CN104290479A - Method for achieving controllable writing of oily dye by using superhydrophilic interface as substrate in water environment - Google Patents
Method for achieving controllable writing of oily dye by using superhydrophilic interface as substrate in water environment Download PDFInfo
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- CN104290479A CN104290479A CN201410476115.8A CN201410476115A CN104290479A CN 104290479 A CN104290479 A CN 104290479A CN 201410476115 A CN201410476115 A CN 201410476115A CN 104290479 A CN104290479 A CN 104290479A
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Abstract
The invention relates to a method for achieving controllable writing of oily dye by using a superhydrophilic interface as a substrate in a water environment and belongs to the technical field of oily dye writing in the water environment. The method comprises the following steps of preparing the superhydrophilic substrate, preparing magnetic gel balls used in a writing process, applying a magnetic field to the other side of the superhydrophilic substrate, moving the magnetic field, and achieving magnetic controllable writing of the oily dye on the superhydrophilic interface on the basis of a water environment system. The hydrophilic degree of the substrate can be regulated and controlled by controlling the surface roughness and chemical compositions of the substrate, and therefore the contact area of an oily dye drop and the substrate, the width and dot diameter of the movement trail of an oily dye liquid ball and other factors are controlled, and controllable writing is achieved. The method for combining substrate surface wettability and controllable writing of the oily dye is a brand new writing method in the water environment and comprises the steps of oily dye image forming, dot matrix preparing and the like.
Description
Technical field
Under the invention belongs to water environment, technical field write by oiliness dyestuff, particularly a kind of in water environment with super hydrophilic interface for substrate realize to the controlled method of writing of oiliness dyestuff.
Background technology
Dyestuff under particular surroundings graphically writes control technology, graphically control technology is write particularly to substrate in aqueous systems, have a wide range of applications in real productive life, as the direct reparation for underbody paint defect part, this will shorten hull repair time greatly, cost-saving; Being placed in the substrate of nutrient solution or the graphical modification on tissue engineering bracket surface again or in life medical domain, to realize its chip, for research cell adhesion processes provides new approach.But relevant control technology of graphically writing is but relatively less, this just significantly limit the development of its related industry.At present, the control technology of graphically writing based on oiliness dyestuff mainly contains stencil methods, physics or chemical vapour deposition (CVD) and hand spray etc.Above method completes mostly in atmosphere, if implement under relating to the particular surroundings such as aqueous systems to be just subject to great restriction, and above method has the shortcomings such as complicated operation, technical costs is high, accuracy is not high in actual applications.Under aqueous systems environment, so how realize the controlled of oiliness dyestuff write, just become the main contents of research.
Summary of the invention
The object of the invention is to be controlled the motion of the oiliness dyestuff drop super hydrophilic group basal surface with magnetic gel ball in aqueous systems by magnetic field, realize controlled the writing on this super hydrophilic group basal surface with the oiliness dyestuff drop of magnetic gel ball, the Superhydrophilic matter of this methods combining substrate and substrate are to features such as the adhesivenesses of oiliness dyestuff, achieved to oiliness dye solution by magnetic field that to drop in aqueous systems controlled writes, namely by applying magnetic field at ultra-hydrophilic surface, local control is carried out to oiliness dyestuff drop in its surface, utilize the pressure between substrate and magnetic gel ball, oiliness dyestuff is stamped at the bottom of super hydrophilic group and writes to complete, comprise and write a little, line, the structures such as dot matrix.This Writing method operating process is simple, and the making at the bottom of super hydrophilic group is relatively simple and easy and cost is low, considerably increases operability.
The size of oiliness dyestuff figure can be realized by the size controlling drop and substrate contact area.Concrete ways mainly contains following two aspects: (1) regulates and controls the hydrophilicrty of substrate to realize the control to oiliness drop and substrate contact area by the degree of roughness (in embodiment, the substrate roughness degree of the polylactic acid based end and metallic aluminium is distinguishing) and chemical composition controlling substrate surface; (2) realize the control with substrate contact area by the oiliness dyestuff drop of magnetropism gel ball dropping different volumes, reach controlled object of writing.Thisly writing controlled to substrate surface wellability and oiliness dyestuff the method combined, is a kind of Writing method under aqueous systems environment completely newly, comprises the shaping and dot matrix of oiliness dye image and prepares.
The polymer-based end is comprised, as poly-N-isopropylacrylamide, dimethyl silicone polymer, PLA, polystyrene, polytetrafluoroethylene (PTFE), shitosan, polyethylene, polypropylene, polyvinyl chloride, polyethylene glycol etc. at the bottom of super hydrophilic group of the present invention; Metallic substrates, as metallic iron, aluminium, magnesium, zinc, copper, steel alloy etc.; Semiconductor base, as silica, monocrystalline silicon, zinc oxide etc.; Composite substrate, as clay and polystyrene, the various material such as the high molecular compound such as polysiloxanes, carry out chemical modification by it to the surface of substrate and regulation and control microstructure controls the Superhydrophilic of substrate.
The present invention prepares gel ball for the natural macromolecular material such as shitosan, alginates coated magnetic particle, is invested by oiliness dyestuff around gel ball to obtain magnetic dye solution ball.Magnetic gel ball material comprises natural macromolecule, as polysaccharide (shitosan, starch, cellulose, alginic acid, hyaluronic acid etc.) and polypeptide class (collagen, polylysine, poly-L-GLU etc.); The macromolecule of synthesis, as polyethylene, alcohol, acrylic acid and derivative class (polyacrylamide, gathers N-poly-for acrylamide etc. for polyacrylic acid, polymethylacrylic acid) thereof.Magnetic-particle is the metal oxides such as ferriferrous oxide particles, ferric oxide particles, cobalt oxide particle, cobaltosic oxide particle, nickel monoxide particle, nickel sesquioxide particle, and particle diameter is 0.01 micron ~ 300 microns.
