CN104290479B - A kind ofly in water environment, realize the controlled method of writing of oiliness dyestuff as substrate to surpass hydrophilic interface - Google Patents
A kind ofly in water environment, realize the controlled method of writing of oiliness dyestuff as substrate to surpass hydrophilic interface Download PDFInfo
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- CN104290479B CN104290479B CN201410476115.8A CN201410476115A CN104290479B CN 104290479 B CN104290479 B CN 104290479B CN 201410476115 A CN201410476115 A CN 201410476115A CN 104290479 B CN104290479 B CN 104290479B
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Abstract
In water environment, to surpass hydrophilic interface as substrate realizes the controlled method of writing of oiliness dyestuff, belong to oiliness dyestuff under water environment and write technical field. Thereby at the bottom of comprising the super hydrophilic group of preparation, prepare writing process magnetic gel ball used, apply magnetic field shifting magnetic field at the opposite side at the bottom of super hydrophilic group and realize the controlled step such as write of the magnetic of oiliness dyestuff in the super hydrophilic interface based under water environment system. The hydrophilicity of substrate can regulate and control by degree of roughness and the chemical composition of controlling substrate surface, and then realize the control of the factors such as size, oiliness dye solution ball movement locus width and spot diameter to oiliness dyestuff drop and substrate contact area, reach controlled object of writing. This by controlled to substrate surface wellability and the oiliness dyestuff method combining of writing, be a kind of brand-new Writing method under aqueous systems environment, comprise that the moulding of oiliness dye image and dot matrix prepared etc.
Description
Technical field
The invention belongs to oiliness dyestuff under water environment and write technical field, particularly a kind of in water environment to surpass parentWater termination is that substrate realizes the controlled method of writing of oiliness dyestuff.
Background technology
Dyestuff under particular surroundings is graphically write control technology, particularly the graphical book to substrate in aqueous systemsWrite control technology, in real productive life, have a wide range of applications, as lacked for underbody paintDamage the direct reparation of part, this will shorten hull repair time greatly, cost-saving; Again or life medical domainIn be placed in the substrate of nutrient solution or the graphical modification on tissue engineering bracket surface, to realize its chip,For research cell adherence process provides new approach. But the relevant control technology of graphically writing is but relatively less,This has just limited the development of its related industry greatly. At present, graphically write control technology based on oiliness dyestuffMainly contain stencil methods, physics or chemical vapour deposition (CVD) and hand spray etc. Above method is mostly in airComplete, implement to be just subject to great restriction if related under the particular surroundings such as aqueous systems, and above method is in realityIn the application of border, there is the shortcomings such as complicated operation, technical costs is high, accuracy is not high. So how at aqueous systems environmentRealize the controlled of oiliness dyestuff and write down, just become the main contents of research.
Summary of the invention
The object of the invention is by magnetic field in aqueous systems to thering is magnetic gel ball on super hydrophilic group basal surfaceThe motion of oiliness dyestuff drop is controlled, and realizes the oil on this super hydrophilic group basal surface with magnetic gel ballControlled the writing of property dyestuff drop, this method combines the Superhydrophilic matter of substrate and substrate to oiliness dyestuffThe features such as adhesiveness, have been realized oiliness dye solution have been dropped in to controlled the writing in aqueous systems by magnetic field, pass throughUltra-hydrophilic surface applies magnetic field, and oiliness dyestuff drop is in its surface carried out to local control, utilizes substrate and magneticPressure between gel ball, writes to complete on oiliness dyestuff is stamped at the bottom of super hydrophilic group, comprise write point,The structure such as line, dot matrix. This Writing method operating process is simple, the relatively simple and easy and cost of the making at the bottom of super hydrophilic groupLow, greatly increase operability.
The size of oiliness dyestuff figure can realize by the size of controlling drop and substrate contact area. Concrete wayFootpath mainly contains following two aspects: (1) is by controlling degree of roughness (the polylactic acid based end in embodiment of substrate surfaceWith the substrate roughness degree of metallic aluminium be distinguishing) and chemical composition to regulate and control the hydrophilicrty of substrate right to realizeThe control of oiliness drop and substrate contact area; (2) by the oiliness dyestuff of magnetropism gel ball dropping different volumesDrop is realized the control with substrate contact area, reaches controlled object of writing. This by substrate surface wellabilityWith the controlled method combining of writing of oiliness dyestuff, be a kind of brand-new Writing method under aqueous systems environment, compriseThe moulding of oiliness dye image and dot matrix are prepared etc.
At the bottom of super hydrophilic group of the present invention, comprise the polymer-based end, as poly-N-isopropylacrylamide, poly dimethylSiloxanes, PLA, polystyrene, polytetrafluoroethylene (PTFE), shitosan, polyethylene, polypropylene, polyvinyl chloride,Polyethylene glycol etc.; Metallic substrates, as metallic iron, aluminium, magnesium, zinc, copper, steel alloy etc.; Semiconductor base, asSilica, monocrystalline silicon, zinc oxide etc.; Composite substrate, as clay and polystyrene, polysiloxanes is contourThe various material such as the compound of molecule, carry out chemical modification by it to the surface of substrate and regulation and control microstructure is controlledThe Superhydrophilic of substrate processed.
