CN110423516B - Ink, preparation method thereof and gas sensor film - Google Patents
Ink, preparation method thereof and gas sensor film Download PDFInfo
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- CN110423516B CN110423516B CN201811027983.2A CN201811027983A CN110423516B CN 110423516 B CN110423516 B CN 110423516B CN 201811027983 A CN201811027983 A CN 201811027983A CN 110423516 B CN110423516 B CN 110423516B
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/36—Inkjet printing inks based on non-aqueous solvents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
Abstract
The invention relates to ink, a preparation method thereof and a gas sensor film. The preparation method of the ink comprises the following steps: providing alpha-Fe with anisotropy2O3A nanoparticle; in the alpha-Fe2O3SnO with mesoporous structure is formed on the surface of the nano particles2Shell layer to obtain alpha-Fe with core-shell structure2O3/SnO2Nanocomposite particles; the alpha-Fe with the core-shell structure2O3/SnO2Dispersing the nano composite particles in water to obtain a dispersion liquid, adding a solvent, and uniformly mixing to obtain the ink. The ink prepared by the method is uniform and stable, is suitable for ink-jet printing, integrates two gas-sensitive materials, can inhibit coffee ring effect, and improves the uniformity and sensitivity of the gas-sensitive sensor film.
Description
Technical Field
The invention relates to the technical field of gas sensor manufacturing, in particular to ink, a preparation method thereof and a gas sensor film.
Background
The semiconductor gas sensor mainly uses a transition metal oxide semiconductor material as a gas sensitive material. SnO commonly used as gas sensitive material2The (tin dioxide) gas-sensitive film has response to a plurality of gases, has the advantages of wide detection range and the like, but also has the defects of low selectivity, low working stability and the like. alpha-Fe2O3Alpha-phase iron sesquioxide (commonly called hematite) is a typical n-type (electron depletion layer) semiconductor, has the advantages of good optical band gap, corrosion resistance, environmental friendliness, easiness in synthesis and preparation and the like, is widely applied to the fields of photoelectrochemistry, gas sensors and the like, and has the defect of poor sensitivity.
The ink-jet printing has the excellent characteristics of precise control, convenient operation, material saving and the like, and has particular advantages in the preparation of electronic elements and the deposition and film preparation of functional materials. By synthesizing related functional materials, carrying out ink hydration on the materials and utilizing the ink-jet printing technology, the gas-sensitive films with various components and thicknesses can be conveniently prepared. However, ink jet printing and the subsequent drying process usually generate capillary flow from the center of the film to the edge, which results in a coffee ring phenomenon with thin center and thick edge, resulting in poor film formation uniformity and affecting device performance. To suppress such capillary flow, a plurality of solvents are generally added and formation of a coffee ring is suppressed by adjusting each solvent component in the ink to form a marangoni flow during drying.
However, the addition of multiple solvents can only reduce the tendency of coffee ring formation, and the relative sizes of the Marangoni stream and the capillary stream are not measured, so that the regulation and control of the drying process have certain blindness, and the operation of inhibiting the coffee ring phenomenon by adding and adjusting the solvent ratio is complex and has low efficiency.
Disclosure of Invention
Based on this, provide a stable ink, can avoid the influence of coffee ring in ink drying process, form homogeneous gas sensitive film layer, improve gas sensor's response sensitivity.
An ink is prepared from alpha-Fe2O3/SnO2Nano composite particles and solvent, the alpha-Fe2O3/SnO2The nano-composite particles have a core-shell structure in which alpha-Fe2O3As a nucleus, SnO2Is coated with alpha-Fe2O3Shell on core, SnO2The shell layer has a mesoporous structure, and the alpha-Fe2O3Is alpha-Fe with anisotropy2O3。
The ink is an even colloid dispersion system, is good in stability and suitable for printing, can inhibit the coffee ring effect in the ink drying film forming process, improves the uniformity of a film layer, can be used for batch printing production of gas sensor films, and improves the response sensitivity of the gas sensor.
In one embodiment, the raw material for preparing the ink further comprises a surfactant, and the alpha-Fe2O3/SnO2With said surfactantThe sum of the weights of the solvents accounts for 5-30% of the total weight of the ink, and the sum of the weights of the solvents accounts for 70-95% of the total weight of the ink.