At the bottom of super hydrophilic group used in the present invention, can be PLA adopt phase disengagement method, or metallic aluminium, copper etc. adopt etching method, also or single crystal silicon semiconductor adopt electron beam lithography method realize super hydrophilic interface.
The oiliness dyestuff carrying out writing operation can be the dye solution of pure oiliness and has the oily solution of certain dyestuff toner density.The insoluble azo dyes such as the dye solution of pure oiliness comprises 2-hydroxyl anthracene-3-formyl ortho-aminotoluene, 3-hydroxyl dibenzofuran-2-formic acid and derivative thereof, the adjacent formyl hydroxy arylamine of carbazole.The oily solution with certain dyestuff toner density can be disperse dyes, as disperse yellow 5G 2 (1H)-Quinolmone, the benzole soln of 4-hydroxy-1-methyl-3-[(3-nitrophenyl) zao], dispersion bright red E-RLN 9,1-Anthracenedione, the benzole soln of 1amino-4-hydroxy-2-[2 (2-methoxyethoxy) ethoxy], Vat Brilliant Orange 3RK, Dibenzo [def, mno] xylene solution of chrysene-5,12-dione; Also can be the commercial oiliness dyestuff with certain dyestuff toner density, as the single-phase highly enriched easy solution body dyestuff of Automate series that DOW Chemical is produced, or oiliness fluorescent dye be as fluorescein 131SC liquid dyes etc.
The solvent of the oiliness dye solution and oiliness fluorescent dye with certain toner density can be organic solvent-benzene, dimethylbenzene etc., or mineral oil, vegetable oil, atoleine, other oil-based solvent of lubrication wet goods, and molar concentration is 0.01M to 10M.
In water environment with super hydrophilic interface for substrate realize to the controlled method of writing of oiliness dyestuff, its step is as follows:
1) for the preparation of the preparation of the super-hydrophobic substrate of gel ball
1. the polylactic acid based end of surface super hydrophobic is prepared: be dissolved in by PLA in organic non-polar solven dioxane, mass percentage concentration is 5% ~ 20%, this solution is added drop-wise to (the PLA sheet material of biomaterial Co., Ltd as global in Ningbo of the polylactic acid based end, thickness is 1.8 ~ 5.5mm) surface, after starting to separate out polylactic acid membrane at substrate surface, rapidly substrate is placed in ethanolic solution to take out after 30 ~ 90 minutes, after vacuum drying, the polylactic acid membrane on surface is peeled off, namely can prepare on the polylactic acid based end have micron and nanometer composite structure (its surface mainly contain diameter be 13 microns microballoon composition, each microballoon has numerous diameter be the projection of 100 ran) surface, thus obtain the polylactic acid based end of surface super hydrophobic,
2. the aluminium flake substrate of surface super hydrophobic is prepared: by 15 ~ 30mL, the hydrochloric acid of mass fraction 37%, the water of 5 ~ 10mL, the hydrofluoric acid mixing of 1 ~ 5mL, mixed solution is dropped on aluminium flake, with water cleaning and ultrasonic water bath 5 ~ 10 minutes after 15 ~ 30 seconds, ethanolic solution 10 ~ 15h that percentage by volume is the perfluorododecyl triethoxysilane of 1 ~ 3% is dipped in after drying again at 70 ~ 90 DEG C, after taking out, nitrogen dries up the aluminium flake substrate namely obtaining surface super hydrophobic, primarily of countless irregular rectangle, (width is about 100-200nm to substrate surface, length 200-800nm) and about 100nm nano particle structure composition, nano particle is random to be distributed in rectangular configuration,
2) the polylactic acid based end of surface super hydrophilic is 1. prepared: be dissolved in by PLA in dioxane, mass percentage concentration is 5% ~ 20%, this solution is added drop-wise to (the PLA sheet material of biomaterial Co., Ltd as global in Ningbo of the polylactic acid based end, thickness is 1.8 ~ 5.5mm) surface, after starting to separate out polylactic acid membrane at substrate surface, rapidly substrate is placed in ethanolic solution to take out after 30 ~ 90 minutes, after vacuum drying, the polylactic acid membrane on surface is peeled off, namely can prepare on the polylactic acid based end have micron and nanometer composite structure (its surface mainly contain diameter be 13 microns microballoon composition, each microballoon has numerous diameter be the projection of 100 ran) surface, then plasma or ultraviolet irradiation 3 ~ 10min is applied, thus it is super hydrophilic to make super-hydrophobic polylactic acid based basal surface realize,
2. the aluminium substrate of surface super hydrophilic is prepared: by the hydrochloric acid of 15 ~ 30mL, mass fraction 37%, the water of 5 ~ 10mL, the hydrofluoric acid mixing of 1 ~ 5mL, mixed solution is dropped on aluminium flake, by clean water and ultrasonic water bath 5 ~ 10 minutes after 15 ~ 30 seconds, under 70 ~ 90 DEG C of conditions, after drying, namely obtain the aluminium substrate with ultra-hydrophilic surface;
3) the magnetic gel ball that writing process is used is prepared: be that the shitosan of 50mg (is dissolved in the acetum of 1% (v/v) obtained by the chitosan-acetic acid solution of 10 ~ 20mg/mL by 5 ~ 10mL, concentration, acetum is that acetic acid is water-soluble obtained by the volume ratio of 1%) and 25mg magnetic particles of ferroferric oxide, mix under two aldehyde crosslinking agent effect such as 2.5 ~ 5mg Geniposide (Genipin) or glutaraldehyde; Get this mixed solution 2 ~ 20 μ L, drop to step 1) in the super-hydrophobic substrate prepared, under being then placed in the environment of room temperature saturated humidity, place 12 ~ 20 hours, take out, the magnetic gel ball of coated magnetic particle after freeze drying, can be obtained; Again 2 ~ 10 μ L oiliness blobs of dye are added on gel ball, thus obtain the magnetic gel ball of oiliness dyestuff parcel;
4) by step 2) substrate with ultra-hydrophilic surface that obtains is placed in water, again by step 3) the magnetic gel ball of the oiliness dyestuff that obtains parcel is placed on the water-wetted surface of this substrate, apply magnetic field and shifting magnetic field at the opposite side of substrate, the controlled line of magnetic of the medium oil dyestuff of water environment based on super hydrophilic interface and writing of figure can be realized;
Or by step 2) substrate with ultra-hydrophilic surface that obtains is placed in water, again by step 3) the magnetic gel ball of the oiliness dyestuff that obtains parcel is placed on the water-wetted surface of this substrate, above this substrate water-wetted surface, 1 ~ 5cm place places at the bottom of another super hydrophilic group, also be placed in water at the bottom of this super hydrophilic group, the water-wetted surface of two substrates is staggered relatively; Opposite side at the bottom of the super hydrophilic group of rear placement applies magnetic field, after the magnetic gel ball of oiliness dyestuff parcel is attracted to the water-wetted surface of top substrate, cancels this magnetic field, can realizes at the bottom of the super hydrophilic group of rear placement that the magnetic of oiliness dyestuff is controlled gets operation ready.