The present invention prepares gel ball as example taking the natural macromolecular material such as shitosan, alginates coated magnetic particle, willOiliness dyestuff invests gel ball around 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, poly-L-Lysine, poly-L-GLU etc.); Synthetic macromolecule, as (poly-in polyethylene, alcohol, acrylic acid and derivative class thereofAcrylic acid, polymethylacrylic acid, polyacrylamide, poly-N-is poly-for acrylamide etc.). Magnetic-particle is four oxidationsThree-iron particle, ferric oxide particles, cobalt oxide particle, cobaltosic oxide particle, nickel monoxide particle, three oxidations twoThe metal oxides such as nickel particle, particle diameter is 0.01 micron～300 microns.
At the bottom of super hydrophilic group used in the present invention, can be that PLA adopts phase disengagement method, or metallic aluminium, copperDeng adopting the method for etching, also or single crystal silicon semiconductor adopts the method for electron beam lithography to realize super hydrophilic interface.
The oiliness dyestuff of writing operation can be the dye solution and the oil with certain dyestuff toner density of pure oilinessProperty solution. The dye solution of pure oiliness comprises 2-hydroxyl anthracene-3-formyl ortho-aminotoluene, 3-hydroxyl dibenzofuran-2-formic acid andDerivative, the insoluble azo dyes such as the adjacent formyl hydroxy arylamine of carbazole. There is the oiliness of certain dyestuff toner densitySolution can be disperse dyes, as disperse yellow 5G2 (1H)-Quinolmone, 4-hydroxy-1-methyl-3-The benzole soln of [(3-nitrophenyl) zao], disperses bright red E-RLN9,1-Anthracenedione, 1Amino-4-hydroxy-2-[2 (2-methoxyethoxy) ethoxy] benzole soln, vat brilliant orange3RK, Dibenzo[def, mno] chrysene-5, the xylene solution of 12-dione; Also can be commercial to have oneDetermine the oiliness dyestuff of dyestuff toner density, as the single-phase highly enriched easy solution of Automate series of DOW Chemical productBody dyestuff, or oiliness fluorescent dye is as fluorescein 131SC liquid dyes etc.
There is the oiliness dye solution of certain toner density and the solvent of oiliness fluorescent dye can be organic solvent-benzene, twoToluene etc., or mineral oil, vegetable oil, atoleine, lubricated other oil-based solvent of wet goods, molar concentration is 0.01MTo 10M.
In water environment, realize the controlled method of writing of oiliness dyestuff, its step as substrate to surpass hydrophilic interfaceAs follows:
1) for the preparation of the preparation of the super-hydrophobic substrate of gel ball
1. prepare the polylactic acid based end of surface super hydrophobic: PLA is dissolved in to organic non-polar solven dioxaneIn, mass percentage concentration is 5%～20%, this solution is added drop-wise to the polylactic acid based end (as global in NingboThe PLA sheet material of biomaterial Co., Ltd, thickness is 1.8～5.5mm) surface, treat at substrate tableFace starts to separate out after polylactic acid membrane, and rapidly substrate is placed in to ethanolic solution and takes out after 30～90 minutes,After vacuum drying, surperficial polylactic acid membrane is peeled off, can on the polylactic acid based end, prepare and have(its surface mainly contains the microballoon composition that diameter is 13 microns of left and right, each microballoon to micron and nanometer composite structureOn to have numerous diameter be the projection of 100 about nanometers) surface, thereby obtain surface super hydrophobicThe polylactic acid based end;
2. prepare the aluminium flake substrate of surface super hydrophobic: by the hydrochloric acid of 15～30mL, mass fraction 37%,The water of 5～10mL, the hydrofluoric acid of 1～5mL mixes, and mixed solution is dropped on aluminium flake to 15～30 secondsRear water cleans and ultrasonic water bath 5～10 minutes, is dipped in percentage by volume after dry at 70～90 DEG C to be againEthanolic solution 10～the 15h of 1～3% perfluor dodecyl triethoxysilane, after taking out, nitrogen dries upObtain the aluminium flake substrate of surface super hydrophobic, substrate surface is mainly by countless irregular rectangle (widthAbout 100-200nm, length 200-800nm) and the nano particle structure composition of 100nm left and right,Nano particle is random to be distributed in rectangular configuration;
2) 1. prepare at the super hydrophilic polylactic acid based end, surface: PLA is dissolved in dioxane, and quality percentage is denseDegree is 5%～20%, and this solution is added drop-wise to (the limited public affairs of biomaterial as global in Ningbo of the polylactic acid based endThe PLA sheet material of department, thickness is 1.8～5.5mm) surface, treat to start to separate out poly-breast at substrate surfaceAfter sorrel, rapidly substrate is placed in to ethanolic solution and takes out after 30～90 minutes, after vacuum drying, will showThe polylactic acid membrane of face peels off, and can on the polylactic acid based end, prepare and have micron and nanometer composite structure(its surface mainly contains the microballoon composition that diameter is 13 microns of left and right, has numerous diameter on each microballoonBe the projection of 100 about nanometers) surface, then apply plasma or ultraviolet irradiation 3～10min,Thereby it is super hydrophilic that super-hydrophobic polylactic acid based basal surface is realized;
