium titanium fluoride, potassium fluosilicate, nickel nitrate, metatitanic acid oxygen zirconium, sodium metaaluminate and phosphorus is added to step a in b, the solution obtaining again
Acid dihydride manganese, is then stirred, and control mixing speed is 45 turns/min, to being completely dissolved；
C, it is eventually adding sodium phytate and oxalic acid, adjust solution ph to 4 with phosphoric acid after stirring and dissolving is uniform, obtain final product tin plate table
Face treatment fluid.
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| CN105506604A (en) * | 2015-12-31 | 2016-04-20 | 芜湖奕辰模具科技有限公司 | Surface treating fluid for tin plate |
| CN105506597A (en) * | 2015-12-31 | 2016-04-20 | 芜湖奕辰模具科技有限公司 | Preparation method of surface treating fluid for tin plate |
| CN107488845B (en) * | 2016-06-11 | 2019-11-19 | 上海梅山钢铁股份有限公司 | A kind of chromium-free passivation liquid and its application method for tin plate |
| CN106800845A (en) * | 2017-01-22 | 2017-06-06 | 安徽臣诺机器人科技有限公司 | A kind of mechanical arm spray metal passivator and preparation method thereof |
| CN110501263B (en) * | 2018-05-16 | 2022-06-28 | 宝山钢铁股份有限公司 | Tin plate surface wettability evaluation method |
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| JP2005120469A (en) * | 2003-09-26 | 2005-05-12 | Nippon Parkerizing Co Ltd | Composition for treating surface of metallic material, and surface treatment method |
| CN101545107B (en) * | 2008-03-25 | 2012-07-04 | 宝山钢铁股份有限公司 | Surface treatment liquid, surface treatment method and tin-plated steel sheet by surface treatment |
| CN101487116B (en) * | 2009-02-13 | 2011-08-17 | 西安建筑科技大学 | Use of passivation film forming liquid on steel surface |
| CN102899651A (en) * | 2011-07-29 | 2013-01-30 | 史学斌 | Multi-function metal surface treatment agent |
| CN103805977A (en) * | 2012-11-08 | 2014-05-21 | 上海丰野表面处理剂有限公司 | Chromium-free passivation liquid for treating tin-plated steel plate |
| CN103060788B (en) * | 2013-01-31 | 2015-10-28 | 宝山钢铁股份有限公司 | A kind of fuel tank one-side electroplating zinc chrome-free surface treated steel plate and surface treatment agent |
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