CN109879246B - Single-nanoparticle precision one-dimensional magnetic assembly array and preparation method and application thereof - Google Patents
Single-nanoparticle precision one-dimensional magnetic assembly array and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the field of one-dimensional arrays, and discloses a single-nanoparticle precision one-dimensional magnetic assembly array, a preparation method and application thereof, wherein the preparation method of the single-nanoparticle precision one-dimensional magnetic assembly array comprises the following steps: (1) jetting aqueous ink containing magnetic nanoparticles onto the surface of a substrate in an array form by an ink-jet printing method, wherein the receding angle of the surface of the substrate is 3-30 degrees; and (2) drying and assembling the ink printed on the surface of the substrate under the induction action of the magnetic field. The preparation method is simple and rapid, saves cost, and can be used for preparing the single-nanoparticle precision one-dimensional magnetic assembly array with controllable size and uniform appearance in a large scale.
Description
Technical Field
The invention relates to the field of one-dimensional arrays, in particular to a single-nanoparticle precision one-dimensional magnetic assembly array and a preparation method and application thereof.
Background
The interaction between axial particles of the one-dimensional magnetic nano-assembly body enables the one-dimensional magnetic nano-assembly body to have anisotropic physical properties, so that the one-dimensional magnetic nano-assembly body has wide application in the aspects of heat generation regulation, cell differentiation, magnetic field induction, structural color display and the like. Due to the head-to-head structure of the single-nanoparticle precision one-dimensional magnetic nano assembly, a certain number of particles have larger length-diameter ratio and more concentrated axial inter-particle interaction, so that the magnetic anisotropy is larger, the sensitivity of magnetic field induction can be remarkably increased, and the attention is more extensive.
At present, in order to obtain a one-dimensional magnetic nano-assembly, a top-down micro-nano processing method such as electron beam lithography, focused ion beam lithography and a template method is generally adopted, but these methods are not only expensive and low in efficiency, but also are difficult to obtain a one-dimensional magnetic nano-assembly with single nano-particle precision. In addition, researchers also adopt a liquid phase external field induction method to prepare the one-dimensional magnetic nano assembly, but the obtained one-dimensional magnetic nano assembly still has the problems of different lengths and uneven appearance. Therefore, it is urgent to explore a simple, fast and cost-effective method for preparing a one-dimensional magnetic nano-assembly with controllable size and uniform morphology and single nano-particle precision.
Ink jet printing is the use of printing tiny droplets to confine particles in a space, and the ordered assembly of particles is controlled by varying the droplets and the substrate. To date, inkjet printing-based particle assembly has primarily involved isotropic ordered assembly of nanoparticles. For example, m.kuang et al, Inkjet Printing Patterned photo Crystal for Wide Viewing-Angle display by Controlling the Sliding of the Sliding Three PhaseContact line.adv.opt.mater.2014,2, 34; wu et al, Printing Patterned Fine 3D structures by Manipulating the thread Phase Contact line adv Funct Mater.2015,25,2237. And so far, the anisotropic assembly of single nanoparticles based on ink-jet printing has not been reported.
Disclosure of Invention
The invention aims to solve the problems of complex preparation method, uneven appearance and the like of a one-dimensional magnetic nano assembly in the prior art, and provides a single-nanoparticle precision one-dimensional magnetic assembly array and a preparation method and application thereof.
In order to achieve the above object, the present invention provides a method for preparing a single-nanoparticle precision one-dimensional magnetic assembly array, comprising the following steps:
(1) jetting aqueous ink containing magnetic nanoparticles onto the surface of a substrate in an array form by an ink-jet printing method, wherein the receding angle of the surface of the substrate is 3-30 degrees; and
(2) and under the induction action of a magnetic field, drying and assembling the ink array printed on the surface of the substrate.
The invention provides a single-nanoparticle precision one-dimensional magnetic assembly array prepared by the method.
The third aspect of the invention provides an application of a single-nanoparticle precision one-dimensional magnetic assembly array in the fields of magnetic field induction, cell differentiation, heat generation modulation and anti-counterfeiting display.