2. the super hydrophilic aluminium substrate in preparation surface: by the hydrochloric acid of 15～30mL, mass fraction 37%, 5～10mLWater, the hydrofluoric acid of 1～5mL mixes, and mixed solution is dropped on aluminium flake, after 15～30 seconds, uses clear waterCleaning ultrasonic water bath 5～10 minutes, obtain have ultra-hydrophilic surface after being dried under 70～90 DEG C of conditionsAluminium substrate;
3) prepare writing process magnetic gel ball used: be 10～20mg/mL by 5～10mL, concentrationChitosan-acetic acid solution (shitosan of 50mg is dissolved in the acetum of 1% (v/v) and makes,Acetum is by 1% water-soluble the making of volume ratio by acetic acid) and 25mg Fe 3 O 4 magneticGrain mixes under the dialdehyde class crosslinking agent effects 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, be then placed in chamberUnder the environment of temperature saturated humidity, place 12～20 hours, take out, after freeze drying, can be wrapped upThe magnetic gel ball of magnetic-particle; Again 2～10 μ L oiliness blobs of dye are added on gel ball, thereby obtainObtain the magnetic gel ball of oiliness dyestuff parcel;
4) by step 2) substrate with ultra-hydrophilic surface that obtains is placed in water, then by step 3) oil that obtainsProperty dyestuff parcel magnetic gel ball be placed on the water-wetted surface of this substrate, apply at the opposite side of substrateMagnetic field shifting magnetic field, the magnetic that can realize oiliness dyestuff in the water environment based on super hydrophilic interface canWriting of control line and figure;
Or by step 2) substrate with ultra-hydrophilic surface that obtains is placed in water, then by step 3)To the magnetic gel ball of oiliness dyestuff parcel be placed on the water-wetted surface of this substrate, hydrophilic in this substrate1～5cm place, top on surface is also placed in water at the bottom of this super hydrophilic group at the bottom of placing another 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 being attracted to the water-wetted surface of top substrate, the magnetic gel ball of oiliness dyestuff parcel cancels this magnetic, can realize 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, to the writing of the various ways under the aqueous systems of oiliness dyestuff, comprising and writing notWith the getting ready of the figure of width, different-diameter, dot matrix etc. In the process moving in magnetic field, oiliness dyestuff parcelMagnetic gel ball also moves thereupon at the bottom of super hydrophilic group, and oiliness dye-coating is at the bottom of super hydrophilic group.
The PLA that said method uses, molecular weight can be 100,000～500,000.
Brief description of the drawings
Fig. 1: in water environment, the controlled straight line of writing of oiliness dyestuff magnetic is write manipulation schematic diagram; 1 represents magneticGrain; At the bottom of the super hydrophilic group of 2 expression; 3 represent magnetic gel ball; 4 represent oiliness dyestuff; 5 represent magnet; 6 representWater environment. Corresponding embodiment 1,2,3,4.
Fig. 2: in water environment oiliness dyestuff magnetic controlled write get manipulation schematic diagram ready at any point; 1 represents magneticProperty particle; At the bottom of the super hydrophilic group of 2 expression; 3 represent magnetic gel ball; 4 represent oiliness dyestuff; 5 represent magnet; 6Represent water environment. Corresponding embodiment 6,7,8.
Fig. 3: the controlled drafting manipulation schematic diagram of writing linear array of oiliness dyestuff magnetic in water environment; 1 represents magneticProperty particle; At the bottom of the super hydrophilic group of 2 expression; 3 represent magnetic gel ball; 4 represent oiliness dyestuff; 5 represent magnet; 6Represent water environment. Corresponding embodiment 5.
Fig. 4: the controlled manipulation schematic diagram that draws a design of writing of oiliness dyestuff magnetic in water environment; 1 represents magneticGrain; At the bottom of the super hydrophilic group of 2 expression; 3 represent magnetic gel ball; 4 represent oiliness dyestuff; 5 represent magnet; 6 representWater 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 to mass percentage concentrationBe 13%, then this solution of 3mL be added drop-wise to polylactic acid based basal surface (2 × 2cm, the global biomaterial in NingboCo., Ltd produces, and thickness is 4mm) surface, until starting to separate out on surface after polylactic acid membrane, be placed in rapidly ethanolIn solution, after 60 minutes, take out, after vacuum drying, after polylactic acid membrane is peeled off, can make and there is micro-nano composite junction(microballoon that its surface is mainly about 13 microns of left and right by diameter forms, and has numerous on each microballoon for the substrate of structureDiameter is the projection of 100 about nanometers) super-hydrophobic PLA surface (as shown in Figure 5). Then application wait fromIt is super hydrophilic that daughter (argon plasma, power 30W) irradiation 3min realizes PLA surface, and surperficial drop connectsFeeler is 0 °. Then stand-by by being placed in water at the bottom of this super hydrophilic group.