Another object of the present invention is a method for preparing an ink, comprising the steps of:
providing alpha-Fe with anisotropy2O3A nanoparticle;
in the alpha-Fe2O3SnO with mesoporous structure is formed on the surface of the nano particles2Shell layer to obtain alpha-Fe with core-shell structure2O3/SnO2Nanocomposite particles;
subjecting the alpha-Fe to a reaction2O3/SnO2Dispersing the nano composite particles in water to obtain a dispersion liquid, adding a solvent, and uniformly mixing to obtain the ink.
According to the preparation method, the anisotropic alpha-Fe with high particle purity and good dispersibility is prepared by a hydrothermal method2O3Nanoparticles capable of attenuating the effect of capillary flow during ink drying and then on alpha-Fe2O3SnO on the surface of nano particles2Coating to form mesoporous alpha-Fe with core-shell structure2O3@SnO2Nano composite particles, thereby making alpha-Fe2O3The particles are isolated from each other and SnO2The coating increases the surface charge density of the particles, increases the thickness of a diffusion layer of colloidal particles, increases the repulsive force potential energy, and prevents mesoporous alpha-Fe2O3@SnO2Agglomeration among colloid particles to form a stable colloid dispersion system; and the core-shell structure can simultaneously improve SnO2And alpha-Fe2O3Stability of (2).
The ink obtained by the preparation method is a uniform and stable colloid dispersion system, is suitable for printing, can inhibit the influence of nonuniform film formation such as coffee rings and the like in the printing and drying process, and improves the uniformity of the thickness of the printed film; and alpha-Fe2O3@SnO2The particles are in loose arrangement, and after the ink is dried, a uniform, loose and porous film layer can be obtained, so that the quality of the ink can be improvedResponse sensitivity of the gas sensor.
In one embodiment, in the alpha-Fe2O3SnO with mesoporous structure is formed on the surface of the nano particles2The shell layer comprises the following steps:
subjecting the alpha-Fe to a reaction2O3Dispersing the nano particles in an ethanol water solution, adding urea, stannate and PVP-K30, uniformly mixing, washing and drying after finishing hydrothermal reaction at 130-110 ℃ to obtain alpha-Fe with a core-shell structure2O3/SnO2Nanocomposite particles of, among others, alpha-Fe2O3As a nucleus, SnO2Is coated with alpha-Fe2O3Shell on core, SnO2The shell layer has a mesoporous structure.
It is understood that PVP-K30 has steric hindrance effect at SnO2Can prevent SnO in the synthesis process2Can not be completely connected in the spherical direction, thereby being densified and easily forming porous SnO2A shell layer; while also limiting alpha-Fe2O3@SnO2The particles are grown so that the particle size is maintained to meet the requirement of the size of the ink solute particles.
In one embodiment, the alpha-Fe2O3The weight ratio of the nano particles, the urea, the stannate and the PVP-K30 is 1 (1.5-2.5): (2.5-3.5): 1-2.
In one embodiment, the method further comprises the step of adding a surfactant to the dispersion;
the alpha-Fe2O3/SnO2The sum of the weight of the nano composite particles and the weight of the surfactant accounts for 5-30% of the total weight of the ink.
In one embodiment, the surfactant is selected from at least one of polyvinylpyrrolidone, polyethylene glycol octylphenyl ether, and carboxymethylcellulose.
From steric stabilization theory, it is known that the presence of polymeric surfactants reduces the Hamaker constant between colloidal particles, thereby reducing the van der Waals attraction energy between particlesMeanwhile, the existence of the high polymer generates new repulsion potential energy-space repulsion potential energy, so that the high polymer has a space steric hindrance effect, and the repulsion potential energy is further increased, thereby preventing the mesoporous alpha-Fe2O3@SnO2The agglomeration of colloidal particles can form a stable colloidal dispersion system.
In one embodiment, the anisotropic alpha-Fe is further included2O3The preparation steps of the nano particles are as follows:
mixing Fe (ClO)4)3The solution is added to the dihydrogen phosphate and CO (NH)2)2The mixed aqueous solution is evenly mixed, after the hydrothermal reaction at 100-160 ℃, solid is separated and taken out, and the anisotropic alpha-Fe is obtained after washing and drying treatment2O3And (3) nanoparticles.
In one embodiment, the concentration of the ethanol aqueous solution is 30 vol% to 50 vol%.
The invention also aims at a gas sensor film prepared by adopting the ink or the ink prepared by the preparation method.
