CN109880143A - A kind of compound super-hydrophobic waterproof nano film of fluorinated polyethylene - Google Patents
A kind of compound super-hydrophobic waterproof nano film of fluorinated polyethylene Download PDFInfo
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- CN109880143A CN109880143A CN201910120690.7A CN201910120690A CN109880143A CN 109880143 A CN109880143 A CN 109880143A CN 201910120690 A CN201910120690 A CN 201910120690A CN 109880143 A CN109880143 A CN 109880143A
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Abstract
The present invention discloses a kind of compound super-hydrophobic waterproof nano film of fluorinated polyethylene, including substrate, membrane waterproofing, hydrophobic film layer, the membrane waterproofing are polyethylene nano water-proof films.The hydrophobic film layer is with by-CF3With-CF2The compact arranged fluoropolymer nanoparticle of-group and polyelectrolyte assemble to obtain the composite nanoparticle of class mosquito compound eye structural, which is deposited on membrane waterproofing upper surface and combines closely.Due to only laying single hydrophobic film layer, the super-hydrophobic layer for having good water-proof function can not be reached, therefore the membrane waterproofing of superpower binding force and super-hydrophobic hydrophobic film layer are combined together by the present invention, reach durability, waterproofness, super-hydrophobicity and light transmittance more preferably, applicability is more extensive.
Description
Technical field
The present invention relates to super-hydrophobic and field of waterproof materials technologies, and it is compound super-hydrophobic anti-to refer in particular to a kind of fluorinated polyethylene
Water nanometer film.
Background technique
Waterproof refers to that water is impermeable.It is hydrophobic to refer to that hydrophobic molecule bunch up in water, and water is hydrophobic
Property solution surface when then will form a very big contact angle into drops.It is super-hydrophobic refer to it is extremely difficult by water bedew
Surface, contact angle of the water on its surface is more than 150 °, super-hydrophobicity substance of the slide angle less than 20 °, such as lotus leaf.Fall in lotus leaf
On raindrop formed droplet slowly roll and fall along blade face, this water-resistance is known as lotus leaf effect.This is because lotus leaf table
The hydrophobic layer presentation nanoscale in face is uneven, reduces the contact area on droplet and blade face.Plant leaf surface has
The characteristic of super-hydrophobic automatic cleaning provides inspiration to construct artificial hydrophobic surface and designing the controllable interface of wellability, causes
The very big concern of researcher.In recent years, the research of super hydrophobic surface has become active one of the research topic of comparison, this is to system
Standby new performance function material surface has important role.The so-called super-hydrophobic ability of plant is exactly that plant leaf surface has significantly
Hydrophobic, desorption, anti-sticking, self-cleaning function etc..There are many animals and plants surfaces that all there is high hydrophobicity and self-cleaning function in nature
Can, such as lotus leaf and Rice Leaf surface, all up to 150 ° or more of the contact angle of surface water, roll angle is less than 20 °.Due to super thin
The self-cleaning for having its excellent of water surface, therefore have in terms of having in national defence, numerous industrial circles wide
Application prospect.
Summary of the invention
In view of this, in view of the deficiencies of the prior art, the present invention aims to provide a kind of fluorinated polyethylenes
Compound super-hydrophobic waterproof nano film, can make membrane waterproofing securely in conjunction with substrate, and dredge in membrane waterproofing surface deposition
Water film reaches super-hydrophobic (hydrophobic contact angle is greater than 155 degree) effect.
To achieve the above object, the present invention is using following technical solution:
A kind of compound super-hydrophobic waterproof nano film of fluorinated polyethylene, including substrate, membrane waterproofing, hydrophobic film layer；It is described anti-
Water film is polyethylene nano water-proof film, which is tightly engaged into substrate；The hydrophobic film layer is with by-CF3
With-CF2The compact arranged fluoropolymer nanoparticle of-group and polyelectrolyte assemble to obtain answering for class mosquito compound eye structural
Nanoparticle is closed, which is deposited on membrane waterproofing upper surface and combines closely.
As a preferred embodiment, the material of the substrate is any in glass, metal, polymer, fiber or cloth
Material.
