CN108359969A - A kind of preparation method of aluminum alloy surface environmental protection self-cure type titanium/zirconium/molybdenum conversion film - Google Patents
A kind of preparation method of aluminum alloy surface environmental protection self-cure type titanium/zirconium/molybdenum conversion film Download PDFInfo
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- CN108359969A CN108359969A CN201810053867.1A CN201810053867A CN108359969A CN 108359969 A CN108359969 A CN 108359969A CN 201810053867 A CN201810053867 A CN 201810053867A CN 108359969 A CN108359969 A CN 108359969A
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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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Abstract
A kind of preparation method of aluminum alloy surface environmental protection self-cure type titanium/zirconium/molybdenum conversion film, includes the following steps：Aluminum alloy specimen surface preparation；Conversion fluid configures, which includes following components：0.5~5 g/L of fluotitanate, 0.5~3 g/L of fluozirconate, 1~6 g/L of molybdate, 0.2~0.5 g/L of 0.2~3 g/L of chelating agent, 0.3~3 g/L of film for additive and pH adjusting agent, water is added after each component mixing and stirs 30~50 minutes, then seals, is aged 1 day；Film preparation is converted, aluminum alloy specimen is immersed in conversion fluid, aluminum alloy surface can form faint yellow titanium/zirconium/molybdenum conversion film of continuous uniform, take out aluminum alloy specimen and be dried wash with distilled water totally, complete the preparation of conversion film.Film-forming temperature of the present invention is low, film formation time is short, and conversion fluid is stablized, chromium-free environment-friendly；The corrosion resistance of aluminum alloy surface is good and has self-healing property, is applicable in all types of aluminium alloys.
Description
Technical field
The present invention relates to a kind of preparation methods of aluminum alloy surface environmental protection self-cure type titanium/zirconium/molybdenum conversion film.
Background technology
It is first to carry out surface chemistry conversion processing that aluminum alloy surface, which protects most common treatment process, then carries out electrostatic
It applies.Traditional surface conversion treatment technique is chromate conversion treatments, however Cr VI has toxicity, is prohibited by many countries
Only use.The research of Trend of Chrome-free treatment technology and mechanism is extremely urgent, but aluminium and its alloy surface chromiumfree conversion treatment technology
It mainly rests in developed country's hand, restricts the development of China's the sector.It is therefore desirable to research and develop aluminium and its alloy
Surfacecti proteon treatment process and analyze to improve China's competitiveness in the international market and break the technical barrier of developed country have it is aobvious
The economic benefit of work, high learning value and far-reaching social effect.
Titanium/zirconium conversion film is considered as the most possible chromiumfree conversion technique for substituting Cr VI.But current aluminum alloy surface
Titanium/zirconium conversion processing remains at the experimental stage, and there are many techniques and learned problem are to be resolved.Titanium/zirconium turns first
Though the research for changing the growth course, membrane formation mechanism of film has been reported that, in order to meet the needs of industrialized production, titanium/zirconium conversion
The formula of liquid becomes increasingly complex, and organic additive is often contained in conversion fluid, and the membrane formation mechanism more sophisticated of film layer has been reported
Membrane formation mechanism has been not suitable for.Secondly, the titanium reported/general color of zirconium conversion film is shallower, and corrosion resistance is not so good as chromate.
Invention content
The technical problem to be solved in the present invention is to provide a kind of aluminum alloy surface environmental protection self-cure type titanium/zirconium/molybdenum conversion films
Preparation method, film-forming temperature is low, film formation time is short, and conversion fluid is stablized, chromium-free environment-friendly；The corrosion resistance of aluminum alloy surface is good and has
Self-healing property is applicable in all types of aluminium alloys.