Compared with the prior art, the invention obtains the one-dimensional magnetic assembly array with controllable size precision and single particle precision by the ink-jet printing method with simple and convenient process and low cost. The magnetic ink for ink-jet printing is induced by a magnetic field, so that superparamagnetic nano particles limited in dispersed micro liquid drops are subjected to dipole attraction to realize head-to-head assembly of single particles penetrating into lines; meanwhile, the three-phase line does not slide enough due to the adoption of the base material with the low receding angle, the particles cannot be pushed to move inwards in the drying process, the one-dimensional assembly appearance is kept in the drying process, the one-dimensional magnetic anisotropy controllable assembly with high-length-diameter ratio single-nanoparticle precision can be finally realized, and the agglomeration of the single nanoparticles is avoided. The preparation method is simple and rapid, saves cost, can be used for preparing the one-dimensional magnetic assembly array with single nano-particle precision, controllable size precision, uniform appearance and high length-diameter ratio on a large scale, and has important significance for popularizing the application of the one-dimensional magnetic assembly array in the fields of magnetic field induction, cell differentiation, heat production modulation, anti-counterfeiting display and the like.
Drawings
FIG. 1 is a schematic diagram of a method for preparing a single nanoparticle precision one-dimensional assembly array by ink-jet printing under the induction of a magnetic field according to the present invention.
Fig. 2 is a dark field microscope image of a single nanoparticle precision one-dimensional magnetic assembly array prepared in example 1.
Fig. 3 is an electron microscope image of a single nanoparticle precision one-dimensional magnetic assembly array prepared in example 1.
Fig. 4 is a magnetic hysteresis loop diagram of a single-nanoparticle precision one-dimensional magnetic assembly array prepared in example 1 under different magnetic field directions.
Fig. 5 is a dark-field microscope photograph of the one-dimensional magnetic assembly obtained by inducing under different magnetic field directions in example 1, wherein the angles are 90 °, 60 ° and 45 °.
Fig. 6 is a photomicrograph of the nanoparticles induced by the magnetic field of example 1 at various stages on a substrate with a receding angle of 15.3 °.
Fig. 7 is a photomicrograph of the nanoparticles induced by the magnetic field in comparative example 1 at various stages on a substrate with a receding angle of 63.4 °.
Fig. 8 is a dark field micrograph (a) of the deposit after droplet drying in example 1 with the application of a magnetic field and a dark field micrograph (b) of the deposit after droplet drying in comparative example 2 without the application of a magnetic field.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
According to the invention, the preparation method of the one-dimensional magnetic assembly array comprises the following steps:
(1) jetting aqueous ink containing magnetic nanoparticles onto the surface of a substrate in an array form by an ink-jet printing method, wherein the receding angle of the surface of the substrate is 3-30 degrees; and
(2) and under the induction action of a magnetic field, drying and assembling the ink array printed on the surface of the substrate.
The concentration of the ink of the present invention reflects the number of particles within a droplet, determining the distance and interaction between the particles. The interparticle distances of the same concentration are also different due to the different spreading area within the droplets of the phase. Therefore, in the range of 3-30 degrees of the receding angle (RCA), the RCA is smaller, the spreading area of the liquid drop is small, and the smaller concentration can meet the requirement of the suction distance of the needed particles; and vice versa. In ultra-low concentration droplets, the interparticle forces are very weak and are not sufficient to attract their assembly. Increasing the drop concentration, adjacent particles assemble nearby. Further increasing the ink drop concentration, the attractive force between the dipoles is enough to attract all the particles to assemble into an assembly with single nanometer particle precision. When the ink droplets are too thick, on the one hand the droplets are not sufficient to take up assemblies larger than their spreading diameter, and on the other hand the short lines formed during assembly coalesce laterally. It is worth noting that the formation of single particle precision one-dimensional magnetic assemblies is guaranteed just as the printed ink droplets confine the particles in discrete droplets, so that the "head-to-head" assembly can occur before lateral coalescence by adjusting the concentration. Therefore, the invention prepares the single-particle precision one-dimensional assembly with different lengths by controlling the ink concentration in a certain range.
