CN106435552A - Cyanide-free galvanized coating passivation liquid and preparing method and application thereof - Google Patents
Cyanide-free galvanized coating passivation liquid and preparing method and application thereof Download PDFInfo
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- CN106435552A CN106435552A CN201610674494.0A CN201610674494A CN106435552A CN 106435552 A CN106435552 A CN 106435552A CN 201610674494 A CN201610674494 A CN 201610674494A CN 106435552 A CN106435552 A CN 106435552A
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- zinc coating
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- cyanide plating
- plating zinc
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- C23C22/44—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
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- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Chemical Treatment Of Metals (AREA)
Abstract
The invention relates to the technical field of coating surfaces, in particular to cyanide-free galvanized coating passivation liquid and a preparing method and application thereof. The chromate serves as a film forming agent, a hole gap filling agent and an auxiliary film forming agent are added, and therefore the passivation liquid can effectively improve the corrosion resisting capability of a coating; in combination of matching treatment of the auxiliary filling agent, an additive and the like, on the premise that the chromate serves as the film forming agent, the corrosion resisting capability of the galvanized coating can be enhanced under the concentration of 4 g/L-6 g/L, and the passivation effect of the medium-concentration chromate passivation liquid can be achieved; and meanwhile, the chromium content in the passivation liquid is reduced, the chromium content in electroplating effluent is reduced, and the subsequent treatment burden of enterprises is effectively reduced.
Description
Technical field
The present invention relates to coating surface technical field, especially a kind of non-cyanide plating zinc coating passivation solution and preparation method thereof and
Application.
Background technology
In order to improve the corrosion resistance of steel plate, in prior art, using carrying out the coating such as zinc-plated, zinc-plated aluminum on steel plate
The fast erosion performance of steel plate is prevented, strengthen the corrosion resistance of steel plate.But, the corrosion resistance of galvanized coatings is still relatively
Low, it is also difficult to meet large area use of the steel plate in some fields, or even can not uses in some fields, this galvanized steel for causing
The range of application of plate is limited to, and hinders the development of galvanized steel plain sheet.For this purpose, in prior art, for the corrosion resistant of galvanized steel plain sheet
Erosion ability is improved using chromating technique, and the corrosion resistance of relative galvanized steel plain sheet coating, can lift 5 times
More than, based on this, chromating technique is widely used in Several Thiourea Derivatives on Zinc Plate Surface treatment industry.
But, in chromating technique, it is typically with middle concentraion chromate or dense of the concentration in 40g/L or so
The high chromium concentration acid salt solution in 120g/L or so is spent as passivating solution, this causes to contain in the waste liquid after being passivated processing
The poisonous and harmful substances such as substantial amounts of Cr VI；And in plating pollutant emission standard《GB 21900-2008》In, in waste water
Cr VI and total chrome content all have strict restriction so that the heavy load of enterprise's subsequent wastewater treatment, economic pressures are larger.
Based on this, in prior art, above-mentioned passivating solution is solved by following several schemes：
(1) Cr VI is replaced to carry out the passivation of zinc coat with trivalent chromium；As Patent No. 201310534260.2《Resistance to height
The preparation method of the wear-resistant Coil Coating Products of temperature》, in preparation process, using trivalent chromium passivator, the change of the trivalent chromium passivator
Consist of 1wt%～3wt% Soluble tartar., 6wt%～10wt% chromic nitrate, 15wt%～20wt% sodium nitrate, 1.5wt%
～3wt% prodan, 2wt%～5wt% nitric acid, 0.5wt%～1wt% hydrochloric acid, 0.1wt%～0.5wt% cobaltic chloride,
0.2wt%～0.6wt% defoamer, balance of water；(2) passivation of zinc coat is carried out using organic capping agent；As Patent No.
200810115662.8《Surface passivation treating liquid for organic-inorganic composite metals》It is organic film former weight using firming agent
1-5%.
But, either the first above-mentioned scheme, or above-mentioned second scheme, which all has many technology and asks
Topic, such as passivation effect is undesirable, and the product quality after passivation is unstable, and coating decay resistance is not directly blunt using chromate
Change the high of liquid.
Content of the invention
In order to solve above-mentioned technical problem present in prior art, the present invention provides a kind of non-cyanide plating zinc coating passivation solution
And its preparation method and application.
It is achieved particular by technical scheme below：
A kind of non-cyanide plating zinc coating passivation solution, film former containing 4-6g in 1L passivating solution, 0.4-0.6g pore filling agent, 1-
2g secondary film formers, 2-8mg aids in filler, 1-3mL additive, and its pH value is 1.8-2.2.
