CN101376969B - Passivating treatment solution for surface of zinc or zinc alloy and passivation treatment method - Google Patents
Passivating treatment solution for surface of zinc or zinc alloy and passivation treatment method Download PDFInfo
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- CN101376969B CN101376969B CN2007101462281A CN200710146228A CN101376969B CN 101376969 B CN101376969 B CN 101376969B CN 2007101462281 A CN2007101462281 A CN 2007101462281A CN 200710146228 A CN200710146228 A CN 200710146228A CN 101376969 B CN101376969 B CN 101376969B
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- 238000002161 passivation Methods 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 50
- 229910001297 Zn alloy Inorganic materials 0.000 title claims abstract description 42
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 33
- 239000011701 zinc Substances 0.000 title claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 150000003839 salts Chemical class 0.000 claims abstract description 17
- 150000003746 yttrium Chemical class 0.000 claims abstract description 12
- 239000008139 complexing agent Substances 0.000 claims abstract description 11
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000000415 inactivating effect Effects 0.000 claims description 62
- 239000007788 liquid Substances 0.000 claims description 62
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000005238 degreasing Methods 0.000 claims description 18
- 239000011734 sodium Substances 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000012190 activator Substances 0.000 claims description 10
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 9
- BXJPTTGFESFXJU-UHFFFAOYSA-N yttrium(3+);trinitrate Chemical group [Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BXJPTTGFESFXJU-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 8
- 238000001994 activation Methods 0.000 claims description 8
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 8
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 8
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 150000007524 organic acids Chemical class 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- QZKRHPLGUJDVAR-UHFFFAOYSA-K EDTA trisodium salt Chemical compound [Na+].[Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O QZKRHPLGUJDVAR-UHFFFAOYSA-K 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 5
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 5
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 239000001384 succinic acid Substances 0.000 claims description 4
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 2
- DUSUCKWNBGMKRV-UHFFFAOYSA-N acetic acid;yttrium Chemical compound [Y].CC(O)=O DUSUCKWNBGMKRV-UHFFFAOYSA-N 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 229940001516 sodium nitrate Drugs 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 229940095064 tartrate Drugs 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 16
- 238000005260 corrosion Methods 0.000 abstract description 10
- 230000007797 corrosion Effects 0.000 abstract description 9
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 238000005303 weighing Methods 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 229910052761 rare earth metal Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000005520 cutting process Methods 0.000 description 10
- 150000002910 rare earth metals Chemical class 0.000 description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 description 8
- 235000017550 sodium carbonate Nutrition 0.000 description 8
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000009849 deactivation Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 229910001335 Galvanized steel Inorganic materials 0.000 description 5
- 239000002390 adhesive tape Substances 0.000 description 5
- 238000005485 electric heating Methods 0.000 description 5
- 239000008397 galvanized steel Substances 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000002203 pretreatment Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000001509 sodium citrate Substances 0.000 description 3
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical class [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 3
- 235000019263 trisodium citrate Nutrition 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229940038773 trisodium citrate Drugs 0.000 description 2
- PAJMKGZZBBTTOY-UHFFFAOYSA-N 2-[[2-hydroxy-1-(3-hydroxyoctyl)-2,3,3a,4,9,9a-hexahydro-1h-cyclopenta[g]naphthalen-5-yl]oxy]acetic acid Chemical compound C1=CC=C(OCC(O)=O)C2=C1CC1C(CCC(O)CCCCC)C(O)CC1C2 PAJMKGZZBBTTOY-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910004835 Na2B4O7 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000009472 formulation Methods 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
- 230000036541 health Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- GOLXNESZZPUPJE-UHFFFAOYSA-N spiromesifen Chemical compound CC1=CC(C)=CC(C)=C1C(C(O1)=O)=C(OC(=O)CC(C)(C)C)C11CCCC1 GOLXNESZZPUPJE-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
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- Chemical Treatment Of Metals (AREA)
Abstract
The invention relates to passivation solution of the surface of zinc or zinc alloy, which contains passivation main salt, oxidant, complexing agent, accelerant and water, wherein, the passivation main salt is water soluble yttrium salt, and the accelerant is soluble metavanadate. The invention also provides a method for passivating the surface of zinc or zinc alloy with the passivation slution. Using the passivation solution and passivation process to passivate the surface of zinc or zinc alloy has high passivation speed, good corrosion of the passivating film, reduces the harm to the environment and the surface resistance of the zinc or zinc alloy passivating film layer, improves the electronic and electromagnetic conductibility, and reduces the hidden danger to the users.