The method of the invention can be used for writing the various ways under the aqueous systems of oiliness dyestuff, comprises the figure, the getting ready of different-diameter, dot matrix etc. of writing different in width.In the process of magnetic field movement, oiliness dyestuff parcel magnetic gel ball also thereupon at the bottom of super hydrophilic group on move, oiliness dye-coating at the bottom of super hydrophilic group on.
The PLA that said method uses, molecular weight can be 100,000 ~ 500,000.
Accompanying drawing explanation
Fig. 1: the controlled straight line write of water environment medium oil dyestuff magnetic writes manipulation schematic diagram; 1 represents magnetic-particle; 2 represent at the bottom of super hydrophilic group; 3 represent magnetic gel ball; 4 represent oiliness dyestuff; 5 represent magnet; 6 represent water environment.Corresponding embodiment 1,2,3,4.
Fig. 2: water environment medium oil dyestuff magnetic is controlled write get manipulation schematic diagram ready at any point; 1 represents magnetic-particle; 2 represent at the bottom of super hydrophilic group; 3 represent magnetic gel ball; 4 represent oiliness dyestuff; 5 represent magnet; 6 represent water environment.Corresponding embodiment 6,7,8.
Fig. 3: the controlled drafting manipulation schematic diagram writing linear array of water environment medium oil dyestuff magnetic; 1 represents magnetic-particle; 2 represent at the bottom of super hydrophilic group; 3 represent magnetic gel ball; 4 represent oiliness dyestuff; 5 represent magnet; 6 represent water environment.Corresponding embodiment 5.
Fig. 4: the controlled manipulation schematic diagram that draws a design write of water environment medium oil dyestuff magnetic; 1 represents magnetic-particle; 2 represent at the bottom of super hydrophilic group; 3 represent magnetic gel ball; 4 represent oiliness dyestuff; 5 represent magnet; 6 represent water environment.Corresponding embodiment 9.
Fig. 5: the electromicroscopic photograph of the super hydrophilic polylactic acid based end with micron and nanometer composite structure.
Fig. 6: the electromicroscopic photograph on super hydrophilic aluminium flake surface.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further elaborated, instead of will limit the invention with this.
Embodiment 1
PLA (molecular weight is 350,000) is dissolved in organic non-polar solven dioxane, mass percentage concentration is 13%, then this solution of 3mL is added drop-wise to polylactic acid based basal surface (2 × 2cm, the global biomaterial Co., Ltd in Ningbo produces, thickness is 4mm) surface, after starting to separate out polylactic acid membrane on surface, be placed in rapidly ethanolic solution to take out after 60 minutes, after vacuum drying, (its surface is about the microballoon composition of 13 microns primarily of diameter can to obtain the substrate with micron and nanometer composite structure after being peeled off by polylactic acid membrane, each microballoon has numerous diameter be the projection of 100 ran) super-hydrophobic PLA surface (as shown in Figure 5).Then applying plasma (argon plasma, power 30W) irradiation 3min, that PLA surface is realized is super hydrophilic, and namely surperficial liquid-drop contact angle is 0 °.Then stand-by by being placed in water at the bottom of this super hydrophilic group.
Be chitosan-acetic acid solution and the mixing under 2.5mg crosslinking agent Geniposide (Genipin) effect of 25mg tri-iron tetroxide of 10mg/mL by 5mL concentration, get this mixed solution 8 μ L, drop at the super-hydrophobic polylactic acid based end described in preceding step, under being placed in the environment of room temperature saturated humidity, place 12 hours, take out, the magnetic gel ball that diameter is about 1.2mm coated ferroferric oxide magnetic-particle can be obtained after freeze drying at-50 DEG C, again the single-phase highly enriched easy solution body blobs of dye of Automate that 2 μ L DOW Chemicals are produced is formed on this magnetic gel ball the magnetic gel ball of oiliness dyestuff parcel, then the substrate with ultra-hydrophilic surface is placed in water, again the magnetic gel ball that oiliness dyestuff wraps up is placed on the water-wetted surface of this substrate, place magnet at the opposite side of substrate and apply Magnetic control oiliness dyestuff drop with rectilinear movement, thus realize straight line write by oiliness dyestuff on ultra-hydrophilic surface control with the live width being about 300 μm.The size of live width and ball, the hydrophily of dye dosage and substrate all has relation.Along with the increase of dye dosage, live width broadens; Along with the increase of bulb diameter, live width broadens.
