CN102873015A - Method for treating metal surface - Google Patents
Method for treating metal surface Download PDFInfo
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- CN102873015A CN102873015A CN2012104191028A CN201210419102A CN102873015A CN 102873015 A CN102873015 A CN 102873015A CN 2012104191028 A CN2012104191028 A CN 2012104191028A CN 201210419102 A CN201210419102 A CN 201210419102A CN 102873015 A CN102873015 A CN 102873015A
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Abstract
The invention discloses a method for treating a metal surface. The method is characterized in that an organic membrane is formed on a metal surface; before the organic membrane is formed, a sol-gel method is firstly adopted to form an inorganic membrane on the metal surface; the organic membrane is wrapped on the surface of the inorganic membrane; and the inorganic membrane is an oxidation metal membrane. An organic-inorganic hybrid membrane is coated on the metal surface, is temperature resistant and corrosion resistant and has strong adhesive force.
Description
Technical field
The present invention relates to a kind of metal surface cladding treatment, be specifically related to a kind of processing method at metal surface plating hybrid organic-inorganic film.
Background technology
The one of the main reasons of metal electrochemical corrosion is because the surface contacts with the atmosphere of electrolyte solution or humidity, produces various corrosion galvanic cells.Accordingly, can make the isolation of metal surface and corrosive environment by changing the metal surface state, prevent the generation of corroding.At present, the methods such as phosphatization and chromate conversion embrane method are generally adopted in the surface treatment of metal plating piece, phosphorization technology is the method that Treatment of Metal Surface generally adopts before the present application, owing to contain a large amount of phosphorus and nitrogen in the bonderite, can bring serious pollution to environment, the heavy metal that contains in the bonderite also can cause possible permanent damage to human body.So be badly in need of new metal surface treating method with the replacement phosphorization technology, and chromate conversion coating has caused severe contamination to environment.
In recent years, a lot of to the alternative techniques research of conventional phosphatizing processing both at home and abroad, special metal surface treating liquid is arranged, and CN1341775A proposes to form metal surface treating liquid by nine kinds of raw materials such as lauryl sodium sulfate, NaOH, citric acids, forms coating by being immersed in the metal surface; CN101139500A proposes by silane coupling agent, organo-metallic compound, silicate, the compositions such as phosphoric acid, by use the line rod balancedly blade coating in the metal surface, heating, drying forms coating, but the thickness of coating that this process forms is thinner, and lower with metal surface adhesive force, coating easily comes off in corrosive medium, antiseptic effect is relatively poor, and report more to the film forming agent technique of silane series in the aseptic technic at present, it is the metal conditioner of main component that CN1380913A proposes to adopt silane coupler, but the ultra-thin organic film that such silane coupled technology forms, mechanical strength is bad, scarcely high temperature resistant, corrosion resistance is poor.
Summary of the invention
To the objective of the invention is the defective that exists in the prior art in order solving, to provide a kind of high temperature resistant, anticorrosive, and the coat of metal processing method of strong adhesion.
In order to achieve the above object, the invention provides a kind of metal surface treating method, the method is to form organic film in described metal surface; And before forming organic film, adopt first sol-gel process to form inoranic membrane in the metal surface; Aforementioned organic film is wrapped in the inoranic membrane surface; Inoranic membrane is the oxidized metal film, preferential oxidation aluminium film.
Specifically may further comprise the steps:
(1) metal surface cleaning and passivation: pending metal is put into 30% hydrochloric acid solution soak 1 ~ 5 minute (preferred 1 ~ 3 minute), take out and put into the acetone ultrasonic cleaning 30 ~ 60 minutes, then carry out rinsing with deionized water and remove inorganic and organic pollution; Metal after take out cleaning is put into baking oven, and at 70 ℃ ~ 100 ℃ lower flash baking surface moistures, so that metal thoroughly eliminates rust, it is totally smooth that the surface reaches, at last metal is put into the pH value and is 10 with surfactant carry out Passivation Treatment;
(2) colloidal sol preparation: with Al (OC
3H
7)
3With water be that 1:80 ~ 100 are contained in the beaker according to mol ratio, be heated to 60 ℃ ~ 85 ℃, carry out magnetic agitation 10 ~ 30min, according to HNO
3And Al (OC
3H
7)
3The amount of mol ratio 0.05 ~ 0.07:1 add HNO
3, under 60 ℃ ~ 85 ℃, carry out magnetic agitation 4 ~ 6h subsequently, so that solution presents glue, stand-by;
(3) inoranic membrane coating: the metal after step (1) passivation is placed in the colloidal sol of step (2) preparation, soak 10 ~ 30 min, 1h is dried in taking-up in air, in 85 ℃ stove, continue oven dry 2h, to in 300 ℃ ~ 500 ℃ atmosphere, calcine the preferred 1h of 0.8-1.5h(through the print that coating is crossed), obtain surface parcel γ-Al
2O
3The metal plating piece of inoranic membrane.