As a preferred embodiment, the membrane waterproofing is polyethylene nanometer film, is that ethylene gas is ionized through PECVD device
It is nanoparticle deposition in substrate surface for plasma polymerization, the basis of film layer is amorphous polyethylene, molecular formula table
It is shown as-[CH2—CH2]n—。
As a preferred embodiment, there is abundant-CH on the surface of the membrane waterproofing2—CH2- group, works as nano particle
After being deposited on substrate surface, composite nanoparticle is securely attached to body surface formation-CH2—CH2The film of-chain structure
The conjugation grade of layer, film layer and substrate is greater than 95%, and hardness is greater than 6H.
As a preferred embodiment, the composite nanoparticle is the perfluor alkane of chain polyethylene and class mosquito compound eye structural
Base chain polymerization object nanoparticle.
As a preferred embodiment, the perfluoroalkyl chain polymer nanocomposite of the chain polyethylene and class mosquito compound eye structural
Particle is the hollow structure of layer stephanoporate.
A method of the compound super-hydrophobic waterproof nano film of fluorinated polyethylene is prepared, is included the following steps
S1 prepares membrane waterproofing: ethylene gas enters in the PECVD device of vacuum condition, keeps vacuum degree 100mt, warp
Electrode ionization is that plasma free crowd is nanoparticle deposition in substrate surface, and the conjugation grade of film layer and substrate is greater than
95%, hardness is greater than 6H；
S2 prepares hydrophobic film layer: after membrane waterproofing is disposed, PECVD stopping is passed through ethylene gas, and vacuum is evacuated to
50mt opens perfluoro hexyl ethylmethyl acrylate liquid medicine steam valve, keeps equipment vacuum degree 50-120mt, perfluoro hexyl second
Methyl acrylate liquid medicine gas is polymerized to the perfluoroalkyl chain polymer nano-particle of class mosquito compound eye structural after ionizing
It is deposited on substrate surface, hydrophobic membrane deposition is completed；
S3 adjusts membrane waterproofing, the sedimentation time of hydrophobic film layer can prepare the film layer of different film thickness.
The present invention has obvious advantages and beneficial effects compared with the existing technology, specifically, by above-mentioned technical proposal
Known to: the present invention uses PECVD technology of preparing, be plasma free crowd is nanoparticle deposition in substrate through electrode ionization
Surface forms membrane waterproofing, the existing good waterproofness of polyethylene nano particle and light transmittance, and is connected firmly with substrate.Solution
The waterproof substrate surface of conventional waterproof of having determined material (such as acrylic compounds) is easy to produce cracking, connect unstable lack with substrate
Point.Meanwhile nanometer materials fillibility is strong, membrane waterproofing surface compact after solidification improves the stability of membrane waterproofing.So
The hardness of optimal proportion membrane waterproofing is 6H, and film surface has excellent wearability, draws lattice experiment and shows that its conjugation exists
95% or more.
The perfluoroalkyl chain polymer nano-particle of class mosquito compound eye structural is deposited on by base using PECVD technology of preparing again
Material surface, by-CF3With-CF2The compact arranged fluoropolymer nanoparticle of-group and polyelectrolyte assemble to obtain class
On the one hand the composite nanoparticle of mosquito compound eye structural ensures the attachment force with membrane waterproofing.This type mosquito compound eye simultaneously
The composite nanoparticle of structure has ideal super-hydrophobic effect, and hydrophilic angle is greater than 155 °.Under scanning electron microscope diagram
Show that the hydrophobic film layer is uniform, fine and close, compact-sized, cross section shows that hydrophobic film layer and membrane waterproofing are connected firmly, and structure is tight
It is close, the anti-reflection function admirable of film layer after solidification.
In short, the present invention by membrane waterproofing directly in conjunction with substrate, then composite hydrophobic film layer, membrane waterproofing not only have anti-
Water effect, and extremely strong linking power is generated between substrate, it avoids generating cracking, connect unstable defect with substrate, then
It is that reason only lays one layer of single hydrophobic film layer in the super-hydrophobic film layer of surface recombination, good waterproof can not be reached and surpassed
Strong bonding effect, thus by two membranes it is compound after, advantage is complementary, compensates for the deficiency of homogenous material structure, processability is excellent
Composite material.So that in substrate surface after the compound super-hydrophobic waterproof nano film plated film solidification of this fluorinated polyethylene of the invention
One layer of fine and close membrane waterproofing is formed, hydrophobic water, anti-reflection, superpower binding force, a variety of excellent performances such as high rigidity have also been gathered.Object
Rationality be capable of measuring the result shows that, double-layered compound film have excellent performance, it is anti-the external world loss ability enhancing, extend the use of substrate
Service life.