The chitosan-acetic acid solution that is 10mg/mL by 5mL concentration and 25mg tri-iron tetroxide are handed at 2.5mgConnection agent Geniposide (Genipin) effect is lower to be mixed, and gets this mixed solution 8 μ L, drops to described in preceding step, be placed under the environment of room temperature saturated humidity at super-hydrophobic the polylactic acid based end, place 12 hours, take out, at-50 DEG CAfter lower freeze drying, can obtain the magnetic gel ball that diameter is about 1.2mm coated ferroferric oxide magnetic-particle,The single-phase highly enriched easy solution body blobs of dye of Automate of again 2 μ L DOW Chemicals being produced is on this magnetic gel ballForm the magnetic gel ball of oiliness dyestuff parcel; Then the substrate with ultra-hydrophilic surface is placed in to water, then by oilProperty dyestuff parcel magnetic gel ball be placed on the water-wetted surface of this substrate, place magnet at the opposite side of substrate and applyOiliness dyestuff drop is controlled with rectilinear movement in magnetic field, thus realize oiliness dyestuff on ultra-hydrophilic surface to be aboutThe live width of 300 μ m is write the control of straight line. The size of live width and ball, the hydrophily of dye dosage and substrate is all relevantSystem. 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 to mass percentage concentrationBe 13%, then this solution of 3mL be added drop-wise to polylactic acid based basal surface, treat to start to separate out polylactic acid membrane on surfaceAfter, be placed in rapidly ethanolic solution and take out after 60 minutes, after vacuum drying, can after the polylactic acid membrane on surface peels offMake and there is micron and nanometer composite structure that (its surface mainly contains the microballoon composition that diameter is about 13 microns of left and right, eachOn microballoon, have the projection of 100 about nanometers) PLA surface (as shown in Figure 5). Application plasma radiationIt is super hydrophilic that 3min realizes PLA surface, and surperficial liquid-drop contact angle is 0 °.
The chitosan solution that is 10mg/mL by 5mL concentration and 25mg tri-iron tetroxide are at 2.5mg crosslinking agentGeniposide (Genipin) effect is lower to be mixed, and gets this mixed solution 8 μ L, drops to super thin described in preceding step, be then placed under the environment of room temperature saturated humidity at the polylactic acid based end of water, place 12 hours, take out, freezing dryAfter dry, can obtain the magnetic gel ball of coated ferroferric oxide; The Automate that the DOW Chemical of 4 μ L is producedSingle-phase highly enriched easy solution body blobs of dye forms the magnetic gel ball of oiliness dyestuff parcel on this magnetic gel ball; SoAfter the substrate with ultra-hydrophilic surface is placed in to water, then the magnetic gel ball of oiliness dyestuff parcel is placed in to this substrateWater-wetted surface on, place magnet at the opposite side of substrate and apply magnetic field and control oiliness dyestuff drop with rectilinear movement,Thereby realize the control of oiliness dyestuff being write on ultra-hydrophilic surface to straight line to be about the live width of 800 μ m.
Embodiment 3
PLA (molecular weight is 350,000) is dissolved in organic non-polar solven dioxane to mass percentage concentrationBe 13%, then this solution of 3mL be added drop-wise to polylactic acid based basal surface, treat to start to separate out polylactic acid membrane on surfaceAfter, be placed in rapidly ethanolic solution and take out after 60 minutes, after vacuum drying, can after the polylactic acid membrane on surface peels offMake and there is micron and nanometer composite structure that (its surface mainly contains the microballoon composition that diameter is about 13 microns of left and right, eachOn microballoon, have the projection of 100 about nanometers) PLA surface (as shown in Figure 5). By controlling plasmaExposure time can control the wellability on PLA surface. Therefore in this example, should use plasma irradiation PLA tableIt is hydrophilic that face 2min realizes PLA surface, makes this surface liquid-drop contact angle become 30 ° from 153.6 °.
The chitosan solution that is 10mg/mL by 5mL concentration and 25mg tri-iron tetroxide are at 2.5mg crosslinking agentGeniposide (Genipin) effect is lower to be mixed, and gets this mixed solution 8 μ L, drops to super thin described in preceding step, be then placed under the environment of room temperature saturated humidity at the polylactic acid based end of water, place 12 hours, take out, freezing dryAfter dry, can obtain the magnetic gel ball of coated ferroferric oxide; The Automate that the DOW Chemical of 2 μ L is producedThe single-phase highly enriched easy solution body blobs of dye of series forms the magnetic gel of oiliness dyestuff parcel on this magnetic gel ballBall; The substrate with ultra-hydrophilic surface is placed in to water, then the magnetic gel ball of oiliness dyestuff parcel is placed in to this baseOn the water-wetted surface at the end, then place magnet at the opposite side of substrate and apply magnetic field control oiliness dyestuff drop with straight lineMobile, in the substrate after irradiation, contrast straight line live width and become 500 μ m from 300 μ m. Compared with embodiment 1,Be surperficial liquid-drop contact angle occurred change can realize the variation of writing live width, i.e. contact angle difference, therebyThe contact area of drop and substrate is different.
