CN107779030B - A kind of preparation method of high strength alumin ium alloy durability super-double-hydrophobic surface - Google Patents
A kind of preparation method of high strength alumin ium alloy durability super-double-hydrophobic surface Download PDFInfo
- Publication number
- CN107779030B CN107779030B CN201711106428.4A CN201711106428A CN107779030B CN 107779030 B CN107779030 B CN 107779030B CN 201711106428 A CN201711106428 A CN 201711106428A CN 107779030 B CN107779030 B CN 107779030B
- Authority
- CN
- China
- Prior art keywords
- high strength
- alumin ium
- solution
- ium alloy
- strength alumin
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special additives
-
- 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
- C23C22/34—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 fluorides or complex fluorides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
Abstract
The present invention provides a kind of preparation method of high strength alumin ium alloy durability super-double-hydrophobic surface, 2 steps are handled including zirconium-manganese salt mixed solution immersion treatment and hydrophobic oleophobic sol coating, wherein zirconium-manganese salt mixed solution immersion treatment is in high strength alumin ium alloy surface construction with specific micro-/micro-nano structure and with the film layer of good protective action, the processing of hydrophobic oleophobic sol coating can then assign film layer super-hydrophobic superoleophobic super-amphiphobic function, so that high strength alumin ium alloy has the abilities such as excellent automatically cleaning, anti-corrosion, resistant, drag reduction.High strength alumin ium alloy super-double-hydrophobic surface durability prepared by the present invention is good, is subjected to a variety of harsh tests such as high temperature low temperature, strong acid and strong base, fretting wear, ultraviolet radiation, water jets under high pressure impact, strong corrosive medium immersion, is expected to be applied in multiple fields.Preparation method simple process of the present invention, easy to operate, the processing of the high strength alumin ium alloy workpiece suitable for various sizes, shape.
Description
Technical field
The invention belongs to technical field of metal material surface treatment, and in particular to a kind of high strength alumin ium alloy durability super-amphiphobic
The preparation method on surface.
Background technique
The wetability of material surface has great influence for its application.Super-double-hydrophobic surface refers to not only super-hydrophobic but also superoleophobic
A kind of surface, this kind of surface and water and oily contact angle are all larger than 150 °.It is this kind of super double compared to single super-hydrophobic surface
The self-cleaning function of hydrophobic surface is stronger, and the performance of anti-corrosion, resistant, drag reduction etc. is also more superior.But due to oil phase substance
There is smaller surface tension than water, cause the preparation difficulty of this kind of super-double-hydrophobic surface bigger.
High strength alumin ium alloy has many advantages, such as that light, specific strength is high, specific stiffness is high, is widely used in national economy and national defence
The every field of construction.Using 7075 aluminium alloys as the Al-Zn-Mg-Cu aluminum alloy (7 ×××) of representative be high strength alumin ium alloy most
Main series is mainly used in the main force support structure of the advanced Grand Equipments such as aircraft, such as covering, bulkhead, spar key portion
Position.In view of abilities such as the excellent automatically cleaning of super-double-hydrophobic surface, anti-corrosion, resistant, drag reductions, high strength alumin ium alloy durability super-amphiphobic is prepared
Surface is expected to obviously improve the advanced Grand Equipments being made of it in military service quality complicated, in harsh natural environment, significantly
Reduce the economic loss as caused by its corrosion and damage and casualties.
Although having had a small amount of report for the preparation of super-amphiphobic aluminium surface at present, such as Chinese patent CN 106381492A
A kind of a kind of " preparation method of super-amphiphobic aluminium surface " and CN 106040561A " preparation method of super-amphiphobic layer surface aluminium flake ",
But high strength alumin ium alloy is especially 7 ××× system Al-Zn-Mg-Cu alloys due to mutually causing its micro-structure very containing a large amount of alloy
Unevenly, this considerably increases the difficulty that durability super-double-hydrophobic surface is prepared on its surface, and therefore, research and development are directed to high strength alumin ium alloy
The durability super-double-hydrophobic surface of especially 7 ××× system Al-Zn-Mg-Cu alloys is significant.