Embodiment 2
PLA (molecular weight is 350,000) is dissolved in organic non-polar solven dioxane, mass percentage concentration is 13%, then this solution of 3mL is added drop-wise to polylactic acid based basal surface, after starting to separate out polylactic acid membrane on surface, be placed in rapidly ethanolic solution to take out after 60 minutes, after vacuum drying, the PLA surface (as shown in Figure 5) with micron and nanometer composite structure (its surface mainly contains the microballoon composition that diameter is about 13 microns, each microballoon has the projection of 100 ran) can be obtained after surperficial polylactic acid membrane peels off.It is super hydrophilic that application plasma radiation 3min makes PLA surface realize, and namely surperficial liquid-drop contact angle is 0 °.
Be chitosan solution and the mixing under 2.5mg crosslinking agent Geniposide (Genipin) effect of 25mg tri-iron tetroxide of 10mg/mL by 5mL concentration, get this mixed solution 8 μ L, drop at the super-hydrophobic polylactic acid based end described in preceding step, then under being placed in the environment of room temperature saturated humidity, place 12 hours, take out, the magnetic gel ball of coated ferroferric oxide after freeze drying, can be obtained; The single-phase highly enriched easy solution body blobs of dye of Automate that the DOW Chemical of 4 μ L is produced is formed on this magnetic gel ball the magnetic gel ball of oiliness dyestuff parcel; Then the substrate with ultra-hydrophilic surface is placed in water, again the magnetic gel ball that oiliness dyestuff wraps up is placed on the water-wetted surface of this substrate, place magnet at the opposite side of substrate and apply Magnetic control oiliness dyestuff drop with rectilinear movement, thus realize the control of oiliness dyestuff being write on ultra-hydrophilic surface to straight line with the live width being about 800 μm.
Embodiment 3
PLA (molecular weight is 350,000) is dissolved in organic non-polar solven dioxane, mass percentage concentration is 13%, then this solution of 3mL is added drop-wise to polylactic acid based basal surface, after starting to separate out polylactic acid membrane on surface, be placed in rapidly ethanolic solution to take out after 60 minutes, after vacuum drying, the PLA surface (as shown in Figure 5) with micron and nanometer composite structure (its surface mainly contains the microballoon composition that diameter is about 13 microns, each microballoon has the projection of 100 ran) can be obtained after surperficial polylactic acid membrane peels off.Namely the wellability on PLA surface can be controlled by controlling the plasma radiation time.Therefore PLA surface should be realized with plasma irradiation PLA surface 2min in this example hydrophilic, make this surperficial liquid-drop contact angle become 30 ° from 153.6 °.
Be chitosan solution and the mixing under 2.5mg crosslinking agent Geniposide (Genipin) effect of 25mg tri-iron tetroxide of 10mg/mL by 5mL concentration, get this mixed solution 8 μ L, drop at the super-hydrophobic polylactic acid based end described in preceding step, then under being placed in the environment of room temperature saturated humidity, place 12 hours, take out, the magnetic gel ball of coated ferroferric oxide after freeze drying, can be obtained; The single-phase highly enriched easy solution body blobs of dye of Automate series of being produced by the DOW Chemical of 2 μ L forms the magnetic gel ball of oiliness dyestuff parcel on this magnetic gel ball; The substrate with ultra-hydrophilic surface is placed in water, again the magnetic gel ball that oiliness dyestuff wraps up is placed on the water-wetted surface of this substrate, then place magnet at the opposite side of substrate and apply Magnetic control oiliness dyestuff drop with rectilinear movement, the substrate after irradiation contrasts straight line live width and become 500 μm from 300 μm.Compared with embodiment 1, just surperficial liquid-drop contact angle there occurs the change that namely change can realize writing live width, and namely contact angle is different, thus the contact area of drop and substrate is different.
Embodiment 4
PLA (molecular weight is 350,000) is dissolved in organic non-polar solven dioxane, concentration is 13% (mass percent), then this solution of 3mL is added drop-wise to polylactic acid based basal surface, after starting to separate out polylactic acid membrane on surface, be placed in rapidly ethanolic solution to take out after 60 minutes, after vacuum drying, the PLA surface (as shown in Figure 5) with micron and nanometer composite structure (its surface mainly contains the microballoon composition that diameter is about 13 microns, each microballoon has the projection of 100 ran) can be obtained after surperficial polylactic acid membrane peels off.It is super hydrophilic that application plasma radiation 3min makes PLA surface realize, and namely surperficial liquid-drop contact angle is 0 °.Then stand-by by being placed in water at the bottom of this super hydrophilic group.
Be chitosan solution and the mixing under 2.5mg crosslinking agent Geniposide (Genipin) effect of 25mg tri-iron tetroxide of 10mg/mL by 5mL concentration, get this mixed solution 8 μ L, drop at the super-hydrophobic polylactic acid based end described in preceding step, then under being placed in the environment of room temperature saturated humidity, place 12 hours, take out, the magnetic gel ball of coated ferroferric oxide after freeze drying, can be obtained; Again the single-phase highly enriched easy solution body blobs of dye of Automate that the DOW Chemical of 6 μ L is produced is formed on this magnetic gel ball the magnetic gel ball of oiliness dyestuff parcel; The substrate with ultra-hydrophilic surface is placed in water, then the magnetic gel ball that oiliness dyestuff wraps up is placed on the water-wetted surface of this substrate; Then place magnet at the opposite side of substrate and apply Magnetic control oiliness dyestuff drop with rectilinear movement, realize the control of oiliness dyestuff being write on ultra-hydrophilic surface to straight line with the live width being about 1000 μm.