In order to solve the above-mentioned technical problem, the present invention takes following technical scheme：
A kind of preparation method of aluminum alloy surface environmental protection self-cure type titanium/zirconium/molybdenum conversion film, includes the following steps：
Aluminum alloy specimen surface preparation；
The configuration of conversion fluid, the conversion fluid include the component of following weight proportion：0.5~5g/L of fluotitanate, fluorine zirconic acid
0.5~3g/L of salt, 1~6g/L of molybdate, 0.2~3g/L of chelating agent, 0.3~3g/L of film for additive and pH adjusting agent 0.2
~0.5g/L is added water and stirs 30~50 minutes, then seals, be aged 1 day after each component mixing；
Film preparation is converted, aluminum alloy specimen is immersed in conversion fluid, aluminum alloy surface can form the yellowish of continuous uniform
Color titanium/zirconium/molybdenum conversion film takes out aluminum alloy specimen, wash with distilled water totally, then is dried, completes the preparation of conversion film.
The fluotitanate is one or more kinds of arbitrary proportions of titanium sodium fluoride, potassium fluotitanate or ammonium titanium fluoride
Mixing；
The fluozirconate is one or more kinds of mixing in sodium fluozirconate, potassium fluorozirconate and ammonium fluozirconate.
The chelating agent is one or more kinds of mixing of tannic acid, phytic acid and gallic acid；
The film for additive is one or two kinds of mixing of pyrovanadate and metavanadate；
The molybdate is one or more kinds of mixing of sodium molybdate, ammonium molybdate and potassium molybdate；
The pH adjusting agent is one or more kinds of mixing of hydrofluoric acid, nitric acid and phosphoric acid.
Soaking time of the aluminum alloy specimen in conversion fluid is 3~10min, and conversion fluid temperature is 20~40 DEG C, is done
Dry temperature is 30~80 DEG C, and drying time is 5min~10min.
The thickness of the conversion film is 1-5 μm.
The pretreatment includes carrying out industrial acids oil removing, washing, mixing acid activation, washing successively to aluminum alloy specimen；Its
The group of middle industrial acids becomes：H2SO420~100g/L, H3PO410~30g/L, HF 2~10g/L, OP-10 emulsifier 0.2
~2.8g/L, pretreatment temperature are 20~40 DEG C, and soaking time is 2~3min；The group of mixed acid becomes：HNO316~24g/
L, H3PO42~20g/L, H2SO413~40g/L, pretreatment temperature are 20~40 DEG C, and soaking time is 3~5min.
The invention has the advantages that：
(1) easy to operate, at low cost：Preparation process of the present invention is simple, strong operability, and film-forming temperature is low, film formation time with
The chromic acid salt treatment used in factory is close, replacement easy to implement, reduces shop equipment input, at low cost；
(2) colored film：Faint yellow, even film layer densification is presented in titanium/zirconium of the present invention/molybdenum conversion film；
(3) film layer forms：Titanium/zirconium/molybdenum conversion film of the present invention is mainly the oxide composition of Ti, Zr, Mo, and what is obtained should
The particle diameter of film forming oxide is about 30~80nm；
(4) corrosion resistance is good：Titanium/zirconium/molybdenum conversion film of the present invention has excellent salt spray corrosion resistance；
(5) self-healing property：There is titanium/zirconium/molybdenum conversion film of the present invention apparent self-healing property, self-healing property can effectively extend film layer
Service life the corrosion resistance of conversion film is enhanced by the self-healing property of formation.
Description of the drawings
Fig. 1 is the optical photograph of titanium/zirconium/molybdenum conversion film prepared by the embodiment of the present invention 1；
Fig. 2-1 is the SEM figures that titanium/zirconium/molybdenum conversion film prepared by the embodiment of the present invention 1 amplifies 5000 times；
Fig. 2-2 is the SEM figures that titanium/zirconium/molybdenum conversion film prepared by the embodiment of the present invention 1 amplifies 50000 times；
Fig. 3 is titanium/zirconium/molybdenum conversion film scratch defects self-healing SEM figures prepared by the embodiment of the present invention 1；
Fig. 4 is titanium/zirconium/molybdenum conversion film scratch defects self-healing SEM figures prepared by the embodiment of the present invention 3.