Summary of the invention
In view of the above shortcomings of the prior art, 7 are especially the object of the present invention is to provide a kind of high strength alumin ium alloy ×
The preparation method of ×× system Al-Zn-Mg-Cu alloy durability super-double-hydrophobic surface, solves current high strength alumin ium alloy and is especially 7 ××s
× be Al-Zn-Mg-Cu alloy super-oleophobic surface preparation technology there is a serious shortage of the problem of.
Realize above-mentioned purpose, the present invention adopts the following technical scheme:
A kind of preparation method of high strength alumin ium alloy durability super-double-hydrophobic surface, includes the following steps:
1. zirconium-manganese salt mixed solution immersion treatment: by clean high strength alumin ium alloy workpiece be immersed in pH value be 2.0~4.0,
10~30 minutes in zirconium-manganese salt mixed solution that temperature is 40~60 DEG C, workpiece is taken out, pure water is cleaned and dried up；
By zirconium sulfate and manganese chloride, 2~4:1 is mixed the zirconium-manganese salt mixed solution in molar ratio, is converted into sulfuric acid
The content of zirconium, concentration are 0.05~0.15mol/L；The solution ph is adjusted by the hydrofluoric acid that concentration is 0.5mol/L；
2. hydrophobic oleophobic sol coating and solidification: appropriate silane resin acceptor kh-550 is added dropwise into hydrophobic oleophobic colloidal sol, it is fast
Speed is vigorously stirred uniformly, then even application to step 1. treated high strength alumin ium alloy workpiece surface, at room temperature by workpiece
It places 12 hours, dries 4~6 hours at 60~80 DEG C to get high strength alumin ium alloy durability super-double-hydrophobic surface；Wherein, add
The volume ratio of the silane resin acceptor kh-550 and colloidal sol that enter is 1:200；Every square metre of high strength alumin ium alloy workpiece surface coating 0.02
~0.1L colloidal sol.
Further, the preparation section of the hydrophobic oleophobic colloidal sol are as follows: by 0.1~0.3mol octadecyl methacrylate
It is added in 500mL ethylene glycol ethyl ether, ultrasound mixes, and obtains solution A；Solution A is heated to 70 DEG C, nitrogen is passed through, then exists
0.4~0.6g azodiisobutyronitrile is added in solution A, persistently stirs 1~2 hour, obtains solution B；Under the conditions of persistently leading to nitrogen
The ethylene glycol ethyl ethers ethereal solution of vinyltriethoxysilane is added dropwise dropwise with constant pressure funnel into solution B, ultrasound mixes, and obtains molten
Liquid C；Solution C is placed to 2~4 hours at 70 DEG C to get hydrophobic oleophobic colloidal sol；The ethylene glycol ethyl ethers ethereal solution medium vinyl three
The concentration of Ethoxysilane is 0.1~0.3mol/L.
The high strength alumin ium alloy is 7 ××× series A l-Zn-Mg-Cu line aluminium alloys.
Compared with prior art, the invention has the following beneficial effects:
1, the present invention utilizes zirconium-manganese salt mixed solution immersion treatment has specific micro- in high strength alumin ium alloy surface construction/to receive
Structure and the film layer with good protective action, so it is super-hydrophobic superoleophobic by hydrophobic oleophobic sol coating processing imparting film layer
Super-amphiphobic function so that high strength alumin ium alloy has the abilities such as excellent automatically cleaning, anti-corrosion, resistant, drag reduction.
2, high strength alumin ium alloy super-double-hydrophobic surface durability prepared by the present invention is good, can be subjected to high temperature low temperature, strong acid and strong base, rub
A variety of harsh tests such as scouring damage, ultraviolet radiation, water jets under high pressure impact, strong corrosive medium immersion, are expected to obtain in multiple fields
It must apply.
3, preparation method simple process of the present invention, easy to operate is suitable for without special experiments conditions such as high temperature, power-up
The processing of the high strength alumin ium alloy workpiece of various sizes, shape, is easy to large-scale industrial production.
Specific embodiment
The present invention is described in further detail combined with specific embodiments below.