Embodiment 5
PLA (molecular weight is 350,000) is dissolved in organic non-polar solven dioxane, concentration is 13% (mass percent), then this solution of 3mL is added drop-wise to polylactic acid based basal surface, after starting to separate out polylactic acid membrane on surface, be placed in rapidly ethanolic solution to take out after 60 minutes, after vacuum drying, the PLA surface (as shown in Figure 5) with micron and nanometer composite structure (its surface mainly contains the microballoon composition that diameter is about 13 microns, each microballoon has the projection of 100 ran) can be obtained after surperficial polylactic acid membrane peels off.It is super hydrophilic that application plasma radiation 3min makes PLA surface realize, and namely surperficial liquid-drop contact angle is 0 °.Then stand-by by being placed in water at the bottom of this super hydrophilic group.
Be chitosan solution and the mixing under 2.5mg crosslinking agent Geniposide (Genipin) effect of 25mg tri-iron tetroxide of 10mg/mL by 5mL concentration, get this mixed solution 8 μ L, drop at the super-hydrophobic polylactic acid based end described in preceding step, then under being placed in the environment of room temperature saturated humidity, place 12 hours, take out, the magnetic gel ball of coated ferroferric oxide after freeze drying, can be obtained; Respectively the single-phase highly enriched easy solution body blobs of dye of Automate that the DOW Chemical of 2 μ L, 4 μ L, 6 μ L is produced is formed on this magnetic gel ball the magnetic gel ball of oiliness dyestuff parcel; The substrate with ultra-hydrophilic surface is placed in water, then the magnetic gel ball that oiliness dyestuff wraps up is placed on the water-wetted surface of this substrate; Then place magnet at the opposite side of substrate and apply Magnetic control oiliness dyestuff drop with rectilinear movement, the controlled of linear array realized oiliness dyestuff is live width with 300 μm, 800 μm, 1000 μm on ultra-hydrophilic surface is write.
Embodiment 6
PLA (molecular weight is 350,000) is dissolved in organic non-polar solven dioxane, concentration is 13% (mass percent), then this solution of 3mL is added drop-wise to polylactic acid based basal surface, after starting to separate out polylactic acid membrane on surface, be placed in rapidly ethanolic solution to take out after 60 minutes, after vacuum drying, the PLA surface (as shown in Figure 5) with micron and nanometer composite structure (its surface mainly contains the microballoon composition that diameter is about 13 microns, each microballoon has the projection of 100 ran) can be obtained after surperficial polylactic acid membrane peels off.It is super hydrophilic that application plasma radiation 3min makes PLA surface realize, and namely surperficial liquid-drop contact angle is 0 °.Then stand-by by being placed in water at the bottom of this super hydrophilic group.
Be chitosan solution and the mixing under 2.5mg crosslinking agent Geniposide (Genipin) effect of 25mg tri-iron tetroxide of 10mg/mL by 5mL concentration, get this mixed solution 8 μ L, drop at the super-hydrophobic polylactic acid based end described in preceding step, then under being placed in the environment of room temperature saturated humidity, place 12 hours, take out, the magnetic gel ball of coated ferroferric oxide after freeze drying, can be obtained; The single-phase highly enriched easy solution body blobs of dye of Automate that the DOW Chemical of 6 μ L is produced is formed on this magnetic gel ball the magnetic gel ball of oiliness dyestuff parcel; The substrate with ultra-hydrophilic surface is placed in water, then the magnetic gel ball that oiliness dyestuff wraps up is placed on the water-wetted surface of this substrate; Above the magnetic gel ball that oiliness dyestuff wraps up at the bottom of above-mentioned super hydrophilic group, 3cm place places at the bottom of another super hydrophilic group, this substrate still remains in water, then at the bottom of this super hydrophilic group, deviate from the applying magnetic field, side of the magnetic gel ball of oiliness dyestuff parcel, after this magnetic gel ball is attracted to top substrate, cancels this magnetic field, the operation got ready for diameter with 300 μm at the bottom of the super hydrophilic group of rear placement can be realized.
Embodiment 7
PLA (molecular weight is 350,000) is dissolved in organic non-polar solven dioxane, concentration range 13% (mass percent), then this solution of 3mL is added drop-wise to polylactic acid based basal surface, after starting to separate out polylactic acid membrane on surface, be placed in rapidly ethanolic solution to take out after 60 minutes, after vacuum drying, the PLA surface (as shown in Figure 5) with micron and nanometer composite structure (its surface mainly contains the microballoon composition that diameter is about 13 microns, each microballoon has the projection of 100 ran) can be obtained after surperficial polylactic acid membrane peels off.Namely can control the wellability on PLA surface by controlling the plasma radiation time, its surface can be made to realize from super-hydrophobic (contact angle 153.6 °) to the change of super hydrophilic (contact angle is 0 °).Therefore PLA surface should be realized with plasma irradiation PLA surface 2min in this example hydrophilic, make this surperficial liquid-drop contact angle become 30 ° from 153.6 °.Then stand-by by being placed in water at the bottom of this super hydrophilic group.
Be chitosan solution and the mixing under 2.5mg crosslinking agent Geniposide (Genipin) effect of 25mg tri-iron tetroxide of 10mg/mL by 5mL concentration, get this mixed solution 8 μ L, drop at the super-hydrophobic polylactic acid based end described in preceding step, then under being placed in the environment of room temperature saturated humidity, place 12 hours, take out, the magnetic gel ball of coated ferroferric oxide after freeze drying, can be obtained; The single-phase highly enriched easy solution body blobs of dye of Automate that the DOW Chemical of 6 μ L is produced is formed on this magnetic gel ball the magnetic gel ball of oiliness dyestuff parcel; Then the substrate with ultra-hydrophilic surface is placed in water, then the magnetic gel ball that oiliness dyestuff wraps up is placed on the water-wetted surface of this substrate; Above the magnetic gel ball that oiliness dyestuff wraps up at the bottom of above-mentioned super hydrophilic group, 3cm place places at the bottom of another super hydrophilic group, this substrate still remains in water, then at the bottom of this super hydrophilic group, deviate from the applying magnetic field, side of the magnetic gel ball of oiliness dyestuff parcel, this magnetic field is cancelled after this magnetic gel ball is attracted to top substrate, can realize the operation got ready at the bottom of the super hydrophilic group of rear placement, after predose, spot diameter becomes 500 μm from 300 μm.
