CN104775110A - Additive for restoring passivation performance of molybdate treating fluid applicable to galvanizing coat surface - Google Patents
Additive for restoring passivation performance of molybdate treating fluid applicable to galvanizing coat surface Download PDFInfo
- Publication number
- CN104775110A CN104775110A CN201510185941.1A CN201510185941A CN104775110A CN 104775110 A CN104775110 A CN 104775110A CN 201510185941 A CN201510185941 A CN 201510185941A CN 104775110 A CN104775110 A CN 104775110A
- Authority
- CN
- China
- Prior art keywords
- molybdate
- additive
- treatment solution
- treating fluid
- passivation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Chemical Treatment Of Metals (AREA)
Abstract
The invention belongs to the technical fields of metal surface corrosion and protective treatment, and particularly relates to an additive for restoring passivation performance of a molybdate treating fluid applicable to a galvanizing coat surface. Every liter of additive comprises 1.5-2.5g of inorganic nickel salt (on the basis of nickel ion content), 1.5-2.5g of hydrogen peroxide and the balance of distilled water. When being added into the molybdate treating fluid without passivation performance, the additive can restore the passivation performance and prolong the service life of the molybdate treating fluid. The passivating film prepared from the molybdate treating fluid with restored passivation performance has the same appearance and corrosion resistance as the passivating film prepared from the newly prepared molybdate treating fluid. The additive is free of chromium, thereby reducing the environmental pollution. The additive has the advantages of low cost, simple components, high controllability and stable technique.
Description
Technical field
The invention belongs to corrosion and protective treatment technical field, particularly relate to the additive that a kind of molybdate treatment solution being used in Several Thiourea Derivatives on Zinc Plate Surface recovers inactivating performance.
Background technology
The steel plate galvanized that steel surface galvanizing and electro-galvanizing obtain and zinc-plated structural part are widely used in fields such as automobile, building, household electrical appliances, machineries.Due to the chemical activity of zinc, easily there is corrosion and produce " white rust " in zinc coating under environment for use, affects product appearance quality, cause zinc coating come off and lose the provide protection to steel substrate time serious.Chromating is the traditional method improving Corrosion Resistance of Zinc Coating, but the severe contamination of hexavalent chromium to human body and ecotope causes chromic salt treatment process to be limited to use or prohibit the use.Large quantity research display both at home and abroad, in the phosphato-molybdic heteropolyacid solution system by molybdate and phosphoric acid salt being main salt, Zinc Deposit can obtain the chemical conversion film of excellent corrosion resistance, due to solution low toxicity, little to environmental influence, be considered to the environmentally friendly chemical conversion membrane process most possibly substituting chromating.
Phosphato-molybdic heteropolyacid solution add adjustment and long lifetime maintenance is the gordian technique of molybdate chemical conversion treatment.There are some researches show, along with the increase for the treatment of solution accumulated process metallic area, because consuming gradually, concentration changes main salt ion, conversion film also relates to the interaction of various composition in the dissolving of metallic matrix and treatment solution in forming process, new ion will be increased in treatment solution, in treatment solution, each composition also may relate to redox reaction and cause the change of chemical valence state simultaneously, therefore, molybdate passivation solution is after the certain area zinc coating of accumulated process, due to the change for the treatment of solution composition and concentration, passivating solution will lose passivation ability gradually.As the Technology being hopeful most alternative traditional chromium hydrochlorate passivating solution, solve the long lifetime maintenance issues for the treatment of solution, make the treatment solution losing passivation ability again recover passivation ability, significant for the application industrially of zinc coating molybdate chemically transformed film technique.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of molybdate treatment solution being used in Several Thiourea Derivatives on Zinc Plate Surface to recover the additive of inactivating performance, thus solve the long lifetime maintenance issues of zine plated layer on metal body surface molybdate treatment solution, make the molybdate treatment solution losing passivation ability again recover inactivating performance.
The present invention is achieved in that a kind of molybdate treatment solution being used in Several Thiourea Derivatives on Zinc Plate Surface recovers the additive of inactivating performance, by often liter of content meter, comprise inorganic nickel 1.5 ~ 2.5g, hydrogen peroxide 1.5 ~ 2.5g, all the other are distilled water, and the content of described inorganic nickel is calculated by contained nickel ion gauge.
Further, described inorganic nickel is one or both in single nickel salt, nickelous chloride.
Further, described inorganic nickel is single nickel salt.