It should be noted that these embodiments are merely to illustrate the present invention, rather than limiting the invention, in the present invention
Concept thereof under this method simple modifications, belong to the scope of protection of present invention.
By 7075 or 7B04 high strength alumin ium alloy be processed into specification be 50mm × 50mm × 2.0mm workpiece, successively with 200#,
400#, 600#, 800#, 1200# liquid honing are smooth to surface, are cleaned by ultrasonic in acetone after being rinsed with water 5 minutes,
Obtain the workpiece of surface cleaning.
Embodiment 1:
7075 high strength alumin ium alloy workpiece of surface cleaning are successively carried out the following processing:
1. zirconium-manganese salt mixed solution immersion treatment: workpiece being immersed in zirconium-manganese salt that pH value is 2.0, temperature is 40 DEG C and is mixed
It closes in solution 20 minutes, takes out workpiece, pure water is cleaned and dried up；
By zirconium sulfate and manganese chloride, 4:1 is mixed the zirconium-manganese salt mixed solution in molar ratio, is converted into zirconium sulfate
Content, concentration 0.10mol/L；The solution ph is adjusted by the hydrofluoric acid that concentration is 0.5mol/L.
2. hydrophobic oleophobic sol coating and solidification: appropriate silane resin acceptor kh-550 is added dropwise into hydrophobic oleophobic colloidal sol, it is fast
Speed is vigorously stirred uniformly, then even application to step 1. treated high strength alumin ium alloy workpiece surface, at room temperature by workpiece
It places 12 hours, dries 6 hours at 60 DEG C to get 7075 high strength alumin ium alloy durability super-double-hydrophobic surfaces；Wherein, addition
The volume ratio of silane resin acceptor kh-550 and colloidal sol is 1:200, and every square metre of high strength alumin ium alloy workpiece surface coats 0.1L colloidal sol.
The preparation section of the hydrophobic oleophobic colloidal sol are as follows: 0.2mol octadecyl methacrylate is added to 500mL
In ethylene glycol ethyl ether, ultrasound is mixed, and obtains solution A；Solution A is heated to 70 DEG C, nitrogen is passed through, is then added in solution A
0.5g azodiisobutyronitrile persistently stirs 1.5 hours, obtains solution B；It is added dropwise dropwise under the conditions of persistently leading to nitrogen with constant pressure funnel
Concentration is the ethylene glycol ethyl ethers ethereal solution of the vinyltriethoxysilane of 0.2mol/L into solution B, and ultrasound mixes, and obtains solution
C；Solution C is placed to 3 hours at 70 DEG C to get hydrophobic oleophobic colloidal sol.
The checking procedure of high strength alumin ium alloy durability super-double-hydrophobic surface is following (other embodiments are same):
A. super-amphiphobic function, which is examined, measures 2 μ L using Germany Dataphysics OCA20 video optics contact angle measurement
Water droplet (pure water) and oil droplet (n-hexane) are evaluated its in the static contact angle and roll angle of high strength alumin ium alloy workpiece surface and hydrophobic are dredged
Oily function, static contact angle be greater than 150 °, surface of the roll angle less than 10 ° be considered as ultraphobic surface, and static contact angle is got over
Greatly, the super thin effect in the smaller surface of roll angle is better.
B. durability is examined using high temperature low-temperature test, strong acid and strong base test, friction-wear test, ultraviolet radiation examination
It tests, the durability of water jets under high pressure impact test, strong corrosive medium soak test inspection high strength alumin ium alloy super-double-hydrophobic surface, in test
The static contact angle of test front and back workpiece surface water and oil and the variation of roll angle are stated, is shown if variation is respectively less than 10 ° high-strength
The excellent in te pins of durability of aluminium alloy super-double-hydrophobic surface, and change and smaller show that durability is better.Specific practice is as follows:
(1) high temperature low-temperature test: by the method for the present invention, treated that high strength alumin ium alloy workpiece is respectively placed in 200 DEG C (high temperature)
With 48 hours in -100 DEG C of (low temperature) environment, the static contact angle of test high temperature low-temperature test front and back workpiece surface water and oil is rolled
The variation at dynamic angle.
