CN104342681A - Passivating film formation liquid and application thereof - Google Patents
Passivating film formation liquid and application thereof Download PDFInfo
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- CN104342681A CN104342681A CN201410487597.7A CN201410487597A CN104342681A CN 104342681 A CN104342681 A CN 104342681A CN 201410487597 A CN201410487597 A CN 201410487597A CN 104342681 A CN104342681 A CN 104342681A
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- free
- film forming
- forming liquid
- passivation film
- steel surface
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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
- C23C22/42—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 phosphates
-
- 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
- C23C22/60—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 alkaline aqueous solutions with pH greater than 8
- C23C22/62—Treatment of iron or alloys based thereon
-
- 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
- C23C22/68—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 solutions with pH between 6 and 8
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The invention discloses passivating film formation liquid and application thereof. Every liter of the passivating film formation liquid comprises 5-40g of molybdate, 0.8-1.2g of tungstate, 20-30g of phosphate, 15-20g of sodium silicate, 20-30g of thiocarbamide, 15-25g of benzotriazole and the balance of water, wherein the pH value is between 4 and 9. The passivating film formation liquid is applicable to chromate-free passivation carried out on a free-cutting steel surface. A passivating film formed by the passivating film formation liquid is continuous and complete, and is capable of converting a metal surface having original active chemical properties into a metal surface having inert chemical properties so as to isolate the metal surface from having chemical reactions with external substances and achieve a long-term rust preventing effect; in addition, the passivating film formation liquid has a good passivating effect. The passivating film formation liquid can be applied to chromate-free passivation carried out on a free-cutting steel surface, is convenient to use, short in film forming time, low in reaction temperature and has obvious advantages in comparison with existing chromate-free passivation techniques.
Description
Technical field
The invention belongs to metal passivation field, more specifically, relate to a kind of passivation film forming liquid and application thereof.
Background technology
Stainless steel is that a kind of silvery white has excellent solidity to corrosion, wear resistance, obdurability and technological alloy metal material.Have the advantages in the majority such as good mechanical property, chemical stability, comfortable surperficial state of nature because of it, be widely used in the fields such as aerospace, military project manufacture, medical equipment, energy source and power at present.Meanwhile, the decoration industry wide world especially such as building decoration, galley equipment, auto parts machinery, daily office product, bring larger space and the challenge of requirements at the higher level to stainless steel.Wherein Cutting free type stainless steel is because having good machining property and bright and clean surface working pattern is dark especially in decoration industry is favored.
The oxide film that tradition stainless material relies on its element such as surface C r and Ni to be formed plays the anti-corrosion effect of good passivation.Wherein especially extensive with the use of austenitic stainless steel, and common dry method and wet method passivation mode can reach comparatively good passivation for stainless steel effect.But free cutting stainless steel is because adding the inclusion that after the elements such as S, Ca, Pb, Mn, Se, Cu, Si, chemically reactive is large between crystal boundary area easily forms metallic matrix and be nonmetal.Sulfide inclusion is the most responsive position of stainless steel germinating spot corrosion, and it is also the position of spot corrosion sensitivity that mixed type sulphide-oxide and sulfide-silicate are mingled with, and this causes free cutting stainless steel passivation very difficult.
Main employing chromating method at present, but this passivating method is because the height of hexavalent chromium is malicious, high pollution, brings very large harm, prohibitted the use by European Union's new standard to environment sustainable development and health of human body.The research of chromium-free deactivation technology mainly concentrates in the Passivation Treatment of zinc coating and the exploitation of Inorganic whisker passivating solution and technique, and needs higher film-forming temperature or longer film formation time.Simultaneously for the not open report of chromium-free passivation liquid of free-cutting steel surface treatment.
Summary of the invention
For above defect or the Improvement requirement of prior art, the invention provides a kind of passivation film forming liquid and application thereof, its object is to be chosen to film and proportioning thereof, solve current passivation film forming liquid containing metal chromium thus, pollute comparatively large or that film formation reaction temperature is higher, passivation effect is undesirable technical problem.