Further, by often liter of content meter, described additive comprises inorganic nickel 2g, hydrogen peroxide 2g, and all the other are distilled water, and the content of described inorganic nickel is calculated by contained nickel ion gauge.
Compared with prior art, beneficial effect is in the present invention: described in be used in Several Thiourea Derivatives on Zinc Plate Surface molybdate treatment solution recover the additive of inactivating performance the molybdate treatment solution of inefficacy can be made to recover inactivating performance, the life-span significantly extends; After utilizing additive of the present invention to make molybdate treatment solution recover passivation ability, prepared passive film is consistent with the passive film outward appearance of newly joining prepared by molybdate treatment solution and solidity to corrosion; Not containing chromium, reduce the pollution to environment; With low cost, composition is simple, is easy to control, process stabilizing.
Accompanying drawing explanation
Below in conjunction with drawings and the embodiments, the present invention is further detailed explanation:
Fig. 1 is the polarization curve of passive film in 3.5%NaCl solution (a: newly join the passive film polarization curve b that molybdate treatment solution is formed: the passive film polarization curve that inefficacy molybdate treatment solution is formed) of different times molybdate treatment solution process Coating process;
Fig. 2 is the polarization curve of passive film in 3.5%NaCl solution (a: the passive film polarization curve b adding additive aftertreatment Coating process of the present invention in the molybdate treatment solution lost efficacy: the passive film polarization curve of the molybdate treatment solution process Coating process again lost efficacy) of the molybdate treatment solution different times process Coating process adding additive of the present invention;
Fig. 3 is the passive film scanning electron microscope pattern of newly joining molybdate treatment solution process Coating process;
Fig. 4 adopts the passive film scanning electron microscope pattern adding additive aftertreatment Coating process of the present invention in the molybdate treatment solution lost efficacy.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is described in further detail.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The invention provides the additive that a kind of molybdate treatment solution being used in Several Thiourea Derivatives on Zinc Plate Surface recovers inactivating performance, by often liter of content meter, described additive comprises inorganic nickel 1.5 ~ 2.5g, hydrogen peroxide 1.5 ~ 2.5g, all the other are distilled water, and the content of wherein said inorganic nickel is calculated by contained nickel ion gauge, specifically, described inorganic nickel can be one or both in single nickel salt or nickelous chloride, and optimal selection is single nickel salt.
Recover in the additive of inactivating performance at the described molybdate treatment solution being used in Several Thiourea Derivatives on Zinc Plate Surface, the effect of inorganic nickel mainly promotes the dissolving of conversion film film forming initial stage metallic matrix; The effect of hydrogen peroxide mainly keeps main salt chemistry in treatment solution in stable condition.
The invention provides the optimization formula that a kind of molybdate treatment solution being used in Several Thiourea Derivatives on Zinc Plate Surface recovers the additive of inactivating performance, by often liter of content meter, comprise inorganic nickel 2g, hydrogen peroxide 2g, all the other are distilled water, and the content of described inorganic nickel is calculated by contained nickel ion gauge.
Below with the pure zinc coating of difference for subjects, with newly joining the pure zinc coating of molybdate treatment solution process until treatment solution loses passivation, additive of the present invention is joined in inefficacy molybdate treatment solution, again passivation is carried out to pure zinc coating and form passive film, finally contrast electrochemical tests and the scanning electron microscope pattern of the passive film of newly joining the formation of molybdate treatment solution process pure zinc coating and the passive film adding the pure zinc coating formation of additive aftertreatment of the present invention in the molybdate treatment solution lost efficacy, result as shown in Figure 1,2,3, 4.