(2) strong acid and strong base is tested: by the method for the present invention, treated that high strength alumin ium alloy workpiece is immersed in 1.0mol/L respectively
48 hours in nitric acid solution (pH=1) and 1.0mol/L sodium hydroxide solution (pH=14), test strong acid and strong base test front and back work
The variation of the static contact angle, roll angle of part surface water and oil.
(3) friction-wear test: on the table by the tiling of 100# abrasive paper for metallograph, by the method for the present invention treated high-strength aluminium
One face contact sand paper of alloy workpiece (face is working face), applies fixed pressure 1.0kPa, drags 1 meter of distance, dragging speed 5mm
s-1, each 50 times of horizontal, longitudinally reciprocal dragging, static contact angle, the rolling of testing friction wear test front and back workpiece surface water and oil
The variation at angle.
(4) ultraviolet radiation is tested: the method for the present invention treated high strength alumin ium alloy workpiece is subjected to ultraviolet radiation, it is purple
Outer light source wavelength is 254nm, and workpiece location is apart from 2~3cm of light source, and radiated time 48 hours, test ultraviolet radiation tried
Test the variation of the static contact angle, roll angle of front and back workpiece surface water and oil.
(5) the method for the present invention treated high strength alumin ium alloy workpiece is carried out water jets under high pressure punching by water jets under high pressure impact test
It hits, hydraulic pressure 200kPa, 1 meter of release altitude, reciprocal 50 times, testing high voltage water column impact test front and back workpiece surface water is quiet with oil
The variation of state contact angle, roll angle.
(6) treated that high strength alumin ium alloy workpiece is immersed in 35 ± 2 DEG C by the method for the present invention for strong corrosive medium soak test
PH value be 3.2 ± 0.1 (glacial acetic acid adjusting) 50 ± 5g/L sodium chloride corrosive medium in 720 hours, test deep-etching Jie
The variation of the static contact angle, roll angle of workpiece surface water and oil before and after matter soak test.
Above-mentioned super-amphiphobic function and its durability test be as the result is shown: through the method for the present invention, treated that 7075 high-strength aluminium close
Golden workpiece surface is super-double-hydrophobic surface: static contact angle and roll angle of the water droplet on its surface are respectively 157 ° and 2 °, and oil droplet exists
The static contact angle and roll angle on its surface are respectively 152 ° and 3 °；High temperature low-temperature test, strong acid and strong base test, fretting wear examination
It tests, ultraviolet radiation test, water jets under high pressure impact test, the static state of strong corrosive medium soak test front and back workpiece surface water and oil
The variation of contact angle and roll angle is respectively less than 5 °, shows excellent durability.
Embodiment 2:
The 7B04 high strength alumin ium alloy workpiece of surface cleaning is successively carried out the following processing:
1. zirconium-manganese salt mixed solution immersion treatment: workpiece being immersed in zirconium-manganese salt that pH value is 4.0, temperature is 60 DEG C and is mixed
It closes in solution 10 minutes, takes out workpiece, pure water is cleaned and dried up；
By zirconium sulfate and manganese chloride, 2:1 is mixed the zirconium-manganese salt mixed solution in molar ratio, is converted into zirconium sulfate
Content, concentration 0.05mol/L；The solution ph is adjusted by the hydrofluoric acid that concentration is 0.5mol/L.
2. hydrophobic oleophobic sol coating and solidification: appropriate silane resin acceptor kh-550 is added dropwise into hydrophobic oleophobic colloidal sol, it is fast
Speed is vigorously stirred uniformly, then even application to step 1. treated high strength alumin ium alloy workpiece surface, at room temperature by workpiece
It places 12 hours, dries 4 hours at 80 DEG C to get 7B04 high strength alumin ium alloy durability super-double-hydrophobic surface；Wherein, addition
The volume ratio of silane resin acceptor kh-550 and colloidal sol is 1:200, and every square metre of high strength alumin ium alloy workpiece surface coating 0.33L is molten
Glue.