Embodiment 4
PLA (molecular weight is 350,000) is dissolved in organic non-polar solven dioxane, and concentration is 13% (matterAmount percentage), then this solution of 3mL is added drop-wise to polylactic acid based basal surface, treat to start to separate out PLA on surfaceAfter film, be placed in rapidly ethanolic solution and take out after 60 minutes, after vacuum drying, after the polylactic acid membrane on surface peels offCan make and there is micron and nanometer composite structure that (its surface mainly contains the microballoon composition that diameter is about 13 microns of left and right, everyOn individual microballoon, have the projection of 100 about nanometers) PLA surface (as shown in Figure 5). Application plasma spokeAccording to 3min, PLA surface is realized super hydrophilic, surperficial liquid-drop contact angle is 0 °. Then by the bottom of this super hydrophilic groupBe placed in water stand-by.
The chitosan solution that is 10mg/mL by 5mL concentration and 25mg tri-iron tetroxide are at 2.5mg crosslinking agentGeniposide (Genipin) effect is lower to be mixed, and gets this mixed solution 8 μ L, drops to super thin described in preceding step, be then placed under the environment of room temperature saturated humidity at the polylactic acid based end of water, place 12 hours, take out, freezing dryAfter dry, can obtain the magnetic gel ball of coated ferroferric oxide; The Automate again DOW Chemical of 6 μ L being producedSingle-phase highly enriched easy solution body blobs of dye forms the magnetic gel ball of oiliness dyestuff parcel on this magnetic gel ball; WillThe substrate with ultra-hydrophilic surface is placed in water, then the magnetic gel ball of oiliness dyestuff parcel is placed in to the parent of this substrateOn water surface; Then place magnet at the opposite side of substrate and apply magnetic field control oiliness dyestuff drop with rectilinear movement,Realize the control of oiliness dyestuff being write on ultra-hydrophilic surface to straight line to be about the live width of 1000 μ m.
Embodiment 5
PLA (molecular weight is 350,000) is dissolved in organic non-polar solven dioxane, and concentration is 13% (matterAmount percentage), then this solution of 3mL is added drop-wise to polylactic acid based basal surface, treat to start to separate out PLA on surfaceAfter film, be placed in rapidly ethanolic solution and take out after 60 minutes, after vacuum drying, after the polylactic acid membrane on surface peels offCan make and there is micron and nanometer composite structure that (its surface mainly contains the microballoon composition that diameter is about 13 microns of left and right, everyOn individual microballoon, have the projection of 100 about nanometers) PLA surface (as shown in Figure 5). Application plasma spokeAccording to 3min, PLA surface is realized super hydrophilic, surperficial liquid-drop contact angle is 0 °. Then by the bottom of this super hydrophilic groupBe placed in water stand-by.
The chitosan solution that is 10mg/mL by 5mL concentration and 25mg tri-iron tetroxide are at 2.5mg crosslinking agentGeniposide (Genipin) effect is lower to be mixed, and gets this mixed solution 8 μ L, drops to surpassing described in preceding step, be then placed under the environment of room temperature saturated humidity at hydrophobic the polylactic acid based end, place 12 hours, take out, freezingAfter dry, can obtain the magnetic gel ball of coated ferroferric oxide; Respectively by the Tao Shiization of 2 μ L, 4 μ L, 6 μ LLearn the single-phase highly enriched easy solution body blobs of dye of Automate of producing and on this magnetic gel ball, form oiliness dyestuff bagThe magnetic gel ball of wrapping up in; The substrate with ultra-hydrophilic surface is placed in to water, then by solidifying the magnetic of oiliness dyestuff parcelGlueballs is placed on the water-wetted surface of this substrate; Then applying magnetic field control oiliness at the opposite side placement magnet of substrate dyesFeed liquid drips to move linearly, realize to oiliness dyestuff on ultra-hydrophilic surface with 300 μ m, 800 μ m, 1000 μ mFor the controlled of linear array of live width write.
Embodiment 6
PLA (molecular weight is 350,000) is dissolved in organic non-polar solven dioxane, and concentration is 13% (matterAmount percentage), then this solution of 3mL is added drop-wise to polylactic acid based basal surface, treat to start to separate out PLA on surfaceAfter film, be placed in rapidly ethanolic solution and take out after 60 minutes, after vacuum drying, after the polylactic acid membrane on surface peels offCan make and there is micron and nanometer composite structure that (its surface mainly contains the microballoon composition that diameter is about 13 microns of left and right, everyOn individual microballoon, have the projection of 100 about nanometers) PLA surface (as shown in Figure 5). Application plasma spokeAccording to 3min, PLA surface is realized super hydrophilic, surperficial liquid-drop contact angle is 0 °. Then by the bottom of this super hydrophilic groupBe placed in water stand-by.
The chitosan solution that is 10mg/mL by 5mL concentration and 25mg tri-iron tetroxide are at 2.5mg crosslinking agentGeniposide (Genipin) effect is lower to be mixed, and gets this mixed solution 8 μ L, drops to super thin described in preceding step, be then placed under the environment of room temperature saturated humidity at the polylactic acid based end of water, place 12 hours, take out, freezing dryAfter dry, can obtain the magnetic gel ball of coated ferroferric oxide; The Automate that the DOW Chemical of 6 μ L is producedSingle-phase highly enriched easy solution body blobs of dye forms the magnetic gel ball of oiliness dyestuff parcel on this magnetic gel ball; WillThe substrate with ultra-hydrophilic surface is placed in water, then the magnetic gel ball of oiliness dyestuff parcel is placed in to the parent of this substrateOn water surface; Above the magnetic gel ball of oiliness dyestuff parcel at the bottom of above-mentioned super hydrophilic group, another is super close for the placement of 3cm placeThe water base end,, this substrate still remains in water, and the magnetic that then deviates from oiliness dyestuff parcel at the bottom of this super hydrophilic group is solidifyingOne side of glueballs applies magnetic field, after this magnetic gel ball is attracted to top substrate, cancels this magnetic field, can realizeThe operation of getting ready as diameter taking 300 μ m at the bottom of the super hydrophilic group of rear placement.