Embodiment 1
With the pure zinc coating of surface of cold-rolled steel plate galvanizing gained for subjects
Pre-treatment
Degreasing: under room temperature, utilizes the pure zinc coating of acetone ultrasonic washing surface of cold-rolled steel plate galvanizing gained, 3 ~ 4 minutes time, then uses tap water 1 ~ 2 minute, deionized water wash 0.5 ~ 1 minute;
Alkaline etch: pure for the surface of cold-rolled steel plate galvanizing gained after degreasing zinc coating is immersed in the NaOH aqueous solution of 5g/L, process 1 minute at 60 DEG C, then tap water 1 ~ 2 point, deionized water wash 0.5 ~ 1 minute;
Newly join the pure zinc coating of molybdate treatment solution process
The pure zinc coating of pretreated surface of cold-rolled steel plate galvanizing gained is carried out Passivation Treatment, adopt molybdate prescription for the treatment of liquid to be: Na
2moO
42H
2o 20 ~ 30g/L, Na
3pO
412H
2o 15 ~ 20g/L, CH
3cOONa 3 ~ 5g/L, all the other are distilled water.Temperature 50 ~ 60 DEG C, time 60 ~ 80s, pH value 2 ~ 3, process to molybdate treatment solution can not obtain qualified passive film continuously;
Molybdate treatment solution recovers passivation to the passivation again of pure zinc coating
Adopt additive of the present invention, it contains inorganic nickel 1.5g/L (calculating by nickeliferous ionic weight), H
2o
21.5g/L, all the other are distilled water, add in inefficacy molybdate treatment solution under room temperature, and by phosphoric acid and sodium hydroxide adjust ph in 2 ~ 3 scopes, control temperature 50 ~ 60 DEG C, process 60 ~ 80s, prepares the passive film made new advances.
Embodiment 2
Be with the difference of embodiment 1:
Recover passivation in pure zinc coating again passivation step at molybdate treatment solution, the additive of the present invention of employing, it contains inorganic nickel 2.5g/L (calculating by nickeliferous ionic weight), H
2o
22.5g/L, all the other are distilled water.
Embodiment 3
Be with the difference of embodiment 1:
Recover passivation in pure zinc coating again passivation step at molybdate treatment solution, the additive of the present invention of employing, it contains inorganic nickel 2g/L (calculating by nickeliferous ionic weight), H
2o
22g/L, all the other are distilled water.
Embodiment 4
Pure zinc coating is electroplated for subjects with surface of cold-rolled steel plate
Pre-treatment
Degreasing: under room temperature, utilizes acetone ultrasonic washing surface of cold-rolled steel plate to electroplate pure zinc coating, 3 ~ 5 minutes time, then uses tap water 1 ~ 2 minute, deionized water wash 0.5 ~ 1 minute;
Alkaline etch: the surface of cold-rolled steel plate after degreasing is electroplated pure zinc coating and immerse in the NaOH aqueous solution of 3g/L, process 1 minute at 50 DEG C, then tap water 1 ~ 2 point, deionized water wash 0.5 ~ 1 minute;
Newly join the pure zinc coating of molybdate treatment solution process
Pretreated surface of cold-rolled steel plate is electroplated pure zinc coating and carries out Passivation Treatment, adopt molybdate prescription for the treatment of liquid to be: Na
2moO
42H
2o 25 ~ 35g/L, Na
3pO
412H
2o 10 ~ 15g/L, CH
3cOONa4 ~ 5g/L, all the other are distilled water.Temperature 60 ~ 65 DEG C, 80 ~ 100 seconds time, pH value 3 ~ 4, process to molybdate treatment solution can not obtain qualified passive film continuously.
Molybdate treatment solution recovers passivation to the passivation again of pure zinc coating
Adopt additive of the present invention, it contains inorganic nickel 1.5g/L (calculating by nickeliferous ionic weight), H
2o
21.5g/L, all the other are distilled water, add in inefficacy molybdate treatment solution under room temperature, and by phosphoric acid and sodium hydroxide adjust ph in 3 ~ 4 scopes, control temperature 60 ~ 65 DEG C, process 80 ~ 100s, prepares the passive film made new advances.
Embodiment 5
Be with the difference of embodiment 4:
Recover passivation in pure zinc coating again passivation step at molybdate treatment solution, the additive of the present invention of employing, it contains inorganic nickel 2.5g/L (calculating by nickeliferous ionic weight), H
2o
22.5g/L, all the other are distilled water.
Embodiment 6
Be with the difference of embodiment 4:
Recover passivation in pure zinc coating again passivation step at molybdate treatment solution, the additive of the present invention of employing, it contains inorganic nickel 2g/L (calculating by nickeliferous ionic weight), H
2o
22g/L, all the other are distilled water.
As shown in Figure 1, curve a anode branch has obvious passivation region, and curve b is accumulated process 0.336m
2(add up through test of many times result, molybdate treatment solution for often liter of newly preparation continues the maximum area processing zinc coating) process the polarization curve of gained passive film afterwards further, anode branch passivation region disappears and presents active dissolution feature, shows that treatment solution loses passivation ability.To lost efficacy molybdate treatment solution in add described additive make treatment solution regenerate after, the polarization curve anode branch of prepared passive film has recovered passivation region, again as shown in a curve in Fig. 2; Recover the molybdate treatment solution accumulated process 0.384m of passivation
2after zinc coating, passive film polarization curve anode branch passivation region disappears, as shown in b curve in Fig. 2.