In the step (1), the content of the magnetic nanoparticles in the magnetic nanoparticle-based aqueous ink is 0.001 to 0.1% by weight. For example, any value in the range of 0.001%, 0.005%, 0.01%, 0.02%, 0.05%, 0.08%, 0.1%, and any two of these values may be selected, and preferably 0.005% to 0.02%.
In the invention, the saturated magnetic moment refers to the magnetic moment of all atoms in an object under the action of an external magnetic field at a certain temperature and can be orderly arranged in a certain direction, and the total magnetic moment is the saturated magnetic moment at the temperature. According to the invention, the magnetic nanoparticles have a saturation moment of 30 to 90 emu/g. For example, any value from the range of 30emu/g, 40emu/g, 45emu/g, 50emu/g, 55emu/g, 60emu/g, 65emu/g, 70emu/g, 75emu/g, 80emu/g, 90emu/g and any two of these values may be selected, preferably 30-80 emu/g.
In the invention, the magnetic nanoparticles are a nanoscale magnetic material, have quantum size effect, surface effect, small-size effect, macroscopic quantum tunneling effect and the like, and have superparamagnetism, good magnetic conductivity, compatibility and the like. According to the invention, the magnetic nanoparticles have a particle size of 40-1000 nm. For example, any value in the range of 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 150nm, 200nm, 250nm, 300nm, 315nm, 350nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1000nm and any two of these values may be selected, and preferably 100nm and 600nm are selected.
According to the invention, the magnetic component in the magnetic nanoparticles can be selected from ferroferric oxide, gamma-ferric oxide, cobalt ferrite, nickel ferrite, cobalt oxide or nickel oxide.
According to the invention, the magnetic nanoparticle-based aqueous ink contains a single-component, two-component or multi-component aqueous solvent with a boiling point of 100-300 ℃, and preferably the boiling point of 120-250 ℃.
Preferably, the one-component aqueous solvent is selected from ethylene glycol, propylene glycol, diethylene glycol, glycerol, dimethyl sulfoxide, N-methylpyrrolidone, N-dimethylacetamide, formamide or acetamide;
preferably, the two-component aqueous solvent is selected from two of water, ethylene glycol, propylene glycol, diethylene glycol, glycerol, dimethyl sulfoxide, N-methylpyrrolidone, N-dimethylacetamide, formamide and acetamide;
preferably, the multi-component aqueous solvent is selected from a plurality of water, ethylene glycol, propylene glycol, diethylene glycol, glycerol, dimethyl sulfoxide, N-methylpyrrolidone, N-dimethylacetamide, formamide and acetamide.
In the invention, the solvent with high boiling point and low surface tension is added, on one hand, the printing is facilitated for adjusting the viscosity and the surface tension of the ink, on the other hand, the volatilization speed is reduced, so that the particles in the liquid drop have enough time to complete the assembly, and the systematic research on the behavior of the tiny liquid drop under the induction of a magnetic field is facilitated.
According to a preferred embodiment of the present invention, the magnetic nanoparticles provided by the present invention are prepared by coating a hydrophilic polymer on the surface of the magnetic component by a hydrothermal method to obtain nanoparticles composed of micro-clusters, such structure can simultaneously ensure particle size, superparamagnetic property and hydrophilic property. The hydrophilic polymer can be selected from polyacrylamide, benzene sulfonic acid maleic anhydride copolymer, etc.
In a preferred embodiment, the present invention provides a method for preparing an aqueous ink containing magnetic nanoparticles, which comprises uniformly mixing magnetic nanoparticles with a dispersion solvent, and ultrasonically dispersing the obtained mixed solution at an ultrasonic frequency of 50-100W (for example, any value in a range formed by any two of these point values) for 5min-2h (for example, any value in a range formed by any two of these point values, 10min, 15min, 20min, 30min, 1h, 1.5h, 2 h), thereby achieving stable dispersion performance of the magnetic nanoparticles in water; and finally, removing impurities by using a filter with the filter membrane pore size of 2-20 μm (for example, any value in a range formed by 2 μm, 5 μm, 10 μm, 20 μm and any two of the values can be selected), thus obtaining the magnetic nanoparticle-based aqueous ink.