For achieving the above object, according to one aspect of the present invention, provide a kind of passivation film forming liquid, containing molybdate 5 ~ 40g, tungstate 0.8 ~ 1.2g in often liter of passivation film forming liquid, phosphoric acid salt 20 ~ 30g, water glass 15 ~ 20g, thiocarbamide 20 ~ 30g, benzotriazole 15 ~ 25g, surplus is water, and its pH value is between 4 to 9.
Preferably, described passivation film forming liquid, its molybdate is one or more the mixture in Sodium orthomolybdate, potassium molybdate and ammonium molybdate.
Preferably, described passivation film forming liquid, its tungstate is one or more the mixture in sodium wolframate, potassium wolframate and ammonium tungstate.
Preferably, described passivation film forming liquid, its phosphoric acid salt is dihydrogen phosphate, one or more the mixture in hydroxyl own fork base di 2 ethylhexyl phosphonic acid, 2-phosphate-1,2,4-butane tricarboxylate and hydroxy ethylene diphosphonic acid.
According to another aspect of the present invention, provide a kind of passivation film forming liquid and be applied to the passivation of free-cutting steel surface chromium-free.
Preferably, described passivation film forming liquid is applied to the passivation of free-cutting steel surface chromium-free, is to make to contact with described passivation film forming liquid through the free-cutting steel surface of steel surface purifying treatment, reacts 20 seconds to 60 seconds at 40 DEG C to 70 DEG C.
Preferably, described passivation film forming liquid is applied to the passivation of free-cutting steel surface chromium-free, and described steel surface purifying treatment comprises processing of rust removing and oil removal treatment.
In general, the above technical scheme conceived by the present invention compared with prior art, following beneficial effect can be obtained:
(1) chromium-free passivation liquid provided by the invention, comprise efficient deposited film membrane-forming agent, molybdate, tungstate, phosphoric acid salt and silicate, and adsorption film membrane-forming agent thiocarbamide and benzotriazole, pass through great many of experiments, determine its proportioning, during use, deposited film membrane-forming agent and metallic surface form firmly deposited film, adsorption film membrane-forming agent is adsorbed on deposited film and forms passive film, the passive film of such formation is continuous and complete, metallic surface active for original chemical property is changed into the metallic surface of chemical inertness, reach chemical reaction that is isolated and external substance, thus reach the effect of long-term rust prevention, good passivation effect,
(2) the present invention can be applicable to the passivation of free-cutting steel surface chromium-free, and easy to use, film formation time is shorter, and temperature of reaction is low, possesses significantly a little compared with existing chromium-free deactivation technology.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.In addition, if below in described each embodiment of the present invention involved technical characteristic do not form conflict each other and just can mutually combine.
Passivation film forming liquid provided by the invention, often liter containing molybdate 5 ~ 40g, tungstate 0.8 ~ 1.2g, phosphoric acid salt 20 ~ 30g, water glass 15 ~ 20g, thiocarbamide 20 ~ 30g, benzotriazole 15 ~ 25g, surplus is water, regulates its pH value between 4 to 9 with highly basic or strong acid.Described molybdate is one or more the mixture in Sodium orthomolybdate, potassium molybdate and ammonium molybdate; Described tungstate is one or more the mixture in sodium wolframate, potassium wolframate and ammonium tungstate; Described phosphoric acid salt is dihydrogen phosphate, one or more the mixture in hydroxyl own fork base di 2 ethylhexyl phosphonic acid, 2-phosphate-1,2,4-butane tricarboxylate and hydroxy ethylene diphosphonic acid.Highly basic is as sodium hydroxide; Strong acid is as nitric acid.