The preparation section of the hydrophobic oleophobic colloidal sol are as follows: 0.1mol octadecyl methacrylate is added to 500mL
In ethylene glycol ethyl ether, ultrasound is mixed, and obtains solution A；Solution A is heated to 70 DEG C, nitrogen is passed through, is then added in solution A
0.4g azodiisobutyronitrile persistently stirs 1 hour, obtains solution B；It is added dropwise dropwise under the conditions of persistently leading to nitrogen with constant pressure funnel dense
Degree is the ethylene glycol ethyl ethers ethereal solution of the vinyltriethoxysilane of 0.1mol/L into solution B, and ultrasound mixes, and obtains solution C；
Solution C is placed to 2 hours at 70 DEG C to get hydrophobic oleophobic colloidal sol.
Super-amphiphobic function and its durability test be as the result is shown: through the method for the present invention treated 7B04 high strength alumin ium alloy work
Part surface is super-double-hydrophobic surface: static contact angle and roll angle of the water droplet on its surface are respectively 163 ° and 1 °, and oil droplet is in its table
The static contact angle and roll angle in face are respectively 156 ° and 2 °；High temperature low-temperature test, strong acid and strong base test, friction-wear test,
The static state of workpiece surface water and oil connects before and after ultraviolet radiation test, water jets under high pressure impact test, strong corrosive medium soak test
The variation of feeler and roll angle is respectively less than 5 °, shows excellent durability.
Embodiment 3:
7075 high strength alumin ium alloy workpiece of surface cleaning are successively carried out the following processing:
1. zirconium-manganese salt mixed solution immersion treatment: workpiece being immersed in zirconium-manganese salt that pH value is 3.0, temperature is 50 DEG C and is mixed
It closes in solution 30 minutes, takes out workpiece, pure water is cleaned and dried up；
By zirconium sulfate and manganese chloride, 3:1 is mixed the zirconium-manganese salt mixed solution in molar ratio, is converted into zirconium sulfate
Content, concentration 0.15mol/L；The solution ph is adjusted by the hydrofluoric acid that concentration is 0.5mol/L.
2. hydrophobic oleophobic sol coating and solidification: appropriate silane resin acceptor kh-550 is added dropwise into hydrophobic oleophobic colloidal sol, it is fast
Speed is vigorously stirred uniformly, then even application to step 1. treated high strength alumin ium alloy workpiece surface, at room temperature by workpiece
It places 12 hours, dries 5 hours at 70 DEG C to get 7075 high strength alumin ium alloy durability super-double-hydrophobic surfaces；Wherein, addition
The volume ratio of silane resin acceptor kh-550 and colloidal sol is 1:200, and every square metre of high strength alumin ium alloy workpiece surface coating 0.02L is molten
Glue.
The preparation section of the hydrophobic oleophobic colloidal sol are as follows: 0.3mol octadecyl methacrylate is added to 500mL
In ethylene glycol ethyl ether, ultrasound is mixed, and obtains solution A；Solution A is heated to 70 DEG C, nitrogen is passed through, is then added in solution A
0.6g azodiisobutyronitrile persistently stirs 2 hours, obtains solution B；It is added dropwise dropwise under the conditions of persistently leading to nitrogen with constant pressure funnel dense
Degree is the ethylene glycol ethyl ethers ethereal solution of the vinyltriethoxysilane of 0.3mol/L into solution B, and ultrasound mixes, and obtains solution C；
Solution C is placed to 4 hours at 70 DEG C to get hydrophobic oleophobic colloidal sol.
Super-amphiphobic function and its durability test be as the result is shown: through the method for the present invention treated 7075 high strength alumin ium alloy works
Part surface is super-double-hydrophobic surface: static contact angle and roll angle of the water droplet on its surface are respectively 161 ° and 2 °, and oil droplet is in its table
The static contact angle and roll angle in face are respectively 154 ° and 3 °；High temperature low-temperature test, strong acid and strong base test, friction-wear test,
The static state of workpiece surface water and oil connects before and after ultraviolet radiation test, water jets under high pressure impact test, strong corrosive medium soak test
The variation of feeler and roll angle is respectively less than 5 °, shows excellent durability.