(4) gel preparation: silane coupler is placed in the beaker, volume ratio in absolute ethyl alcohol and silane coupler is 8 ~ 12: 1, the volume ratio of water and silane is 3 ~ 5: 1 ratio adding, add again a small amount of formic acid and make catalyst, the addition of formic acid makes the pH value be adjusted to 9 ~ 10, after stirring 2 ~ 4h and make each evenly miscible mutually with electric blender, with the solution good seal, carry out sonic oscillation 1h ~ 3h at supersonic wave cleaning machine, be placed at last in 30 ℃ ~ 40 ℃ (preferred 35 ℃) water-baths and react to gel;
(5) organic film coating: the gel of preparation in the step (4) is put in the beaker, the adding quality is that 3 ~ 4 times oxolane (THF) of gel makes its dissolving, the curing agent that adds 2% ~ 4% (mass fraction) of gel content, the employing magnetic stirrer stirs, and this solution is coating solution.Adopt after soaking and apply coating solution on the metal of czochralski method with the surface parcel inoranic membrane of step (3) preparation, solidify, namely get the metal of surperficial coating organic-inorganic film.
Wherein, surfactant is Brij92 type, ethoxylation methyl glucoside stearate type, polysorbas20 type (polyoxyethylene sorbitan acid anhydride mono laurate fat) in the step (1), preferred Brij92 type, concentration is 20%, take ethanol as solvent; Step adds the thermal recovery ultra thermostat in (2), and 60 ℃ ~ 85 ℃ of constant temperature utilize magnetic stirrer to stir 10 ~ 30min, and mixing speed is 150 r/min; Tube furnace is adopted in calcining in the step (3), and temperature is 300 ℃ ~ 500 ℃; Silane coupler adopts vinyltrimethoxy silane, γ-(methacryloxypropyl) propyl trimethoxy silicane and γ-glycidyl ether trimethoxy silane in the step (4), the preferred vinyl trimethoxy silane, adopt formic acid to make catalyst, regulate pH value to 9 ~ 10, utilize electric blender to stir 2 ~ 4h, mixing speed is 350 r/min; Adopt oxolane (THF) dissolving gel in the step (5), curing agent adopts benzoyl peroxide, and solidification temperature is 80 ℃ ~ 100 ℃, and be 4 ~ 6h hardening time.
The present invention has the following advantages compared to existing technology: the present invention utilizes hybrid organic-inorganic film to be wrapped in the metal surface, combines with chemical bond between organic phase and the inorganic phase, has good mechanical property; And the existence of organo-functional group makes material surface be hydrophobicity, and the hybrid organic-inorganic film material can combine with chemical bond with the metal surface simultaneously, has greatly strengthened adhesive ability and the resistance to corrosion of film.The present invention is simple to the preparation technology of metal surface parcel hybrid organic-inorganic film, environmental protection, and the hybridized film of preparation is the environment-friendly material of desirable effectively substitute chromium hydrochlorate oxide-film.
The specific embodiment
Below in conjunction with specific embodiment metal surface treating method of the present invention is elaborated.