Specific implementation mode
For that can further appreciate that the feature, technological means and the specific purposes reached, function of the present invention, with reference to
Present invention is further described in detail with specific implementation mode for attached drawing.
Embodiment one
A kind of preparation method of aluminum alloy surface environmental protection self-cure type titanium/zirconium/molybdenum conversion film, includes the following steps：
Aluminum alloy specimen surface preparation.First carry out sample preparation, from wire cutting on 6061 aluminium alloys obtain 20mm ×
The aluminium flake sample of 20mm × 2mm sizes, every piece of sample punch in corner, and specimen surface is polishing to 1200 mesh with sand paper, and
Drying is rinsed well with tap water, is hung with thin wire at punching.
6061 aluminum alloy specimens are suspended in industrial acids and impregnate 2min progress oil removings, is rinsed, is placed into mixed with tap water
It closes and impregnates 3min progress activation process in acid, rinsed with tap water.The group of the industrial acids becomes 40g/L H2SO4、15g/L
H3PO4, 8g/L HF, 0.8g/L OP-10 emulsifiers, solvent is water, and the total volume of the industrial acids of composition is 1L.The mixed acid
Group become 16g/L HNO3、10g/L H3PO4、20g/L H2SO4, solvent is water, and the total volume of the mixed acid of composition is 1L.
The configuration of conversion fluid configures the conversion fluid of 1L in total, which includes the component of following weight proportion：Fluotitanic acid
Salt 1g/L, fluozirconate 0.5g/L, molybdate 1g/L, chelating agent 0.2g/L, film for additive 0.3g/L and pH adjusting agent
0.1g/L, remaining is water, and the summation of water and the above components is 1L.Each component mixing after be added water and stir 30 minutes, then
Sealing is aged 1 day.
Film preparation is converted, aluminum alloy specimen is immersed in conversion fluid, soaking time 3min, conversion fluid temperature maintains
25 DEG C, aluminum alloy surface can form faint yellow titanium/zirconium/molybdenum conversion film of continuous uniform, take out aluminum alloy specimen, clear with distilled water
Wash clean, then be dried, drying temperature is 70 DEG C, drying time 9min, completes the preparation of conversion film, the thickness of conversion film
It is 1.5 μm.
Obtained conversion film is mainly the oxide composition of Ti, Zr, Mo, and the particle diameter of the conversion film oxide is about
30nm。
The optical photograph of gained titanium/zirconium/molybdenum conversion film of 6061 aluminum alloy surfaces obtained through embodiment 1 is shown in Fig. 1.From
As can be seen that titanium/zirconium/molybdenum conversion film surfacing is fine and close in Fig. 1, present faint yellow.Fig. 2-1 and 2-2 is titanium/zirconium/molybdenum conversion
The SEM shape appearance figures of film, it is known that the smooth densification of film layer obtained in example 1, existing micro-crack are mainly film layer in drying course
Caused by syneresis, surface be distributed particulate material is mainly Mo2O5, white molecule is MoO3Object phase.Through 1 institute of example
Titanium/zirconium/molybdenum conversion film of 6061 aluminum alloy surfaces obtained, the 500h of resistance to Neutral Salt Spray Corrosion.Using cross-cut tester to conversion film point
Under the conditions of not being dried and boiling water under the conditions of draw lattice experiment, it is no it is any fall off, still remain good adhesive force.Through embodiment
Titanium/zirconium/molybdenum conversion film of 1 6061 aluminum alloy surfaces obtained has good self-healing property, sees Fig. 3 and Fig. 3, to film layer into
Pedestrian's work cut is placed on after destroying in salt mist tester after 1 day, and self-healing phenomenon obviously occurs at cut.
In addition, fluotitanate is titanium sodium fluoride；Fluozirconate is sodium fluozirconate；Chelating agent is tannic acid；Film for additive
For pyrovanadate；Molybdate is sodium molybdate；PH adjusting agent is hydrofluoric acid.