Passivation film forming liquid provided by the invention should can be used for the passivation of free-cutting steel surface chromium-free, and concrete grammar is: make to contact with described passivation film forming liquid through the free-cutting steel surface of steel surface purifying treatment, react 20 seconds to 60 seconds at 40 DEG C to 70 DEG C.Described steel surface purifying treatment comprises processing of rust removing and oil removal treatment.
Be below embodiment:
Embodiment 1
Passivation film forming liquid provided by the invention, often liter contains potassium molybdate 5g, sodium wolframate 1.2g, and SODIUM PHOSPHATE, MONOBASIC 30, water glass 18g, thiocarbamide 30, g, benzotriazole 15g, surplus is water, regulates its pH value to be 7.5.
With above-mentioned passivation film forming liquid, process 303CU free cutting stainless steel, step is as follows:
Make to contact with described passivation film forming liquid through the free-cutting steel surface of steel surface purifying treatment, react 20 seconds at 70 DEG C.Described steel surface purifying treatment comprises processing of rust removing and oil removal treatment, is specially:
(1) steel surface processing of rust removing: the steel surface heavier for surface contamination carries out processing of rust removing;
(2) steel surface oil removal treatment: use acetone to soak 12h oil removing, then use ethanol purge, cold wind dries up.
Neutral salt spray test: according to the test of GB/T 10125-1997 artificial atmosphere corrosion test salt-fog test, through 24 hours neutral salt spray tests, specimen surface iron is embroidered area and is less than 0.1%, illustrates that passive film solidity to corrosion is good.
Embodiment 2
Passivation film forming liquid provided by the invention, often liter contains Sodium orthomolybdate 40g, potassium wolframate 0.8g, 2-phosphate-1,2,4-butane tricarboxylate 20g, and water glass 15g, thiocarbamide 25g, benzotriazole 25g, surplus is water, regulates its pH value to be 4.
With above-mentioned passivation film forming liquid, process 303CU free cutting stainless steel, step is as follows:
Make to contact with described passivation film forming liquid through the free-cutting steel surface of steel surface purifying treatment, react 60 seconds at 40 DEG C.Described steel surface purifying treatment comprises processing of rust removing and oil removal treatment, is specially:
(1) steel surface processing of rust removing: the steel surface heavier for surface contamination carries out processing of rust removing;
(2) steel surface oil removal treatment: use acetone to soak 12h oil removing, then use ethanol purge, cold wind dries up.
Neutral salt spray test: according to the test of GB/T 10125-1997 artificial atmosphere corrosion test salt-fog test, through 24 hours neutral salt spray tests, specimen surface iron is embroidered area and is less than 0.1%, illustrates that passive film solidity to corrosion is good.
Embodiment 3
Passivation film forming liquid provided by the invention, often liter contains ammonium molybdate 20g, ammonium tungstate 1.0g, hydroxyl own fork base di 2 ethylhexyl phosphonic acid 25g, and water glass 20g, thiocarbamide 20g, benzotriazole 20g, surplus is water, regulates its pH value to be to 9.
With above-mentioned passivation film forming liquid, process 303CU free cutting stainless steel, step is as follows:
Make to contact with described passivation film forming liquid through the free-cutting steel surface of steel surface purifying treatment, react 40 seconds at 50 DEG C.Described steel surface purifying treatment comprises processing of rust removing and oil removal treatment, is specially:
(1) steel surface processing of rust removing: the steel surface heavier for surface contamination carries out processing of rust removing;
(2) steel surface oil removal treatment: use acetone to soak 12h oil removing, then use ethanol purge, cold wind dries up.
Neutral salt spray test: according to the test of GB/T 10125-1997 artificial atmosphere corrosion test salt-fog test, through 24 hours neutral salt spray tests, specimen surface iron is embroidered area and is less than 0.1%, illustrates that passive film solidity to corrosion is good.