Embodiment one
(1) metal surface cleaning and passivation: pending metalwork is put into 30% hydrochloric acid solution soaked 3 minutes, then take out and put into the acetone ultrasonic cleaning 30 minutes, then carry out rinsing with deionized water and remove inorganic and organic pollution, take out metalwork and put into 70 ℃ of baking oven flash baking surface waters, so that metal thoroughly eliminates rust, it is totally smooth that the surface reaches, and it is that 9 concentration is that 20% polysorbas20 type activating agent carries out Passivation Treatment that metal is put into the pH value;
(2) colloidal sol preparation: with Al (OC
3H
7)
3With water be that 1:80 is contained in the beaker according to mol ratio, be heated to 60 ℃ and carry out magnetic agitation 10min, according to HNO
3And Al (OC
3H
7)
3The amount of mol ratio 0.05:1 add HNO
3, so that solution presents glue, stirred 4 hours at 60 ℃ of lower magnetic forces subsequently, stand-by;
(3) inoranic membrane coating: the metal plating piece is placed in the colloidal sol for preparing, soak 10 min, take out and in air, dry 1h, in 85 ℃ stove, continue oven dry 2h, to in 300 ℃ atmosphere, calcine 1h through the print that coating is crossed, obtain surface parcel γ-Al
2O
3The metal plating piece of inoranic membrane;
(4) gel preparation: γ-(methacryloxypropyl) propyl trimethoxy silicane is placed in the beaker, be that the volume ratio of 8: 1, water and silane is that 3: 1 ratio adds absolute ethyl alcohol and water in the volume ratio of absolute ethyl alcohol and silane, add again a small amount of formic acid and make catalyst, regulate pH value to 9, after stirring 2h and make each evenly miscible mutually with electric blender, with the solution good seal, carry out sonic oscillation 1h at supersonic wave cleaning machine, be placed at last in 35 ℃ of water-baths and react to gel;
(5) organic film coating: get gel and be put in the beaker, the adding quality is that 3 times oxolane (THF) of gel makes its dissolving, the curing agent benzoyl peroxide that adds 2% (mass fraction) of gel content adopts magnetic stirrer to stir, and this solution is coating solution.Czochralski method is coated with coating solution at the metal of surface parcel inoranic membrane after adopting immersion, at 80 ℃ of lower 6h that solidify, namely gets the metalwork of surperficial coating organic-inorganic film.
Embodiment two
(1) metal surface cleaning and passivation: pending metalwork is put into 30% hydrochloric acid solution soaked 3 minutes, then take out and put into the acetone ultrasonic cleaning and then carried out rinsing with deionized water in 60 minutes and remove inorganic and organic pollution, take out metalwork and put into 100 ℃ of baking oven flash baking surface waters, so that metal thoroughly eliminates rust, it is totally smooth that the surface reaches, and the concentration that metal is put into pH value 10 is that 20% Brij92 type activating agent carries out Passivation Treatment;
(2) colloidal sol preparation: with Al (OC
3H
7)
3With water be that 1:100 is contained in the beaker according to mol ratio, be heated to 85 ℃ and carry out magnetic agitation 30min, according to HNO
3And Al (OC
3H
7)
3The amount of mol ratio 0.07:1 add HNO
3, so that solution presents glue, 85 ℃ of magnetic agitation 6 hours, stand-by subsequently;
(3) inoranic membrane coating: the metal plating piece is placed in the colloidal sol for preparing, soak 30 min, take out and in air, dry 1h, in 85 ℃ stove, continue oven dry 2h, to in 500 ℃ atmosphere, calcine 1h through the print that coating is crossed, obtain surface parcel γ-Al
2O
3The metal plating piece of inoranic membrane;
(4) gel preparation: vinyltrimethoxy silane is placed in the beaker, be that the volume ratio of 12: 1, water and silane is that 5: 1 ratio adds absolute ethyl alcohol and water in the volume ratio of absolute ethyl alcohol and silane, add again a small amount of formic acid and make catalyst, regulate pH value to 10, after stirring 4h and make each evenly miscible mutually with electric blender, with the solution good seal, carry out sonic oscillation 3h at ultrasonic cleaning agent, be placed at last in 35 ℃ of water-baths and react to gel;
(5) organic film coating: get gel and be put in the beaker, the adding quality is that 4 times oxolane (THF) of gel makes its dissolving, the curing agent benzoyl peroxide that adds 4% (mass fraction) of gel content adopts magnetic stirrer to stir, and this solution is coating solution.Czochralski method is coated with coating solution at the metal of surface parcel inoranic membrane after adopting immersion, at 100 ℃ of lower 4h that solidify, namely gets the metalwork of surperficial coating organic-inorganic film.