In order to explain the structural features and functions of the invention more clearly, come with reference to the accompanying drawing with specific embodiment to this hair
It is bright to be described in detail.
Detailed description of the invention
Fig. 1 is the compound super-hydrophobic waterproof nano membrane stratiform structural schematic diagram of the fluorinated polyethylene of embodiments of the present invention.
Fig. 2 is the microgram that membrane waterproofing amplifies 2000 times in embodiments of the present invention.
Fig. 3 is the layer structure of scanning electron microscopy measurement membrane waterproofing in embodiments of the present invention (100,000 times of amplifications)
Schematic diagram.
Fig. 4 is the schematic diagram that hydrophobic film layer amplifies after 5000 times under the microscope in embodiments of the present invention.
Fig. 5 is the composite nanoparticle signal that the class mosquito compound eye structural that 100 times show high permeability is further amplified in Fig. 4
Figure.
Fig. 6 is the schematic diagram of about 155 ° of the water droplet angle test of hydrophobic film layer in embodiments of the present invention.
Description of drawing identification:
10, substrate 20, membrane waterproofing
30, hydrophobic film layer.
Specific embodiment
In order to which the purpose of the present invention and technical solution and advantage is more clearly understood, make with reference to embodiments specifically
It is bright.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not intended to limit the present invention.
It please refers to Fig. 1-5 to show, the compound super-hydrophobic waterproof nano film of fluorinated polyethylene of the invention includes substrate 10, waterproof
Film layer 20, hydrophobic film layer 30.The membrane waterproofing 20 is polyethylene gas through PECVD device ionization be plasma polymerization to receive
Rice grain is deposited on substrate surface, and the basis of film layer is amorphous polyethylene nanometer film, the membrane waterproofing 20 and substrate
10 are tightly engaged into.The hydrophobic film layer 30 is compound eye shape perfluoroalkoxy polymer nanoparticle, which is deposited on anti-
It 20 upper surface of water film and combines closely.
The present invention is mainly the conjugation enhanced with substrate 10 by two layers of film layer, membrane waterproofing 20 is devised, and is guaranteed anti-
Water film has good waterproofness and light transmittance simultaneously, and can guarantee that it is connected firmly with substrate 10.The hydrophobicity of hydrophobic film layer
Can be stronger, it is the porous membrane of graininess arrangement, which has super-hydrophobicity, and contact angle is greater than 155 °, to reach
Good hydrophobic performance.
In the present embodiment, the material of the substrate 10 is any material in glass, metal, polymer, fiber or cloth.
Increase the compound super-hydrophobic waterproof nano film film layer of fluorinated polyethylene on these substrates 10, can be improved the application of substrate 10
Can, such as translucent cover on glasses, vehicle glass, raincoat, clothes etc., it is hydrophobic added, after water-proof function, using more
It is convenient.
The preparation of membrane waterproofing 20 is entered in the PECVD device of vacuum condition with ethylene gas, and vacuum degree is kept
It is nanoparticle deposition in substrate surface that 100mt, which be plasma free crowd through electrode ionization, membrane waterproofing after molding and
The conjugation grade of substrate is greater than 95%, and hardness is greater than 6H.Basis is polyethylene, and molecular formula is expressed as-[CH2—CH2]n—。
As a preferred embodiment, there is abundant-CH on the surface of the membrane waterproofing2—CH2- group, when nanoparticle deposition is in base
Behind material surface, composite nanoparticle is securely attached to body surface formation-CH2—CH2The film layer of-chain structure, film layer with
The conjugation grade of substrate is greater than 95%, and hardness is greater than 6H, and binding force is superpower, and hardness is high, can be not easy to be damaged with effective protection substrate
It is bad.
The hydrophobic film layer 30 is with by-CF3With-CF2The compact arranged fluoropolymer nanoparticle of-group and poly-
Electrolyte assembles to obtain the composite nanoparticle of class mosquito compound eye structural, and for spherical fluoropolymer nanoparticle, these are spherical
Fluoropolymer nanoparticle has the surface of coarse structure, good super-hydrophobic waterproof performance.Further, in order to increase
The spherical fluoropolymer nanoparticle is made as the hollow structure of layer stephanoporate, the diameter of the hollow structure by the transparency
Size is less than 100nm, so as to cause fabulous translucency.Compensate for lacking for class mosquito compound eye structural nano-particles size limitation
Point increases the light transmittance of film layer.