Embodiment 4:
The 7B04 high strength alumin ium alloy workpiece of surface cleaning is successively carried out the following processing:
1. zirconium-manganese salt mixed solution immersion treatment: workpiece being immersed in zirconium-manganese salt that pH value is 3.0, temperature is 50 DEG C and is mixed
It closes in solution 20 minutes, takes out workpiece, pure water is cleaned and dried up；
By zirconium sulfate and manganese chloride, 4:1 is mixed the zirconium-manganese salt mixed solution in molar ratio, is converted into zirconium sulfate
Content, concentration 0.10mol/L；The solution ph is adjusted by the hydrofluoric acid that concentration is 0.5mol/L.
2. hydrophobic oleophobic sol coating and solidification: appropriate silane resin acceptor kh-550 is added dropwise into hydrophobic oleophobic colloidal sol, it is fast
Speed is vigorously stirred uniformly, then even application to step 1. treated high strength alumin ium alloy workpiece surface, at room temperature by workpiece
It places 12 hours, dries 5 hours at 70 DEG C to get 7B04 high strength alumin ium alloy durability super-double-hydrophobic surface；Wherein, addition
The volume ratio of silane resin acceptor kh-550 and colloidal sol is 1:200, and every square metre of high strength alumin ium alloy workpiece surface coating 0.33L is molten
Glue.
The preparation section of the hydrophobic oleophobic colloidal sol are as follows: 0.2mol octadecyl methacrylate is added to 500mL
In ethylene glycol ethyl ether, ultrasound is mixed, and obtains solution A；Solution A is heated to 70 DEG C, nitrogen is passed through, is then added in solution A
0.5g azodiisobutyronitrile persistently stirs 2 hours, obtains solution B；It is added dropwise dropwise under the conditions of persistently leading to nitrogen with constant pressure funnel dense
Degree is the ethylene glycol ethyl ethers ethereal solution of the vinyltriethoxysilane of 0.2mol/L into solution B, and ultrasound mixes, and obtains solution C；
Solution C is placed to 3 hours at 70 DEG C to get hydrophobic oleophobic colloidal sol.
Super-amphiphobic function and its durability test be as the result is shown: through the method for the present invention treated 7B04 high strength alumin ium alloy work
Part surface is super-double-hydrophobic surface: static contact angle and roll angle of the water droplet on its surface are respectively 162 ° and 2 °, and oil droplet is in its table
The static contact angle and roll angle in face are respectively 155 ° and 3 °；High temperature low-temperature test, strong acid and strong base test, friction-wear test,
The static state of workpiece surface water and oil connects before and after ultraviolet radiation test, water jets under high pressure impact test, strong corrosive medium soak test
The variation of feeler and roll angle is respectively less than 5 °, shows excellent durability.
Above embodiments are process object with 7075 and 7B04 high strength alumin ium alloy, it should be noted that the present invention is equally applicable
In other 7 ××× system Al-Zn-Mg-Cu alloys, it is also applied for fine aluminium and non-7 ××× series high-strength aluminum alloy.
Finally, it is stated that the above embodiments are merely illustrative of the technical solutions of the present invention, other technologies according to the present invention
The modification or equivalent replacement that scheme carries out, are intended to be within the scope of the claims of the invention.