Embodiment three
(1) metal surface cleaning and passivation: pending metalwork (aluminium alloy) is put into 30% hydrochloric acid solution soaked 5 minutes, then take out and put into the acetone ultrasonic cleaning and then carried out rinsing with deionized water in 40 minutes and remove inorganic and organic pollution, take out metalwork and put into 100 ℃ of baking oven flash baking surface waters, so that metal thoroughly eliminates rust, it is totally smooth that the surface reaches, and the concentration that metal is put into pH value 10 is that 20% Brij92 type activating agent carries out Passivation Treatment;
(2) colloidal sol preparation: the butyl titanate of 100ml is dissolved in the absolute ethyl alcohol of 400ml, adds the acetylacetone,2,4-pentanedione of 30ml as inhibitor, 20 ℃ are stirred 15 min, obtain solution A, stand-by;
Get the absolute ethyl alcohol of 100ml, add the nitric acid of 10ml and the deionized water of 20ml, stirring at room 15min obtains solution B.The solution B of 50ml is added drop-wise in the solution A of 150ml, and 20 ℃ are stirred 2h, obtain nano-TiO
2Colloidal sol.
(3) inoranic membrane coating: will clean and dried metal immersion nano-TiO
2Colloidal sol soaks 10min, takes out and dry 1h in air, continues oven dry 2h in 80 ℃ baking oven, has obtained wrapping up the aluminium alloy of inoranic membrane.
(4) preparation of organic film solution: the 100ml vinyltrimethoxy silane is placed in the beaker, add the absolute ethyl alcohol of 800ml and the water of 300ml, add again 10ml formic acid and make catalyst, regulate pH value to 9, after stirring 2h and make each evenly miscible mutually with electric blender, with the solution good seal, carry out sonic oscillation 1h at supersonic wave cleaning machine, be placed at last in 35 ℃ of water-baths and react to gel, namely get organogel;
The organogel of getting 100g is put in the beaker, add 300g oxolane (THF) and make its dissolving, add the benzoyl peroxide that 2g is arranged, adopt magnetic stirrer to stir, this solution is organic film solution.
(5) coat organic film solution with the constant speed czochralski method in the aluminum alloy surface of having wrapped up inoranic membrane, obtain the metal that the surface has coated organic film and inoranic membrane.The time of staying of aluminium alloy in coating solution is 1min, and pull rate is 27cm/min, repeatedly film 3 times, both.
Embodiment four
(1) metal surface cleaning and passivation: pending metalwork (aluminium alloy) is put into 30% hydrochloric acid solution soaked 5 minutes, then take out and put into the acetone ultrasonic cleaning and then carried out rinsing with deionized water in 40 minutes and remove inorganic and organic pollution, take out metalwork and put into 100 ℃ of baking oven flash baking surface waters, so that metal thoroughly eliminates rust, it is totally smooth that the surface reaches, and the concentration that metal is put into pH value 10 is that 20% Brij92 type activating agent carries out Passivation Treatment;
(2) colloidal sol preparation: the butyl titanate of 100ml is dissolved in the absolute ethyl alcohol of 500ml, adds the acetylacetone,2,4-pentanedione of 20ml as inhibitor, 30 ℃ are stirred 20 min, obtain solution A, stand-by;
Get the absolute ethyl alcohol of 100ml, add the nitric acid of 15ml and the deionized water of 230ml, stirring at room 15min obtains solution B.The solution B of 50ml is added drop-wise in the solution A of 200ml, and 20 ℃ are stirred 2h, obtain nano-TiO
2Colloidal sol.
(3) inoranic membrane coating: will clean and dried metal immersion nano-TiO
2Colloidal sol soaks 10min, takes out and dry 1h in air, continues oven dry 2h in 80 ℃ baking oven, has obtained wrapping up the aluminium alloy of inoranic membrane.