In the invention, an ultrasonic instrument KH3200B from Kunshan grass ultrasonic instrument Limited is adopted to carry out ultrasonic dispersion at an ultrasonic frequency of 50-100W.
In the present invention, the smoothness, cleanliness and uniformity of the substrate surface all have an effect on the contact angle. The receding angle is the contact angle between the liquid and the wetted or dewetting substrate, as is the advancing angle, and the receding angle is the dynamic contact angle, which is a measure of the extent of slippage on the substrate surface and also represents the capillary force during drying of a droplet on the substrate surface. According to the invention, in step (1), the receding angle of the base surface is 3 ° to 30 °, and for example, any value in the range of 3 °, 7.3 °, 10.7 °, 11.5 °, 12 °, 15.3 °, 15.9 °, 17.5 °, 22.0 °, 25.5 °, 28.8 °, 30 °, and any two of these values, preferably 7.3 ° to 28.8 °, may be selected.
In the step (1), the surface of the substrate may be untreated or may be modified by plasma sputtering or a silane coupling agent.
According to the invention, the gas used for plasma sputtering is selected from oxygen or air, the sputtering power is 5-50W, and the sputtering time is 10-50 s.
In the present invention, the surface of the substrate was treated by using an Ompus plasma science and technology Ltd, DT02S low temperature plasma processor.
According to the invention, the silane coupling agent modification is that the substrate is heated for 2 to 12 hours (for example, optionally 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours and any value in the range of any two of the point values, preferably 3 to 5 hours) in an oven with a silane coupling agent atmosphere at 80 to 120 ℃ (for example, optionally 80 ℃, 90 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃ and any value in the range of any two of the point values, preferably 115 ℃ to 120 ℃);
preferably, the silane coupling agent is selected from 3- (2, 3-glycidoxy) propyltrimethoxysilane or 3-mercaptopropyltrimethoxysilane.
According to the present invention, the substrate may be selected from the group consisting of a silicon wafer, a glass sheet, a quartz sheet, a mica sheet, a metal sheet (e.g., an aluminum sheet, a copper sheet, etc.) and a polymer sheet (e.g., a polyimide sheet, a polyethylene terephthalate sheet, etc.), preferably a silicon wafer, a quartz sheet or a mica sheet.
In step (1), the volume of the ink droplets ejected onto the substrate surface is 10 to 100pL, and for example, may be selected from any value in the range of 10pL, 20pL, 30pL, 40pL, 50pL, 60pL, 70pL, 80pL, 90pL, 100pL and any two of these point values, and preferably 10 to 40 pL.
In the present invention, ink-jet printing was performed with a 10pL head using a Dimatix 2800 ink-jet printer from Fujifilm corporation, japan, and ink droplets of different volumes were obtained by controlling the array pattern.
The preset array of the present invention can be obtained by computer software, and the gap of the preset array is 100-1000 μm, for example, any value in the range of 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, 1000 μm and any two of these values can be selected; preferably 100-300 μm.
In step (2), the magnetic field is a uniform magnetic field provided by an electromagnetic field or a ferromagnetic field, and the magnetic field strength is 50-500mT, for example, any value in the range of 50mT, 100mT, 200mT, 300mT, 400mT, 500mT and any two of these values can be selected, preferably 100mT and 400 mT.
In step (2), the conditions of the drying temperature and relative humidity in the magnetic field may be those conventional in the art as long as ice is not condensed, for example, the drying temperature is 5 to 25 ℃ and the relative humidity is 20 to 90%.
The invention also provides a one-dimensional magnetic assembly array prepared by the method.
The invention also provides the application of the one-dimensional magnetic assembly array in the fields of magnetic field induction, cell differentiation, heat generation modulation and anti-counterfeiting display.
The present invention will be described in detail with reference to specific examples, but the present invention is not limited thereto.
In the following examples, the test methods and raw materials are referred to as follows:
contact angle: the measurement was carried out by means of a contact angle meter, OCA20 from DataPhysics, Germany, using a glycol solution with a mass fraction of 80%.
Back off angle: the measurement was carried out by means of a DCAT 11 dynamic contact angle meter from DataPhysics, Germany, using a glycol solution with a mass fraction of 80%.
Magnetic nanoparticle saturation moment: measuring with superconducting quantum interferometer magnetometer, specifically placing magnetic dispersion liquid in packaged plastic shell, with maximum magnetic field intensity (H) of 106A/m, the measurement temperature is 300K.
Magnetic field strength: the measurement is carried out by adopting a PPMS-9 physical property test system of the American Quantum Design company.
The morphology characterization of the single-nanoparticle precision one-dimensional magnetic array: measured by a Scanning Electron Microscope (SEM) using S-4800, JEOL Ltd.
Atomic spatial resolution: measured using a Multimode 8 Atomic Force Microscope (AFM) from Bruker, Germany.
Magnetic gradient distribution: measured using a Multimode 8 Magnetic Force Microscope (MFM) from Bruker, Germany.
The room temperature means 23. + -. 2 ℃.
Preparing ferroferric oxide-benzenesulfonic acid Maran anhydride copolymer magnetic spheres: see J.Gao et al, One-stepSolvothermal Synthesis of high ply Water-soluble, novel Charge Tarelserparamagnetic Fe3O4Colloidal Nanocrystal Clusters.Nanoscale 2013,5,7026-7033.
Preparing zinc ferrite-polyacrylamide nano magnetic spheres: see W.Cheng et al, high way Water-solvent Superparaimaging ferromagnetic Spheres with Composition and size. chem.Eur.J.2010,16, 3608-phase 3612.
In the case where no particular mention is made, the starting materials used are commercially available products in which:
poly (styrenesulfonic acid maleic anhydride) sodium salt (PSSMA): Sigma-Aldrich, USA, Mw-20000.
3- (2, 3-Glycidoxy) Propyltrimethoxysilane (GPTS): fluorochem chemical Co., Ltd, UK;
n-Decyltrichlorosilane (DTCS): fluorochem chemical Co., Ltd, UK.
Examples 1-3 are presented to illustrate one-dimensional magnetic assembly arrays, methods of preparation and applications of the present invention with single nanoparticle precision.
Example 1:
1. the preparation of the one-dimensional magnetic assembly array with single nano-particle precision comprises the following steps:
(1) the RCA of a cut untreated polished silicon wafer (the thickness: 380 +/-10 mu m, purchased from semiconductor research institute of Tianjin) is 15.3 degrees for later use;
(2) the ferroferric oxide-benzene sulfonic acid Maran anhydride copolymer magnetic sphere, namely the ferroferric oxide nano microsphere coated by poly (styrene sulfonic acid Maran anhydride) sodium salt is prepared by a hydrothermal method, 0.5g of PSSMA is dissolved in 20ml of ethylene glycol, and then 0.54g of FeCl is added in sequence3·6H2O and 1.5g Na3C6H5O7(ii) a Magnetically stirring the mixed liquid at normal temperature for 3 hours, transferring the mixed liquid into a 25ml reaction kettle, and reacting at 200 ℃ for 12 hours; when the temperature is reduced to normal temperature, washing for 3 times by using deionized water and ethanol mixed liquor to obtain superparamagnetic nano particles, wherein the saturation magnetic moment is 50emu/g, the nano particle structure is uniform, and the particle size is about 315nm for later use;
(3) carrying out ultrasonic dispersion on ferroferric oxide-benzenesulfonic acid-maleic anhydride copolymer magnetic spheres with the mass fraction of 0.02%, the saturation magnetic moment of 50emu/g and the particle size of 315nm in a mixed solvent of deionized water and ethylene glycol in a mass ratio of 2:8 at an ultrasonic frequency of 80W for 3h, and finally removing impurities by using a filter with a filter membrane aperture of 10 mu m to obtain magnetic nanoparticle-based water-based ink for later use;
(4) loading the obtained magnetic nanoparticle-based aqueous ink into an ink cartridge (DMP2800 ink cartridge) of an ink-jet printer at room temperature, and printing the ink onto the surface of a high-adhesion substrate with 15.3 DEG RCA by the ink-jet printer according to an array pattern with a gap of 100 mu m and an ink drop volume of 10 pL;
(5) the printed substrate was rapidly transferred to a magnetic field (consisting of two parallel rubidium iron boron magnets, 30 x 10mm, purchased from commercial magnets) with a magnetic field strength of 180mT, assembled and dried under the induction of the magnetic field at a drying temperature of 20 ℃ and a relative humidity of 50% to obtain a one-dimensional magnetic assembly array with single nanoparticle precision, as shown in fig. 1.
As can be seen from FIG. 2, the single-nanoparticle precision one-dimensional magnetic assembly array has a neat structure and consistent direction; in the SEM image of fig. 3(a), the line length is about 31.0 μm, and in the local SEM enlarged view of fig. 3(b), it can be seen that the single one-dimensional assembly is single nanoparticle accurate, and each particle is connected end to end.
2. Application of one-dimensional magnetic assembly array with single nano-particle precision
The printed one-dimensional magnetic assembly array with single nanoparticle precision is placed in test magnetic fields in different directions to test a magnetic hysteresis loop, so that the change of the saturation magnetization of the one-dimensional array of single-precision particles along with the direction of the magnetic field is obtained, as shown in fig. 4, the included angle between the direction of the test magnetic field and the orientation direction of the one-dimensional array is increased, and the saturation magnetization is reduced. It is worth pointing out that the ratio of the saturation magnetization in the direction of the magnetic field parallel to the one-dimensional direction of the assembly to the saturation magnetization in the perpendicular direction is up to 6.03 times. It can be seen that the angle dependence of the magnetization of the one-dimensional array ensures high magnetic field sensitivity, and has great significance for simulating the direction of the biological induction geomagnetic field.
In addition, the single-particle precision magnetic one-dimensional magnetic assemblies are assembled under magnetic fields of different angles, and assemblies of different angles can be obtained, as shown in fig. 5(a), (b), and (c). The direction of the assembly body and the arrangement pattern of the assembly body are combined according to the phenomenon, and the dual information is utilized to realize application in the anti-counterfeiting display field.
In addition, the single-particle precision magnetic one-dimensional magnetic assembly can also have potential application in the fields of heat production regulation, cell differentiation, heat production modulation and the like.
Example 2:
the preparation of the one-dimensional magnetic assembly array with single nano-particle precision comprises the following steps:
(1) sputtering the cut mica sheet by using oxygen plasma, wherein the sputtering power is 20W, and the sputtering time is 10s, so as to obtain a high-adhesion base material with a receding angle of 7.3 degrees for later use;
(2) 0.25mmol of ZnCl2、0.5mmol FeCl3·6H2O、1.5mmol C6H5Na3O7·2H2O and 3mmol of uric acid were dissolved in 20mL of distilled water, and 0.3g of polyacrylamide was added to the above solution. The mixed liquid was magnetically stirred at room temperature for 3 hours, and then transferred to a 25ml reaction vessel and reacted at 200 ℃ for 12 hours. When the temperature is close to normal temperature, washing the mixture for three times by using deionized water and ethanol mixed solution to obtain zinc iron zinc ferrite Zn coated by the monodisperse polyacrylamide0.41Fe0.59Fe2O4Magnetic ball, namely zinc iron ferrite-polyacrylamide nano magnetic ball, for standby.
