CN107779030A - 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
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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 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 good endurance prepared by the present invention, a variety of harsh experiments 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 are subjected to, are expected to be applied in multiple fields.Preparation method technique of the present invention is simple and convenient to operate, suitable for various sizes, the processing of the high strength alumin ium alloy workpiece of 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 technology
The wetability of material surface has material impact 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 higher 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 the advantages that light, specific strength is high, specific stiffness is high, is widely used in national economy and national defence
The every field of construction.Al-Zn-Mg-Cu aluminum alloy (7 ×××) using 7075 aluminium alloys as representative be high strength alumin ium alloy most
Main series, it is mainly used in the main force support structure of the advanced Grand Equipments such as aircraft, such as crucial portion of covering, bulkhead, spar
Position.In view of the ability such as the excellent automatically cleaning of super-double-hydrophobic surface, anti-corrosion, resistant, drag reduction, prepares high strength alumin ium alloy durability super-amphiphobic
Surface is expected to obviously improve military service quality of the advanced Grand Equipments being made up of it in complicated, harsh natural environment, significantly
Reduce due to economic loss and casualties caused by its corrosion and damage.
Although the preparation for super-amphiphobic aluminium surface has had a small amount of report 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 particularly 7 ××× system Al-Zn-Mg-Cu alloys due to mutually causing its micro-structural very containing substantial amounts of alloy
Uneven, 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 particularly 7 ××× system Al-Zn-Mg-Cu alloys is significant.
The content of the invention
For deficiencies of the prior art, 7 are particularly it is an object of the invention 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 particularly 7 ××s
× the problem of being Al-Zn-Mg-Cu alloy super-oleophobic surface preparation technology famine.
Above-mentioned purpose is realized, the present invention adopts the following technical scheme that：
A kind of preparation method of high strength alumin ium alloy durability super-double-hydrophobic surface, comprises the following steps：
1. zirconium-manganese salt mixed solution immersion treatment：By the high strength alumin ium alloy workpiece of cleaning be immersed in pH value for 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；
The zirconium-manganese salt mixed solution is by zirconium sulfate and manganese chloride in molar ratio 2~4:1 mixes, and 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 stirred vigorously uniformly, the high strength alumin ium alloy workpiece surface after then 1. even application is handled to step, by workpiece at room temperature
Place 12 hours, dried 4~6 hours at 60~80 DEG C, produce high strength alumin ium alloy durability super-double-hydrophobic surface；Wherein, add
The silane resin acceptor kh-550 and the volume ratio of colloidal sol entered is 1:200；Every square metre of high strength alumin ium alloy workpiece surface coating 0.02
~0.1L colloidal sols.
Compared with prior art, the present invention has the advantages that：
1st, 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.
2nd, high strength alumin ium alloy super-double-hydrophobic surface good endurance prepared by the present invention, can be subjected to high temperature low temperature, strong acid and strong base, rub
A variety of harsh experiments 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.
3rd, preparation method technique of the present invention is simple and convenient to operate, and without the special experiment condition such as high temperature, power-up, is applied to
Various sizes, shape high strength alumin ium alloy workpiece processing, be easy to large-scale industrial production.
Embodiment
With reference to specific embodiment, the present invention is described in further detail.
It should be noted that these embodiments are merely to illustrate the present invention, rather than limitation of the present 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 alloys 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 subjected to following handle successively：
1. zirconium-manganese salt mixed solution immersion treatment：Workpiece is immersed in into zirconium-manganese salt that pH value is 2.0, temperature is 40 DEG C to mix
Close in solution 20 minutes, take out workpiece, pure water is cleaned and dried up；
The zirconium-manganese salt mixed solution is by zirconium sulfate and manganese chloride in molar ratio 4:1 mixes, and 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 stirred vigorously uniformly, the high strength alumin ium alloy workpiece surface after then 1. even application is handled to step, by workpiece at room temperature
Place 12 hours, dried 6 hours at 60 DEG C, produce 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, every square metre of high strength alumin ium alloy workpiece surface coats 0.1L colloidal sols.