Those skilled in the art will readily understand; the foregoing is only preferred embodiment of the present invention; not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. a passivation film forming liquid, is characterized in that, containing molybdate 5 ~ 40g, tungstate 0.8 ~ 1.2g in often liter of passivation film forming liquid, phosphoric acid salt 20 ~ 30g, water glass 15 ~ 20g, thiocarbamide 20 ~ 30g, benzotriazole 15 ~ 25g, surplus is water, and its pH value is between 4 to 9.
2. passivation film forming liquid as claimed in claim 1, it is characterized in that, described molybdate is one or more the mixture in Sodium orthomolybdate, potassium molybdate and ammonium molybdate.
3. passivation film forming liquid as claimed in claim 1, it is characterized in that, described tungstate is one or more the mixture in sodium wolframate, potassium wolframate and ammonium tungstate.
4. passivation film forming liquid as claimed in claim 1, it is characterized in that, described phosphoric acid salt is dihydrogen phosphate, one or more the mixture in hydroxyl own fork base di 2 ethylhexyl phosphonic acid, 2-phosphate-1,2,4-butane tricarboxylate and hydroxy ethylene diphosphonic acid.
5. the passivation film forming liquid as described in Claims 1-4 is applied to the passivation of free-cutting steel surface chromium-free.
6. passivation film forming liquid as claimed in claim 5 is applied to the passivation of free-cutting steel surface chromium-free, it is characterized in that, makes to contact with described passivation film forming liquid through the free-cutting steel surface of steel surface purifying treatment, reacts 20 seconds to 60 seconds at 40 DEG C to 70 DEG C.
7. passivation film forming liquid as claimed in claim 5 is applied to the passivation of free-cutting steel surface chromium-free, and it is characterized in that, described steel surface purifying treatment comprises processing of rust removing and oil removal treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201410487597.7A CN104342681A (en) | 2014-09-22 | 2014-09-22 | Passivating film formation liquid and application thereof |
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| CN201410487597.7A CN104342681A (en) | 2014-09-22 | 2014-09-22 | Passivating film formation liquid and application thereof |
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| CN201410487597.7A Pending CN104342681A (en) | 2014-09-22 | 2014-09-22 | Passivating film formation liquid and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109097766A (en) * | 2018-08-31 | 2018-12-28 | 北京科技大学广州新材料研究院 | A kind of alkalinity molybdate chromium-free passivation liquid and its passivating method |
| CN109161881A (en) * | 2018-09-20 | 2019-01-08 | 惠州联合铜箔电子材料有限公司 | The anti-oxidation liquid of a kind of Chrome-free of electrolytic copper foil and without washing anti-oxidation technique |
| CN109382287A (en) * | 2018-10-31 | 2019-02-26 | 安徽芜湖海螺建筑安装工程有限责任公司 | High stability anchoring piece and preparation method thereof |
| CN112626511A (en) * | 2020-11-27 | 2021-04-09 | 瑞声科技（南京）有限公司 | Steel sheet passivation process, passivated steel sheet and temperature-equalizing plate |
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| CN101353204A (en) * | 2007-07-27 | 2009-01-28 | 首钢总公司 | Silicon tungsten phosphor corrosion inhibitor for demineralized water circulation and cooling system |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109097766A (en) * | 2018-08-31 | 2018-12-28 | 北京科技大学广州新材料研究院 | A kind of alkalinity molybdate chromium-free passivation liquid and its passivating method |
| CN109161881A (en) * | 2018-09-20 | 2019-01-08 | 惠州联合铜箔电子材料有限公司 | The anti-oxidation liquid of a kind of Chrome-free of electrolytic copper foil and without washing anti-oxidation technique |
| CN109382287A (en) * | 2018-10-31 | 2019-02-26 | 安徽芜湖海螺建筑安装工程有限责任公司 | High stability anchoring piece and preparation method thereof |
| CN112626511A (en) * | 2020-11-27 | 2021-04-09 | 瑞声科技（南京）有限公司 | Steel sheet passivation process, passivated steel sheet and temperature-equalizing plate |
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