Embodiment 7
PLA (molecular weight is 350,000) is dissolved in organic non-polar solven dioxane to concentration range 13%(mass percent), is then added drop-wise to polylactic acid based basal surface by this solution of 3mL, treats to start to separate out on surface poly-After lactic acid film, be placed in rapidly ethanolic solution and take out after 60 minutes, after vacuum drying, the polylactic acid membrane stripping on surfaceBackwardness can make and there is micron and nanometer composite structure (its surface mainly contains the microballoon composition that diameter is about 13 microns of left and right,On each microballoon, have the projection of 100 about nanometers) PLA surface (as shown in Figure 5). By control wait fromDaughter exposure time can control the wellability on PLA surface, can make its surface realize from super-hydrophobic (contact153.6 °, angle) to the variation of super hydrophilic (contact angle is 0 °). Therefore in this example, should use plasma irradiation PLAIt is hydrophilic that surface 2min realizes PLA surface, makes this surface liquid-drop contact angle become 30 ° from 153.6 °. ThenStand-by by being placed in water at the bottom of this super hydrophilic group.
The chitosan solution that is 10mg/mL by 5mL concentration and 25mg tri-iron tetroxide are at 2.5mg crosslinking agentGeniposide (Genipin) effect is lower to be mixed, and gets this mixed solution 8 μ L, drops to super thin described in preceding step, be then placed under the environment of room temperature saturated humidity at the polylactic acid based end of water, place 12 hours, take out, freezing dryAfter dry, can obtain the magnetic gel ball of coated ferroferric oxide; The Automate that the DOW Chemical of 6 μ L is producedSingle-phase highly enriched easy solution body blobs of dye forms the magnetic gel ball of oiliness dyestuff parcel on this magnetic gel ball; SoAfter the substrate with ultra-hydrophilic surface is placed in to water, then the magnetic gel ball of oiliness dyestuff parcel is placed in to this substrateWater-wetted surface on; Above the magnetic gel ball of oiliness dyestuff parcel at the bottom of above-mentioned super hydrophilic group, another is placed by 3cm placeAt the bottom of super hydrophilic group, this substrate still remains in water, then at the bottom of this super hydrophilic group, deviates from the magnetic of oiliness dyestuff parcelProperty gel ball a side apply magnetic field, cancel this magnetic field when this magnetic gel ball is attracted to top after substrate,Realize the operation of getting ready at the bottom of the super hydrophilic group of rear placement, after predose, spot diameter becomes 500 μ m from 300 μ m.
Embodiment 8
By the hydrochloric acid of 40mL, mass fraction 37%, the water of 12.5mL, the hydrofluoric acid of 2.5mL mixes, thenThis solution of 3mL is dropped on aluminium flake, after 15 seconds, clean and ultrasonic water bath 5 minutes with clear water, then put into 80 DEG CEmpty van in dry, thereby obtain super hydrophilic aluminium flake substrate (its surface topography as shown in Figure 6). Then this is superAt the bottom of hydrophilic group, be placed in water stand-by.
The chitosan solution that is 10mg/mL by 5mL concentration and 25mg tri-iron tetroxide are at 2.5mg crosslinking agentGeniposide (Genipin) effect is lower to be mixed, and gets this mixed solution 8 μ L, drops to super thin described in preceding step, be then placed under the environment of room temperature saturated humidity at the polylactic acid based end of water, place 12 hours, take out, freezing dryAfter dry, can obtain the magnetic gel ball of coated ferroferric oxide; The Automate that the DOW Chemical of 4 μ L is producedSingle-phase highly enriched easy solution body blobs of dye forms the magnetic gel ball of oiliness dyestuff parcel on this magnetic gel ball; SoAfter the aluminium flake substrate with ultra-hydrophilic surface is placed in to water, then the magnetic gel ball of oiliness dyestuff parcel is placed in to thisOn the water-wetted surface of substrate; Above the magnetic gel ball of oiliness dyestuff parcel at the bottom of above-mentioned super hydrophilic group, place at 3cm placeAt the bottom of another super hydrophilic group, this substrate still remains in water, then at the bottom of this super hydrophilic group, deviates from oiliness dyestuff parcelA side of magnetic gel ball apply magnetic field, after this magnetic gel ball is attracted to top substrate, cancel this magnetic field,Can realize the operation of getting ready as diameter taking 800 μ m at the bottom of the super hydrophilic group of rear placement.