The invention has the beneficial effects that:
1) the ink of the invention is prepared by mixing anisotropic alpha-Fe2O3Mesoporous SnO on surface of nano particles2Coating to form alpha-Fe with mesopores2O3@SnO2The PVP-K30 is introduced into the nano composite particles to improve the dispersibility and stability of the colloidal particles, and then the nano composite particles are prepared into ink suitable for printing, so that the two gas-sensitive materials are compounded into a whole, the advantages of the two gas-sensitive materials are exerted simultaneously, the mesoporous material is formed, the contact area of gas and the gas-sensitive materials can be increased, and the response sensitivity is enhanced; and solute migration caused by capillary flow can be automatically inhibited, the coffee ring effect in ink-jet printing is avoided, the flatness of the gas-sensitive film is improved, and the response sensitivity is further enhanced.
2) In the ink drying process, the mesoporous alpha-Fe2O3@SnO2Colloidal particles having strong capillarity between each otherThe acting force makes the particles stably and uniformly kept near the gas-liquid interface, and the strong capillary action among the particles makes the holding force among the particles, so that the particles cannot be easily driven by capillary flow, the particles are relatively kept stable and fixed in position, and the loose arrangement appearance is presented in the ink, thereby improving the uniformity of the film.
3) The surface tension and cohesive force of the ink can be adjusted by adding the high polymer surfactant such as PVP and the like into the ink, so that the ink is suitable for printing, and the mesoporous alpha-Fe can be reduced by the high polymer2O3@SnO2The Van der Waals attractive force among the colloid particles simultaneously generates a steric hindrance effect, the stability among the colloid particles is enhanced, and the addition of the high polymer has good effects on film forming property, adhesive property and the like after printing and drying.
4) The ink is suitable for batch printing production of gas sensor films, the gas sensor films obtained after drying are good in uniformity, two gas sensitive materials are compounded, the gas sensor films are loose and porous, and response sensitivity and stability of the gas sensor can be enhanced.
Drawings
FIG. 1 is a schematic diagram illustrating the coffee ring effect of a conventional ink during drying;
FIG. 2 is a schematic diagram of an ink printing drying process according to an embodiment of the present invention.
Detailed Description
In order that the invention may be more fully understood, a more particular description of the invention will now be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
α-Fe2O3The N-type semiconductor is a typical n-type semiconductor, has the advantages of good optical band gap, corrosion resistance, environmental friendliness, easiness in synthesis and preparation and the like, and is widely applied to the fields of photoelectrochemistry, gas sensors and the like. But alpha-Fe alone2O3The gas-sensitive sensing sensitivity of one material is not high, and the stability is not good. SnO2The gas-sensitive film has response to a plurality of gases and has the advantages of wide detection range and the like. Thus, alpha-Fe2O3And SnO2The two materials are compounded into a whole, so that more excellent gas-sensitive performance can be obtained.
The ink-jet printing technology is an effective method for realizing the preparation of the gas sensor film. The gas-sensitive functional material is prepared into ink, the functional material can be conveniently deposited by utilizing the ink-jet printing technology, the position, the composition, the shape and the film thickness of the film unit can be accurately controlled, the accurate doping is easy to implement, and the like.
However, the inventors of the present application have found that the following two problems mainly exist in the current inkjet printing:
(1) as shown in fig. 1, the solute in the conventional ink is isotropic spherical particles, during the evaporation and drying process of the ink, the vapor pressure at the edge of the ink droplet is small, the vapor pressure in the middle is large, so that the evaporation rate of the solvent at the edge part is high, the evaporation of the solvent at the middle part is slow, a transverse flow difference is caused, the middle part is compensated towards the edge part, and compensation capillary flow from the middle part to the edge is generated, and in addition, the capillary attraction among the isotropic spherical particles is weak, the spherical particles in the ink are easily brought to the edge part and are deposited at the contact line, and the phenomenon of 'pinning' of the contact line is generated; during the further drying process, the solvent is evaporated to form a central thin and thick-edged coffee ring structure, so that the ink deposition is not uniform, the surface flatness of the ink-jet printing film is seriously affected, and the application of the ink-jet printing film in the aspect of device preparation is limited.
(2) The precondition of the ink-jet printing technology is to form stable functional ink on a target material, and how to form uniform and stable ink on a gas-sensitive film material is also a difficult point. The ink functional material usually exists in the form of nanoparticles, but because the nanoparticles have small size and large specific surface area, the surface energy of the nanoparticles is high, the nanoparticles are easy to aggregate and deposit, a stable dispersion system cannot be formed, and the ink hydration of the functional material is not facilitated.
Based on this, it is necessary to combine the gas-sensitive material α -Fe2O3And SnO2The advantage of (2) provide an even, stable ink, can avoid the influence of coffee ring in printing and drying process, form the gas-sensitive thin layer of homogeneity.