Description
Technical field
The invention relates to a kind of inactivating treatment liquid and deactivating process for the treatment of, specifically about the inactivating treatment liquid and the deactivating process for the treatment of of a kind of zinc or zinc alloy surface.
Background technology
In order to improve zinc or the zinc alloy erosion resistance of (comprising foundry goods and plating piece), increase surface luster and contamination resistance, need carry out Passivation Treatment, so that its surface generates the form compact and stable passive film of one deck.At present, the passivating method of zinc or zinc alloy surface comprises zinc or zinc alloy is contacted with passivating solution that according to the composition of passivating solution, passivating method can be divided into sexavalent chrome deactivation method and non-sexavalent chrome deactivation method.
Sexavalent chrome deactivation method deactivating solution contains sexavalent chrome, can form fine and close, stable, corrosion resistant passive film, but sexavalent chrome toxicity is big, environmental pollution is serious, plating piece produce and removal process in easily HUMAN HEALTH is produced harm, by the ROHS of European Union (some objectionable impurities is used in restriction in electronic electric equipment) instruct forbid.Therefore the sexavalent chrome deactivation method is replaced by non-sexavalent chrome deactivation method now gradually.
Rare earth passivating technique in the non-sexavalent chrome deactivation method, because of its have nontoxic pollution-free, corrosion protection result preferably characteristics receive increasing concern.For example, Long Jinming, Han Xiayun etc. have studied the rare earth surface modification of zinc and galvanized steel, studies show that cerous nitrate solution (pH value about 5.4) the dipping galvanized steel long period (for example 3 days) of utilizing 0.005 mol, can obtain good solidity to corrosion (Long Jinming, Han Xiayun etc., the rare earth surface modification of zinc and galvanized steel, rare earth, 2003,23 (5): 52-56).
At present, the efficient of rare earth passivation and corrosion protection result thereof are still waiting to improve, so that can substitute traditional high chromic acid content salt passivation veritably, and the resistance that preferably can reduce passive film simultaneously reduces the hidden danger to the user to improve electronics, electromagnetism conductivity.
Summary of the invention
The objective of the invention is in order to overcome the defective that passivation efficiency is lower or anticorrosion ability is not good of existing rare earth passivation technology, and consider that reducing resistance reduces hidden danger to the user to improve electronics, electromagnetism conductivity, provide a kind of to zinc or zinc alloy surface carries out the solution of Passivation Treatment and utilize this solution to carry out the technology of Passivation Treatment.
The invention provides the inactivating treatment liquid of a kind of zinc or zinc alloy surface, this inactivating treatment liquid contains passivation master salt, oxygenant, complexing agent, promotor and water, and wherein, described passivation master salt is water-soluble yttrium salt, and described promotor is the solubility metavanadate.
The present invention also provides a kind of method to zinc or zinc alloy surface Passivation Treatment, and this method comprises zinc or zinc alloy surface are contacted with inactivating treatment liquid that wherein, described Passivation Treatment is an inactivating treatment liquid provided by the present invention.
The present invention widens and has optimized the application of rare earth element in the metal passivation process field, a kind of new inactivating treatment liquid that does not contain the Cr element is provided and has utilized this inactivating treatment liquid to carry out the method for Passivation Treatment.Utilize inactivating treatment liquid provided by the invention and passivation process, zinc or zinc alloy surface are carried out Passivation Treatment, its passivation is fast; Good corrosion resistance; Also reduced the surface resistivity of zinc or zinc alloy passivation film to a certain extent, be easier to make electronics, electromagnetism to disperse, drained into elsewhere and go, reduced hidden danger the user.
