CN107413599B - The preparation method of concentration tension gradient self-assembled coating - Google Patents
The preparation method of concentration tension gradient self-assembled coating Download PDFInfo
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- CN107413599B CN107413599B CN201710685661.6A CN201710685661A CN107413599B CN 107413599 B CN107413599 B CN 107413599B CN 201710685661 A CN201710685661 A CN 201710685661A CN 107413599 B CN107413599 B CN 107413599B
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Abstract
A kind of preparation method of concentration tension gradient self-assembled coating, comprising: provide substrate and colloidal solution, the colloidal solution includes the first liquid and the colloidal solid that is scattered in first liquid；Second liquid is provided, the second liquid dissolves each other with first liquid, and the surface tension of the second liquid is less than the surface tension of first liquid, forms a liquid film in the substrate surface with the second liquid；And contact the liquid film with the colloidal solution, to form concentration tension gradient self-assembled coating in the substrate surface.The present invention can simply and efficiently obtain the concentration tension gradient self-assembled coating of uniformity in different substrates.
Description
Technical field
The present invention relates to Material Fields, more particularly to a kind of preparation method of concentration tension gradient self-assembled coating.
Background technique
Colloidal solid is monodispersed, scale in nanometer, the other organic or inorganic particle of submicron order.Nanometer, sub-micron
Sized materials light, electricity, magnetic, in terms of there are many peculiar properties, in terms of colloidal solid in people's lives very much
It plays an increasingly important role.Colloidal solid is formed into single-layer or multi-layer colloidal solid film in substrate surface, not only may be used
Overall performance can also be made to go out property not available for colloidal solid the protection of substrate to realize, can be used for anticorrosion, urge
The fields such as change, photoelectric device, sensor and biomedicine.
The preparation of colloidal solid film utilizes colloidal solid and colloid mainly by way of colloidal solid self assembly
Interaction force (Coulomb force, Van der Waals force and hydrophobic forces etc.) between particle and between colloidal solid and substrate surface,
It moves colloidal solid under these effects towards the direction that free energy reduces, is formed when maximum system energy reaches minimum stable
Single-layer or multi-layer colloidal solid film.In general, the self-assembling method for preparing colloidal solid film has spin-coating method, convection current method, lifting
The methods of method and electrostatic force method, wherein spin-coating method, convection current method and czochralski method are all to utilize the profit of colloidal solution on the surface of the substrate
Wet and formation film effect, electrostatic force method are that colloidal solid is made to be assembled into substrate surface under electrostatic attraction effect.
However, spin-coating method can not form uniform single-layer or multi-layer colloidal solid film, the operation of convection current method on curved surface
Method is complex, and required control parameter is more.Although electrostatic force method is suitable for curved surface, usually require to change substrate
Property, it is more difficult to control the number of plies of colloidal solid.Czochralski method be using colloidal solution liquid level formed in the place contacted with substrate it is curved
The evaporation induction of lunar surface, the region solution produces the convection current of solution, and colloidal solid is moved to meniscus top in this role,
As the thinned particle of meniscus is precipitated and is adsorbed in substrate, while the liquid level for controlling colloidal solution and substrate progress are slowly
Relative movement, to constantly form new meniscus in the different location of substrate surface and adsorb new colloidal solid, finally exists
Substrate surface forms colloidal solid film.The time that this method forms colloidal solid film is longer, inefficiency, and applies
When on curved substrate, in relative movement thereof, the shape of the meniscus formed with liquid level due to curved substrate is constantly to change
, so as to cause cannot get uniform colloidal solid film.
Summary of the invention
Based on this, it is necessary to provide and a kind of be simple and efficient, have to different substrates and wide applicability and be capable of forming
The preparation method of uniform concentration tension gradient self-assembled coating.
A kind of preparation method of concentration tension gradient self-assembled coating, comprising:
There is provided substrate and colloidal solution, the colloidal solution includes the first liquid and the glue that is scattered in first liquid
Body particle；
Second liquid is provided, the second liquid dissolves each other with first liquid, and the surface tension of the second liquid
Less than the surface tension of first liquid, a liquid film is formed in the substrate surface with the second liquid；And
The liquid film is contacted with the colloidal solution, to form the self assembly of concentration tension gradient in the substrate surface
Coating.
The method that the liquid film is contacted with the colloidal solution includes: that will be formed in one of the embodiments,
There is the substrate of the liquid film to be put into the colloidal solution, contacts the liquid film with the colloidal solution；The concentration
The preparation method of tension gradient self-assembled coating further comprises: will be formed with the institute of the concentration tension gradient self-assembled coating
It states substrate and is lifted from the colloidal solution and come out.