Claims (2)
1. a kind of preparation method of high strength alumin ium alloy durability super-double-hydrophobic surface, which comprises the steps of:
1. zirconium-manganese salt mixed solution immersion treatment: it is 2.0 ~ 4.0, temperature that clean high strength alumin ium alloy workpiece, which is immersed in pH value,
It is 10 ~ 30 minutes in 40 ~ 60 °C of zirconiums-manganese salt mixed solution, takes out workpiece, pure water is cleaned and dried up；
By zirconium sulfate and manganese chloride, 2 ~ 4:1 is mixed the zirconium-manganese salt mixed solution in molar ratio, is converted into containing for zirconium sulfate
Amount, concentration are 0.05 ~ 0.15mol/L；The solution ph is adjusted by the hydrofluoric acid that concentration is 0.5 mol/L；
2. hydrophobic oleophobic sol coating and solidification: appropriate silane resin acceptor kh-550 is added dropwise into hydrophobic oleophobic colloidal sol, it is acute rapidly
Strong to stir evenly, then even application to step 1. treated high strength alumin ium alloy workpiece surface, workpiece is placed at room temperature
12 hours, 4 ~ 6 hours are dried at 60 ~ 80 DEG C to get high strength alumin ium alloy durability super-double-hydrophobic surface；Wherein, the silicon of addition
The volume ratio of alkane coupling agent KH-550 and colloidal sol is 1:200；Every square metre of high strength alumin ium alloy workpiece surface coats 0.02 ~ 0.1L
Colloidal sol；
The preparation section of the hydrophobic oleophobic colloidal sol are as follows: 0.1 ~ 0.3 mol octadecyl methacrylate is added to 500
In mL ethylene glycol ethyl ether, ultrasound is mixed, and obtains solution A；Solution A is heated to 70 DEG C, is passed through nitrogen, is then added in solution A
Enter 0.4 ~ 0.6g azodiisobutyronitrile, persistently stirs 1 ~ 2 hour, obtain solution B；Persistently lead to nitrogen under the conditions of with constant pressure funnel by
The ethylene glycol ethyl ethers ethereal solution of vinyltriethoxysilane is added dropwise into solution B in drop, and ultrasound mixes, and obtains solution C；By solution C
2 ~ 4 hours are placed at 70 DEG C to get hydrophobic oleophobic colloidal sol；The ethylene glycol ethyl ethers ethereal solution medium vinyl triethoxysilane
Concentration is 0.1 ~ 0.3 mol/L.
2. a kind of preparation method of high strength alumin ium alloy durability super-double-hydrophobic surface according to claim 1, which is characterized in that
The high strength alumin ium alloy is 7 ××× series A l-Zn-Mg-Cu line aluminium alloys.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711106428.4A CN107779030B (en) | 2017-11-10 | 2017-11-10 | A kind of preparation method of high strength alumin ium alloy durability super-double-hydrophobic surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711106428.4A CN107779030B (en) | 2017-11-10 | 2017-11-10 | A kind of preparation method of high strength alumin ium alloy durability super-double-hydrophobic surface |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107779030A CN107779030A (en) | 2018-03-09 |
| CN107779030B true CN107779030B (en) | 2019-10-25 |
Family
ID=61432716
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711106428.4A Active CN107779030B (en) | 2017-11-10 | 2017-11-10 | A kind of preparation method of high strength alumin ium alloy durability super-double-hydrophobic surface |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107779030B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111632804B (en) * | 2020-06-08 | 2022-04-26 | 重庆工业职业技术学院 | Preparation method of aluminum alloy self-cleaning super-hydrophobic surface |
| CN113289876B (en) * | 2021-04-30 | 2022-07-29 | 重庆大学 | Preparation method of metal protective film with self-repairing function and super-amphiphobic function |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003037947A2 (en) * | 2001-10-25 | 2003-05-08 | Ntc Nano Tech Coatings Gmbh | Hardenable mixture based on products of hydrolysis of organosilanes and blocked polyisocyanates |
| CN102847668A (en) * | 2012-08-30 | 2013-01-02 | 重庆大学 | Preparation method for super hydrophobic protective film on surface of high strength aluminum alloy |
| WO2014097309A1 (en) * | 2012-12-17 | 2014-06-26 | Asian Paints Ltd. | Stimuli responsive self cleaning coating |
| CN105524497A (en) * | 2016-01-06 | 2016-04-27 | 南京理工大学 | Superhydrophobic self-healing intelligent nano-coating and preparation method thereof |
| CN106040561A (en) * | 2016-07-11 | 2016-10-26 | 雷春生 | Preparation method of super hydrophobic oleophobic layer surface aluminum sheet |