An ink is prepared from alpha-Fe2O3/SnO2Nano composite particles and solvent, alpha-Fe2O3/SnO2The nano-composite particles have a core-shell structure in which alpha-Fe2O3As a nucleus, SnO2Is coated with alpha-Fe2O3Shell on core, SnO2The shell layer has a mesoporous structure and is alpha-Fe2O3Is alpha-Fe with anisotropy2O3。
According to the DLVO theory, solute particles form colloids in a solvent, and whether the colloid particles are coagulated or stably dispersed in the colloid depends on whether the mutual attraction and the electrostatic repulsion between the colloid particles are strong or weak. If the repulsive force is greater than the attractive force, the sol is stable, otherwise, the sol is unstable to generate coagulation. The colloidal particles have an electric double layer structure, and when diffusion layers between the colloidal particles overlap, electrostatic repulsive force is generated between the colloidal particles by the electric double layer.
The solute in the ink is alpha-Fe with a core-shell structure2O3/SnO2Nanocomposite particles of alpha-Fe2O3Has anisotropy, can reduce the influence of capillary flow in the ink drying process, and has SnO on the surface2Coating layer of alpha-Fe2O3The particles being isolated from each other while allowing electricity to be drawn from the surface of the solute particlesThe charge density is increased, thereby increasing the thickness of the diffusion layer of the colloidal particles, increasing the repulsive force potential energy and preventing the mesoporous alpha-Fe2O3@SnO2Agglomeration among colloid particles to form a stable colloid dispersion system; and the core-shell structure can simultaneously improve SnO2And alpha-Fe2O3Stability of (2).
The ink is a uniform and stable colloid dispersion system, is suitable for printing, can automatically inhibit the influence of nonuniform film formation of coffee rings and the like in the printing and drying process, and improves the uniformity of the thickness of a printed film, as shown in figure 2, the solute (mesoporous alpha-Fe) in the ink2O3@SnO2Colloidal particles) are in an anisotropic ellipsoid shape, and have strong capillary action force among the particles, so that the particles are stably and uniformly kept near a gas-liquid interface, and the capillary action among the particles causes a restraining force among the particles, so that the particles cannot be easily driven by capillary flow, and therefore, the particles are relatively stable and fixed in position, the influence of capillary flow is weakened, and the coffee ring effect is inhibited; and the particles are in a loose arrangement shape, and after the ink is dried, a uniform, loose and porous film layer can be obtained, so that the response sensitivity of the gas sensor can be improved.
In one embodiment, the ink is prepared from a material further comprising a surfactant, alpha-Fe2O3/SnO2The total weight of the ink and the surfactant accounts for 5-30% of the total weight of the ink, and the solvent accounts for 70-95% of the total weight of the ink.
Further, the surfactant is at least one selected from the group consisting of a high polymer surfactant such as polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), polyethylene glycol octylphenyl ether (Triton X-100), and carboxymethylcellulose (CMC). Preferably, the surfactant is PVP.
It can be understood that the existence of the high polymer can reduce the Hamaker constant among colloidal particles so as to reduce the van der Waals attraction energy among the particles, and meanwhile, the existence of the high polymer can also generate new repulsive potential energy, namely, spatial repulsive potential energy so as to enable the repulsive potential energy to have a steric hindrance effect and further increase the repulsive potential energy so as to prevent alpha-Fe2O3/SnO2The agglomeration of the nano composite particles forms a stable colloid dispersion system. Therefore, the addition of the high polymer such as PVP improves the stability of the ink, can adjust the printability of the ink such as surface tension and viscosity, and can improve the film forming property and the caking property of the dried ink.
Further, alpha-Fe2O3/SnO2The weight ratio of the nano composite particles to PVP is (0.1-0.5): 1.
Another embodiment of the present invention provides a method for preparing ink, including the following steps S1 to S3:
s1, providing alpha-Fe with anisotropy2O3And (3) nanoparticles.
In one embodiment, anisotropic α -Fe is prepared2O3The steps of the nano-particles are as follows: mixing Fe (ClO)4)3The solution is added to the dihydrogen phosphate and CO (NH)2)2Mixing the solution in mixed water solution of (urea), hydrothermal reaction at 100-160 deg.c, separating to obtain solid, washing and drying to obtain anisotropic alpha-Fe2O3And (3) nanoparticles.