Embodiment 8
By the hydrochloric acid of 40mL, mass fraction 37%, 12.5mL water, the hydrofluoric acid mixing of 2.5mL, then this solution of 3mL is dropped on aluminium flake, by clean water and ultrasonic water bath 5 minutes after 15 seconds, then the empty van putting into 80 DEG C is dry, thus obtains super hydrophilic aluminium flake substrate (its surface topography as shown in Figure 6).Then stand-by by being placed in water at the bottom of this super hydrophilic group.
Be chitosan solution and the mixing under 2.5mg crosslinking agent Geniposide (Genipin) effect of 25mg tri-iron tetroxide of 10mg/mL by 5mL concentration, get this mixed solution 8 μ L, drop at the super-hydrophobic polylactic acid based end described in preceding step, then under being placed in the environment of room temperature saturated humidity, place 12 hours, take out, the magnetic gel ball of coated ferroferric oxide after freeze drying, can be obtained; The single-phase highly enriched easy solution body blobs of dye of Automate that the DOW Chemical of 4 μ L is produced is formed on this magnetic gel ball the magnetic gel ball of oiliness dyestuff parcel; Then the aluminium flake substrate with ultra-hydrophilic surface is placed in water, then the magnetic gel ball that oiliness dyestuff wraps up is placed on the water-wetted surface of this substrate; Above the magnetic gel ball that oiliness dyestuff wraps up at the bottom of above-mentioned super hydrophilic group, 3cm place places at the bottom of another super hydrophilic group, this substrate still remains in water, then at the bottom of this super hydrophilic group, deviate from the applying magnetic field, side of the magnetic gel ball of oiliness dyestuff parcel, after this magnetic gel ball is attracted to top substrate, cancels this magnetic field, the operation got ready for diameter with 800 μm at the bottom of the super hydrophilic group of rear placement can be realized.
Embodiment 9
PLA (molecular weight is 350,000) is dissolved in organic non-polar solven dioxane, concentration is 13% (mass percent), then this solution of 3mL is added drop-wise to polylactic acid based basal surface, after starting to separate out polylactic acid membrane on surface, be placed in rapidly ethanolic solution to take out after 60 minutes, after vacuum drying, the PLA surface (as shown in Figure 5) with micron and nanometer composite structure (its surface mainly contains the microballoon composition that diameter is about 13 microns, each microballoon has the projection of 100 ran) can be obtained after surperficial polylactic acid membrane peels off.It is super hydrophilic that application plasma radiation 3min makes PLA surface realize, and namely surperficial liquid-drop contact angle is 0 °.Then stand-by by being placed in water at the bottom of this super hydrophilic group.
Be chitosan solution and the mixing under 2.5mg crosslinking agent Geniposide (Genipin) effect of 25mg tri-iron tetroxide of 10mg/mL by 5mL concentration, get this mixed solution 8 μ L, drop at the super-hydrophobic polylactic acid based end described in preceding step, then under being placed in the environment of room temperature saturated humidity, place 12 hours, take out, the magnetic gel ball of coated ferroferric oxide after freeze drying, can be obtained; Again the fluorescein 131SC liquid dyes that the DOW Chemical of 2 μ L is produced are dripped the magnetic gel ball forming oiliness dyestuff parcel on this magnetic gel ball; The substrate with ultra-hydrophilic surface is placed in water, then the magnetic gel ball that oiliness dyestuff wraps up is placed on the water-wetted surface of this substrate; Then place magnet applying Magnetic control oiliness dyestuff drop at the opposite side of substrate to move, realize the control of oiliness dyestuff being write on ultra-hydrophilic surface to figure with the live width being about 300 μm.
Embodiment 10
PLA (molecular weight is 350,000) is dissolved in organic non-polar solven dioxane, concentration is 13% (mass percent), then this solution of 3mL is added drop-wise to polylactic acid based basal surface, after starting to separate out polylactic acid membrane on surface, be placed in rapidly ethanolic solution to take out after 60 minutes, after vacuum drying, the PLA surface (as shown in Figure 5) with micron and nanometer composite structure (its surface mainly contains the microballoon composition that diameter is about 13 microns, each microballoon has the projection of 100 ran) can be obtained after surperficial polylactic acid membrane peels off.It is super hydrophilic that application plasma radiation 3min makes PLA surface realize, and namely surperficial liquid-drop contact angle is 0 °.Then stand-by by being placed in water at the bottom of this super hydrophilic group.
Be after the alginates aqueous solution of 10mg/mL and the mixing of 50mg ferroferric oxide particle by 5mL concentration, get this mixed solution 8 μ L, drop at the super-hydrophobic polylactic acid based end described in preceding step, be that the calcium chloride water of 4mol/L drips and is cross-linked on the mixing drop of magnetic-particle and alginates again by the concentration at 0.5 μ L, then under being placed in the environment of room temperature saturated humidity, place 12 hours, take out, the magnetic gel ball of coated ferroferric oxide after freeze drying, can be obtained; Again the fluorescein 131SC liquid dyes that the DOW Chemical of 2 μ L is produced are dripped the magnetic gel ball forming oiliness dyestuff parcel on this magnetic gel ball; The substrate with ultra-hydrophilic surface is placed in water, then the magnetic gel ball that oiliness dyestuff wraps up is placed on the water-wetted surface of this substrate; Then place magnet applying Magnetic control oiliness dyestuff drop at the opposite side of substrate to move, realize the control of oiliness dyestuff being write on ultra-hydrophilic surface to figure with the live width being about 300 μm.