| CN106381492A (en) * | 2016-09-13 | 2017-02-08 | 昆明理工大学 | Method for preparing super-amphiphobic aluminum surface |
-
2017
- 2017-11-10 CN CN201711106428.4A patent/CN107779030B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003037947A2 (en) * | 2001-10-25 | 2003-05-08 | Ntc Nano Tech Coatings Gmbh | Hardenable mixture based on products of hydrolysis of organosilanes and blocked polyisocyanates |
| CN102847668A (en) * | 2012-08-30 | 2013-01-02 | 重庆大学 | Preparation method for super hydrophobic protective film on surface of high strength aluminum alloy |
| WO2014097309A1 (en) * | 2012-12-17 | 2014-06-26 | Asian Paints Ltd. | Stimuli responsive self cleaning coating |
| CN105524497A (en) * | 2016-01-06 | 2016-04-27 | 南京理工大学 | Superhydrophobic self-healing intelligent nano-coating and preparation method thereof |
| CN106040561A (en) * | 2016-07-11 | 2016-10-26 | 雷春生 | Preparation method of super hydrophobic oleophobic layer surface aluminum sheet |
| CN106381492A (en) * | 2016-09-13 | 2017-02-08 | 昆明理工大学 | Method for preparing super-amphiphobic aluminum surface |
Non-Patent Citations (1)
| Title |
|---|
| 疏水疏油二氧化硅增透膜的制备;晏良宏等;《无机材料学报》;20071130;第22卷(第6期);第1247-1250页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107779030A (en) | 2018-03-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Cui et al. | A long-term stable and environmental friendly self-healing coating with polyaniline/sodium alginate microcapsule structure for corrosion protection of water-delivery pipelines | |
| Zheng et al. | Development of stable superhydrophobic coatings on aluminum surface for corrosion-resistant, self-cleaning, and anti-icing applications | |
| CN104561999B (en) | A kind of method for preparing super-hydrophobic film layer in Mg alloy surface | |
| CN111320918A (en) | Curable wear-resistant super-hydrophobic coating system, product, preparation method and application thereof | |
| CN113249726B (en) | Method for preparing micron-sized spherical super-hydrophobic composite coating on surface of magnesium alloy | |
| Golru et al. | Effects of different surface cleaning procedures on the superficial morphology and the adhesive strength of epoxy coating on aluminium alloy 1050 | |
| JP7381173B2 (en) | Superhydrophobic coating layer and its preparation method and use | |
| CN107779030B (en) | A kind of preparation method of high strength alumin ium alloy durability super-double-hydrophobic surface | |
| CN107012464B (en) | A kind of pretreatment liquid and pre-treating method improving corrosion resistance of aluminum alloy | |
| CN102643967B (en) | Preparation method of steel bionic multiscale dewatering function surface | |
| CN101880881A (en) | High aluminum zinc alloy etching agent and use method thereof | |
| CN104846359A (en) | Composite treatment agent for metal surface pretreatment, preparation method and applications thereof | |
| CN106733564A (en) | The preparation method of the resistance to corrosive magnesium alloy super-hydrophobic surface of biological fluid | |
| CN108018591A (en) | A kind of aluminium and aluminium alloy anode oxide film are without nickel free-floride sealer | |
| CN102206848A (en) | Cathode electrophoresis protective coating modified by silicane and application thereof | |
| CN106929840A (en) | A kind of preparation method with corrosion proof superhydrophobic surface of aluminum alloy | |
| CN110157291A (en) | A kind of graphene anticorrosive paint and preparation method thereof for marine environment | |
| Li et al. | Construction and properties of a multifunctional stearic acid modified CeO2 coating on anodized AZ31B Mg alloy | |
| CN105755453B (en) | A kind of nano chemical composite plating layer preparation method of anti-underground heat aqueous corrosion | |
| CN110735172A (en) | Preparation method of cerium-based coating on surface of magnesium alloys | |
| CN106040561A (en) | Preparation method of super hydrophobic oleophobic layer surface aluminum sheet | |
| CN110066977A (en) | A kind of preparation method of super-hydrophobic metal surface | |
| RU2528285C1 (en) | Method of anticorrosion processing of aluminium alloys | |
| CN109504238A (en) | A kind of one-component self-curing chromium-free zinc aluminum anticorrosive paint and preparation and application | |
| CN104878379B (en) | A kind of metal automatically cleaning, resistant surfaces treatment fluid and preparation method and applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |