CN104059430A - Method for batch preparation of anisotropic particles by ink-jet printing and anisotropic particles thereof - Google Patents
Method for batch preparation of anisotropic particles by ink-jet printing and anisotropic particles thereof Download PDFInfo
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Abstract
The invention relates to a method for batch preparation of anisotropic particles by ink-jet printing and anisotropic particles thereof. The method is characterized in that a polymer aqueous dispersion is taken as an ink-jet printing ink for injecting to a solid base material, the formed ink droplet can form annular semispherical particles with different length diameter according to different wellability of solid base materials; or a response functional material is dispersed in the polymer aqueous dispersion, then is injected to the solid base material, and is deformed under the effect of outfield stimulation, so that taper shape or hat shape particles are formed; or the metal nanoparticles or inorganic oxide nanoparticles are dispersed in the polymer aqueous dispersion, then is injected to the solid base material, because that the metal nanoparticles or inorganic oxide nanoparticles are separated with a phase between the polymers, the anisotropic particles which are characterized in that one end of particle is metal nanoparticle or inorganic oxide nanoparticle, and the other end is the polymer. The method has the advantages of simple operation and low cost, and is suitable for large scale preparation of the anisotropic particles.
Description
Technical field
The present invention relates to the preparation of anisotropic particles, particularly spray ink Printing is prepared the method for anisotropic particles in batches.
Background technology
Different from isotropy particle, anisotropic particles refers to the particle that its shape or chemical constitution can not isotropic distribution.The particle of shape anisotropy comprises the nonspherical particles such as linear particle, rectangular particle, mushroom head particle, pyriform particle and dumbbell shape particle.Chemical constitution anisotropy refers to the chemical constitution difference at the two ends of particle, comprises that particle one end is metal, and the other end is nonmetal; Or one end is wetting ability, the other end is hydrophobicity; Or one end is organism, the other end is inorganics etc.Anisotropic particles also comprises the particle that its shape and chemical constitution all can not isotropic distribution.
Just because of anisotropic particles, asymmetric shape or the even contrary chemical constitution material of difference are integrated on a microcosmic particle, and shown important application prospect at aspects such as stabilized emulsion system, intellectual drug release, the assembling of bionical colloid and self-assembly heterojunction structures, so the research of anisotropic particles receives much concern.The preparation of anisotropic particles was once becoming study hotspot.Research method comprises physical method and chemical process.Physical method comprises orientated deposition, directly at the another kind of material of jet surface of particle, or with the mould of special shape, prepares the particle of special shape.Chemical process comprises the chemical constitution of controlling particle different sites by micro-fluidic method, or by controlling emulsion polymerization process, realizes the control of particle morphology and performance.Although above-mentioned preparation method can realize the preparation of anisotropic particles, exist process complicated, or the difficult shortcomings such as preparation in batches that realize.The preparation method of the mass of the anisotropic particles of Development of Novel is very important.Inkjet printing methods is easily realized sample batch deposition, and the chemical constitution of inkjet materials can flexible design regulation and control.The present invention proposes to prepare in batches anisotropic particles by spray ink Printing, and this provides new approaches by the mass-producing preparation for anisotropic particles.The present invention is by being printed on ink-jet printing ink on solid substrate, utilizes the special wetting property of solid substrate to realize the preparation of the anisotropic particles that shape anisotropy distributes; Or responsiveness material is incorporated in ink-jet printing ink, utilizes responsiveness material to be out of shape the regulation and control to ink droplet shape in the accumulation of outer field action, realized the preparation of the anisotropic particles of shape and the distribution of chemical constitution anisotropy; Or the different material of deposition properties is incorporated in ink-jet printing ink, utilizes the phase separation of differing materials, realize the deposition location of different positions on ink droplet, prepare the anisotropic particles preparation that chemical constitution anisotropy distributes.The inventive method is simple, cost is low, easy operation, easily in batches prepare anisotropic particles.
Summary of the invention
One of object of the present invention is to provide a kind of preparation method who realizes easy, low-cost, the mass-producing of anisotropic particles by spray ink Printing.
Two of object of the present invention is to provide the anisotropic particles that has shape anisotropy and distribute, have the anisotropic particles that anisotropic particles that shape and the equal anisotropy of chemical constitution distribute or chemical constitution anisotropy distribute.
The method that spray ink Printing of the present invention is prepared anisotropic particles is in batches: the aqueous polymer dispersion that the concentration obtaining in using polymer dispersed (preferred ultrasonic dispersion) to water is 10～30wt% is as ink-jet printing ink; Or responsiveness functional materials is distributed to the blending liquid that obtains in aqueous polymer dispersion as ink-jet printing ink, and wherein the content of the responsiveness functional materials in blending liquid is 1～15wt%, and the content of polymkeric substance is 10～30wt%, and surplus is water; Or the functional particles different from polymer deposition performance (as metal nanoparticle or inorganic oxide nanoparticles) is distributed to the blending liquid that obtains in aqueous polymer dispersion as ink-jet printing ink, wherein the content of the functional particles in blending liquid is 1～15wt%, the content of polymkeric substance is 10～30wt%, and surplus is water; The ink-jet printing ink obtaining is loaded in the print cartridge of ink jet printing device, then adopt the method for spray ink Printing, described ink-jet printing ink is injected on the surface of solid substrate, dry, because selected solid substrate has different wetting properties, the ink droplet being formed by ink-jet printing ink all can form the drop with anisotropy shape having on different infiltrating solid substrates, can prepare in batches respectively thus and have the anisotropic particles that shape anisotropy distributes;
Or responsiveness functional materials is distributed to the blending liquid that obtains in aqueous polymer dispersion as ink-jet printing ink, and wherein the content of the responsiveness functional materials in blending liquid is 1～15wt%, and the content of polymkeric substance is 10～30wt%, and surplus is water, the ink-jet printing ink obtaining is loaded in the print cartridge of ink jet printing device, then adopt the method for spray ink Printing, described ink-jet printing ink is injected on the surface of solid substrate, then to arriving solid substrate surface and uncured ink droplet, apply outfield stimulation, dry, because volume change or directed accumulation can occur responsiveness functional materials under the effect of outfield stimulation, the ink droplet that induction ink-jet printing ink forms deforms, obtain having the ink droplet of the anisotropic structure that the equal anisotropy of shape and chemical constitution distributes, can prepare in batches thus the anisotropic particles with shape and the equal anisotropy distribution of chemical constitution,
Or the functional particles different from polymer deposition performance (as metal nanoparticle or inorganic oxide nanoparticles) is distributed to the blending liquid that obtains in aqueous polymer dispersion as ink-jet printing ink, wherein the content of the functional particles in blending liquid is 1～15wt%, the content of polymkeric substance is 10～30wt%, and surplus is water, the ink-jet printing ink obtaining is loaded in the print cartridge of ink jet printing device, then adopt the method for spray ink Printing, after described ink-jet printing ink being injected on the surface of solid substrate, be positioned over temperature and be 60～90 ℃ and humidity from 10%～90% environment changing (time of described placement is preferably 2～3 hours), the phase separation of the different composition materials in the ink droplet forming due to ink-jet printing ink can cause the different composition materials in ink droplet to be piled up at the different sites of ink droplet, can prepare in batches thus the anisotropic particles that chemical constitution anisotropy distributes.
The ink droplet being formed by ink-jet printing ink if spray ink Printing to having on different infiltrating solid substrates, ink droplet all can form the anisotropic particles that the anisotropy of the hemispherical shape that length-to-diameter ratio changes distributes, and its length-to-diameter ratio increases along with the increase of the contact angle of ink droplet and solid substrate.That is to say, on hydrophilic solid substrate, can obtain the smaller semisphere particle of major diameter; And on hydrophobic solid substrate, can obtain the semisphere particle that length-to-diameter ratio is larger; When ink-jet printing ink being ejected on the super-hydrophobic and low solid substrate sticking, can obtain ring-type particle.If responsiveness functional materials is blended in aqueous polymer dispersion, not dry ink droplet is applied to outfield to stimulate, and the volume change of responsiveness functional materials or the variation of directed stacking states can make ink droplet be deformed into the anisotropic particles of shape and the distribution of chemical constitution anisotropy; Wherein the anisotropy of chemical constitution refers to that responsiveness functional materials can be gathered in one end of ink droplet because of the effect that outfield stimulates, distribute the chemical constitution heterogeneity at ink droplet two ends.If solid substrate used is the low solid substrate sticking, can obtain the shape of pyramidal structure and the anisotropic particles that chemical constitution anisotropy distributes; If solid substrate used is to have the solid substrate that height sticks performance, can obtain the shape of hat-shaped and the anisotropic particles that chemical constitution anisotropy distributes.If the different functional particles of deposition properties (as metal nanoparticle or inorganic oxide nanoparticles) is mixed up in aqueous polymer dispersion, ink-jet printing ink is injected in the environment that is placed on certain temperature and humidity on the surface with hydrophilic solid substrate, because the deposition properties of metal nanoparticle or inorganic oxide nanoparticles and polymer particle is different, can finally be positioned at the different positions of ink droplet, prepare the anisotropic particles that chemical constitution anisotropy distributes.
Described polymkeric substance is selected from urethane, polyoxyethylene glycol, polyoxyethylene glycol-diacrylate, polyvinyl alcohol, epoxy resin, a kind of in the water-soluble polymerss such as polypyrrole alkane ketone.
Described responsiveness functional materials be selected from have magnetic field responsiveness particle, have electric field response particle, there is a kind of in the polymkeric substance of pH responsiveness.
The described particle with magnetic field responsiveness is commercially available prod, and particle diameter is 20～100nm; Be selected from Z 250 particle or ferric oxide particle.
The described particle with electric field response is commercially available prod, and particle diameter is 20～100nm; Be selected from barium titanate particles or TiO 2 particles.
The described polymkeric substance with pH responsiveness is commercially available prod, is selected from a kind of in polyacrylic acid, Styrene And Chloroalkyl Acrylates segmented copolymer, poly 2 vinyl pyridine, vinylbenzene-2-vinyl pyridine segmented copolymer.
Described functional particles is selected from metal nanoparticle or inorganic oxide nanoparticles.
Described metal nanoparticle is golden nanometer particle or Nano silver grain etc.
Described inorganic oxide nanoparticles is TiO
2nanoparticle or SiO
2nanoparticle etc.
The described outfield stimulation that applies arranges magnetic field above perpendicular to solid substrate, to arriving solid substrate surface and the uncured ink droplet with magnetic field responsiveness, applies magnetic field; Or above perpendicular to solid substrate, electric field is set, to arriving solid substrate surface and the uncured ink droplet with electric field response, apply electric field; Or surface is placed in to acid atmosphere or alkaline atmosphere with the solid substrate of the ink droplet of the uncured polymkeric substance with pH responsiveness, to arriving, solid substrate surface and the uncured ink droplet with pH responsiveness carry out acid atmosphere or alkaline atmosphere is processed.
The described magnetic field that applies is that the magneticstrength scope that makes to be applied to the magnetic field on solid substrate surface is 100～200 Gausses; Have the ink droplet of magnetic field responsiveness under the effect in applied magnetic field, the ink droplet that spreads over solid substrate surface is drawn as cone-shaped ink droplet, makes ink droplet generation change in shape and volumetric shrinkage.
Described magnetic field is the magnetic field that the block Ru-Fe-Mn permanent magnet of magnetic field, sintering of permanent-magnet ferrite generation produces, or the electromagnetic field of hot-wire coil generation.
The described electric field that applies is that the strength of electric field scope that makes to be applied to the electric field on solid substrate surface is 200～400V/cm; Have the ink droplet of electric field response under the effect of applied electric field, the ink droplet that spreads over solid substrate surface is drawn as cone-shaped ink droplet, makes ink droplet generation change in shape and volumetric shrinkage.
Described electric field is the flat field that plate condenser produces.
Described acid atmosphere is the acid atmosphere that the pH value scope that produced by hydrochloric acid is 1～3, and described alkaline atmosphere is the alkaline atmosphere that the pH value scope that produced by ammoniacal liquor is 9～11; Have the ink droplet of pH responsiveness under the processing of acid atmosphere or alkaline atmosphere, the pH of ink droplet changes, and spreads over the ink droplet generation volumetric shrinkage on solid substrate surface, and the ink droplet spreading area after solidifying is less than the ink droplet spreading area before solidifying.
The described different infiltrating solid substrates that have are have hydrophilic solid substrate, the super-hydrophobic and low solid substrate sticking, the low solid substrate sticking or have the solid substrate that height sticks performance.
It is described that to have hydrophilic solid substrate be that the contact angle on water and solid substrate surface is the solid substrates of 30～85 degree; Described solid substrate is selected from common glass baseplate, polymeric substrate, quartz plate, a kind of in silicon chip etc.
The described super-hydrophobic and low solid substrate sticking is clean and coarse solid substrate to be placed in to the silicon fluoride atmosphere of 80 ℃ within 3～8 hours, obtain, and the surface of this base material and the contact angle of water are 150～160 °; Described coarse solid substrate is that solid substrate is placed in to the SiO that concentration is 0.8～5wt%
2in aqueous dispersions, soak and obtain for 1～3 minute; Described solid substrate is selected from common glass baseplate, polymeric substrate, quartz plate, a kind of in silicon chip etc.
The described low solid substrate sticking is that clean solid substrate is obtained for 3～8 hours in the silicon fluoride atmosphere of 80 ℃; Described solid substrate is selected from common glass baseplate, polymeric substrate, quartz plate, a kind of in silicon chip etc.
Described have the solid substrate that height sticks performance and refer to clean glass, quartz plate or silicon chip.
Described polymeric substrate is selected from a kind of in poly tetrafluoroethylene, Polystyrene Film, polymethyl methacrylate film, polyvinyl acetate (PVA) film, PDMS membrane, polyethylene film, polychloroethylene film, PET film etc.
Described PDMS membrane comprises common PDMS membrane or in silicone oil, steeps the PDMS membrane of 12 hours.
Described ink jet printing device is piezoelectric ink jet printer or industrial sites colloid system etc., and the aperture of their shower nozzle is preferably 10 μ m, 20 μ m, 50 μ m or 150 μ m.
The size of described ink droplet depends primarily on the aperture of the shower nozzle of ink jet printing device, the concentration of the wetting property of solid substrate, ink-jet printing ink or External field response degree etc.Method of the present invention is preferably ejected into the lip-deep ink droplet of solid substrate and is of a size of 200 microns～10 microns.
The anisotropic particles that anisotropy that method of the present invention prepares distributes is to have anisotropic particles that shape anisotropy distributes, have the anisotropic particles that anisotropic particles that shape and the equal anisotropy of chemical constitution distribute or chemical constitution anisotropy distribute.