Embodiment
Inactivating treatment liquid provided by the invention contains passivation master salt, oxygenant, complexing agent, promotor and water, and wherein, described passivation master salt is water-soluble yttrium salt, and described promotor is the solubility metavanadate.
The pH value of described inactivating treatment liquid is 2.0-5.0, is preferably 2.5-4, more preferably 3.0-3.5.
The content of described water-soluble yttrium salt is counted the 0.01-0.3 mol with yttrium, is preferably the 0.02-0.1 mol, more preferably the 0.05-0.06 mol; The content of described oxygenant is the 0.5-50 grams per liter, is preferably the 10-30 grams per liter, more preferably the 15-25 grams per liter; The content of described complexing agent is the 1-10 grams per liter, is preferably the 1-2 grams per liter, more preferably the 1.5-1.8 grams per liter; The content of solubility metavanadate is the 0.1-3 grams per liter, is preferably the 0.5-2 grams per liter, more preferably the 0.8-1.5 grams per liter.
Wherein, described water-soluble yttrium salt can for various can yttrium salt soluble in water, for example can be Yttrium trinitrate and/or acetic acid yttrium.
Described oxygenant can be the various oxygenants that contained in the conventional inactivating treatment liquid, is preferably in superoxide and the nitrate (for example SODIUMNITRATE, saltpetre, nitrocalcite and magnesium nitrate) one or more, more preferably hydrogen peroxide.
Described complexing agent is one or more in organic acid and soluble salt and the complexone.Described organic acid can be selected from one or more in citric acid, Succinic Acid and the tartrate.Described organic acid soluble salt can be selected from one or more in citric acid, Succinic Acid and tartaric sodium salt and the sylvite.Described complexone can be ethylenediamine tetraacetic acid (EDTA) (EDTA) and/or EDTA trisodium.
Optional in ammonium meta-vanadate, sodium metavanadate and potassium metavanadate one or more of described solubility metavanadate are preferably ammonium meta-vanadate.
Described inactivating treatment liquid can be prepared according to the preparation method of routine, for example, add water-soluble yttrium salt, oxygenant, complexing agent and solubility metavanadate in the entry and mix, then, the pH value of this inactivating treatment liquid is adjusted to 2.0-5.0, be preferably 2.5-4, more preferably 3.0-3.5.The consumption of each material makes in the inactivating treatment liquid that makes, and the content of described water-soluble yttrium salt is counted the 0.01-0.3 mol with yttrium, is preferably the 0.02-0.1 mol, more preferably the 0.05-0.06 mol; The content of described oxygenant is the 0.5-50 grams per liter, is preferably the 10-30 grams per liter, more preferably the 15-25 grams per liter; The content of described complexing agent is the 1-10 grams per liter, is preferably the 1-2 grams per liter, more preferably the 1.5-1.8 grams per liter; The content of solubility metavanadate is the 0.1-3 grams per liter, is preferably the 0.5-2 grams per liter, more preferably the 0.8-1.5 grams per liter.
Method to zinc or zinc alloy surface Passivation Treatment provided by the invention comprises zinc or zinc alloy surface is contacted with inactivating treatment liquid that wherein, described inactivating treatment liquid is an inactivating treatment liquid provided by the present invention.
Described inactivating treatment liquid has been done detailed description in preamble, do not repeat them here.
Can be identical with the condition of zinc or zinc alloy surface and inactivating treatment liquid contact with the contact conditions of routine, under the preferable case, the temperature of described contact is 25 ℃-45 ℃, the time of contact is 20 seconds to 60 minutes.
The method of Passivation Treatment provided by the invention can also comprise pre-treatment, described pre-treatment can comprise polishing, degreasing, ultra-sonic oscillation cleaning, washing, activation and washing successively, can save polishing, ultra-sonic oscillation cleaning and activate one or more steps in these steps, for example, can carry out degreasing, washing, activation and washing successively and finish pre-treatment, also can only carry out the step of degreasing or washing and finish pre-treatment.