The surface tension of the second liquid is less than or equal to the surface of first liquid in one of the embodiments,
The 1/2 of tension.
The substrate surface for being used to form the liquid film in one of the embodiments, is plane or curved surface.
The substrate surface for being used to form the liquid film in one of the embodiments, is continuous surface or noncontinuous surface.
First liquid is water in one of the embodiments, and the second liquid is ethyl alcohol, acetone, acetic acid and first
At least one of alcohol.
During in one of the embodiments, the substrate being lifted out from the colloidal solution, make to be formed with
The angle of the substrate surface of the concentration tension gradient self-assembled coating and the liquid level of the colloidal solution is greater than 45 ° and small
In 135 °.
The speed the in one of the embodiments, substrate being lifted out from the colloidal solution is less than 5mm/s.
The speed the in one of the embodiments, substrate being lifted out from the colloidal solution is greater than 2mm/s.
It after lifting comes out in the colloidal solution, is further wrapped by the substrate in one of the embodiments,
The step of including the dry substrate.
The preparation method of concentration tension gradient self-assembled coating provided by the invention, when the liquid film and the colloidal solution
When contact, the second liquid is diffused to first liquid, and surface distance of the formation one from the substrate is closer, institute
State the higher concentration gradient of the concentration of second liquid.Since the surface tension of the second liquid is less than the table of first liquid
Face tension, interfacial tension smaller interfacial tension gradient closer so as to form a surface distance from the substrate.Described
Under the action of interfacial tension gradient, the colloidal solid is moved to the direction that interfacial tension reduces until the surface with the substrate
It contacts, and is attracted to the surface formation self-assembled coating of the substrate under the action of Van der Waals force.
The present invention can rapidly realize the colloid using the interfacial tension gradient that the first liquid and second liquid are formed
The preparation of the self assembly of particle and the self-assembled coating, and can form the uniform self assembly in different substrates and apply
Layer, preparation efficiency is high, easy to operate, easily controllable and cost is relatively low, is conducive to large area preparation of industrialization.
Detailed description of the invention
Fig. 1 is the flow chart of the preparation method of concentration tension gradient self-assembled coating provided by the invention；
Fig. 2 is the stereoscan photograph for the concentration tension gradient self-assembled coating that the embodiment of the present invention 1 provides；
Fig. 3 is the stereoscan photograph for the concentration tension gradient self-assembled coating that the embodiment of the present invention 2 provides；
Fig. 4 is the stereoscan photograph for the concentration tension gradient self-assembled coating that the embodiment of the present invention 3 provides.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, by the following examples, it and combines attached
Figure, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only to explain this hair
It is bright, it is not intended to limit the present invention.
Referring to Fig. 1, first embodiment of the invention provides a kind of preparation method of concentration tension gradient self-assembled coating,
Include:
S1, provides substrate and colloidal solution, and the colloidal solution includes the first liquid and is scattered in first liquid
Colloidal solid；
S2 provides second liquid, and the second liquid dissolves each other with first liquid, and the surface of the second liquid
Power is less than the surface tension of first liquid, forms a liquid film in the substrate surface with the second liquid；And
S3 contacts the liquid film with the colloidal solution, so that the colloidal solid is assembled in the substrate surface
Form self-assembled coating.
In step sl, the material of the substrate and type are unlimited, can be selected according to actual needs.The substrate
The surface for being used to form the liquid film can be plane, be also possible to curved surface.The substrate is used to form the surface of the liquid film
It can be continuous surface, be also possible to noncontinuous surface, such as netted face.The substrate can be by organic material, inorganic material
It is prepared at least one of metal material.The substrate can also be fibrous substrates.
The type of the colloidal solid and first liquid is unlimited, as long as being capable of forming the colloidal solution.Institute
Stating the first liquid can be at least one of organic solvent and inorganic solvent, such as first liquid can be water.It is described
Colloidal solid can be inorganic particle (such as nano-Ag particles) or organic granular (such as polytetrafluoroethylene (PTFE) capsule shape particle,
PTFE).The colloidal solid shape can be spherical or capsule shape.
In step s 2, the type of the second liquid is unlimited, as long as the substrate can be soaked to form the liquid
Film.Preferably, described second liquid itself has lesser surface tension, to form the liquid on the substrate
Film.The second liquid can be at least one of ethyl alcohol, acetone, acetic acid and methanol.
The method for forming the liquid film on the substrate with the second liquid is unlimited.In one embodiment, with described
The method that second liquid forms the liquid film on the substrate includes: that the substrate is totally immersed into the second liquid,
Then the substrate is lifted from the second liquid and is come out, to form the liquid film on the substrate.Using lifting
Method can quickly and easily obtain the more uniform liquid film.Preferably, the substrate can be erected from the second liquid
Directly lift out.