The preparation section of the hydrophobic oleophobic colloidal sol is：0.2mol octadecyl methacrylates are added to 500mL
In ethylene glycol ethyl ether, ultrasound mixes, and obtains solution A；Solution A is heated to 70 DEG C, nitrogen is passed through, is then added in solution A
0.5g azodiisobutyronitriles, persistently stir 1.5 hours, obtain solution B；It is added dropwise dropwise with constant pressure funnel under the conditions of nitrogen is persistently led to
Concentration be 0.2mol/L VTES ethylene glycol ethyl ethers ethereal solution into solution B, ultrasound mix, obtain solution
C；Solution C is placed 3 hours at 70 DEG C, produces hydrophobic oleophobic colloidal sol.
The checking procedure of high strength alumin ium alloy durability super-double-hydrophobic surface is following (other embodiment is same)：
A. super-amphiphobic function is examined measures 2 μ L using German 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 dredged
Oily function, static contact angle is considered as ultraphobic surface more than the surface that 150 °, roll angle are less than 10 °, 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 experiment, friction-wear test, ultraviolet radiation examination
Test, 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 change of the static contact angle and roll angle of workpiece surface water and oil before and after testing is stated, is shown if change 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：High strength alumin ium alloy workpiece after the inventive method is handled is respectively placed in 200 DEG C (high temperature)
With 48 hours in -100 DEG C of (low temperature) environment, test high temperature low-temperature test before and after workpiece surface water and oil static contact angle, rolling
The change at dynamic angle.
(2) strong acid and strong base is tested：High strength alumin ium alloy workpiece after the inventive method is handled is immersed in 1.0mol/L respectively
48 hours in salpeter solution (pH=1) and 1.0mol/L sodium hydroxide solutions (pH=14), work before and after test strong acid and strong base experiment
The change of the static contact angle, roll angle of part surface water and oil.
(3) friction-wear test：By the tiling of 100# abrasive paper for metallograph on the table, the high-strength aluminium after the inventive method is handled
Alloy workpiece one side contact sand paper (face is working face), apply fixed pressure 1.0kPa, drag 1 meter of distance, dragging speed 5mm
s-1, horizontal, longitudinally reciprocal to drag each 50 times, the static contact angle of workpiece surface water and oil, rolling before and after testing friction wear test
The change at angle.
(4) ultraviolet radiation is tested：High strength alumin ium alloy workpiece after the inventive method is handled carries out ultraviolet radiation, purple
Outer light source wavelength is 254nm, and workpiece location is apart from 2~3cm of light source, radiated time 48 hours, test ultraviolet radiation examination
Test the change of the static contact angle, roll angle of front and rear workpiece surface water and oil.
(5) the high strength alumin ium alloy workpiece after water jets under high pressure impact test handles the inventive method carries out water jets under high pressure punching
Hit, hydraulic pressure 200kPa, 1 meter of release altitude, reciprocal 50 times, before and after testing high voltage water column impact test workpiece surface water and oil it is quiet
The change of state contact angle, roll angle.
(6) the high strength alumin ium alloy workpiece after strong corrosive medium soak test handles the inventive method is immersed in 35 ± 2 DEG C
PH value for 3.2 ± 0.1 (glacial acetic acid regulations) 50 ± 5g/L sodium chloride corrosive medium in 720 hours, test deep-etching Jie
The change 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 result are shown：The 7075 high-strength aluminium after the inventive method is handled 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 experiment, fretting wear examination
Test, ultraviolet radiation experiment, the static state of workpiece surface water and oil before and after water jets under high pressure impact test, strong corrosive medium soak test
The change of contact angle and roll angle is respectively less than 5 °, shows excellent durability.