Embodiment two
A kind of preparation method of aluminum alloy surface environmental protection self-cure type titanium/zirconium/molybdenum conversion film, includes the following steps：
Aluminum alloy specimen surface preparation.First carry out sample preparation, from wire cutting on 6062 aluminium alloys obtain 20mm ×
The aluminium flake sample of 20mm × 2mm sizes, every piece of sample punch in corner, and specimen surface is polishing to 1200 mesh with sand paper, and
Drying is rinsed well with tap water, is hung with thin wire at punching.
6062 aluminum alloy specimens are suspended in industrial acids and impregnate 3min progress oil removings, is rinsed, is placed into mixed with tap water
It closes and impregnates 5min progress activation process in acid, rinsed with tap water.The group of the industrial acids becomes 80g/L H2SO4、30g/L
H3PO4, 10g/L HF, 2.8g/L OP-10 emulsifiers, solvent is water, and the total volume of the industrial acids of composition is 1L.The mixing
The group of acid becomes 24g/L HNO3、20g/L H3PO4、40g/L H2SO4, solvent is water, and the total volume of the mixed acid of composition is
1L。
The configuration of conversion fluid configures the conversion fluid of 1L in total, which includes the component of following weight proportion：Fluotitanic acid
Salt 3g/L, fluozirconate 2g/L, molybdate 3g/L, chelating agent 2g/L, film for additive 2g/L and pH adjusting agent 0.3g/L,
The summation of Yu Weishui, water and the above components is 1L.Water is added after each component mixing and stirs 40 minutes, then seals, ageing 1
It.
Film preparation is converted, aluminum alloy specimen is immersed in conversion fluid, soaking time 3min, conversion fluid temperature maintains
25 DEG C, aluminum alloy surface can form faint yellow titanium/zirconium/molybdenum conversion film of continuous uniform, take out aluminum alloy specimen, clear with distilled water
Wash clean, then be dried, drying temperature is 75 DEG C, drying time 10min, completes the preparation of conversion film, the thickness of conversion film
Degree is 2 μm.
Obtained conversion film is mainly the oxide composition of Ti, Zr, Mo, and the particle diameter of the conversion film oxide is about
60nm。
In addition, fluotitanate is the mixing of titanium sodium fluoride and potassium fluotitanate；Fluozirconate is sodium fluozirconate and potassium fluorozirconate
Mixing.Chelating agent is the mixing of tannic acid and phytic acid；Film for additive is the mixing of pyrovanadate and metavanadate；Molybdate
It is mixed for the ammonium molybdate of sodium molybdate；PH adjusting agent is the mixing of hydrofluoric acid and nitric acid.It should be noted that for above each mixing
The component of composition, the ratio of each element is not particularly limited in mixture.For example, titanium sodium fluoride and potassium fluotitanate can be 1：1 or
Person 1：2 or other.
Embodiment three
A kind of preparation method of aluminum alloy surface environmental protection self-cure type titanium/zirconium/molybdenum conversion film, includes the following steps：
Aluminum alloy specimen surface preparation.First carry out sample preparation, from wire cutting on 6063 aluminium alloys obtain 20mm ×
The aluminium flake sample of 20mm × 2mm sizes, every piece of sample punch in corner, and specimen surface is polishing to 1200 mesh with sand paper, and
Drying is rinsed well with tap water, is hung with thin wire at punching.
6063 aluminum alloy specimens are suspended in industrial acids and impregnate 3min progress oil removings, is rinsed, is placed into mixed with tap water
It closes and impregnates 5min progress activation process in acid, rinsed with tap water.The group of the industrial acids becomes 80g/L H2SO4、30g/L
H3PO4, 10g/L HF, 2.8g/L OP-10 emulsifiers, solvent is water, and the total volume of the industrial acids of composition is 1L.The mixed acid
Group become 24g/L HNO3、20g/L H3PO4、40g/L H2SO4, solvent is water, and the total volume of the mixed acid of composition is 1L.