Further, it is formed before the liquid film on the substrate, may also include the step cleaned to the substrate
Suddenly, to remove the remaining spot of the substrate surface.At least one of acetone, ethyl alcohol and deionized water can be used to described
Substrate is cleaned.After cleaning, the liquid film is re-formed after the surface of the substrate is dried up.
In step s3, when the liquid film and the colloidal solution contact, the second liquid is to first liquid
It is diffused, and surface distance of the formation one from the substrate is closer, the higher concentration gradient of the concentration of the second liquid.By
It is less than the surface tension of first liquid in the surface tension of the second liquid, so as to form a table from the substrate
Identity distance is from closer, the smaller interfacial tension gradient of interfacial tension.Under the action of the interfacial tension gradient, the colloidal solid
The direction reduced to interfacial tension is moved to be contacted until with the surface of the substrate, and is adsorbed under the action of Van der Waals force
The self-assembled coating is formed on the surface of the substrate.
The preparation method of concentration tension gradient self-assembled coating provided by the invention, utilizes the first liquid and second liquid shape
At interfacial tension gradient can rapidly realize the self assembly of the colloidal solid, it is easy to operate efficiently, easy to accomplish, control
Parameter is less, and has universality to different substrates.In addition, no matter using which kind of substrate, the self assembly of the colloidal solid
Condition is all the same, therefore, the uniform self-assembled coating can be obtained.
When the second liquid be volatile solvent (such as ethyl alcohol) when, can by the liquid film rapidly with the colloid
Solution contact, prevents second liquid from volatilizing before the liquid film is contacted with the colloidal solution.
The surface tension of the second liquid and the surface tension gap of first liquid are bigger, and the colloidal solid is got over
It smoothly can rapidly be adsorbed in the substrate to be more smoothly rapidly formed the self-assembled coating.Preferably, described
The surface tension of second liquid is less than or equal to the 1/2 of first surface tension of liquid.
After self-assembled coating formation, even if first liquid and the second liquid pass through diffusion
Uniformly mixing makes the interfacial tension gradient disappear, and the self-assembled coating is since there are Van der Waals forces etc. to make between substrate
Firmly, it still is able to be adsorbed in the substrate surface securely.
In one embodiment, the mode that the substrate for being formed with the liquid film is put into the colloidal solution can be used,
Come so that the liquid film is contacted with the colloidal solution.Since the colloidal solid in colloidal solution may be largely, except in base
Bottom surface is self-assembly of outside self-assembled coating, may be freely present in second liquid there are also part colloidal solid, described dense
The preparation method for spending tension gradient self-assembled coating can be wrapped further after forming the concentration tension gradient self-assembled coating
It includes:
The substrate for being formed with the concentration tension gradient self-assembled coating is lifted from the colloidal solution and is come out by S4.
In step s 4, the substrate is lifted to come out from the colloidal solution and specifically refers to be detached from institute in the substrate
During stating colloidal solution, so that being formed with the substrate surface of the self-assembled coating and the liquid level of the colloidal solution
Angle is greater than 0 ° and less than 180 °, during preventing the substrate to be detached from from the colloidal solution, make be containing unassembled
The colloidal solution of the free colloidal solid of self-assembled coating remains on the self-assembled coating and influences the self assembly and apply
The homogeneity of layer.Preferably, during lifting the substrate from the colloidal solution out, so that being formed with described
The angle of the substrate surface of concentration tension gradient self-assembled coating and the liquid level of the colloidal solution is greater than 45 ° and is less than
135 °, to guarantee that extra colloidal solution will not be remained in the substrate.
The substrate can slowly be lifted from the colloidal solution and be come out, so that the colloidal solution will not be by institute
It states substrate to take out of, to guarantee the homogeneity of the self-assembled coating finally obtained.Preferably, by the substrate from the glue
The speed for lifting out in liquid solution is less than 5mm/s, to guarantee that the colloidal solution will not be taken out of by the substrate.It is more highly preferred to
The speed that the substrate is lifted out by ground from the colloidal solution is greater than 2mm/s, so that the substrate can be rapidly
It is detached from the colloidal solution.
After the step S4, it may also include the step of drying the substrate to remove the first liquid of the substrate surface
Body and/or second liquid.The method of the dry substrate can be selected according to actual needs, such as naturally dry can be used
The dry substrate of method.