As can be seen from the contrast of Fig. 1 and Fig. 2, by the passive film polarization curve that obtains after adding additive of the present invention and making molybdate treatment solution again recover passivation ability with newly to join the passive film polarization curve that molybdate obtains basically identical, after explanation adds additive of the present invention, molybdate treatment solution has recovered passivation ability.
As can be seen from the contrast of Fig. 3 and Fig. 4; the molybdate passivating liquid lost efficacy is after adding additive of the present invention and recovering passivation ability; prepared passive film to newly join molybdate treatment solution gained passive film there is similar shape characteristic; Several Thiourea Derivatives on Zinc Plate Surface defines uniform passive film; illustrate that the passivation ability of the passivation ability after the recovery of molybdate treatment solution and new configuration process liquid is suitable, protection can be provided to zinc coating equally.
Claims (4)
1. the molybdate treatment solution being used in Several Thiourea Derivatives on Zinc Plate Surface recovers an additive for inactivating performance, it is characterized in that, by often liter of content meter, comprise inorganic nickel 1.5 ~ 2.5g, hydrogen peroxide 1.5 ~ 2.5g, all the other are distilled water, and the content of described inorganic nickel is calculated by contained nickel ion gauge.
2. the molybdate treatment solution being used in Several Thiourea Derivatives on Zinc Plate Surface according to claim 1 recovers the additive of inactivating performance, it is characterized in that, described inorganic nickel is one or both in single nickel salt, nickelous chloride.
3. the molybdate treatment solution being used in Several Thiourea Derivatives on Zinc Plate Surface according to claim 2 recovers the additive of inactivating performance, and it is characterized in that, described inorganic nickel is single nickel salt.
4. the molybdate treatment solution being used in Several Thiourea Derivatives on Zinc Plate Surface according to claim 1 recovers the additive of inactivating performance, it is characterized in that, by often liter of content meter, described additive comprises inorganic nickel 2g, hydrogen peroxide 2g, all the other are distilled water, and the content of described inorganic nickel is calculated by contained nickel ion gauge.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510185941.1A CN104775110A (en) | 2015-04-17 | 2015-04-17 | Additive for restoring passivation performance of molybdate treating fluid applicable to galvanizing coat surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510185941.1A CN104775110A (en) | 2015-04-17 | 2015-04-17 | Additive for restoring passivation performance of molybdate treating fluid applicable to galvanizing coat surface |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104775110A true CN104775110A (en) | 2015-07-15 |
Family
ID=53616871
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510185941.1A Pending CN104775110A (en) | 2015-04-17 | 2015-04-17 | Additive for restoring passivation performance of molybdate treating fluid applicable to galvanizing coat surface |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104775110A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109943835A (en) * | 2019-04-30 | 2019-06-28 | 兴化市华成镀锌管件有限公司 | A kind of preparation method of hot galvanized layer rare-earth salt passivation liquid |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101886259A (en) * | 2010-06-25 | 2010-11-17 | 武汉钢铁(集团)公司 | Zinc coat environmental-friendly passivation solution and use method thereof |
| CN102031510A (en) * | 2010-12-30 | 2011-04-27 | 合肥华清金属表面处理有限责任公司 | Metal zinc coating blackening agent and preparation method thereof |
| CN102418095A (en) * | 2011-11-18 | 2012-04-18 | 东莞市东辉贸易有限公司 | Galvanized chromium-free black passivating agent and preparation method thereof |
| CN103849868A (en) * | 2014-02-14 | 2014-06-11 | 浙江工业大学 | Blackening liquid for chromium-free titanium-zinc panel surface and using method of blackening liquid |
| WO2014104428A1 (en) * | 2012-12-26 | 2014-07-03 | 주식회사 포스코 | Surface-processing composition for galvanized steel sheet, surface processing method for galvanized steel sheet, and galvanised steel sheet |