Described passivating solution, per liter in film former containing 5g, 0.5g pore filling agent, 1.5g secondary film formers, 6mg auxiliary fill out
Agent, 2mL additive is filled, and its pH value is 2.
Described pH value is adjusted using phosphoric acid.
Described film former is chromic acid.Here film former can also be chromate, such as sodium chromate, Neutral potassium chromate etc.；
Described pore filling agent is fluosilicate.Here pore filling agent can also be prodan, potassium fluosilicate
Deng；
Described secondary film formers are ammonium molybdate.
Described auxiliary filler is yittrium oxide.
Described additive is monoethanolamine.
The preparation method of above-mentioned non-cyanide plating zinc coating passivation solution, comprises the following steps：
(1) film former is dissolved in deionized water, to be dissolved completely after, add pore filling agent, mix homogeneously, then adopt
Phosphoric acid adjustment pH value is 1.8-2.2, to obtain A liquid；
(2) secondary film formers are dissolved in deionized water, after dissolving completely, add auxiliary filler, interpolation under agitation
Agent, stirs, and obtains B liquid；
(3) by A liquid and B liquid according to volume ratio be:1 mixing, add water adjustment volume, then using phosphorus acid for adjusting pH value is
1.8-2.2, you can.
Deactivating process for the treatment of is that passivating solution is formulated in deactivation slot, adjustment temperature be 60-80 DEG C, and will be zinc-plated after carbon
Steel plating piece carry out zinc-plated process after, and deionized water clean up plating piece surface, then put it in passivating solution soak blunt
Change and 8-15min processed, take out, the passivating solution on surface is cleaned up, is dried, you can.
The invention according to the principle of passivation film forming, with chromate as film former, by add hole filler and
Secondary film formers so that passivating solution can effectively improve the corrosion resistance of coating；In conjunction with auxiliary filler, additive etc.
Allocate process into so that on the premise of chromate is as film former, and in concentration under 4-6g/L, enable to galvanized coatings
Corrosion resistance strengthen, and the passivation effect of middle concentration chromating liquid can be reached, while reducing in passivating solution
Chromium content, reduce chromium content in electroplating effluent, effective burden for alleviating enterprise's subsequent treatment.
The invention during film former, pore filling agent mixed preparing passivating solution, by ammonium molybdate, yittrium oxide
Addition with monoethanolamine so that ammonium molybdate, yittrium oxide and monoethanolamine and film former, pore filling agent occur Synergistic work
With enhancing passivation effect of the passivating solution to galvanized coatings, improve the decay resistance of galvanized coatings.
The invention plates piece, its result by the 45# carbon steel for processing in Neutral Salt Spray Corrosion Processing Example 5-8
For：The corrosion-resistant neutral salt spray time is more than 48h, and coating surface fine uniform has no obvious local crowning or gully.
In the passivating solution of the invention, chromium content is only 1/8th effects of chromium content in traditional chromium passivating solution,
And various material compositions are easily obtained, and cost is relatively low, and in Neutral Salt Spray Corrosion is processed, its corrosion-resistant time is more than
48h, passivating solution that can be effectively with concentration for the middle concentration chromium content of 40g/L compares favourably, and effectively reduces in passivating solution
Chromium content, alleviate processing load of the enterprise to electroplating effluent.
Description of the drawings
Fig. 1 is schemed for the SEM that low concentrations of chromium is passivated.
Fig. 2 is the SEM figure of middle concentration chromium passivating.
Fig. 3 is adopted after low concentrations of chromium passivation and middle concentration chromium passivating for coating, then right after Neutral Salt Spray Corrosion 48h
Than figure.
Specific embodiment
Limited come further to technical scheme with specific embodiment below in conjunction with the accompanying drawings, but required
The scope of protection is not only limited to description.
Embodiment 1
A kind of non-cyanide plating zinc coating passivation solution, film former containing 4g in 1L passivating solution, 0.4g pore filling agent, 1g is aided in into
Membrane, 2mg aids in filler, 1mL additive, and its pH value is 1.8.Described pH value is adjusted using phosphoric acid.Described
Film former be chromic acid.Here film former can also be chromate, such as sodium chromate, Neutral potassium chromate etc.；Described hole is filled out
Agent is filled for fluosilicate.Here pore filling agent can also be prodan, potassium fluosilicate etc.；Described secondary film formers are
Ammonium molybdate.Described auxiliary filler is yittrium oxide.Described additive is monoethanolamine.