(4) preparation of organic film solution: the 100ml vinyltrimethoxy silane is placed in the beaker, add the absolute ethyl alcohol of 800ml and the water of 300ml, add again 10ml formic acid and make catalyst, regulate pH value to 9, after stirring 2h and make each evenly miscible mutually with electric blender, with the solution good seal, carry out sonic oscillation 1h at supersonic wave cleaning machine, be placed at last in 35 ℃ of water-baths and react to gel, namely get organogel;
The organogel of getting 100g is put in the beaker, add 300g oxolane (THF) and make its dissolving, add the benzoyl peroxide that 2g is arranged, adopt magnetic stirrer to stir, this solution is organic film solution.
(5) coat organic film solution with the constant speed czochralski method in the aluminum alloy surface of having wrapped up inoranic membrane, obtain the metal that the surface has coated organic film and inoranic membrane.The time of staying of aluminium alloy in coating solution is 1min, and pull rate is 27cm/min, repeatedly film 3 times, both.
Effect embodiment
Metalwork and the untreated metalwork got after embodiment 1 ~ 4 processes carry out salt fog and brine soaking experiment, and the result is as shown in the table.
Metalwork salt mist experiment result before and after table 1 is processed
| ? | 1d | 4d | 8d | 12d | 16d | Weightless before and after the experiment |
| Metalwork before processing | The skin covering of the surface look evenly fades, corrosion appears in the corner | Heavy corrosion, skin covering of the surface look fade seriously, | Heavy corrosion produces a large amount of white things | ? | ? | 0.0085 |
| Metalwork after embodiment 1 processes | Unchanged | Unchanged | Unchanged | The film look shoals, | The film look shoals, and a small amount of white thing appears in the surface | 0.0008 |
| Metalwork after embodiment 2 processes | Unchanged | Unchanged | Unchanged | The film look shoals, and a small amount of white thing appears in the surface | Several white corrosion points appear in the surface | 0.0004 |
| Metalwork after embodiment 3 processes | Unchanged | Unchanged | Unchanged | The film look shoals, | A small amount of white thing appears in the surface | 0.0006 |
| Metalwork after embodiment 4 processes | Unchanged | Unchanged | Unchanged | The film look shoals, | A small amount of white thing appears in the surface | 0.0005 |
Metalwork carried out the brine soaking experiment result before and after table 2 was processed
| ? | 1d | 4d | 8d | 12d | 16d | Weightless before and after the experiment |
| Metalwork before processing | Heavy corrosion | ? | ? | ? | ? | 0.0065 |
| Metalwork after embodiment 1 processes | Unchanged | Unchanged | Unchanged | Unchanged | ? | ? |
| Metalwork after embodiment 2 processes | Unchanged | Unchanged | Unchanged | Fading appears in the surface | White point appears in the surface | 0.0007 |
| Metalwork after embodiment 3 processes | Unchanged | Unchanged | Unchanged | Unchanged | Fading appears in the surface | 0.0004 |
| Metalwork after embodiment 4 processes | Unchanged | Unchanged | Unchanged | Unchanged | Fading appears in the surface | 0.0005 |
Table 1 and table 2 show that the surface corrosion in corrosive atmosphere of untreated metallic bond is serious, produce a large amount of corrosion impurity, and treated metalwork surface in 16 days salt fog and brine soaking experiment is unchanged, and the organic-inorganic film of metal surface has good adhesive ability and resistance to corrosion.
Claims (6)
1. metal surface treating method, the method are to form organic film in described metal surface; It is characterized in that: before forming organic film, adopt first sol-gel process to form inoranic membrane in the metal surface; Described organic film is wrapped in described inoranic membrane surface; Described inoranic membrane is the oxidized metal film.
2. metal surface treating method according to claim 1, it is characterized in that: described inoranic membrane is pellumina.
3. metal surface treating method according to claim 2 is characterized in that: form inoranic membrane by following steps in described metal surface:
(1) colloidal sol preparation: with Al (OC
3H
7)
3Be that mix 1:80 ~ 100 with water according to mol ratio, at 60 ℃ ~ 85 ℃ lower 10 ~ 30min that stir; Then according to HNO
3And Al (OC
3H
7)
3The amount of mol ratio 0.05 ~ 0.07:1 add HNO
3, 60 ℃ ~ 85 ℃ lower stirrings, make solution be collosol state, stand-by;
(2) inoranic membrane coating: described metal is placed in the colloidal sol for preparing in the step (1), soaks 10 ~ 30 min, take out dry; Dried metal is calcined 0.8-1.5h in 300 ℃ ~ 500 ℃ atmosphere, obtain surface parcel γ-Al
2O
3The metal plating piece of inoranic membrane.