The wetting property that changes merely as mentioned above solid substrate obtains having the anisotropic particles that shape anisotropy distributes; The effect stimulating by outfield obtains having the anisotropic particles of shape and the equal anisotropy distribution of chemical constitution; Different and realize and being separated by the deposition properties of the different composition materials in ink droplet, obtain the anisotropic particles that chemical constitution anisotropy distributes.
The anisotropic particles that described anisotropy distributes is to have anisotropic particles that shape anisotropy distributes, have the anisotropic particles that anisotropic particles that shape and the equal anisotropy of chemical constitution distribute or chemical constitution anisotropy distribute.
The described anisotropic particles with shape anisotropy distribution is the semisphere particle of annular particle, different length-to-diameter ratios, and the material of its anisotropic particles is polymkeric substance.
The described anisotropic particles with shape and the equal anisotropy distribution of chemical constitution is taper particle or hat-shaped particle, responsiveness functional materials be take as main in the top of the top of its taper particle or hat-shaped particle, and the bottom of the bottom of taper particle or hat-shaped particle (with base material contact jaw) take polymer materials as main.
One end that the anisotropic particles that described chemical constitution anisotropy distributes is anisotropic particles is metal nanoparticle, and the other end is polymkeric substance; Or one end of anisotropic particles is polymkeric substance, the other end is inorganic oxide particle.
Described polymkeric substance is selected from urethane, polyoxyethylene glycol, polyoxyethylene glycol-diacrylate, polyvinyl alcohol, epoxy resin, a kind of in polypyrrole alkane ketone.
Described responsiveness functional materials be selected from have magnetic field responsiveness particle, have electric field response particle, there is a kind of in the polymkeric substance of pH responsiveness.
The particle diameter of the described particle with magnetic field responsiveness is 20～100nm; Be selected from Z 250 particle or ferric oxide particle.
The particle diameter of the described particle with electric field response is 20～100nm; Be selected from barium titanate particles or TiO 2 particles.
The described polymkeric substance with pH responsiveness is selected from a kind of in polyacrylic acid, Styrene And Chloroalkyl Acrylates segmented copolymer, poly 2 vinyl pyridine, vinylbenzene-2-vinyl pyridine segmented copolymer.
Described metal nanoparticle is golden nanometer particle or Nano silver grain etc.
Described inorganic oxide nanoparticles is TiO
2nanoparticle or SiO
2nanoparticle etc.
Spray ink Printing of the present invention is prepared in the method for anisotropic particles in batches, using certain density aqueous polymer dispersion, after ink-jet printing ink is ejected into solid substrate, formed ink droplet can be because of the infiltrating different hemispheric particles that form annular, different length-to-diameter ratios of solid substrate; Or responsiveness functional materials is dispersed in aqueous polymer dispersion, is ejected into after solid substrate, under the effect stimulating in outfield, make it distortion, can form the particle of the special shapes such as taper, hat-shaped; Or metal nanoparticle is dispersed in aqueous polymer dispersion, is ejected into after solid substrate, due to being separated between metal nanoparticle and polymkeric substance, can form particle one end is metal nanoparticle, the anisotropic particles that the other end is polymkeric substance; If inorganic oxide nanoparticles is dispersed in aqueous polymer dispersion, be ejected into after solid substrate, due to being separated between inorganic oxide nanoparticles and polymkeric substance, can form particle one end is inorganic oxide particle, the anisotropic particles that the other end is polymkeric substance.The method of the present invention anisotropic particles of preparing on a large scale simple to operate, with low cost, applicable.
Accompanying drawing explanation
Fig. 1. the anisotropic particles of the hat-shaped structure that the embodiment of the present invention 3 is prepared.
Embodiment
Embodiment 1.
At room temperature, by polyvinyl alcohol, polyoxyethylene glycol-diacrylate and polyoxyethylene glycol ultrasonic being dispersed in water respectively, the polyvinyl alcohol aqueous dispersions that is 10wt% by the concentration obtaining, the polyoxyethylene glycol aqueous dispersions that polyoxyethylene glycol-diacrylate aqueous dispersions that concentration is 20wt% and concentration are 30wt% is respectively as ink-jet printing ink, the ink-jet printing ink obtaining is loaded into respectively in the print cartridge of three ink-jet printers (aperture of the shower nozzle of ink-jet printer is 100 μ m), by the ink-jet printing ink described in three kinds be ejected into respectively the sheet glass that contact angle increases successively (with the contact angle of water be 30 °), polyvinyl acetate (PVA) film (with the contact angle of water be 40 °), polychloroethylene film (with the contact angle of water be 55 °), polymethyl methacrylate film (with the contact angle of water be 65 °), PET film (with the contact angle of water be 68 °), polyethylene film (with the contact angle of water be 80 °), Polystyrene Film (with the contact angle of water be 85 °), PDMS membrane (with the contact angle of water be 100 °), poly tetrafluoroethylene (with the contact angle of water be 110 °) surface, after dry, obtain respectively the anisotropic particles that is shaped as hemispheric anisotropy distribution that length-to-diameter ratio increases successively.The kind of the size of resulting anisotropic particles and polymkeric substance used is irrelevant, but increases with the concentration of polymkeric substance used.The deposit size of anisotropic particles reduces with the increase of the contact angle of base material used and water, and its length-to-diameter ratio increases with the increase of the contact angle of base material used and water.When ink-jet printing ink used is concentration while being the polyoxyethylene glycol aqueous dispersions of 30wt%, on the surface of above-mentioned base material, the resulting depositional area that is shaped as the anisotropic particles that hemispheric anisotropy distributes is 150 μ m successively, 145 μ m, 140 μ m, 130 μ m, 120 μ m, 110 μ m, 100 μ m, 95 μ m, 90 μ m, its major diameter ratio is respectively 0.00328,0.0156,0.0378,0.0769,0.105,0.164,0.204,0.258,0.375.
Embodiment 2.
At room temperature, by polyvinyl alcohol, polyoxyethylene glycol-diacrylate and polyoxyethylene glycol ultrasonic being dispersed in water respectively, the polyvinyl alcohol aqueous dispersions that is 10wt% by the concentration preparing, the polyoxyethylene glycol aqueous dispersions that polyoxyethylene glycol-diacrylate aqueous dispersions that concentration is 20wt% and concentration are 30wt% is respectively as ink-jet printing ink; The ink-jet printing ink obtaining is loaded into respectively in the print cartridge of three ink-jet printers (aperture of the shower nozzle of ink-jet printer is 100 μ m), the ink-jet printing ink described in three kinds is ejected into respectively to the super-hydrophobic and low sheet glass sticking and (clean sheet glass is placed in to the SiO that concentration is 0.8～5wt%
2in aqueous dispersions, soak and within 1～3 minute, obtain shaggy sheet glass, then the silicon fluoride atmosphere that this shaggy sheet glass is placed in to 80 ℃ obtains for 3～8 hours, the surface of this sheet glass and the contact angle of water are 150～160 °) surface, after dry, obtain respectively the anisotropic particles of the shape anisotropy distribution of ring texture.When ink-jet printing ink used is concentration while being the polyvinyl alcohol aqueous dispersions of 10wt%, the deposit size of ink droplet is 120 μ m; When being concentration while being polyoxyethylene glycol-diacrylate aqueous dispersions of 20wt%, the deposit size of ink droplet is 130 μ m; When being concentration while being the polyoxyethylene glycol aqueous dispersions of 30wt%, the deposit size of ink droplet is 140 μ m.
Embodiment 3.
At room temperature, the magnetic nano-particle Fe that is 20nm by particle diameter
3o
4be distributed to respectively the blending liquid that obtains respectively having magnetic field responsiveness in the aqueous dispersions of urethane, epoxy resin and polypyrrole alkane ketone, wherein the magnetic nano-particle Fe in blending liquid
3o
4content be 1wt%, the content of urethane is 20wt%, surplus is water; Magnetic nano-particle Fe
3o
4content be 8wt%, the content of epoxy resin is 20wt%, surplus is water; Magnetic nano-particle Fe
3o
4content be 15wt%, the content of polypyrrole alkane ketone is 20wt%, surplus is water; The blending liquid obtaining, respectively as ink-jet printing ink, is loaded into the ink-jet printing ink with magnetic field responsiveness obtaining respectively in the print cartridge of three ink-jet printers (aperture of the shower nozzle of ink-jet printer is 150 μ m).By three kinds of ink-jet printing inks be injected in respectively contact angle with water be 30 ° silicon chip and with the contact angle of water be on the surface of swelling PDMS membrane (swelling obtained after 12 hours in silicone oil) of 100 °, then to arriving silicon chip and swelling PDMS membrane surface and the uncured ink droplet with magnetic field responsiveness, apply the action of a magnetic field (above perpendicular to silicon chip and swelling PDMS membrane, magnetic field being set), the magneticstrength that is applied to the magnetic field on silicon chip and swelling PDMS membrane surface is 100 Gausses; Have the ink droplet of magnetic field responsiveness under the effect in applied magnetic field, the ink droplet that spreads over silicon chip and swelling PDMS membrane surface is drawn as cone-shaped ink droplet, makes ink droplet generation change in shape and volumetric shrinkage; Be dried, obtain having the anisotropic particles of shape and the equal anisotropy distribution of chemical constitution.The kind relation of the size of gained ink droplet and polymkeric substance used is little, with wetting property and the magnetic nano-particle Fe of silicon chip and swelling PDMS membrane
3o
4concentration affects larger.Wherein the ink droplet on silicon chip, owing to being subject to the strong bonding strength of silicon chip, only has ink droplet and air contact part to be easily out of shape, and final formation bottom is large, the hat-shaped particle (as shown in Figure 1) that top is little.Along with containing 1wt% magnetic nano-particle Fe as ink-jet printing ink
3o
4urethane blending liquid, contain 8wt% magnetic nano-particle Fe
3o
4epoxy resin blending liquid, contain 15wt% magnetic nano-particle Fe
3o
4the pyrrolidone variation of mixing up liquid, on silicon chip, the bottom depositional area of resulting anisotropic particles is 180 μ m, and the size at its anisotropic particles top is followed successively by 30 μ m, 100 μ m and 120 μ m.When solid substrate used is swelling PDMS membrane, low bonding strength due to swelling PDMS membrane, under the action of a magnetic field, the rapid travelling backwards of three-phase line of contact of ink droplet, cause forming the anisotropic particles of the high length-diameter ratio with pyramidal structure, wherein bore the sharp size of the end and cone close, and with magnetic nano-particle Fe
3o
4content increase and make to bore sharp size reduction; Along with containing 1wt% magnetic nano-particle Fe as ink-jet printing ink
3o
4urethane blending liquid, contain 8wt% magnetic nano-particle Fe
3o
4epoxy resin blending liquid, contain 15wt% magnetic nano-particle Fe
3o
4the pyrrolidone variation of mixing up liquid, the size of the cone floorage of taper deposition is respectively 180 μ m, 120 μ m, 80 μ m; Chemical constitution by the cone point structure to ink droplet is analyzed, and finds magnetic nano-particle Fe
3o
4mainly be distributed in cone point part; And urethane, epoxy resin or polypyrrole alkane ketone are mainly distributed in semisphere cone bottom structure.
Embodiment 4.
At room temperature, the magnetic nano-particle Fe that is 100nm by particle diameter
3o
4be distributed to respectively the blending liquid that obtains respectively having magnetic field responsiveness in the aqueous dispersions of urethane, epoxy resin and polypyrrole alkane ketone, wherein the magnetic nano-particle Fe in blending liquid
3o
4content be 5wt%, the content of urethane is 10wt%, surplus is water; Magnetic nano-particle Fe
3o
4content be 10wt%, the content of epoxy resin is 10wt%, surplus is water; Magnetic nano-particle Fe
3o
4content be 15wt%, the content of polypyrrole alkane ketone is 10wt%, surplus is water; The blending liquid obtaining, respectively as ink-jet printing ink, is loaded into the ink-jet printing ink with magnetic field responsiveness obtaining respectively in the print cartridge of three ink-jet printers (aperture of the shower nozzle of ink-jet printer is 10 μ m).By three kinds of ink-jet printing inks be injected in respectively contact angle with water be 30 ° quartz plate and with the contact angle of water be on the surface of PDMS membrane of 100 °, then to arriving quartz plate and PDMS membrane magnetic field surperficial and that the uncured ink droplet with magnetic field responsiveness produces by permanent-magnet ferrite, apply the action of a magnetic field (above perpendicular to quartz plate and PDMS membrane, permanent-magnet ferrite being set), the magneticstrength that is applied to the magnetic field on silicon chip and PDMS membrane surface is 200 Gausses; Have the ink droplet of magnetic field responsiveness under the effect in applied magnetic field, the ink droplet that spreads over quartz plate and PDMS membrane surface is drawn as cone-shaped ink droplet, makes ink droplet generation change in shape and volumetric shrinkage; Be dried, obtain having the anisotropic particles of shape and the equal anisotropy distribution of chemical constitution.The kind relation of the size of gained ink droplet and polymkeric substance used is little, with wetting property and the magnetic nano-particle Fe of quartz plate and PDMS membrane
3o
4concentration affects larger.Wherein the ink droplet on quartz plate, owing to being subject to the strong bonding strength of quartz plate, only has ink droplet and air contact part to be easily out of shape, and final formation bottom is large, the hat-shaped particle that top is little.Along with containing 5wt% magnetic nano-particle Fe as ink-jet printing ink
3o
4urethane blending liquid, contain 10wt% magnetic nano-particle Fe
3o
4epoxy resin blending liquid, contain 15wt% magnetic nano-particle Fe
3o
4the pyrrolidone variation of mixing up liquid, on quartz plate, the bottom depositional area of resulting anisotropic particles is 40 μ m, and the size at its anisotropic particles top is followed successively by 10 μ m, 15 μ m and 20 μ m.When solid substrate used is PDMS membrane, for the ink droplet that spreads over PDMS membrane surface, low bonding strength due to PDMS membrane, under the action of a magnetic field, the rapid travelling backwards of three-phase line of contact of ink droplet, cause forming the anisotropic particles of the high length-diameter ratio with pyramidal structure, wherein bore the sharp size of the end and cone close, and with magnetic nano-particle Fe
3o
4content increase and length-to-diameter ratio increased, depositional area reduces; Along with containing 5wt% magnetic nano-particle Fe as ink-jet printing ink
3o
4urethane blending liquid, contain 10wt% magnetic nano-particle Fe
3o
4epoxy resin blending liquid, contain 15wt% magnetic nano-particle Fe
3o
4the variation of mixing up liquid of polypyrrole alkane ketone, the size of the cone floorage of taper deposition is respectively 30 μ m, 20 μ m, 15 μ m; Chemical constitution by the cone point structure to ink droplet is analyzed, and finds magnetic nano-particle Fe
3o
4mainly be distributed in cone point part; And urethane, epoxy resin or polypyrrole alkane ketone are mainly distributed in semisphere cone bottom structure.
Embodiment 5.
At room temperature, the magnetic nano-particle Fe that is 60nm by particle diameter
2o
3be distributed to respectively the blending liquid that obtains respectively having magnetic field responsiveness in the aqueous dispersions of polyvinyl alcohol, wherein the magnetic nano-particle Fe in blending liquid
2o
3content be 1wt%, the content of polyvinyl alcohol is 20wt%, surplus is water; Magnetic nano-particle Fe
2o
3content be 8wt%, the content of polyvinyl alcohol is 20wt%, surplus is water; Magnetic nano-particle Fe
2o
3content be 15wt%, the content of polyvinyl alcohol is 20wt%, surplus is water; The blending liquid obtaining, respectively as ink-jet printing ink, is loaded into the ink-jet printing ink with magnetic field responsiveness obtaining respectively in the print cartridge of three ink-jet printers (aperture of the shower nozzle of ink-jet printer is 50 μ m).By three kinds of ink-jet printing inks be injected in respectively contact angle with water be 85 ° Polystyrene Film and with the contact angle of water be on the surface of poly tetrafluoroethylene of 110 °, then to arriving Polystyrene Film and poly tetrafluoroethylene surface and the uncured ink droplet with magnetic field responsiveness, apply the action of a magnetic field (above perpendicular to Polystyrene Film and poly tetrafluoroethylene, magnetic field being set), the magneticstrength that is applied to the magnetic field on Polystyrene Film and poly tetrafluoroethylene surface is 200 Gausses; Have the ink droplet of magnetic field responsiveness under the effect in applied magnetic field, the ink droplet that spreads over Polystyrene Film and poly tetrafluoroethylene surface is drawn as cone-shaped ink droplet, makes ink droplet generation change in shape and volumetric shrinkage; Be dried, obtain having the anisotropic particles of shape and the equal anisotropy distribution of chemical constitution.The kind relation of the size of gained ink droplet and polymkeric substance used is little, with wetting property and the magnetic nano-particle Fe of Polystyrene Film and poly tetrafluoroethylene
2o
3concentration affects larger.Wherein the ink droplet on Polystyrene Film, owing to being subject to the strong bonding strength of base material, only has ink droplet and air contact part to be easily out of shape, and final formation bottom is large, the hat-shaped particle that top is little.Along with containing magnetic nano-particle Fe as ink-jet printing ink
2o
3polyvinyl alcohol blending liquid in magnetic nano-particle Fe
2o
3content from 1wt%, to 8wt% and 15% variation, on Polystyrene Film, the bottom depositional area of resulting anisotropic particles is 80 μ m, and the size at its anisotropic particles top is followed successively by 10 μ m, 35 μ m and 40 μ m.When solid substrate used is poly tetrafluoroethylene, low bonding strength due to poly tetrafluoroethylene, under the action of a magnetic field, the rapid travelling backwards of three-phase line of contact of ink droplet, cause forming the anisotropic particles of the high length-diameter ratio with pyramidal structure, wherein bore the sharp size of the end and cone close, and with magnetic nano-particle Fe
2o
3content increase and particle deposition area and the sharp size of cone all reduced, length-to-diameter ratio increases; Along with containing 1wt% magnetic nano-particle Fe as ink-jet printing ink
2o
3polyvinyl alcohol blending liquid, contain 8wt% magnetic nano-particle Fe
3o
4polyvinyl alcohol blending liquid, contain 15wt% magnetic nano-particle Fe
2o
3the variation of polyvinyl alcohol blending liquid, the size of the cone floorage of the taper deposition of resulting Anisotropic Conical particle is respectively 50 μ m, 30 μ m, 10 μ m, and bore sharp undersized in the size of cone floorage; Chemical constitution by the cone point structure to ink droplet is analyzed, and finds magnetic nano-particle Fe
2o
3mainly be distributed in cone point part; And urethane, epoxy resin or polypyrrole alkane ketone are mainly distributed in semisphere cone bottom structure.
Embodiment 6.
At room temperature, the barium titanate nano particle that is 20nm and 100nm by particle diameter is distributed to respectively in the aqueous dispersions of urethane, obtain respectively six kinds of blending liquid with electric field response, wherein the particle diameter of the electrical response performance in blending liquid is that the content of 20nm or the particle diameter barium titanate nano particle that is 100nm is 1wt%, the content of urethane is 30wt%, and surplus is water; The particle diameter of electrical response performance is that the content of 20nm or the particle diameter barium titanate nano particle that is 100nm is 8wt%, and the content of urethane is 30wt%, and surplus is water; The particle diameter of electrical response performance is that the content of 20nm or the particle diameter barium titanate nano particle that is 100nm is 15wt%, and the content of urethane is 30wt%, and surplus is water; Using six kinds of blending liquid that obtain, respectively as ink-jet printing ink, the ink-jet printing ink that six kinds of obtaining are had to an electric field response is loaded into respectively in the print cartridge of six ink-jet printers (aperture of the shower nozzle of ink-jet printer is 20 μ m).It is on the polychloroethylene film of 78 ° that six kinds of ink-jet printing inks are injected in respectively to contact angle with water, then and the uncured ink droplet with electric field response surperficial to arrival polychloroethylene film applies electric field action and (electric field is set above polychloroethylene film, by plate condenser, produce flat field, strength of electric field is respectively 200V/cm and 400V/cm), the strength of electric field that is applied to the electric field on polychloroethylene film surface is respectively 200V/cm and 400V/cm; Have the ink droplet of electric field response under the effect of applied electric field, the ink droplet that spreads over polychloroethylene film surface is drawn as cone-shaped ink droplet, makes ink droplet generation change in shape and volumetric shrinkage; Be dried, obtain having the anisotropic particles of shape and the equal anisotropy distribution of chemical constitution.The particle diameter relation of the barium titanate nano particle of the size of resulting ink droplet and electrical response performance used is little, larger with concentration and the strength of electric field impact of the wetting property of polychloroethylene film and the barium titanate nano particle of electrical response performance.Wherein the ink droplet on polychloroethylene film, owing to being subject to the strong bonding strength of film, only has ink droplet and air contact part to be easily out of shape, and final formation bottom is large, the hat-shaped particle that top is little.When strength of electric field is 200V/cm, urethane blending liquid along with the barium titanate nano particle that contains 1wt% electrical response performance as ink-jet printing ink, the urethane blending liquid of the barium titanate nano particle that contains 8wt% electrical response performance, the variation that the urethane of the barium titanate nano particle that contains 15wt% electrical response performance mixs up liquid, on polychloroethylene film, the bottom depositional area of resulting anisotropic particles is 40 μ m, and the size at its anisotropic particles top is followed successively by 10 μ m, 15 μ m and 20 μ m.When strength of electric field is 400V/cm, urethane blending liquid along with the barium titanate nano particle that contains 1wt% electrical response performance as ink-jet printing ink, the urethane blending liquid of the barium titanate nano particle that contains 8wt% electrical response performance, the variation that the urethane of the barium titanate nano particle that contains 15wt% electrical response performance mixs up liquid, on polychloroethylene film, the bottom depositional area of resulting anisotropic particles is 40 μ m, and the size at its anisotropic particles top is followed successively by 15 μ m, 25 μ m and 30 μ m, chemical constitution by the cone point structure to ink droplet is analyzed, find that electroresponse barium titanate nano particle is mainly distributed in cone point part, and urethane is mainly distributed in semisphere cone bottom structure.
Embodiment 7.
At room temperature, the TiO 2 particles that is 20nm, 80nm and 100nm by particle diameter is distributed to respectively in the aqueous dispersions of polyoxyethylene glycol-diacrylate, obtain respectively nine kinds of blending liquid with electric field response, wherein the particle diameter of the electrical response performance in blending liquid is that the content of the titanium dioxide nano-particle of 20nm, 80nm or 100nm is 1wt%, the content of polyoxyethylene glycol-diacrylate is 20wt%, and surplus is water; The particle diameter of electrical response performance is that the content of the titanium dioxide nano-particle of 20nm, 80nm or 100nm is 8wt%, and the content of polyoxyethylene glycol-diacrylate is 20wt%, and surplus is water; The particle diameter of electrical response performance is that the content of the titanium dioxide nano-particle of 20nm, 80nm or 100nm is 15wt%, and the content of polyoxyethylene glycol-diacrylate is 20wt%, and surplus is water; Using nine kinds of blending liquid that obtain, respectively as ink-jet printing ink, the ink-jet printing ink that nine kinds of obtaining are had to an electric field response is loaded into respectively in the print cartridge of nine ink-jet printers (aperture of the shower nozzle of ink-jet printer is 20 μ m).Nine kinds of ink-jet printing inks are injected in respectively on the silicon chip and glass sheet surface that contact angle with water is 30 °, then to arriving silicon chip and glass sheet surface and the uncured ink droplet with electric field response, apply electric field action and (above perpendicular to silicon chip and glass sheet surface, electric field is set, the flat field being produced by plate condenser), the strength of electric field that is applied to the electric field of silicon chip and glass sheet surface is 350V/cm; Have the ink droplet of electric field response under the effect of applied electric field, the ink droplet that spreads over silicon chip and glass sheet surface is drawn as cone-shaped ink droplet, makes ink droplet generation change in shape and volumetric shrinkage; Be dried, obtain having the anisotropic particles of shape and the equal anisotropy distribution of chemical constitution.The particle diameter relation of the size of gained ink droplet and TiO 2 particles used is little, with the wetting property of silicon chip and sheet glass, the impact of the concentration of the titanium dioxide nano-particle of electric field response and strength of electric field is larger.Because the wetting property of silicon chip and sheet glass is approaching, little to the size impact of prepared particle.Wherein the ink droplet on silicon chip and sheet glass, owing to being subject to the strong bonding strength of silicon chip and sheet glass, only has ink droplet and air contact part to be easily out of shape, and final formation bottom is large, the hat-shaped particle that top is little.Polyoxyethylene glycol-diacrylate blending liquid along with the titanium dioxide nano-particle that contains 1wt% electrical response performance as ink-jet printing ink, polyoxyethylene glycol-diacrylate blending liquid of the titanium dioxide nano-particle that contains 8wt% electrical response performance, the variation of polyoxyethylene glycol-diacrylate blending liquid of the titanium dioxide nano-particle that contains 15wt% electrical response performance, on silicon chip and sheet glass, the bottom depositional area of resulting anisotropic particles is 60 μ m, and the size at its anisotropic particles top is followed successively by 10 μ m, 15 μ m and 20 μ m.Chemical constitution by the cone point structure to ink droplet is analyzed, and finds that electrical response performance titanium dioxide nano-particle is mainly distributed in cone point part; And polyoxyethylene glycol-diacrylate is mainly distributed in semisphere cone bottom structure.
Embodiment 8.
At room temperature, commercially available polyacrylic acid is distributed to respectively in the aqueous dispersions of urethane, obtains respectively three kinds of blending liquid with pH responsiveness, wherein the acrylic acid content in blending liquid is 1wt%, and the content of urethane is 20wt%, and surplus is water; Acrylic acid content in blending liquid is 8wt%, and the content of urethane is 20wt%, and surplus is water; Acrylic acid content in blending liquid is 1wt%, and the content of urethane is 20wt%, and surplus is water; Using three kinds of blending liquid that obtain, respectively as ink-jet printing ink, the ink-jet printing ink that three kinds of obtaining are had to a pH responsiveness is loaded into respectively in the print cartridge of three ink-jet printers (aperture of the shower nozzle of ink-jet printer is 20 μ m).Three kinds of ink-jet printing inks are injected in respectively on the polychloroethylene film surface that contact angle with water is 78 °, then will arrive polychloroethylene film surface and the uncured ink droplet with pH responsiveness and be placed in the atmosphere of the hydrogen chloride gas of pH=1.The ink droplet with pH responsiveness is owing to being subject to the effect that pH value is 1 hydrogen chloride gas, polyacrylic acid component in ink droplet can with urethane generation phase separation, gather the surface of ink droplet, the surface that obtains ink droplet is that polyacrylic acid forms, and the anisotropic particles that the chemical property anisotropy that the inside of ink droplet is urethane composition distributes.The size of ink droplet is main relevant to the wetting property of base material, and the increase of pH responsiveness material is little on the shape and size impact of ink droplet, the polyacrylic ratio on major effect ink droplet surface.Resulting ink droplet is hemispherical dome structure, and the depositional area of ink droplet is 40 μ m.By the chemical constitution of the structure of ink droplet is analyzed, the polyacrylic acid of finding to have pH responsiveness is mainly distributed in the surperficial part of semisphere ink droplet; And urethane is mainly distributed in the structure of domed bottom.
Embodiment 9.
At room temperature, by in the ultrasonic aqueous dispersions that is distributed to epoxy resin of commercially available Styrene And Chloroalkyl Acrylates segmented copolymer, obtain having the blending liquid of pH responsiveness, wherein the content of the Styrene And Chloroalkyl Acrylates segmented copolymer in blending liquid is 15wt%, the content of epoxy resin is 20wt%, and surplus is water; Using the blending liquid obtaining as ink-jet printing ink, the ink-jet printing ink with pH responsiveness obtaining is loaded in the print cartridge of ink-jet printer (aperture of the shower nozzle of ink-jet printer is 20 μ m).It is on the surface of PDMS membrane of 100 ° that ink-jet printing ink is injected in to contact angle with water, then will arrive PDMS membrane surface and the uncured ink droplet with pH responsiveness and be placed in the atmosphere of the hydrogen chloride gas of pH=3.The ink droplet with pH responsiveness is owing to being subject to the effect that pH value is 2 hydrogen chloride gas, Styrene And Chloroalkyl Acrylates segmented copolymer in ink droplet can with epoxy resin generation phase separation, gather the surface of ink droplet, the surface that obtains ink droplet is that Styrene And Chloroalkyl Acrylates segmented copolymer forms, and the anisotropic particles that the chemical property anisotropy that the inside of ink droplet is epoxy resin composition distributes.The size of ink droplet is main relevant to the wetting property of base material.Resulting ink droplet is hemispherical dome structure, and the depositional area of ink droplet is 30 μ m.By the chemical constitution of the structure of ink droplet is analyzed, the Styrene And Chloroalkyl Acrylates segmented copolymer of finding to have pH responsiveness is mainly distributed in the surperficial part of semisphere ink droplet; And epoxy resin is mainly distributed in the structure of domed bottom.
Embodiment 10.
At room temperature, commercially available vinylbenzene-2-vinyl pyridine segmented copolymer, poly 2 vinyl pyridine are obtained respectively having respectively the blending liquid of pH responsiveness in the ultrasonic aqueous dispersions that is distributed to polypyrrole alkane ketone, wherein the content of the vinylbenzene-2-vinyl pyridine segmented copolymer in blending liquid is 15wt%, the content of polypyrrole alkane ketone is 30wt%, and surplus is water; The content of poly 2 vinyl pyridine is 15wt%, and the content of polypyrrole alkane ketone is 30wt%, and surplus is water; Using two kinds of blending liquid that obtain as ink-jet printing ink, the ink-jet printing ink that two kinds of obtaining are had to a pH responsiveness is loaded into respectively in the print cartridge of two ink-jet printers (aperture of the shower nozzle of ink-jet printer is 50 μ m).It is on the poly tetrafluoroethylene surface of 110 ° that ink-jet printing ink is injected in respectively to contact angle with water, and then by arriving poly tetrafluoroethylene surface and the uncured ink droplet with pH responsiveness, to be placed in respectively pH value be in 9,10,11 ammonia atmosphere.There is the ink droplet of pH responsiveness due to the alkaline atmosphere effect being subject in ammonia, vinylbenzene-2-vinyl pyridine segmented copolymer in ink droplet or poly 2 vinyl pyridine can with polypyrrole alkane ketone generation phase separation, gather ink droplet surface, the surface composition of the ink droplet obtaining is vinylbenzene-2-vinyl pyridine segmented copolymer or poly 2 vinyl pyridine, and the anisotropic particles that the chemical property anisotropy that consists of polypyrrole alkane ketone of ink droplet inside distributes.The size of resulting ink droplet is main relevant to the wetting property of base material, affects not quite from the atmosphere of the kind of pH responsive polymer and different pH.Wherein the kind of responsive polymer affects the chemical constitution on ink droplet surface, and the speed that the impact of the pH value of ammonia atmosphere is separated is little on final chemical constitution impact.Resulting ink droplet is hemispherical dome structure, and the depositional area of ink droplet is 30 μ m.By the chemical constitution of the structure of ink droplet is analyzed, find that pH responsiveness vinylbenzene-2-vinyl pyridine segmented copolymer or poly 2 vinyl pyridine are mainly distributed in the surperficial part of semisphere ink droplet; And polypyrrole alkane ketone is mainly distributed in the structure of domed bottom.
Embodiment 11.
At room temperature, by the golden nanometer particle different from polyoxyethylene glycol deposition properties, Nano silver grain respectively in the ultrasonic aqueous dispersions that is distributed to polyoxyethylene glycol, obtain respectively the blending liquid that contains golden nanometer particle, Nano silver grain, wherein the content of the golden nanometer particle in blending liquid is 1wt%, the content of polyoxyethylene glycol is 15wt%, and surplus is water; The content of Nano silver grain is 8wt%, and the content of polyoxyethylene glycol is 15wt%, and surplus is water; Using two kinds of blending liquid that obtain as ink-jet printing ink, two kinds of ink-jet printing inks that contain the different golden nanometer particle of deposition properties or Nano silver grain that obtain are loaded into respectively in the print cartridge of two ink-jet printers (aperture of the shower nozzle of ink-jet printer is 10 μ m).It is on the surface of Polystyrene Film of 85 ° that ink-jet printing ink is injected in to contact angle with water, then by arriving Polystyrene Film surface and the uncured Polystyrene Film that contains the different blending ink droplet of deposition properties, to be placed in respectively temperature be 60 ℃, and humidity is 95%; Or temperature is 90 ℃, in the environment that humidity is 10%, place respectively 2 hours.Due to the golden nanometer particle in the ink droplet of ink-jet printing ink formation or the phase separation of Nano silver grain and polyoxyethylene glycol material, cause the different composition materials in ink droplet to be piled up at the different sites of ink droplet, wherein golden nanometer particle or Nano silver grain can be deposited in the top of ink droplet, and polyoxyethylene glycol material stacking is in the bottom of ink droplet, forms and form the anisotropic particles that anisotropy distributes.
Wherein the size of gained ink droplet is only relevant with the aperture of the shower nozzle of the wetting property of base material, the concentration of polymkeric substance and ink-jet printer, and with the content of golden nanometer particle or Nano silver grain, and the kind of polymkeric substance used is irrelevant.Resulting ink droplet is hemispherical dome structure, and the deposit size of ink droplet is 25 μ m.By the chemical constitution of the structure of ink droplet is analyzed, find that golden nanometer particle or Nano silver grain are mainly distributed in the surperficial part of semisphere ink droplet; And polyoxyethylene glycol is mainly distributed in the structure of domed bottom.
Embodiment 12.
At room temperature, by the TiO different from polyvinyl alcohol deposition properties
2nanoparticle, SiO
2nanoparticle obtains respectively containing TiO in the ultrasonic aqueous dispersions that is distributed to polyvinyl alcohol respectively
2nanoparticle, SiO
2the blending liquid of nanoparticle, the wherein TiO in blending liquid
2the content of nanoparticle is 1wt%, and the content of polyvinyl alcohol is 15wt%, and surplus is water; SiO
2the content of nanoparticle is 8wt%, and the content of polyvinyl alcohol is 15wt%, and surplus is water; Using two kinds of blending liquid that obtain as ink-jet printing ink, two kinds of obtaining are contained to the different TiO of deposition properties
2nanoparticle or SiO
2the ink-jet printing ink of nanoparticle is loaded into respectively in the print cartridge of two ink-jet printers (aperture of the shower nozzle of ink-jet printer is 50 μ m).It is on the polymethyl methacrylate film surface of 80 ° that ink-jet printing ink is injected in to contact angle with water, then the surperficial and uncured polymethyl methacrylate film that contains the different blending ink droplets of deposition properties of arrival polymethyl methacrylate film being placed in to temperature is 80 ℃, places 3 hours in the environment that humidity is 80%.Due to the TiO in the ink droplet of ink-jet printing ink formation
2nanoparticle or SiO
2the phase separation of nanoparticle and polyvinyl alcohol material, causes the different composition materials in ink droplet to be piled up at the different sites of ink droplet, wherein TiO
2nanoparticle or SiO
2nanoparticle can be deposited in the top of ink droplet, and polyvinyl alcohol material is deposited in the bottom of ink droplet, forms and forms the anisotropic particles that anisotropy distributes.
Wherein the size of gained ink droplet is only relevant with the aperture of the shower nozzle of the wetting property of base material, the concentration of polymkeric substance and ink-jet printer, with TiO
2nanoparticle or SiO
2the content of nanoparticle, and the kind of polymkeric substance used is all irrelevant.Resulting ink droplet is hemispherical dome structure, and the deposit size of ink droplet is 80 μ m.By the chemical constitution of the structure of ink droplet is analyzed, find TiO
2nanoparticle or SiO
2nanoparticle is mainly distributed in the surperficial part of semisphere ink droplet; And polyvinyl alcohol is mainly distributed in the structure of domed bottom.