The present invention is that following methods prepare the compound super-hydrophobic waterproof nano film of above-mentioned fluorinated polyethylene, specifically includes following step
It is rapid:
S1 prepares membrane waterproofing 20: referring to fig. 2, S1 prepares membrane waterproofing: ethylene gas enters the PECVD of vacuum condition
In equipment, vacuum degree 100mt is kept, be plasma free crowd through electrode ionization is nanoparticle deposition in substrate surface,
Prepare that nanoscale is anti-reflection, high-hardness water-proof film (see Fig. 3) using chemical deposition addition polymerization process, membrane waterproofing connects with substrate 10
Right to be greater than 95%, hardness is greater than 6H.
S2 prepares hydrophobic film layer 30: referring to fig. 4, after membrane waterproofing is disposed, PECVD stopping is passed through ethylene gas, will
Vacuum is evacuated to 50mt, opens perfluoro hexyl ethylmethyl acrylate liquid medicine steam valve, keeps equipment vacuum degree 120mt.Perfluor
Hexyl ethylmethyl acrylate liquid medicine gas is polymerized to the perfluoroalkyl chain polymer nano of class mosquito compound eye structural after ionizing
Rice corpuscles is deposited on substrate surface, completes hydrophobic membrane deposition.
S3, adjusts waterproof, and the sedimentation time of hydrophobic film layer can prepare the film layer of different film thickness.
In conclusion design focal point of the invention is, the present invention uses PECVD technology of preparing, be through electrode ionization etc.
Gas ions free crowd is nanoparticle deposition in substrate surface, forms membrane waterproofing, polyethylene nano particle is existing good
Waterproofness and light transmittance, and be connected firmly with substrate.Solves the waterproof group table of conventional waterproof material (such as acrylic compounds)
Face is also easy to produce cracking, connect unstable disadvantage with substrate.Meanwhile nanometer materials fillibility is strong, membrane waterproofing after solidification
Surface compact improves the stability of membrane waterproofing.So the hardness of optimal proportion membrane waterproofing is 6H, film surface has excellent
Good wearability draws lattice experiment and shows its conjugation 95% or more.
The perfluoroalkyl chain polymer nano-particle of class mosquito compound eye structural is deposited on by base using PECVD technology of preparing again
Material surface, by-CF3With-CF2The compact arranged fluoropolymer nanoparticle of-group and polyelectrolyte assemble to obtain class
On the one hand the composite nanoparticle of mosquito compound eye structural ensures the attachment force with membrane waterproofing.This type mosquito compound eye simultaneously
The composite nanoparticle of structure has ideal super-hydrophobic effect, and hydrophilic angle is greater than 155 °.Under scanning electron microscope diagram
Show that the hydrophobic film layer is uniform, fine and close, compact-sized, cross section shows that hydrophobic film layer and membrane waterproofing are connected firmly, and structure is tight
It is close, the anti-reflection function admirable of film layer after solidification.
In short, the present invention by membrane waterproofing directly in conjunction with substrate, then composite hydrophobic film layer, membrane waterproofing not only have anti-
Water effect, and extremely strong linking power is generated between substrate, it avoids generating cracking, connect unstable defect with substrate, then
It is that reason only lays one layer of single hydrophobic film layer in the super-hydrophobic film layer of surface recombination, good waterproof can not be reached and surpassed
Strong bonding effect, thus by two membranes it is compound after, advantage is complementary, compensates for the deficiency of homogenous material structure, processability is excellent
Composite material.So that in substrate surface after the compound super-hydrophobic waterproof nano film plated film solidification of this fluorinated polyethylene of the invention
One layer of fine and close membrane waterproofing is formed, hydrophobic water, anti-reflection, superpower binding force, a variety of excellent performances such as high rigidity have also been gathered.Object
Rationality be capable of measuring the result shows that, double-layered compound film have excellent performance, it is anti-the external world loss ability enhancing, extend the use of substrate
Service life.