Embodiment 2
A kind of non-cyanide plating zinc coating passivation solution, film former containing 6g in 1L passivating solution, 0.6g pore filling agent, 2g is aided in into
Membrane, 8mg aids in filler, 3mL additive, and its pH value is 2.2.Described pH value is adjusted using phosphoric acid.Described
Film former be chromic acid.Here film former can also be chromate, such as sodium chromate, Neutral potassium chromate etc.；Described hole is filled out
Agent is filled for fluosilicate.Here pore filling agent can also be prodan, potassium fluosilicate etc.；Described secondary film formers are
Ammonium molybdate.Described auxiliary filler is yittrium oxide.Described additive is monoethanolamine.
Embodiment 3
A kind of non-cyanide plating zinc coating passivation solution, per liter in film former containing 5g, 0.5g pore filling agent, 1.5g aid in film forming
Agent, 6mg aids in filler, 2mL additive, and its pH value is 2.Described pH value is adjusted using phosphoric acid.Described becomes
Membrane is chromic acid.Here film former can also be chromate, such as sodium chromate, Neutral potassium chromate etc.；Described pore filling agent
For fluosilicate.Here pore filling agent can also be prodan, potassium fluosilicate etc.；Described secondary film formers are molybdic acid
Ammonium.Described auxiliary filler is yittrium oxide.Described additive is monoethanolamine.
Embodiment 4
On the basis of embodiment 1, other all with embodiment 1, the preparation method of non-cyanide plating zinc coating passivation solution, including with
Lower step：
(1) film former is dissolved in deionized water, to be dissolved completely after, add pore filling agent, mix homogeneously, then adopt
Phosphoric acid adjustment pH value is 1.8-2.2, to obtain A liquid；
(2) secondary film formers are dissolved in deionized water, after dissolving completely, add auxiliary filler, interpolation under agitation
Agent, stirs, and obtains B liquid；
(3) by A liquid and B liquid according to volume ratio be:1 mixing, add water adjustment volume, then using phosphorus acid for adjusting pH value is
1.8-2.2, you can.
Embodiment 5
The Passivation Treatment that 45# carbon steel plates piece is carried out using the passivating solution of embodiment 1, deactivating process for the treatment of is to join passivating solution
Make in deactivation slot, adjustment temperature be 60 DEG C, and will be zinc-plated after 45# carbon steel plating piece carry out zinc-plated process after, and use deionization
Water cleans up the surface of plating piece, then puts it into immersion Passivation Treatment 8min in passivating solution, takes out, cleans up the blunt of surface
Change liquid, dry, you can.
Embodiment 6
The Passivation Treatment that 45# carbon steel plates piece is carried out using the passivating solution of embodiment 2, deactivating process for the treatment of is to join passivating solution
Make in deactivation slot, adjustment temperature be 80 DEG C, and will be zinc-plated after 45# carbon steel plating piece carry out zinc-plated process after, and use deionization
Water cleans up the surface of plating piece, then puts it into immersion Passivation Treatment 15min in passivating solution, takes out, cleans up surface
Passivating solution, dries, you can.
Embodiment 7
The Passivation Treatment that 45# carbon steel plates piece is carried out using the passivating solution of embodiment 3, deactivating process for the treatment of is to join passivating solution
Make in deactivation slot, adjustment temperature be 70 DEG C, and will be zinc-plated after 45# carbon steel plating piece carry out zinc-plated process after, and use deionization
Water cleans up the surface of plating piece, then puts it into immersion Passivation Treatment 10min in passivating solution, takes out, cleans up surface
Passivating solution, dries, you can.
Embodiment 8
The Passivation Treatment that 45# carbon steel plates piece is carried out using the passivating solution of embodiment 4, deactivating process for the treatment of is to join passivating solution
Make in deactivation slot, adjustment temperature be 60 DEG C, and will be zinc-plated after 45# carbon steel plating piece carry out zinc-plated process after, and use deionization
Water cleans up the surface of plating piece, then puts it into immersion Passivation Treatment 15min in passivating solution, takes out, cleans up surface
Passivating solution, dries, you can.Cleaning is cleaned using deionized water.