The configuration of conversion fluid configures the conversion fluid of 1L in total, which includes the component of following weight proportion：Fluotitanic acid
Salt 5g/L, fluozirconate 3g/L, molybdate 6g/L, chelating agent 3g/L, film for additive 3g/L and pH adjusting agent 0.5g/L,
The summation of Yu Weishui, water and the above components is 1L.Water is added after each component mixing and stirs 50 minutes, then seals, ageing 1
It.
Film preparation is converted, aluminum alloy specimen is immersed in conversion fluid, soaking time 3min, conversion fluid temperature maintains
25 DEG C, aluminum alloy surface can form faint yellow titanium/zirconium/molybdenum conversion film of continuous uniform, take out aluminum alloy specimen, clear with distilled water
Wash clean, then be dried, drying temperature is 70 DEG C, drying time 9min, completes the preparation of conversion film, the thickness of conversion film
It is 2 μm.
Obtained conversion film is mainly the oxide composition of Ti, Zr, Mo, and the particle diameter of the conversion film oxide is about
60nm。
Uniform yellow is presented in the titanium/zirconium/molybdenum conversion film obtained on 6063 aluminium alloys.The resistance to Neutral Salt Spray Corrosion of conversion film
For 500h.Under the conditions of being dried respectively using cross-cut tester and boiling water under the conditions of draw lattice experiment, it is no it is any fall off, still remain very
Good adhesive force.Titanium/zirconium/molybdenum conversion film of 6063 aluminum alloy surfaces obtained obtains self-healing property with good, sees Fig. 4, to conversion
Film is placed on after carrying out artificial cut destruction in salt mist tester after 1 day, and self-healing phenomenon obviously occurs at cut.
In addition, fluotitanate is the mixing of titanium sodium fluoride, potassium fluotitanate and ammonium titanium fluoride；Fluozirconate be sodium fluozirconate,
The mixing of potassium fluorozirconate and ammonium fluozirconate.Chelating agent is the mixing of tannic acid, phytic acid and gallic acid；Film for additive is pyrovanadium
The mixing of hydrochlorate and metavanadate；Molybdate is the mixing of sodium molybdate, ammonium molybdate and potassium molybdate；PH adjusting agent is hydrofluoric acid and nitre
The mixing of acid.It should be noted that for the component that above each mixing is constituted, the ratio of each element has no special limit in mixture
It is fixed.For example, titanium sodium fluoride and potassium fluotitanate can be 1：1 or 1：2 or other.
NSS self-healing procedures at the cut of titanium zirconium molybdenum conversion film can be divided into following 3 stages：
It should be noted that these are only the preferred embodiment of the present invention, it is not intended to restrict the invention, although ginseng
According to embodiment, invention is explained in detail, for those skilled in the art, still can be to aforementioned reality
The technical solution recorded in example is applied to modify or equivalent replacement of some of the technical features, but it is all in this hair
Within bright spirit and principle, any modification, equivalent replacement, improvement and so on should be included in protection scope of the present invention
Within.
Claims (5)
1. a kind of preparation method of aluminum alloy surface environmental protection self-cure type titanium/zirconium/molybdenum conversion film, includes the following steps：
Aluminum alloy specimen surface preparation；
The configuration of conversion fluid, the conversion fluid include the component of following weight proportion：0.5~5 g/L of fluotitanate, fluozirconate
0.5~3 g/L, 1~6 g/L of molybdate, 0.2~3 g/L of chelating agent, 0.3~3 g/L of film for additive and pH adjusting agent
0.2~0.5 g/L is added water and stirs 30~50 minutes, then seals, be aged 1 day after each component mixing；
Convert film preparation, aluminum alloy specimen be immersed in conversion fluid, aluminum alloy surface can be formed the faint yellow titanium of continuous uniform/
Zirconium/molybdenum conversion film takes out aluminum alloy specimen, wash with distilled water totally, then is dried, completes the preparation of conversion film.