Grease-removing agent used when carrying out degreasing can use commercially available skimmed prod, also can make the degreasing alkaline solution by oneself, and it can contain one or more alkali or basic salt, for example contains NaOH, Na
2CO
3, Na
3PO
4And Na
2B
4O
7, preferred prescription is:
The NaOH:5-10 grams per liter;
Na
2CO
3: the 10-15 grams per liter;
Na
3PO
4: the 5-15 grams per liter;
Na
2B
4O
7: the 1-10 grams per liter.
Used activator can be commercially available activator product, also can make by oneself, and the aqueous solution that for example prepares silicofluoric acid and fatty alcohol-polyoxyethylene ether is as activator, and its screening formulation is:
Silicofluoric acid: the 1-20 milliliter/liter;
Fatty alcohol-polyoxyethylene ether (AEO series): 0.5-2 grams per liter.
Described washing is meant with pure water washes, and flush time is preferably 1.5-10 minute.
The step of Passivation Treatment has been used above-described Passivation Treatment solution of the present invention, and the temperature of inactivating treatment liquid is 25 ℃-45 ℃, and the Passivation Treatment time is 20 seconds-60 minutes.
With zinc or zinc alloy surface with after inactivating treatment liquid contacts, method of the present invention also comprises the zinc after the passivation or zinc alloy surface is washed and drying, washing can be with pure water rinsing 1.5-10 minute, drying can be that nature dries or dries, the temperature of oven dry can be 60-80 ℃, more preferably 65 ℃-75 ℃; Drying time can be 5-30 minute, is preferably 10-20 minute.
Below by embodiment the present invention is described in more detail.
Embodiment 1
The preparation of inactivating treatment liquid: weighing Yttrium trinitrate 3 grams, EDTA trisodium 1 gram are poured 1 liter of beaker into, adding distil water stirs and all dissolves up to solid, drip hydrogen peroxide 0.5 gram with transfer pipet then, stir back weighing and add ammonium meta-vanadate 0.5 gram, last adding distil water to 1 liter also is adjusted to 2.0 with the sodium carbonate solution of 0.1 mol with the pH value.
Deactivating process for the treatment of: pressure cast zinc alloy product ZA-8, through degreasing fluid (NaOH:5 grams per liter; The Na2CO3:10 grams per liter; The Na3PO4:5 grams per liter; The degreasing Na2B4O7:1 grams per liter) (temperature: 55 ℃, the time: 5 minutes), pure water cleaned 20 seconds; With activator (silicofluoric acid: 1 milliliter/liter; Fatty alcohol-polyoxyethylene ether (AEO-9): 0.5 grams per liter) product after the degreasing is carried out activation treatment, activation is 3 minutes under the room temperature, pure water cleaned after 20 seconds, zinc alloy product is put into the above-mentioned inactivating treatment liquid for preparing carry out Passivation Treatment, the art breading parameter is: 25 ℃ of treatment temps, in 60 minutes treatment times, pure water cleaned 20 seconds, afterwards at experiment baking oven (GZX-9070MBE electric heating constant temperature air dry oven; Medical Equipment Plant of Shanghai Boxun Industrial Co., Ltd.) under 60 ℃, toasted 30 minutes in.
Embodiment 2
This embodiment is used to illustrate inactivating treatment liquid of the present invention and utilizes this inactivating treatment liquid to carry out the method for Passivation Treatment.
The preparation of inactivating treatment liquid: pour 5 gram Yttrium trinitrates and 1.0 gram Trisodium Citrates into 1 liter of beaker, adding distil water stirs and all dissolves up to solid, add 10 gram hydrogen peroxide and 0.5 gram ammonium meta-vanadate and stirring then, last adding distil water to 1 liter also is adjusted to 4.5 with the sodium carbonate solution of 0.1 mol with the pH value.