Embodiment 9
1250g chromic acid being dissolved with 35L pure water, after dissolving completely, adds 125g prodan, be uniformly mixed,
Being regulation volume 1.8-2.2, to be added water to 50L using phosphorus acid for adjusting pH value, is obtaining A liquid；
375g ammonium molybdate being dissolved with 35L pure water, after dissolving completely, under agitation, adds yittrium oxide 1.5g, monoethanolamine
500mL, is thoroughly mixed uniformly, adds water and be settled to 50L, obtain B liquid；
In deactivation slot, 10LA liquid is added, 20L is added water, add B liquid 10L under agitation, after mix homogeneously, using phosphorus
Acid for adjusting pH value is 2, adds water and is settled to 50L, obtains passivating solution；
45# carbon steel is carried out zinc-plated process, obtains 45# carbon steel plating piece；The temperature of adjustment passivating solution is 70 DEG C, by 45# carbon
Steel plating piece is placed in immersion Passivation Treatment 10min in passivating solution, obtains passivation 45# carbon steel plating piece；Passivation 45# carbon steel plating piece is carried out
Neutral salt spray corrosion test, is placed on corrosion treatmentCorrosion Science in neutral salt fog environments, and its corrosion-resistant time reaches more than 48h, and
Passivation 45# carbon steel plating piece surface fine uniform, has no obvious local crowning or gully.With using concentration be 40g/L in
Chromium passivating liquid Passivation Treatment is compared, and its corrosion-resistance treatment effect can be matched in excellence or beauty with the middle chromium passivating liquid phase of 40g/L.
Claims (10)
1. a kind of non-cyanide plating zinc coating passivation solution, it is characterised in that film former containing 4-6g in 1L passivating solution, 0.4-0.6g hole
Filler, 1-2g secondary film formers, 2-8mg aids in filler, 1-3mL additive, and its pH value is 1.8-2.2.
2. non-cyanide plating zinc coating passivation solution as claimed in claim 1, it is characterised in that described passivating solution, per liter in contain 5g
Film former, 0.5g pore filling agent, 1.5g secondary film formers, 6mg aids in filler, 2mL additive, and its pH value is 2.
3. non-cyanide plating zinc coating passivation solution as claimed in claim 1 or 2, it is characterised in that described pH value is to adopt phosphoric acid
Adjust.
4. non-cyanide plating zinc coating passivation solution as claimed in claim 1 or 2, it is characterised in that described film former is three oxidations
Chromium.
5. non-cyanide plating zinc coating passivation solution as claimed in claim 1 or 2, it is characterised in that described pore filling agent be
Silicate.
6. non-cyanide plating zinc coating passivation solution as claimed in claim 1 or 2, it is characterised in that described secondary film formers be
Sour ammonium.
7. non-cyanide plating zinc coating passivation solution as claimed in claim 1 or 2, it is characterised in that described auxiliary filler be
Change yttrium.
8. non-cyanide plating zinc coating passivation solution as claimed in claim 1 or 2, it is characterised in that described additive be
Amine.
9. the preparation method of the non-cyanide plating zinc coating passivation solution as described in any one of claim 1-8, it is characterised in that include with
Lower step：
(1) film former is dissolved in deionized water, to be dissolved completely after, add pore filling agent, mix homogeneously, then adopt phosphoric acid
Adjustment pH value is 1.8-2.2, obtains A liquid；
(2) secondary film formers are dissolved in deionized water, after dissolving completely, add auxiliary filler, additive under agitation, stir
Mix uniformly, obtain B liquid；
(3) by A liquid and B liquid according to volume ratio be:1 mixing, add water adjustment volume, then is 1.8- using phosphorus acid for adjusting pH value
2.2, you can.
10. prepared by non-cyanide plating zinc coating passivation solution as described in any one of claim 1-8 or method as claimed in claim 9
Non-cyanide plating zinc coating passivation solution be used for galvanized coatings Passivation Treatment, it is characterised in that deactivating process for the treatment of is to join passivating solution
Make in deactivation slot, adjustment temperature be 60-80 DEG C, and will be zinc-plated after carbon steel plating piece carry out zinc-plated process after, and use deionization
Water cleans up the surface of plating piece, then puts it into immersion Passivation Treatment 8-15min in passivating solution, takes out, cleans up surface
Passivating solution, dry, you can.
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| CN201610674494.0A CN106435552A (en) | 2016-08-16 | 2016-08-16 | Cyanide-free galvanized coating passivation liquid and preparing method and application thereof |
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Cited By (1)
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|---|---|---|---|---|
| CN107523821A (en) * | 2017-07-24 | 2017-12-29 | 贵州理工学院 | A kind of chromium-free passivation liquid and its application |
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