Claims (7)
1. in water environment with super hydrophilic interface for substrate realize to the controlled method of writing of oiliness dyestuff, its step is as follows:
1) by 5 ~ 10mL, concentration be gel ball material solution and the 25mg magnetic-particle of 10 ~ 20mg/mL, mix under 2.5 ~ 5mg Geniposide or glutaraldehyde cross-linking agent effect; Get this mixed solution 2 ~ 20 μ L, drop in the substrate of surface super hydrophobic, under being then placed in the environment of room temperature saturated humidity, place 12 ~ 20 hours, take out, the magnetic gel ball of coated magnetic particle after freeze drying, can be obtained; Again 2 ~ 10 μ L oiliness blobs of dye are added on gel ball, thus obtain the magnetic gel ball of oiliness dyestuff parcel;
2) substrate of surface super hydrophilic is placed in water, again by step 1) the magnetic gel ball of the oiliness dyestuff that obtains parcel is placed on the water-wetted surface of this substrate, apply magnetic field and shifting magnetic field at the opposite side of substrate, the controlled line of magnetic of the medium oil dyestuff of water environment based on super hydrophilic interface and writing of figure can be realized; Maybe the substrate with surface super hydrophilic is placed in water, again by step 1) the magnetic gel ball of the oiliness dyestuff that obtains parcel is placed on the water-wetted surface of this substrate, above this substrate water-wetted surface, 1 ~ 5cm place places at the bottom of another super hydrophilic group, also be placed in water at the bottom of this super hydrophilic group, the water-wetted surface of two substrates is staggered relatively; Opposite side at the bottom of the super hydrophilic group of rear placement applies magnetic field, after the magnetic gel ball of oiliness dyestuff parcel is attracted to the water-wetted surface of top substrate, cancels this magnetic field, can realizes at the bottom of the super hydrophilic group of rear placement that the magnetic of oiliness dyestuff is controlled gets operation ready;
Described gel ball material is that shitosan, starch, cellulose, alginic acid, hyaluronic acid, collagen, polylysine, poly-L-GLU, polyethylene, alcohol, acrylic acid, polyacrylic acid, polymethylacrylic acid, polyacrylamide or poly-N-are poly-for acrylamide;
Described dyestuff is 2-hydroxyl anthracene-3-formyl ortho-aminotoluene, the derivative of 3-hydroxyl dibenzofuran-2-formic acid, the adjacent formyl hydroxy arylamine of carbazole, disperse yellow 5G 2 (1H)-Quinolmone, the benzole soln of 4-hydroxy-1-methyl-3-[(3-nitrophenyl) zao], dispersion bright red E-RLN 9, 1-Anthracenedione, the benzole soln of 1amino-4-hydroxy-2-[2 (2-methoxyethoxy) ethoxy], Vat Brilliant Orange 3RK, Dibenzo [def, mno] chrysene-5, the xylene solution of 12-dione, the Automate single-phase highly enriched easy solution body dyestuff of series that DOW Chemical is produced or fluorescein 131SC liquid dyes.
2. as claimed in claim 1 a kind of in water environment with super hydrophilic interface for substrate realize to the controlled method of writing of oiliness dyestuff; it is characterized in that: magnetic-particle is ferriferrous oxide particles, ferric oxide particles, cobalt oxide particle, cobaltosic oxide particle, nickel monoxide particle or nickel sesquioxide particle, particle diameter is 0.01 micron ~ 300 microns.
3. a kind ofly as claimed in claim 1 to realize the controlled method of writing of oiliness dyestuff for substrate with super hydrophilic interface in water environment, it is characterized in that: substrate is acrylamide, dimethyl silicone polymer, PLA, polystyrene, polytetrafluoroethylene (PTFE), shitosan, polyethylene, polypropylene, polyvinyl chloride, polyethylene glycol, iron, aluminium, magnesium, zinc, copper, steel alloy, silica, monocrystalline silicon, zinc oxide, clay and polystyrene complex or rare earth and silicone composites.
4. as claimed in claim 1 a kind of in water environment with super hydrophilic interface for substrate realize to the controlled method of writing of oiliness dyestuff, it is characterized in that: the polylactic acid based end of preparing surface super hydrophobic is dissolved in by PLA in organic non-polar solven dioxane, mass percentage concentration is 5% ~ 20%, this solution is added drop-wise to the surface at the polylactic acid based end, after starting to separate out polylactic acid membrane at substrate surface, rapidly substrate is placed in ethanolic solution to take out after 30 ~ 90 minutes, after vacuum drying, the polylactic acid membrane on surface is peeled off, namely the surface with micron and nanometer composite structure can be prepared on the polylactic acid based end, thus obtain the polylactic acid based end of surface super hydrophobic.
5. as claimed in claim 1 a kind of in water environment with super hydrophilic interface for substrate realize to the controlled method of writing of oiliness dyestuff, it is characterized in that: the aluminium flake substrate preparing surface super hydrophobic is by 15 ~ 30mL, the hydrochloric acid of mass fraction 37%, the water of 5 ~ 10mL, the hydrofluoric acid mixing of 1 ~ 5mL, mixed solution is dropped on aluminium flake, with water cleaning and ultrasonic water bath 5 ~ 10 minutes after 15 ~ 30 seconds, ethanolic solution 10 ~ 15h that percentage by volume is the perfluorododecyl triethoxysilane of 1 ~ 3% is dipped in after drying again at 70 ~ 90 DEG C, after taking out, nitrogen dries up the aluminium flake substrate namely obtaining surface super hydrophobic.