Claims (10)
1. spray ink Printing is prepared a method for anisotropic particles in batches, it is characterized in that: the aqueous polymer dispersion that the concentration obtaining in using polymer dispersed to water is 10～30wt% is as ink-jet printing ink; Or responsiveness functional materials is distributed to the blending liquid that obtains in aqueous polymer dispersion as ink-jet printing ink, and wherein the content of the responsiveness functional materials in blending liquid is 1～15wt%, and the content of polymkeric substance is 10～30wt%, and surplus is water; Or the metal nanoparticle different from polymer deposition performance or inorganic oxide nanoparticles are distributed to the blending liquid that obtains in aqueous polymer dispersion as ink-jet printing ink, wherein the content of the metal nanoparticle in blending liquid or inorganic oxide nanoparticles is 1～15wt%, the content of polymkeric substance is 10～30wt%, and surplus is water; The ink-jet printing ink obtaining is loaded in the print cartridge of ink jet printing device, described ink-jet printing ink is injected on the surface of solid substrate, dry, obtain thering is the anisotropic particles that shape anisotropy distributes;
Or responsiveness functional materials is distributed to the blending liquid that obtains in aqueous polymer dispersion as ink-jet printing ink, and wherein the content of the responsiveness functional materials in blending liquid is 1～15wt%, and the content of polymkeric substance is 10～30wt%, and surplus is water; The ink-jet printing ink obtaining is loaded in the print cartridge of ink jet printing device, described ink-jet printing ink is injected on the surface of solid substrate, then to arriving solid substrate surface and uncured ink droplet, apply outfield stimulation, be dried, obtain having the anisotropic particles of shape and the equal anisotropy distribution of chemical constitution;
Or the metal nanoparticle different from polymer deposition performance or inorganic oxide nanoparticles are distributed to the blending liquid that obtains in aqueous polymer dispersion as ink-jet printing ink, wherein the content of the metal nanoparticle in blending liquid or inorganic oxide nanoparticles is 1～15wt%, the content of polymkeric substance is 10～30wt%, and surplus is water; The ink-jet printing ink obtaining is loaded in the print cartridge of ink jet printing device, after described ink-jet printing ink being injected on the surface of solid substrate, be positioned over temperature and be 60～90 ℃ and humidity from 10%～90% environment changing, obtain the anisotropic particles that chemical constitution anisotropy distributes;
Described responsiveness functional materials be selected from have magnetic field responsiveness particle, have electric field response particle, there is a kind of in the polymkeric substance of pH responsiveness.
2. method according to claim 1, is characterized in that: described polymkeric substance is selected from urethane, polyoxyethylene glycol, polyoxyethylene glycol-diacrylate, polyvinyl alcohol, epoxy resin, a kind of in polypyrrole alkane ketone.
3. method according to claim 1, is characterized in that: the described outfield stimulation that applies arranges magnetic field above perpendicular to solid substrate, to arriving solid substrate surface and the uncured ink droplet with magnetic field responsiveness, applies magnetic field; Or above perpendicular to solid substrate, electric field is set, to arriving solid substrate surface and the uncured ink droplet with electric field response, apply electric field; Or surface is placed in to acid atmosphere or alkaline atmosphere with the solid substrate of the ink droplet of the uncured polymkeric substance with pH responsiveness, to arriving, solid substrate surface and the uncured ink droplet with pH responsiveness carry out acid atmosphere or alkaline atmosphere is processed.
4. according to the method described in claim 1 or 3, it is characterized in that: the particle diameter of the described particle with magnetic field responsiveness is 20～100nm; Be selected from Z 250 particle or ferric oxide particle;
The particle diameter of the described particle with electric field response is 20～100nm; Be selected from barium titanate particles or TiO 2 particles;
The described polymkeric substance with pH responsiveness is selected from a kind of in polyacrylic acid, Styrene And Chloroalkyl Acrylates segmented copolymer, poly 2 vinyl pyridine, vinylbenzene-2-vinyl pyridine segmented copolymer.
5. method according to claim 3, is characterized in that: the described magnetic field that applies is that the magneticstrength scope that makes to be applied to the magnetic field on solid substrate surface is 100～200 Gausses;
The described electric field that applies is that the strength of electric field scope that makes to be applied to the electric field on solid substrate surface is 200～400V/cm;
Described acid atmosphere is the acid atmosphere that the pH value scope that produced by hydrochloric acid is 1～3, and described alkaline atmosphere is the alkaline atmosphere that the pH value scope that produced by ammoniacal liquor is 9～11.
6. method according to claim 1, is characterized in that: described metal nanoparticle is golden nanometer particle or Nano silver grain;
Described inorganic oxide nanoparticles is TiO
2nanoparticle or SiO
2nanoparticle.
7. according to the method described in claim 1 or 3, it is characterized in that: described solid substrate is have hydrophilic solid substrate, the super-hydrophobic and low solid substrate sticking, the low solid substrate sticking or have the solid substrate that height sticks performance;
It is described that to have hydrophilic solid substrate be that the contact angle on water and solid substrate surface is the solid substrates of 30～85 degree; Described solid substrate is selected from common glass baseplate, polymeric substrate, quartz plate, a kind of in silicon chip;
The described super-hydrophobic and low solid substrate sticking is clean and coarse solid substrate to be placed in to the silicon fluoride atmosphere of 80 ℃ within 3～8 hours, obtain, and the surface of this base material and the contact angle of water are 150～160 °; Described coarse solid substrate is that solid substrate is placed in to the SiO that concentration is 0.8～5wt%
2in aqueous dispersions, soak and obtain for 1～3 minute; Described solid substrate is selected from common glass baseplate, polymeric substrate, quartz plate, a kind of in silicon chip;
The described low solid substrate sticking is that clean solid substrate is obtained for 3～8 hours in the silicon fluoride atmosphere of 80 ℃; Described solid substrate is selected from common glass baseplate, polymeric substrate, quartz plate, a kind of in silicon chip;
It is described that to have the solid substrate that height sticks performance be clean glass, quartz plate or silicon chip.
8. method according to claim 7, is characterized in that: described polymeric substrate is selected from a kind of in poly tetrafluoroethylene, Polystyrene Film, polymethyl methacrylate film, polyvinyl acetate (PVA) film, PDMS membrane, polyethylene film, polychloroethylene film, PET film.
9. the anisotropic particles that the anisotropy that prepared by the method described in claim 1～8 any one distributes, is characterized in that: the anisotropic particles that described anisotropy distributes is to have anisotropic particles that shape anisotropy distributes, have the anisotropic particles that anisotropic particles that shape and the equal anisotropy of chemical constitution distribute or chemical constitution anisotropy distribute;
The described anisotropic particles with shape anisotropy distribution is the semisphere particle of annular particle, different length-to-diameter ratios, and the material of its anisotropic particles is polymkeric substance;
The described anisotropic particles with shape and the equal anisotropy distribution of chemical constitution is, taper particle or hat-shaped particle, responsiveness functional materials be take as main in the top of the top of its taper particle or hat-shaped particle, and polymer materials be take as main in the bottom of the bottom of taper particle or hat-shaped particle;
One end that the anisotropic particles that described chemical constitution anisotropy distributes is anisotropic particles is metal nanoparticle, and the other end is polymkeric substance; Or one end of anisotropic particles is polymkeric substance, the other end is inorganic oxide particle.
10. the anisotropic particles that anisotropy according to claim 9 distributes, is characterized in that: described polymkeric substance is selected from urethane, polyoxyethylene glycol, polyoxyethylene glycol-diacrylate, polyvinyl alcohol, epoxy resin, a kind of in polypyrrole alkane ketone;
Described responsiveness functional materials be selected from have magnetic field responsiveness particle, have electric field response particle, there is a kind of in the polymkeric substance of pH responsiveness;
The particle diameter of the described particle with magnetic field responsiveness is 20～100nm; Be selected from Z 250 particle or ferric oxide particle;
The particle diameter of the described particle with electric field response is 20～100nm; Be selected from barium titanate particles or TiO 2 particles;
The described polymkeric substance with pH responsiveness is selected from a kind of in polyacrylic acid, Styrene And Chloroalkyl Acrylates segmented copolymer, poly 2 vinyl pyridine, vinylbenzene-2-vinyl pyridine segmented copolymer;
Described metal nanoparticle is golden nanometer particle or Nano silver grain;
Described inorganic oxide nanoparticles is TiO
2nanoparticle or SiO
2nanoparticle.
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Application publication date: 20140924 |