2. the preparation method of aluminum alloy surface environmental protection self-cure type titanium/zirconium/molybdenum conversion film according to claim 1, feature
It is, the fluotitanate is that one or more kinds of arbitrary proportions of titanium sodium fluoride, potassium fluotitanate or ammonium titanium fluoride are mixed
It closes；
The fluozirconate is one or more kinds of mixing in sodium fluozirconate, potassium fluorozirconate and ammonium fluozirconate；
The chelating agent is one or more kinds of mixing of tannic acid, phytic acid and gallic acid；
The film for additive is one or two kinds of mixing of pyrovanadate and metavanadate；
The molybdate is one or more kinds of mixing of sodium molybdate, ammonium molybdate and potassium molybdate；
The pH adjusting agent is one or more kinds of mixing of hydrofluoric acid, nitric acid and phosphoric acid.
3. the preparation method of aluminum alloy surface environmental protection self-cure type titanium/zirconium/molybdenum conversion film according to claim 2, feature
It is, soaking time of the aluminum alloy specimen in conversion fluid is 3~10 min, and conversion fluid temperature is 20~40 DEG C, dry
Temperature is 30~80 DEG C, and drying time is the min of 5 min~10.
4. the preparation method of aluminum alloy surface environmental protection self-cure type titanium/zirconium/molybdenum conversion film according to claim 3, feature
It is, the thickness of the conversion film is 1~5 μm.
5. the preparation method of aluminum alloy surface environmental protection self-cure type titanium/zirconium/molybdenum conversion film according to claim 4, feature
It is, the pretreatment includes carrying out industrial acids oil removing, washing, mixing acid activation, washing successively to aluminum alloy specimen；
The group of wherein industrial acids becomes：H2SO420~100 g/L, H3PO410~30 g/L, HF 2~10 g/L, OP-10 breast
0.2~2.8 g/L of agent, pretreatment temperature are 20~40 DEG C, and soaking time is 2~3 min；
The group of mixed acid becomes：HNO316~24 g/L, H3PO42~20 g/L, H2SO413~40 g/L, pretreatment temperature
It it is 20~40 DEG C, soaking time is 3~5 min.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109537012A (en) * | 2019-01-23 | 2019-03-29 | 安徽启明表面技术有限公司 | Chromium-free deactivation preparation of zinc coat and preparation method thereof |
| CN109652790A (en) * | 2018-11-30 | 2019-04-19 | 华南理工大学 | Aluminum alloy environment-friendly type Conversion Coating Technology |
| CN109930142A (en) * | 2019-04-28 | 2019-06-25 | 祝亚琴 | A kind of chromium-free passivation liquid |
| CN114045478A (en) * | 2021-10-13 | 2022-02-15 | 东莞理工学院 | Preparation method of aluminum alloy conductive conversion film |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103866311A (en) * | 2014-03-06 | 2014-06-18 | 武汉材料保护研究所 | Method for preparing chemical conversion film on aluminum alloy surface on basis of molybdate |
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2018
- 2018-01-19 CN CN201810053867.1A patent/CN108359969A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103866311A (en) * | 2014-03-06 | 2014-06-18 | 武汉材料保护研究所 | Method for preparing chemical conversion film on aluminum alloy surface on basis of molybdate |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109652790A (en) * | 2018-11-30 | 2019-04-19 | 华南理工大学 | Aluminum alloy environment-friendly type Conversion Coating Technology |
| CN109652790B (en) * | 2018-11-30 | 2022-07-29 | 华南理工大学 | Environment-friendly chemical conversion treatment method for aluminum alloy |
| CN109537012A (en) * | 2019-01-23 | 2019-03-29 | 安徽启明表面技术有限公司 | Chromium-free deactivation preparation of zinc coat and preparation method thereof |
| CN109930142A (en) * | 2019-04-28 | 2019-06-25 | 祝亚琴 | A kind of chromium-free passivation liquid |
| CN114045478A (en) * | 2021-10-13 | 2022-02-15 | 东莞理工学院 | Preparation method of aluminum alloy conductive conversion film |
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Application publication date: 20180803 |