6. as claimed in claim 1 a kind of in water environment with super hydrophilic interface for substrate realize to the controlled method of writing of oiliness dyestuff, it is characterized in that: the polylactic acid based end of preparation surface super hydrophilic is dissolved in by PLA in organic non-polar solven dioxane, mass percentage concentration is 5% ~ 20%, this solution is added drop-wise to the surface at the polylactic acid based end, after starting to separate out polylactic acid membrane at substrate surface, rapidly substrate is placed in ethanolic solution to take out after 30 ~ 90 minutes, after vacuum drying, the polylactic acid membrane on surface is peeled off, namely the surface with micron and nanometer composite structure can be prepared on the polylactic acid based end, then plasma or ultraviolet irradiation 3 ~ 10min is applied, thus it is super hydrophilic to make super-hydrophobic polylactic acid based basal surface realize.
7. as claimed in claim 1 a kind of in water environment with super hydrophilic interface for substrate realize to the controlled method of writing of oiliness dyestuff, it is characterized in that: the aluminium substrate of preparation surface super hydrophilic is by the hydrochloric acid of 15 ~ 30mL, mass fraction 37%, the water of 5 ~ 10mL, the hydrofluoric acid mixing of 1 ~ 5mL, mixed solution is dropped on aluminium flake, by clean water and ultrasonic water bath 5 ~ 10 minutes after 15 ~ 30 seconds, under 70 ~ 90 DEG C of conditions, after drying, namely obtain the aluminium substrate with ultra-hydrophilic surface.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108249539A (en) * | 2018-01-03 | 2018-07-06 | 广东石油化工学院 | PAM molecules spherical shape and net form accumulation body pattern controllable method repeatedly in a kind of aqueous solution |
| CN109206652A (en) * | 2018-09-05 | 2019-01-15 | 吉林大学 | It is able to achieve the intelligent surface construction method and its device used of wetability conversion |
| CN109772480A (en) * | 2017-11-15 | 2019-05-21 | 中国科学院青岛生物能源与过程研究所 | Single particle package drop is formed in micro-fluidic chip and the derived method of difference |
| CN110082063A (en) * | 2019-03-04 | 2019-08-02 | 中国科学院化学研究所 | The method and purposes of rotary motion after a kind of control droplet collision |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1718619A (en) * | 2005-08-08 | 2006-01-11 | 北京师范大学 | Magnetic composite microglobule possessing inorganic/organic core shell structure and its preparation method |
| JP2006213844A (en) * | 2005-02-04 | 2006-08-17 | Dainippon Ink & Chem Inc | Active energy ray-curable screen ink composition |
| JP2008105379A (en) * | 2006-09-29 | 2008-05-08 | Fujifilm Corp | Method and equipment for inkjet recording |
| JP2009202344A (en) * | 2008-02-26 | 2009-09-10 | Fuji Xerox Co Ltd | Image forming method and image forming device |
| EP1905609B1 (en) * | 2006-09-29 | 2013-11-06 | FUJIFILM Corporation | Inkjet recording method |
-
2014
- 2014-09-16 CN CN201410476115.8A patent/CN104290479B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006213844A (en) * | 2005-02-04 | 2006-08-17 | Dainippon Ink & Chem Inc | Active energy ray-curable screen ink composition |
| CN1718619A (en) * | 2005-08-08 | 2006-01-11 | 北京师范大学 | Magnetic composite microglobule possessing inorganic/organic core shell structure and its preparation method |
| JP2008105379A (en) * | 2006-09-29 | 2008-05-08 | Fujifilm Corp | Method and equipment for inkjet recording |
| EP1905609B1 (en) * | 2006-09-29 | 2013-11-06 | FUJIFILM Corporation | Inkjet recording method |
| JP2009202344A (en) * | 2008-02-26 | 2009-09-10 | Fuji Xerox Co Ltd | Image forming method and image forming device |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109772480A (en) * | 2017-11-15 | 2019-05-21 | 中国科学院青岛生物能源与过程研究所 | Single particle package drop is formed in micro-fluidic chip and the derived method of difference |
| CN109772480B (en) * | 2017-11-15 | 2020-11-10 | 中国科学院青岛生物能源与过程研究所 | Method for forming and respectively guiding single particle-wrapped liquid drops in microfluidic chip |
| CN108249539A (en) * | 2018-01-03 | 2018-07-06 | 广东石油化工学院 | PAM molecules spherical shape and net form accumulation body pattern controllable method repeatedly in a kind of aqueous solution |
| CN108249539B (en) * | 2018-01-03 | 2020-09-15 | 广东石油化工学院 | Method for repeatedly controlling morphology of spherical and net-shaped accumulation body of PAM (polyacrylamide) molecules in aqueous solution |
| CN109206652A (en) * | 2018-09-05 | 2019-01-15 | 吉林大学 | It is able to achieve the intelligent surface construction method and its device used of wetability conversion |
| CN110082063A (en) * | 2019-03-04 | 2019-08-02 | 中国科学院化学研究所 | The method and purposes of rotary motion after a kind of control droplet collision |
| CN113049567A (en) * | 2021-03-04 | 2021-06-29 | 北京工业大学 | Preparation method and application of writing type surface enhanced Raman scattering substrate |
| CN113049567B (en) * | 2021-03-04 | 2022-11-04 | 北京工业大学 | Preparation method and application of writing type surface enhanced Raman scattering substrate |
| CN113908897A (en) * | 2021-11-16 | 2022-01-11 | 中山大学 | Micro-fluidic device for realizing droplet control by magnetic excitation and control method thereof |
| CN113908897B (en) * | 2021-11-16 | 2022-07-12 | 中山大学 | Micro-fluidic device for realizing droplet control by magnetic excitation and control method thereof |
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