(3) Carrying out ultrasonic dispersion on zinc ferrite iron-polyacrylamide nano magnetic spheres with the mass fraction of 0.01%, the saturation magnetic moment of 40emu/g and the particle size of 100nm in a mixed solvent of deionized water and ethylene glycol with the mass ratio of 4:6 at the ultrasonic frequency of 50W for 4h, and finally removing impurities by using a filter with the filter membrane aperture of 5 mu m to obtain magnetic nano particle-based water-based ink for later use;
(4) loading the obtained magnetic nanoparticle-based aqueous ink into an ink box of an ink-jet printer at room temperature, and printing the ink onto the surface of a high-adhesion substrate with RCA of 7.3 DEG by the ink-jet printer according to an array pattern with a gap of 600 mu m and an ink drop volume of 40 pL;
(5) and (3) rapidly transferring the printed substrate to a magnetic field with the magnetic field intensity of 400mT, assembling and drying under the induction of the magnetic field at the drying temperature of 15 ℃ and the relative humidity of 30% to obtain the one-dimensional magnetic assembly array with single nanoparticle precision, as shown in figure 1.
Example 3:
the preparation of the one-dimensional magnetic assembly array with single nano-particle precision comprises the following steps:
(1) heating the cut polished silicon wafer (the thickness is 380 +/-10 mu m, purchased from semiconductor research institute of Tianjin) in an oven with GPTS atmosphere at 120 ℃ for 3h to obtain a high-adhesion base material with RCA of 28.8 ℃ for later use;
(2) performing ultrasonic dispersion on ferroferric oxide-benzenesulfonic acid-maleic anhydride copolymer magnetic spheres (the preparation method is the same as that in example 1) with the mass fraction of 0.005%, the saturation magnetic moment of 80emu/g and the particle size of 600nm in a mixed solvent of deionized water and glycerol with the mass ratio of 6:4 at the ultrasonic frequency of 60W for 1h, and finally removing impurities by using a filter with the filter membrane aperture of 20 mu m to obtain magnetic nanoparticle-based water-based ink for later use;
(3) the obtained magnetic nanoparticle-based aqueous ink was loaded into an ink cartridge of an inkjet printer at room temperature, and the ink was printed by the inkjet printer in an array pattern with a gap of 150 μm and an ink droplet volume of 10pL onto a surface of a highly adhesive substrate with RCA of 28.8 °.
(4) And (3) rapidly transferring the printed substrate to a magnetic field with the magnetic field intensity of 100mT, assembling and drying under the induction of the magnetic field at the drying temperature of 10 ℃ and the relative humidity of 20 percent to obtain the one-dimensional magnetic assembly array with single nanoparticle precision, as shown in figure 1.
Comparative example 1
A single nanoparticle precision one-dimensional magnetically assembled array was prepared as in example 1, except that the polished silicon wafer was modified by DTCS to give a high back off angle wafer with RCA of 63.4 °.
Through microscope observation, on a low-receding-angle substrate with 15.3-degree RCA, particles are firstly assembled to a one-dimensional shape, and in the process of drying liquid drops, a three-phase line is pinned on the substrate, so that the shape of an assembly is not influenced, as shown in figure 6. On the high receding angle substrate with RCA of 63.4 °, the particles are assembled into a one-dimensional morphology first, but during the drying process, the three-phase line slides inward, the three-phase line is compressed and shortened, and finally, an aggregate is formed, as shown in fig. 7.
Comparative example 2
A single nanoparticle precision one-dimensional magnetically assembled array was prepared as in example 1, except that no magnetic field was applied and dried. As can be seen from a comparison of fig. 8(a) and 8(b), the particles form a one-dimensional assembly under the application of the magnetic field; the particles are uniformly dispersed on the substrate without the application of a magnetic field.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (25)
1. A preparation method of a single-nanoparticle precision one-dimensional magnetic assembly array is characterized by comprising the following steps:
(1) jetting aqueous ink containing magnetic nanoparticles onto the surface of a substrate in an array form by an ink-jet printing method, wherein the receding angle of the surface of the substrate is 3-30 degrees; and
(2) under the induction of a magnetic field, drying and assembling the ink array printed on the surface of the substrate;
the single one-dimensional assembly is the single nanoparticle precision, and each particle is connected end to end.
2. The method according to claim 1, wherein in step (1), the content of the magnetic nanoparticles in the magnetic nanoparticle-based aqueous ink is 0.001 to 0.1% by weight.