| CN104404492A (en) * | 2014-12-24 | 2015-03-11 | 湖南金裕化工有限公司 | Chromium-free passivation solution as well as preparation and using methods thereof |
-
2015
- 2015-04-17 CN CN201510185941.1A patent/CN104775110A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101886259A (en) * | 2010-06-25 | 2010-11-17 | 武汉钢铁(集团)公司 | Zinc coat environmental-friendly passivation solution and use method thereof |
| CN102031510A (en) * | 2010-12-30 | 2011-04-27 | 合肥华清金属表面处理有限责任公司 | Metal zinc coating blackening agent and preparation method thereof |
| CN102418095A (en) * | 2011-11-18 | 2012-04-18 | 东莞市东辉贸易有限公司 | Galvanized chromium-free black passivating agent and preparation method thereof |
| WO2014104428A1 (en) * | 2012-12-26 | 2014-07-03 | 주식회사 포스코 | Surface-processing composition for galvanized steel sheet, surface processing method for galvanized steel sheet, and galvanised steel sheet |
| CN103849868A (en) * | 2014-02-14 | 2014-06-11 | 浙江工业大学 | Blackening liquid for chromium-free titanium-zinc panel surface and using method of blackening liquid |
| CN104404492A (en) * | 2014-12-24 | 2015-03-11 | 湖南金裕化工有限公司 | Chromium-free passivation solution as well as preparation and using methods thereof |
Non-Patent Citations (3)
| Title |
|---|
| 刘艳荣 等: "镀锌板表面无铬钝化的研究进展", 《电镀与精饰》 * |
| 周婉秋 等: "热镀锌板钼酸盐转化膜制备及耐腐蚀性能研究", 《沈阳师范大学学报(自然科学版)》 * |
| 王建 等: "热浸镀Zn-Al合金钝化工艺及耐蚀性能研究", 《电镀与精饰》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109943835A (en) * | 2019-04-30 | 2019-06-28 | 兴化市华成镀锌管件有限公司 | A kind of preparation method of hot galvanized layer rare-earth salt passivation liquid |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103422082B (en) | Neodymium-iron-boron magnetic material Zinc phosphating solution and its application method | |
| CN101532153B (en) | Amorphous nano-alloy plating layer of electrodeposition nickel-based series, electroplating liquid and electroplating process | |
| CN103255453B (en) | Method for plating copper on stainless steel | |
| CN102828210B (en) | Method for electroplating zinc-nickel alloy through neodymium iron boron magnet ionic liquid | |
| CN101824619B (en) | Preparation method of foam tin material | |
| CN204918772U (en) | A high corrosion resistance cadmium plating layer for aerospace spare part | |
| CN101418443A (en) | Chromium-free inactivating liquor for continuous galvanizing by hot-dip galvanized steel sheet | |
| CN102383156A (en) | Electroplating and spraying composite protection method of neodymium iron boron magnet | |
| CN102260889B (en) | High-corrosion-resistance bright soft zinc-cobalt alloy electroplating process | |
| WO2014157105A1 (en) | Zinc-nickel alloy plating solution and plating method | |
| CN104562107A (en) | Highly-corrosion-resistant environment-friendly black tin-cobalt alloy electroplating liquid and electroplating method thereof. | |
| CN102312238A (en) | Preparation of zinc nickel plating layer and trivalent chromium passivation process thereof | |
| CN102677033B (en) | Wear-resistant manganese phosphating solution | |
| CN104087927B (en) | Magnesium-alloy material surface modifying treatment | |
| CN102108533A (en) | Multi-layer electroplating process for making coins by using cyanide-free plating copper-tin alloy layer as surface layer | |
| CN103215574B (en) | Magnesium-alloy chemical nickel plating solution and nickel plating process thereof | |
| CN102747360A (en) | Chromium-free passivation method for galvanized steel sheet by using molybdate/polyphosphate composite system | |
| CN1896307A (en) | Copper-alloy chemical nickeling process | |
| Yan et al. | Electrochemical reduction process of Co (II) in citrate solution | |
| CN102888601A (en) | Trivalent chromium black passivation plating solution for zinc coating | |
| CN104775110A (en) | Additive for restoring passivation performance of molybdate treating fluid applicable to galvanizing coat surface | |
| CN205556812U (en) | Compound plating layer structure of black chromium is electroplated to high corrosion resistance trivalent chromium | |
| CN103774126B (en) | Electricimpulse improves the method for Ni-P Chemical Plating Layer thickness | |
| CN107236977A (en) | A kind of electroplating pretreatment process optimization method | |
| CN104404584A (en) | Zinc-nickel alloy electroplating technique |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150715 |