Embodiment 2：
The 7B04 high strength alumin ium alloys workpiece of surface cleaning is subjected to following handle successively：
1. zirconium-manganese salt mixed solution immersion treatment：Workpiece is immersed in into zirconium-manganese salt that pH value is 4.0, temperature is 60 DEG C to mix
Close in solution 10 minutes, take out workpiece, pure water is cleaned and dried up；
The zirconium-manganese salt mixed solution is by zirconium sulfate and manganese chloride in molar ratio 2:1 mixes, and 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 stirred vigorously uniformly, the high strength alumin ium alloy workpiece surface after then 1. even application is handled to step, by workpiece at room temperature
Place 12 hours, dried 4 hours at 80 DEG C, produce 7B04 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, 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 is：0.1mol octadecyl methacrylates are added to 500mL
In ethylene glycol ethyl ether, ultrasound mixes, and obtains solution A；Solution A is heated to 70 DEG C, nitrogen is passed through, is then added in solution A
0.4g azodiisobutyronitriles, persistently stir 1 hour, obtain solution B；It is added dropwise dropwise with constant pressure funnel under the conditions of nitrogen is persistently led to dense
The ethylene glycol ethyl ethers ethereal solution of the VTES for 0.1mol/L is spent into solution B, and ultrasound mixes, and obtains solution C；
Solution C is placed 2 hours at 70 DEG C, produces hydrophobic oleophobic colloidal sol.
Super-amphiphobic function and its durability test result are shown：7B04 high strength alumin ium alloy works after the inventive method is handled
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 experiment, friction-wear test,
The static state of workpiece surface water and oil connects before and after ultraviolet radiation experiment, water jets under high pressure impact test, strong corrosive medium soak test
The change 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 subjected to following handle successively：
1. zirconium-manganese salt mixed solution immersion treatment：Workpiece is immersed in into zirconium-manganese salt that pH value is 3.0, temperature is 50 DEG C to mix
Close in solution 30 minutes, take out workpiece, pure water is cleaned and dried up；
The zirconium-manganese salt mixed solution is by zirconium sulfate and manganese chloride in molar ratio 3:1 mixes, and 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 stirred vigorously uniformly, the high strength alumin ium alloy workpiece surface after then 1. even application is handled to step, by workpiece at room temperature
Place 12 hours, dried 5 hours at 70 DEG C, produce 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, 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 is：0.3mol octadecyl methacrylates are added to 500mL
In ethylene glycol ethyl ether, ultrasound mixes, and obtains solution A；Solution A is heated to 70 DEG C, nitrogen is passed through, is then added in solution A
0.6g azodiisobutyronitriles, persistently stir 2 hours, obtain solution B；It is added dropwise dropwise with constant pressure funnel under the conditions of nitrogen is persistently led to dense
The ethylene glycol ethyl ethers ethereal solution of the VTES for 0.3mol/L is spent into solution B, and ultrasound mixes, and obtains solution C；
Solution C is placed 4 hours at 70 DEG C, produces hydrophobic oleophobic colloidal sol.
Super-amphiphobic function and its durability test result are shown：The 7075 high strength alumin ium alloy works after the inventive method is handled
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 experiment, friction-wear test,
The static state of workpiece surface water and oil connects before and after ultraviolet radiation experiment, water jets under high pressure impact test, strong corrosive medium soak test
The change of feeler and roll angle is respectively less than 5 °, shows excellent durability.