3. The method according to claim 2, wherein in step (1), the content of the magnetic nanoparticles in the magnetic nanoparticle-based aqueous ink is 0.005 to 0.02 wt.%.
4. The method of claim 1 or 2, wherein the magnetic nanoparticles have a saturation magnetic moment of 30-90 emu/g; the particle size is 40-1000 nm.
5. The method of claim 4, wherein the magnetic nanoparticles have a saturation magnetic moment of 30-80 emu/g; the particle size is 100-600 nm.
6. The method according to claim 1 or 2, wherein the magnetic component in the magnetic nanoparticles is selected from at least one of ferroferric oxide, gamma-ferric oxide, cobalt ferrite, nickel ferrite, cobalt oxide, and nickel oxide.
7. The method as claimed in claim 1 or 2, wherein the magnetic nanoparticle-based aqueous ink comprises a one-, two-or multi-component aqueous solvent having a boiling point of 100-300 ℃.
8. The method as claimed in claim 7, wherein the magnetic nanoparticle-based aqueous ink comprises a single-, two-or multi-component aqueous solvent having a boiling point of 120-250 ℃.
9. The method of claim 7, wherein the one-component aqueous solvent is selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, glycerol, dimethyl sulfoxide, N-methylpyrrolidone, N-dimethylacetamide, formamide, and acetamide.
10. The method of claim 7, wherein the two-component aqueous solvent is selected from two of water, ethylene glycol, propylene glycol, diethylene glycol, glycerol, dimethyl sulfoxide, N-methylpyrrolidone, N-dimethylacetamide, formamide, and acetamide.
11. The method of claim 7, wherein the multi-component aqueous solvent is selected from the group consisting of water, ethylene glycol, propylene glycol, diethylene glycol, glycerol, dimethyl sulfoxide, N-methylpyrrolidone, N-dimethylacetamide, formamide, and acetamide.
12. The method according to claim 1 or 2, wherein in step (1), the receding angle of the substrate surface is 7.3 to 28.8 °.
13. The method according to claim 1 or 2, wherein in step (1), the surface of the substrate is not treated or is obtained by subjecting the surface of the substrate to plasma sputtering or silane coupling agent modification.
14. The method of claim 13, wherein the plasma sputtering is performed with a gas selected from oxygen and air, the sputtering power is 5-50W, and the sputtering time is 10-50 s.
15. The method as claimed in claim 13, wherein the silane coupling agent modification is heating the substrate in an oven with silane coupling agent atmosphere at 80-120 ℃ for 2-12 h.
16. The method according to claim 15, wherein the silane coupling agent is (3-epoxyethylmethoxypropyl) trimethoxysilane and/or 3-mercaptopropyltrimethoxysilane.
17. The method of claim 13, wherein the substrate is selected from the group consisting of silicon wafers, glass sheets, quartz sheets, mica sheets, metal sheets, and polymer sheets.
18. The method of claim 17, wherein the substrate is a silicon wafer, a quartz wafer, or a mica wafer.
19. The method according to claim 1 or 2, wherein in step (1), the droplet volume of the ink ejected onto the substrate surface is 10 to 100 pL; the gap of the array is 100-.
20. The method according to claim 19, wherein in step (1), the droplet volume of the ink ejected onto the substrate surface is 10-40 pL; the gap of the array is 100-300 μm.
21. The method according to claim 1 or 2, wherein in step (2), the magnetic field is a uniform magnetic field provided by an electromagnetic field or a ferromagnetic field, and the magnetic field strength is 50-500 mT.
22. The method as claimed in claim 21, wherein the magnetic field strength is 100-.
23. The method according to claim 1 or 2, wherein in the step (2), the drying temperature is 5-25 ℃ and the drying relative humidity is 20-90%.
24. A single nanoparticle precision one-dimensional magnetically assembled array prepared according to the method of any one of claims 1 to 23.
25. The use of a single nanoparticle precision one-dimensional magnetic assembly array according to claim 24 in the fields of magnetic field induction, cell differentiation, thermal modulation, and anti-counterfeiting display.
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