Embodiment 1:
Silicon wafer is successively used acetone, ethyl alcohol, deionized water respectively clean 5 minutes, cleaning is finished to be dried up using argon gas.Silicon
Piece is put into dehydrated alcohol, lifts out liquid level vertically, and ethyl alcohol sprawls into film in silicon chip surface.It is 60% by mass fraction
PTFE colloidal solution is diluted to the PTFE colloidal solution that mass fraction is 6% with deionized water, 10min is stirred by ultrasonic, in ethyl alcohol
Before volatilization, substrate is put into vertically in the PTFE colloidal solution that mass fraction is 6%, then lifted vertically with the speed of 3mm/s
Silicon wafer is put and is spontaneously dried in air by liquid level out, characterizes after moisture evaporation through scanning electron microscope, as shown in Fig. 2, can
To find out that silicon wafer is covered by PTFE self-assembled coating, PTFE self-assembled coating is single layer and has preferable uniformity.
Embodiment 2:
The present embodiment and the embodiment 1 are essentially identical, the difference is that deionized water is by PTFE colloidal solution quality
Score is diluted to 12%.It is characterized through scanning electron microscope, as shown in figure 3, silicon wafer is covered by PTFE self-assembled coating, PTFE is certainly
Assembling coating is double-deck and has preferable uniformity.
Embodiment 3:
The present embodiment and the embodiment 1 are essentially identical, the difference is that substrate is stainless (steel) wire.It is aobvious through scanning electron
Micro mirror characterization, as shown in figure 4, stainless (steel) wire is covered by PTFE self-assembled coating, the PTFE self-assembled coating has preferable
Uniformity.
As can be seen from the above embodiments, the self-assembling method of colloidal solid provided by the invention, is not only simple and efficient, and holds
It easily realizes, can apply in the substrate surfaces such as plane and curved surface, there is stronger applicability, and glue in the self-assembled coating
The number of plies of body particle can be precisely controlled according to the concentration of the colloidal solution, and the concentration of the colloidal solution is bigger, institute
The number of plies for stating self-assembled coating is more, so that the self-assembled coating of single-layer or multi-layer can be obtained.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (9)
1. a kind of preparation method of concentration tension gradient self-assembled coating, comprising:
There is provided substrate and colloidal solution, the colloidal solution includes the first liquid and the colloid that is scattered in first liquid
Grain；
Second liquid is provided, the second liquid dissolves each other with first liquid, and the surface tension of the second liquid is less than
The surface tension of first liquid forms a liquid film in the substrate surface with the second liquid；And
The liquid film is contacted with the colloidal solution, so that the colloidal solid, which is assembled in the substrate surface, forms concentration
Tension gradient self-assembled coating.
2. the preparation method of concentration tension gradient self-assembled coating according to claim 1, which is characterized in that described by institute
Stating the method that liquid film is contacted with the colloidal solution includes: that the substrate for being formed with the liquid film is put into the colloidal solution
In, contact the liquid film with the colloidal solution；
The preparation method of the concentration tension gradient self-assembled coating further comprises: will be formed with the concentration tension gradient certainly
The substrate of assembling coating is lifted from the colloidal solution to be come out.
3. the preparation method of concentration tension gradient self-assembled coating according to claim 1, which is characterized in that described second
The surface tension of liquid is less than or equal to the 1/2 of the surface tension of first liquid.
4. the preparation method of concentration tension gradient self-assembled coating according to claim 1, which is characterized in that be used to form
The substrate surface of the liquid film is plane or curved surface.
5. the preparation method of concentration tension gradient self-assembled coating according to claim 1, which is characterized in that described first
Liquid is water, and the second liquid is at least one of ethyl alcohol, acetone, acetic acid and methanol.
6. the preparation method of concentration tension gradient self-assembled coating according to claim 2, which is characterized in that by the base
During bottom lifts out from the colloidal solution, make the substrate for being formed with the concentration tension gradient self-assembled coating
The angle of the liquid level of surface and the colloidal solution is greater than 45 ° and less than 135 °.
7. the preparation method of concentration tension gradient self-assembled coating according to claim 2, which is characterized in that by the base
The speed that bottom lifts out from the colloidal solution is less than 5mm/s.
8. the preparation method of concentration tension gradient self-assembled coating according to claim 2, which is characterized in that by the base
The speed that bottom lifts out from the colloidal solution is greater than 2mm/s.
9. the preparation method of concentration tension gradient self-assembled coating according to claim 2, which is characterized in that will be described
Substrate is after lifting comes out in the colloidal solution, the step of further comprising the dry substrate.
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| CN116251951B (en) * | 2023-03-10 | 2023-11-10 | 清华大学 | Method for preparing metal nanoparticle self-assembled layer based on interfacial tension gradient-electrostatic attraction composite and application thereof |
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| WO2016047306A1 (en) * | 2014-09-26 | 2016-03-31 | 富士フイルム株式会社 | Process for producing film of metal oxide particles and process for producing metal film |
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