The above described is only a preferred embodiment of the present invention, be not intended to limit the scope of the present invention,
Therefore any subtle modifications, equivalent variations and modifications to the above embodiments according to the technical essence of the invention, still
Belong in the range of technical solution of the present invention.
Claims (8)
1. a kind of compound super-hydrophobic waterproof nano film of fluorinated polyethylene, it is characterised in that: including substrate, membrane waterproofing, hydrophobic membrane
Layer；The membrane waterproofing is polyethylene nano water-proof film, which is tightly engaged into substrate；The hydrophobic film layer is to use
By-CF3With-CF2The compact arranged fluoropolymer nanoparticle of-group and polyelectrolyte assemble to obtain class mosquito compound eye knot
The composite nanoparticle of structure, the hydrophobic film layer are deposited on membrane waterproofing upper surface and combine closely.
2. the compound super-hydrophobic waterproof nano film of fluorinated polyethylene according to claim 1, it is characterised in that: the substrate
Material is any material in glass, metal, polymer, fiber or cloth.
3. the compound super-hydrophobic waterproof nano film of fluorinated polyethylene according to claim 1, it is characterised in that: the waterproof membrane
Layer is polyethylene nanometer film, be ethylene gas be plasma polymerization through PECVD device ionization is nanoparticle deposition in substrate
Surface, the basis of film layer are amorphous polyethylenes, and molecular formula is expressed as-[CH2—CH2]n—。
4. the compound super-hydrophobic waterproof nano film of fluorinated polyethylene according to claim 1, it is characterised in that: the waterproof membrane
There is abundant-CH on the surface of layer2—CH2- group, when nanoparticle deposition is after substrate surface, composite nanoparticle is securely
It is attached to body surface formation-CH2—CH2The conjugation grade of the film layer of-chain structure, film layer and substrate is greater than 95%, and hardness is big
In 6H.
5. the compound super-hydrophobic waterproof nano film of fluorinated polyethylene according to claim 1, it is characterised in that: described compound to receive
Rice corpuscles is the perfluoroalkyl chain polymer nano-particle of chain polyethylene and class mosquito compound eye structural.
6. the compound super-hydrophobic waterproof nano film of fluorinated polyethylene according to claim 5, it is characterised in that: the chain is poly-
The perfluoroalkyl chain polymer nano-particle of ethylene and class mosquito compound eye structural is the hollow structure of layer stephanoporate.
7. the compound super-hydrophobic waterproof nano film of fluorinated polyethylene according to claim 6, it is characterised in that: the hollow knot
The diameter dimension of structure is less than 100nm, so as to cause fabulous translucency.
8. a kind of method for the compound super-hydrophobic waterproof nano film of fluorinated polyethylene for preparing claim 1, it is characterised in that: including
Following steps
S1 prepares membrane waterproofing: polyethylene gas enters in the PECVD device of vacuum condition, vacuum degree 100mt is kept, through electricity
Pole ionization be that plasma free crowd is nanoparticle deposition in substrate surface, the conjugation grade of film layer and substrate greater than 95%,
Hardness is greater than 6H；
S2 prepares hydrophobic film layer: after membrane waterproofing is disposed, PECVD stopping is passed through ethylene gas, and vacuum is evacuated to 50mt,
Perfluoro hexyl ethylmethyl acrylate liquid medicine steam valve is opened, equipment vacuum degree 50-120mt, perfluoro hexyl ethyl first are kept
Base acrylate liquid medicine gas is polymerized to the perfluoroalkyl chain polymer nano-particle deposition of class mosquito compound eye structural after ionizing
In substrate surface, hydrophobic membrane deposition is completed；
S3 adjusts membrane waterproofing, the sedimentation time of hydrophobic film layer can prepare the film layer of different film thickness.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112123893A (en) * | 2020-09-14 | 2020-12-25 | 衡阳市雁证不锈钢商贸有限公司 | Hydrophobic door and window glass |
| CN112979915A (en) * | 2021-03-22 | 2021-06-18 | 漳州佳联化工有限公司 | Ultra-soft low-surface-energy modified polyurethane resin and preparation method thereof |
| CN113399227A (en) * | 2021-06-07 | 2021-09-17 | 百腾科技(苏州)有限公司 | Waterproof and hydrophobic composite film layer suitable for battery pack and preparation method thereof |
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