Deactivating process for the treatment of: pressure cast zinc alloy product ZA-8, through degreasing fluid (NaOH:5 grams per liter; Na
2CO
3: 10 grams per liters; Na
3PO
4: 15 grams per liters; Na
2B
4O
7: degreasing 3 grams per liters) (temperature: 55 ℃, the time: 5 minutes), pure water cleaned 3 minutes; Then zinc alloy product is put into the above-mentioned inactivating treatment liquid for preparing and carried out Passivation Treatment (treatment temp: 35 ℃, treatment time: 40 seconds), pure water cleaned 5 minutes; Afterwards at baking oven (GZX-9070MBE electric heating constant temperature air dry oven; Medical Equipment Plant of Shanghai Boxun Industrial Co., Ltd.) 75 ℃ were toasted 10 minutes down in.
Embodiment 3
This embodiment is used to illustrate inactivating treatment liquid of the present invention and utilizes this inactivating treatment liquid to carry out the method for Passivation Treatment.
The preparation of inactivating treatment liquid: weighing Yttrium trinitrate 7 grams, EDTA trisodium 1.2 grams are poured 1 liter of beaker into, adding distil water stirs and all dissolves up to solid, the back drips hydrogen peroxide 15 grams with transfer pipet, stir back weighing and add ammonium meta-vanadate 0.7 gram, last adding distil water to 1 liter also is adjusted to 4.0 with the sodium carbonate solution of 0.1 mol with the pH value.
Deactivating process for the treatment of: zinc alloy product and identical with embodiment 2 to its technology of carrying out skimming treatment, the product after the degreasing is made by oneself activator (silicofluoric acid: 10 milliliters/liter; Fatty alcohol-polyoxyethylene ether (AEO-9): activation treatment 0.6 grams per liter), under the room temperature, activate 60 seconds, pure water cleaned after 5 minutes, zinc alloy product is put into the above-mentioned inactivating treatment liquid for preparing carry out Passivation Treatment, the art breading parameter is: 35 ℃ of treatment temps, 90 seconds treatment times, pure water cleaned 5 minutes, afterwards at experiment baking oven (GZX-9070MBE electric heating constant temperature air dry oven; Medical Equipment Plant of Shanghai Boxun Industrial Co., Ltd.) under 75 ℃, toasted 10 minutes in.
Embodiment 4
This embodiment is used to illustrate inactivating treatment liquid of the present invention and utilizes this inactivating treatment liquid to carry out the method for Passivation Treatment.
The preparation of inactivating treatment liquid: weighing Yttrium trinitrate 10 grams, Trisodium Citrate 1.5 grams are poured 1 liter of beaker into, adding distil water stirs and all dissolves up to solid, the back drips hydrogen peroxide 18 grams with transfer pipet, stir back weighing and add ammonium meta-vanadate 0.9 gram, last adding distil water to 1 liter also is adjusted to 3.5 with the sodium carbonate solution of 0.1 mol with the pH value.
Deactivating process for the treatment of: carry out Passivation Treatment according to the method identical with embodiment 2, different is, uses the inactivating treatment liquid of this embodiment preparation, and the Passivation Treatment time is 200 seconds.
Embodiment 5
This embodiment is used to illustrate inactivating treatment liquid of the present invention and utilizes this inactivating treatment liquid to carry out the method for Passivation Treatment.
The preparation of inactivating treatment liquid: different with the preparation of the inactivating treatment liquid of embodiment 4 is finally is adjusted to 2.9 with the sodium carbonate solution of 0.1 mol with the pH value.
Deactivating process for the treatment of: activate outside (45 ℃ of activation temperatures, 60 seconds time) except use the zinc alloy activator P3-METCH of Shanghai Henkel Co., Ltd after degreasing, other condition is identical with embodiment 4 with step.
Embodiment 6
This embodiment is used to illustrate inactivating treatment liquid of the present invention and utilizes this inactivating treatment liquid to carry out the method for Passivation Treatment.
The preparation of inactivating treatment liquid: weighing Yttrium trinitrate 15 grams, Trisodium Citrate 1.7 grams are poured 1 liter of beaker into, adding distil water stirs and all dissolves up to solid, the back drips hydrogen peroxide 20 grams with transfer pipet, stir back weighing and add ammonium meta-vanadate 1.0 gram, last adding distil water to 1 liter also is adjusted to 3.3 with the sodium carbonate solution of 0.1 mol with the pH value.