Embodiment 9
PLA (molecular weight is 350,000) is dissolved in organic non-polar solven dioxane, and concentration is 13% (matterAmount percentage), then this solution of 3mL is added drop-wise to polylactic acid based basal surface, treat to start to separate out PLA on surfaceAfter film, be placed in rapidly ethanolic solution and take out after 60 minutes, after vacuum drying, after the polylactic acid membrane on surface peels offCan make and there is micron and nanometer composite structure that (its surface mainly contains the microballoon composition that diameter is about 13 microns of left and right, everyOn individual microballoon, have the projection of 100 about nanometers) PLA surface (as shown in Figure 5). Application plasma spokeAccording to 3min, PLA surface is realized super hydrophilic, surperficial liquid-drop contact angle is 0 °. Then by the bottom of this super hydrophilic groupBe placed in water stand-by.
The chitosan solution that is 10mg/mL by 5mL concentration and 25mg tri-iron tetroxide are at 2.5mg crosslinking agentGeniposide (Genipin) effect is lower to be mixed, and gets this mixed solution 8 μ L, drops to super thin described in preceding step, be then placed under the environment of room temperature saturated humidity at the polylactic acid based end of water, place 12 hours, take out, freezing dryAfter dry, can obtain the magnetic gel ball of coated ferroferric oxide; The fluorescein of again DOW Chemical of 2 μ L being produced131SC liquid dyes drip the magnetic gel ball that forms oiliness dyestuff parcel on this magnetic gel ball; To have super closeThe substrate of water surface is placed in water, then the magnetic gel ball of oiliness dyestuff parcel is placed on the water-wetted surface of this substrate;Then apply magnetic field control oiliness dyestuff drop at the opposite side placement magnet of substrate and move, realize oiliness dyestuff is existedOn ultra-hydrophilic surface, write the control of figure to be about the live width of 300 μ m.
Embodiment 10
PLA (molecular weight is 350,000) is dissolved in organic non-polar solven dioxane, and concentration is 13% (matterAmount percentage), then this solution of 3mL is added drop-wise to polylactic acid based basal surface, treat to start to separate out PLA on surfaceAfter film, be placed in rapidly ethanolic solution and take out after 60 minutes, after vacuum drying, after the polylactic acid membrane on surface peels offCan make and there is micron and nanometer composite structure that (its surface mainly contains the microballoon composition that diameter is about 13 microns of left and right, everyOn individual microballoon, have the projection of 100 about nanometers) PLA surface (as shown in Figure 5). Application plasma spokeAccording to 3min, PLA surface is realized super hydrophilic, surperficial liquid-drop contact angle is 0 °. Then by the bottom of this super hydrophilic groupBe placed in water stand-by.
The alginates aqueous solution that is 10mg/mL by 5mL concentration and 50mg ferroferric oxide particle are got after mixingThis mixed solution 8 μ L drop at the super-hydrophobic polylactic acid based end described in preceding step, then by 0.5 μ L'sConcentration is that the calcium chloride water dropping of 4mol/L is cross-linked on the mixing drop of magnetic-particle and alginates,Then be placed under the environment of room temperature saturated humidity, place 12 hours, take out, after freeze drying, can be wrapped upThe magnetic gel ball of tri-iron tetroxide; The fluorescein 131SC liquid dyes of again DOW Chemical of 2 μ L being produced dripOn this magnetic gel ball, form the magnetic gel ball of oiliness dyestuff parcel; The substrate with ultra-hydrophilic surface is placed inIn water, then the magnetic gel ball of oiliness dyestuff parcel is placed on the water-wetted surface of this substrate; Then another in substrateOne is sidelong and puts magnet and apply magnetic field and control oiliness dyestuff drop and move, realize to oiliness dyestuff on ultra-hydrophilic surface withThe live width that is about 300 μ m is write the control of figure.
Claims (7)
1. in water environment, realize the controlled method of writing of oiliness dyestuff, its step as substrate to surpass hydrophilic interfaceAs follows:
1) the gel ball material solution that is 10～20mg/mL by 5～10mL, concentration and 25mg magnetic-particle,Under the dialdehyde class crosslinking agent effects such as 2.5～5mg Geniposide or glutaraldehyde, mix; Get this mixed solution2～20 μ L, drop in the substrate of surface super hydrophobic, are then placed under the environment of room temperature saturated humidity,Place 12～20 hours, take out, after freeze drying, can obtain the magnetic gel ball of coated magnetic particle;Again 2～6 μ L oiliness blobs of dye are added on gel ball, thereby obtain the magnetic gel that oiliness dyestuff wraps upBall;
2) super surface hydrophilic substrate is placed in to water, then by step 1) magnetic of the oiliness dyestuff parcel that obtainsGel ball is placed on the water-wetted surface of this substrate, applies magnetic field shifting magnetic field at the opposite side of substrate,Can realize the controlled line of magnetic of oiliness dyestuff in the water environment based on super hydrophilic interface and the book of figureWrite; Maybe be placed in water by thering is the super hydrophilic substrate in surface, then by step 1) the oiliness dyestuff that obtainsThe magnetic gel ball of parcel is placed on the water-wetted surface of this substrate, above this substrate water-wetted surfacePlace at the bottom of another super hydrophilic group at 1～5cm place, at the bottom of this super hydrophilic group, is also placed in water, two substrates hydrophilicSurface is staggered relatively; Opposite side at the bottom of the super hydrophilic group of rear placement applies magnetic field, when oiliness dyestuff bagAbove the magnetic gel ball of wrapping up in is attracted to, after the water-wetted surface of substrate, cancel this magnetic field, can realizeOn at the bottom of the super hydrophilic group of rear placement, the magnetic of oiliness dyestuff is controlled gets operation ready;
Described gel ball material be shitosan, starch, cellulose, alginic acid, hyaluronic acid, collagen,Polylysine, poly-L-GLU, polyethylene, alcohol, acrylic acid, polyacrylic acid, polymethylAcid, polyacrylamide or poly-N-are poly-for acrylamide;
Described dyestuff is derivative, the click of 2-hydroxyl anthracene-3-formyl ortho-aminotoluene, 3-hydroxyl dibenzofuran-2-formic acidThe adjacent formyl hydroxy arylamine of azoles, disperse yellow 5G2 (1H)-Quinolmone, 4-hydroxy-1-methyl-3-The benzole soln of [(3-nitrophenyl) zao], dispersion bright red E-RLN9,1-Anthracenedione, 1Amino-4-hydroxy-2-[2 (2-methoxyethoxy) ethoxy] benzole soln, vat brilliant orange3RK, Dibenzo[def, mno] chrysene-5, xylene solution, the DOW Chemical of 12-dione are producedThe single-phase highly enriched easy solution body dyestuff of Automate series or fluorescein 131SC liquid dyes.