Embodiment 4：
The 7B04 high strength alumin ium alloys workpiece of surface cleaning is subjected to following handle successively：
1. zirconium-manganese salt mixed solution immersion treatment：Workpiece is immersed in into zirconium-manganese salt that pH value is 3.0, temperature is 50 DEG C to mix
Close in solution 20 minutes, take out workpiece, pure water is cleaned and dried up；
The zirconium-manganese salt mixed solution is by zirconium sulfate and manganese chloride in molar ratio 4:1 mixes, and 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 stirred vigorously uniformly, the high strength alumin ium alloy workpiece surface after then 1. even application is handled to step, by workpiece at room temperature
Place 12 hours, dried 5 hours at 70 DEG C, produce 7B04 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, 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 is：0.2mol octadecyl methacrylates are added to 500mL
In ethylene glycol ethyl ether, ultrasound mixes, and obtains solution A；Solution A is heated to 70 DEG C, nitrogen is passed through, is then added in solution A
0.5g azodiisobutyronitriles, persistently stir 2 hours, obtain solution B；It is added dropwise dropwise with constant pressure funnel under the conditions of nitrogen is persistently led to dense
The ethylene glycol ethyl ethers ethereal solution of the VTES for 0.2mol/L is spent into solution B, and ultrasound mixes, and obtains solution C；
Solution C is placed 3 hours at 70 DEG C, produces hydrophobic oleophobic colloidal sol.
Super-amphiphobic function and its durability test result are shown：7B04 high strength alumin ium alloy works after the inventive method is handled
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 experiment, friction-wear test,
The static state of workpiece surface water and oil connects before and after ultraviolet radiation experiment, water jets under high pressure impact test, strong corrosive medium soak test
The change of feeler and roll angle is respectively less than 5 °, shows excellent durability.
Above example is using 7075 and 7B04 high strength alumin ium alloys as process object, it is necessary to which explanation is that the present invention is equally applicable
In other 7 ××× system Al-Zn-Mg-Cu alloys, fine aluminium and non-7 ××× series high-strength aluminum alloy are also applied for.
Finally illustrate, the above embodiments are merely illustrative of the technical solutions of the present invention, and other are according to the technology of the present invention
The modification or equivalent substitution that scheme is carried out, all should cover among scope of the presently claimed invention.
Claims (3)
1. a kind of preparation method of high strength alumin ium alloy durability super-double-hydrophobic surface, it is characterised in that comprise the following steps：
1. zirconium-manganese salt mixed solution immersion treatment：The high strength alumin ium alloy workpiece of cleaning is immersed in pH value as 2.0 ~ 4.0, temperature
For 10 ~ 30 minutes in 40 ~ 60 °C of zirconiums-manganese salt mixed solution, workpiece is taken out, pure water is cleaned and dried up；
The zirconium-manganese salt mixed solution is by zirconium sulfate and manganese chloride in molar ratio 2 ~ 4:1 mixes, and is converted into containing for zirconium sulfate
Amount, concentration is 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 rapid acute
It is strong to stir, the high strength alumin ium alloy workpiece surface after then 1. even application is handled to step, workpiece is placed at room temperature
12 hours, dried 4 ~ 6 hours at 60 ~ 80 DEG C, produce 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.
A kind of 2. preparation method of high strength alumin ium alloy durability super-double-hydrophobic surface according to claim 1, it is characterised in that
The preparation section of the hydrophobic oleophobic colloidal sol is：0.1 ~ 0.3 mol octadecyl methacrylates are added to 500 mL second
In glycol ether, ultrasound mixes, and obtains solution A；Solution A is heated to 70 DEG C, nitrogen is passed through, 0.4 is then added in solution A
~ 0.6g azodiisobutyronitriles, persistently stir 1 ~ 2 hour, obtain solution B；Dripped dropwise with constant pressure funnel under the conditions of nitrogen is persistently led to
Add the ethylene glycol ethyl ethers ethereal solution of VTES into solution B, ultrasound mixes, and obtains solution C；By solution C in 70
Placed 2 ~ 4 hours at DEG C, produce hydrophobic oleophobic colloidal sol；The concentration of the ethylene glycol ethyl ethers ethereal solution medium vinyl triethoxysilane
For 0.1 ~ 0.3 mol/L.
A kind of 3. preparation method of high strength alumin ium alloy durability super-double-hydrophobic surface according to claim 1, it is characterised in that
The high strength alumin ium alloy is 7 ××× series A l-Zn-Mg-Cu line aluminium alloys.
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