Deactivating process for the treatment of: pressure cast zinc alloy product ZA-8, use the zinc alloy grease-removing agent Ridoline 336 of Shanghai Henkel Co., Ltd to carry out cleaning by degreasing, weighing grease-removing agent 30 grams, be dissolved in 1 liter of beaker, (processing parameter setting: 55 ℃ of temperature, 5 minutes treatment times), pure water cleaned after 3 minutes afterwards, made activator (silicofluoric acid: 10 milliliters/liter by oneself; Fatty alcohol-polyoxyethylene ether (AEO-9): pickling 0.6 grams per liter), carrying out pure water afterwards cleaned 5 minutes, then zinc alloy product is put into the above-mentioned inactivating treatment liquid for preparing and carried out Passivation Treatment, the art breading parameter is: 35 ℃ of treatment temps, 10 minutes treatment times, pure water cleaned 5 minutes, afterwards at experiment baking oven (GZX-9070MBE electric heating constant temperature air dry oven; Medical Equipment Plant of Shanghai Boxun Industrial Co., Ltd.) under 75 ℃, toasted 10 minutes in.
Embodiment 7
The preparation of inactivating treatment liquid: weighing Yttrium trinitrate 80 grams, EDTA trisodium 10 grams are poured 1 liter of beaker into, adding distil water stirs and all dissolves up to solid, the back drips hydrogen peroxide 50 grams with transfer pipet, stir back weighing and add ammonium meta-vanadate 3 gram, last adding distil water to 1 liter also is adjusted to 5.0 with the sodium carbonate solution of 0.1 mol with the pH value.
Deactivating process for the treatment of: pressure cast zinc alloy product ZA-8, through degreasing fluid (NaOH:10 grams per liter; Na
2CO
3: 15 grams per liters; Na
3PO
4: 15 grams per liters; Na
2B
4O
7: degreasing 10 grams per liters) (temperature: 55 ℃, the time: 1 minute), pure water cleaned 10 minutes, and the product after the degreasing is made by oneself activator (silicofluoric acid: 20 milliliters/liter; Fatty alcohol-polyoxyethylene ether (AEO-9): activation treatment 2 grams per liters), under the room temperature, activate 30 seconds, pure water cleaned after 10 minutes, zinc alloy product is put into the above-mentioned inactivating treatment liquid for preparing carry out Passivation Treatment, the art breading parameter is: 45 ℃ of treatment temps, 20 seconds treatment times, pure water cleaned 10 minutes, afterwards at experiment baking oven (GZX-9070MBE electric heating constant temperature air dry oven; Medical Equipment Plant of Shanghai Boxun Industrial Co., Ltd.) under 80 ℃, toasted 5 minutes in.
Comparative Examples 1
The preparation of inactivating treatment liquid: according to existing document record (Long Jinming, Han Xiayun etc., the rare earth surface modification of zinc and galvanized steel, rare earth), weighing cerous nitrate 2.17 grams are prepared into the inactivating treatment liquid that cerous nitrate is 0.005 mol.
Deactivating process for the treatment of: identical with embodiment 4.
Comparative Examples 2
The preparation of inactivating treatment liquid: according to existing document record (Long Jinming, Han Xiayun etc., the rare earth surface modification of zinc and galvanized steel, rare earth), weighing cerous nitrate 2.17 grams are prepared into the inactivating treatment liquid that cerous nitrate is 0.005 mol.
Deactivating process for the treatment of: except that the Passivation Treatment time became 30 minutes, other treatment condition are identical with Comparative Examples 1 with step.
Comparative Examples 3
Except main salt was 15 grams per liter cerous nitrates, other component of inactivating treatment liquid and the condition of Passivation Treatment of carrying out were identical with embodiment 6 with step.
Embodiment 8 resistance measurements
Purpose is to determine electronics, the electromagnetism conductive properties of passive film by measuring resistance sizes.Because electronics 3C Product (communication product, computer product and consumer electronics product) produces some unused little electric currents in normal use, especially mobile phone component, also might produce some hertzian wave, when if alloy passivation processing rear surface resistance is low, can be easier to make electric current, hertzian wave to disperse, drain into other place and go, be unlikely to secular user is caused some hidden danger.So electronics, the electromagnetism conductive properties of resistance decision passive film.
The UT51 MULTIMETER digital multimeter of utilizing UNI-T to produce is tested the point in the zone, cornerwise both ends of product.
Embodiment 9NSS SaltSprayTest
Purpose is by SaltSprayTest, according to the size of passive film corroded area, judges the anti-corrosion effect of its passivation.
In temperature is 35 ℃ laboratory, the product that makes is placed in the salt fog cabinet, under 46 ℃, spray with the air pressure of 1.0 ± 0.025 kilogram force/square centimeters with the sodium chloride brine that pH is 7.0, temperature is 35 ℃ 5 ± 0.5 weight %.Spraying sample after 8 hours, after taking-up dries up, observation sample, the corroded area of record sample surfaces accounts for the per-cent of the product total area.
The test of embodiment 10 sticking power
Utilize ASTM D 3359-93 method, the paint adhesive ability of test passive film.
Used paint vehicle is produced by KUBOKO coating company limited, and the priming paint model is Mgtite type3670-071; Middle lacquer model is MGTOP 585-628901; The finish paint model is MGTOP 585-62895.
The passivation product of the above-mentioned paint vehicle of coating is made 6 tangent lines with blade with the interval of 2mm, gently grind cutting edge with fine oil stone, with above-mentioned 6 vertical directions of tangent line, cut 2mm other 6 tangent lines at interval that intersect with above-mentioned 6 tangent lines, make grid, above-mentioned tangent line is all cut enamelled coating.With the above-mentioned grid region of softish brush outwash, be stained with Permacell 99 type adhesive tapes then, and rub on adhesive tape with rubber and to make adhesive tape well contact with paint film, 30-90 is within second, catch the free end of adhesive tape, with as far as possible near 180 ° angle, (rather than wrench) pull-up adhesive tape fast, dropping situations with coating on illuminated magnifier inspection bottom or the last coating is divided into following grade according to the area that comes off:
The edge of 5B cutting is fully smooth, and the zone in the grid does not all come off;
4B has the material of little part to come off in the point of crossing of coating, and the area that comes off is less than whole cutting zone 5%;
3B has the material of little part to come off along the edge in the point of crossing of cutting, and the area that comes off is in whole cutting zone 5-15% scope;
2B is along the edge of cutting or have material partly to come off in the zone of cutting, and the area that comes off is in whole cutting zone 15-35% scope;
1B has expanse of material to come off along the edge that cuts or the material of all zones comes off, and the area that comes off is in whole cutting zone 35-65% scope;
The area that 0B comes off is greater than whole cutting zone＞65%.
Embodiment 11 product appearances
The appearance color of passive film is judged in range estimation.In the practical application, can determine the component concentration and the processing condition of concrete passivating solution according to the color needs.
Utilize the measuring method of aforementioned every passivation effect, the Passivation Treatment effect measuring of each embodiment and Comparative Examples following (wherein,, the Passivation Treatment time of each embodiment and Comparative Examples also being listed in the table) in order to demonstrate the high advantage of passivation efficiency of the present invention:
Table 1
With reference to table 1, the present invention has very high passivation efficiency (for example, after embodiment 2 and identical time of Comparative Examples 1 Passivation Treatment, the corrosion resistance nature of embodiment 2 obviously is better than Comparative Examples 1) as can be seen; It can also be seen that with Yttrium trinitrate as passivation master salt obviously than little as the resistance that passivation master salt carries out after the Passivation Treatment with cerous nitrate; Compare with the passive film that Comparative Examples 1-3 obtains, the solidity to corrosion of the passive film that embodiment 1-7 obtains obviously improves, this may be because generated the finer and close oxide membranous layer that one deck is made up of for principal element yttrium, zinc etc. at zinc alloy surface, thereby has improved resistance to corrosion; Compare with the passive film that Comparative Examples 1-3 obtains, the resistance value of the passive film that embodiment 1-7 obtains obviously reduces, and the electronics, the electromagnetism conductivity that adopt passivating solution of the present invention and passivating method can improve the zinc alloy passive film are described.