One as claimed in claim 1 in water environment taking surpass hydrophilic interface as substrate realize controlled to oiliness dyestuffThe method of writing, is characterized in that: magnetic-particle is ferriferrous oxide particles, ferric oxide particles, cobalt oxideParticle, cobaltosic oxide particle, nickel monoxide particle or nickel sesquioxide particle, particle diameter is 0.01 micron～300 microns.
One as claimed in claim 1 in water environment taking surpass hydrophilic interface as substrate realize controlled to oiliness dyestuffThe method of writing, is characterized in that: the polylactic acid based end or table that the substrate of surface super hydrophobic is surface super hydrophobicThe aluminium flake substrate that face is super-hydrophobic; The super hydrophilic substrate in surface is that the super hydrophilic polylactic acid based end, surface or surface are superHydrophilic aluminium flake substrate.
One as claimed in claim 3 in water environment taking surpass hydrophilic interface as substrate realize controlled to oiliness dyestuffThe method of writing, is characterized in that: the polylactic acid based end of preparing surface super hydrophobic be PLA is dissolved in organicIn non-polar solven dioxane, mass percentage concentration is 5%～20%, and this solution is added drop-wise to polylactic acid basedThe surface at the end, until starting to separate out after polylactic acid membrane at substrate surface, is placed in ethanolic solution by substrate rapidlyAfter 30～90 minutes, take out, after vacuum drying, surperficial polylactic acid membrane is peeled off, can be at the polylactic acid based endOn prepare the surface with micron and nanometer composite structure, thereby obtain the polylactic acid based end of surface super hydrophobic.
One as claimed in claim 3 in water environment taking surpass hydrophilic interface as substrate realize controlled to oiliness dyestuffThe method of writing, is characterized in that: the aluminium flake substrate of preparing surface super hydrophobic is that 15～30mL, quality are dividedSeveral 37% hydrochloric acid, the water of 5～10mL, the hydrofluoric acid of 1～5mL mixes, mixed solution dropped on aluminium flake,After 15～30 seconds, water cleans and ultrasonic water bath 5～10 minutes, is dipped in volume hundred after dry at 70～90 DEG C againMark is the ethanolic solution 10～15h of 1～3% perfluor dodecyl triethoxysilane, and after taking out, nitrogen blowsThe dry aluminium flake substrate that obtains surface super hydrophobic.
One as claimed in claim 3 in water environment taking surpass hydrophilic interface as substrate realize controlled to oiliness dyestuffThe method of writing, is characterized in that: the super hydrophilic polylactic acid based end, preparation surface be PLA is dissolved in organicIn non-polar solven dioxane, mass percentage concentration is 5%～20%, and this solution is added drop-wise to polylactic acid basedThe surface at the end, until starting to separate out after polylactic acid membrane at substrate surface, is placed in ethanolic solution by substrate rapidlyAfter 30～90 minutes, take out, after vacuum drying, surperficial polylactic acid membrane is peeled off, can be at the polylactic acid based endOn prepare the surface with micron and nanometer composite structure, then apply plasma or ultraviolet irradiation3～10min, thus it is super hydrophilic that super-hydrophobic polylactic acid based basal surface is realized.
One as claimed in claim 3 in water environment taking surpass hydrophilic interface as substrate realize controlled to oiliness dyestuffThe method of writing, is characterized in that: the preparation super hydrophilic aluminium flake substrate in surface is that 15～30mL, quality are dividedSeveral 37% hydrochloric acid, the water of 5～10mL, the hydrofluoric acid of 1～5mL mixes, mixed solution dropped on aluminium flake,After 15～30 seconds, clean and ultrasonic water bath 5～10 minutes with clear water, obtain after dry under 70～90 DEG C of conditionsThere is the aluminium flake substrate of ultra-hydrophilic surface.
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