4. metal surface treating method according to claim 1 is characterized in that: form organic film by following steps on described inoranic membrane surface:
(1) gel preparation: silane coupler and absolute ethyl alcohol, water are mixed, add catalyst formic acid, regulating the pH value is 9 ~ 10, stirs 2 ~ 4h; Then carry out ultrasonic cleaning 1h ~ 3h, be placed at last to react in 30 ℃ ~ 40 ℃ water-baths to solution and be gel; The volume ratio of described absolute ethyl alcohol, water and silane coupler is 8 ~ 12: 3 ~ 5: 1;
(2) organic film coating: get the gel of preparation in the step (1), add oxolane and make its dissolving, then add curing agent, stir and make coating solution; Apply described coating solution in the metal surface of described parcel inoranic membrane, solidify, namely get the metal of the machine of being coated with-inorganic hybrid membrane; The mass ratio of described oxolane, curing agent and gel is 3 ~ 4:0.02 ~ 0.04:1.
5. metal surface treating method according to claim 4, it is characterized in that: described silane coupler is vinyltrimethoxy silane, γ-(methacryloxypropyl) propyl trimethoxy silicane or γ-glycidyl ether trimethoxy silane; Described curing agent is benzoyl peroxide; Described solidification temperature is 80 ℃ ~ 100 ℃, and be 4 ~ 6h hardening time.
6. metal surface treating method according to claim 1, it is characterized in that: before the metal surface forms inoranic membrane, first the metal surface is cleaned and Passivation Treatment: described metal is put into 30% hydrochloric acid solution soaked 1 ~ 3 minute, taking-up was put into the acetone ultrasonic cleaning after 30 ~ 60 minutes, carried out rinsing with deionized water and removed inorganic and organic pollution; After having cleaned, take out metal and put into 70 ℃ ~ 100 ℃ lower flash baking surface waters of baking oven, at last metal is put into surfactant and carried out Passivation Treatment; Described surfactant is Brij92 type, ethoxylation methyl glucoside stearate type or polysorbas20 type surfactant.
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|---|---|---|---|
| CN201210419102.8A CN102873015B (en) | 2012-10-29 | 2012-10-29 | Method for treating metal surface |
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|---|---|---|---|
| CN201210419102.8A CN102873015B (en) | 2012-10-29 | 2012-10-29 | Method for treating metal surface |
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| CN102873015B CN102873015B (en) | 2014-04-09 |
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| CN103695904A (en) * | 2013-12-26 | 2014-04-02 | 常熟市美尔特金属制品有限公司 | Metal surface treatment method |
| CN103757619A (en) * | 2013-12-26 | 2014-04-30 | 常熟市美尔特金属制品有限公司 | Metal surface treating agent |
| CN105331964A (en) * | 2015-09-29 | 2016-02-17 | 安徽瑞林汽配有限公司 | Rust-protection aluminum alloy curing film and preparation method thereof |
| CN110643979A (en) * | 2019-09-17 | 2020-01-03 | 佛山市海化表面处理科技有限公司 | Metal surface treatment process |
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| CN1439742A (en) * | 2003-03-27 | 2003-09-03 | 厦门大学 | Metal surface anti-corrosion method based on surface nanometer construct |
| CN1539888A (en) * | 2003-08-25 | 2004-10-27 | 胡立江 | Organic and non-organic hybrid, preservative, protective film |
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| CN105331964A (en) * | 2015-09-29 | 2016-02-17 | 安徽瑞林汽配有限公司 | Rust-protection aluminum alloy curing film and preparation method thereof |
| CN110643979A (en) * | 2019-09-17 | 2020-01-03 | 佛山市海化表面处理科技有限公司 | Metal surface treatment process |
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| CN102873015B (en) | 2014-04-09 |
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