Claims (8)
1. the inactivating treatment liquid of zinc or zinc alloy surface, this inactivating treatment liquid contains passivation master salt, oxygenant, complexing agent, promotor and water, it is characterized in that, described passivation master salt is water-soluble yttrium salt, described promotor is the solubility metavanadate, described oxygenant is a hydrogen peroxide, SODIUMNITRATE, in saltpetre and the nitrocalcite one or more, described complexing agent is one or more in organic acid and soluble salt and the complexone, described organic acid is for being selected from citric acid, in Succinic Acid and the tartrate one or more, described organic acid soluble salt is for being selected from citric acid, in Succinic Acid and tartaric sodium salt and the sylvite one or more, described complexone are ethylenediamine tetraacetic acid (EDTA) and/or trisodium EDTA; The pH value of described inactivating treatment liquid is 2.0-5.0, the content of described water-soluble yttrium salt is counted the 0.01-0.3 mol with yttrium, the content of described oxygenant is the 0.5-50 grams per liter, and the content of described complexing agent is the 1-10 grams per liter, and the content of solubility metavanadate is the 0.1-3 grams per liter.
2. inactivating treatment liquid according to claim 1, wherein, the content of described water-soluble yttrium salt is counted the 0.02-0.1 mol with yttrium, and the content of described oxygenant is the 10-30 grams per liter, the content of described complexing agent is the 1-2 grams per liter, and the content of solubility metavanadate is the 0.5-2 grams per liter.
3. inactivating treatment liquid according to claim 1, wherein, described water-soluble yttrium salt is Yttrium trinitrate and/or acetic acid yttrium.
4. inactivating treatment liquid according to claim 1, wherein, described solubility metavanadate is an ammonium meta-vanadate.
5. method to zinc or zinc alloy surface Passivation Treatment, this method comprise zinc or zinc alloy surface are contacted with inactivating treatment liquid, it is characterized in that described inactivating treatment liquid is any described inactivating treatment liquid among the claim 1-4.
6. method according to claim 5, wherein, the temperature of described contact is 25 ℃-45 ℃, the treatment time of contact is 20 seconds to 60 minutes.
7. method according to claim 6, wherein, with zinc or zinc alloy surface with before inactivating treatment liquid contacts, this method also comprises carries out degreasing, washing and activation to zinc or zinc alloy surface.
8. method according to claim 7, wherein, the method for described degreasing comprises zinc or zinc alloy surface is contacted with grease-removing agent that this grease-removing agent is for containing NaOH, Na
2CO
3, Na
3PO
4And Na
2B
4O
7The aqueous solution, the content of NaOH is the 5-10 grams per liter, Na
2CO
3Content be the 10-15 grams per liter, Na
3PO
4Content be the 5-15 grams per liter, Na
2B
4O
7Content be the 1-10 grams per liter; Described activatory method comprises zinc or zinc alloy surface is contacted with activator that this activator is the aqueous solution that contains silicofluoric acid and fatty alcohol-polyoxyethylene ether, the content of silicofluoric acid be the 1-20 milliliter/liter, the content of fatty alcohol-polyoxyethylene ether is the 0.5-2 grams per liter.
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| CN107326357A (en) * | 2017-08-02 | 2017-11-07 | 合肥市田源精铸有限公司 | A kind of passivation process of galvanized steel plain sheet |
| CN110670055A (en) * | 2019-11-20 | 2020-01-10 | 安徽汇源镀锌有限公司 | Preparation method of vanadate conversion film on hot galvanizing layer |
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| CN1858306A (en) * | 2005-05-08 | 2006-11-08 | 北京化工大学 | Process for cathode electrolytic deposition of rare-earth conversion film |
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