In one embodiment, the dihydrogen phosphate salt is KH2PO4Or NaH2PO4。
In one embodiment, Fe (ClO)4)3The concentration of the solution is 0.05 mol/L-0.2 mol/L.
In one embodiment, dihydrogen phosphate is reacted with Fe (ClO)4)3The molar ratio of (0.02-0.06) to (1); CO (NH)2)2With Fe (ClO)4)3The molar ratio of (1-1.5) to (1).
Thus, anisotropic alpha-Fe is prepared by controlling the conditions of the dosage of each raw material, the hydrothermal reaction time, the temperature and the like in the reaction process2O3The anisotropic nano particles have strong capillary force during the ink printing and drying process, so that the particles can be stably and uniformly kept near a gas-liquid interface, and strong capillary force among the particlesThe action ensures that the particles have drag force and cannot be easily driven by capillary flow, so that the particles are relatively stable and fixed in position, the influence of capillary flow is weakened, the loose arrangement appearance is presented, and the uniformity of ink drying and film forming is improved.
In one embodiment, in step S1, the temperature of the drying process is 40 ℃ to 60 ℃ for 1h to 12 h.
Specifically, Fe (ClO)4)3Adding into NaH2PO4、CO(NH2)2And (3) mixing and stirring the mixed aqueous solution for 30 min-1 h to uniformly mix all phases in the system to obtain a yellow solution. And then transferring the precursor yellow solution into a hydrothermal reaction kettle, preserving the heat for 4 to 24 hours in an oven at the temperature of between 100 and 160 ℃, and naturally cooling to room temperature to obtain a red mixture. Wherein, Fe (ClO)4)30.1mol/L of NaH2PO4With Fe (ClO)4)3The molar ratio of (0.02-0.06): 1, CO (NH)2)2With Fe (ClO)4)3The molar ratio of (1-1.5) to (1). Centrifuging the obtained red substance, washing the red substance for 2-3 times by using deionized water and/or absolute ethyl alcohol, and drying the obtained substance for 1-12 h at the temperature of 40-60 ℃ to obtain the anisotropic alpha-Fe2O3And (3) nanoparticles.
S2 from the alpha-Fe2O3SnO with mesoporous structure is formed on the surface of the nano particles2Shell layer to obtain alpha-Fe with core-shell structure2O3/SnO2A nanocomposite particle.
Specifically, the α -Fe obtained in step S12O3Dispersing the nano particles in an ethanol water solution, adding urea, stannate and PVP-K30 (polyvinylpyrrolidone-K30), mixing uniformly, cooling after finishing hydrothermal reaction at 130-110 ℃, separating to obtain colloid, washing and drying to obtain alpha-Fe with a core-shell structure2O3/SnO2Nanocomposite particles of, among others, alpha-Fe2O3As a nucleus, SnO2Is coated with alpha-Fe2O3Shell on core, SnO2The shell layer hasA mesoporous structure.
In one embodiment, the concentration of the ethanol solution is 30 vol% to 50 vol%. It is understood that alpha-Fe2O3The nano particles have good dispersibility in 30-50 vol% ethanol solution, do not agglomerate and are beneficial to subsequent coating treatment.
In one embodiment, α -Fe2O3The weight ratio of the nanoparticles to urea is 1: (1.5 to 2.5), alpha-Fe2O3The weight ratio of nanoparticles to stannate is 1: (2.5 to 3.5), alpha-Fe2O3The weight ratio of the nanoparticles to PVP-K30 was 1: (1-2). Thus, CO generated by decomposition of urea is utilized by controlling the amount of each raw material, hydrothermal reaction time, temperature and the like during hydrothermal reaction2The bubbles are used as soft templates, and SnO is generated by hydrolyzing stannate2Nanoparticles with anisotropic alpha-Fe2O3The surface of the nano particles is combined and self-assembled to obtain SnO with a porous structure2Coating with a layer of anisotropic alpha-Fe2O3The nano particles are coated to form PVP-K30 surface modified alpha-Fe2O3@m-SnO2A core-shell structure. In addition, α -Fe2O3@m-SnO2alpha-Fe in (1)2O3As a nucleus, SnO2For the coating layer, m represents a mesopore, i.e., α -Fe2O3Coated with SnO having a porous structure2And (3) a layer.
In one embodiment, the temperature of the drying process in step S2 is 70 ℃ to 90 ℃ for 1h to 12 h.
In one embodiment, the stannate is selected from one of sodium stannate and hydrates thereof, and potassium stannate and hydrates thereof.
Specifically, alpha-Fe2O3Dispersing the nano particles in 30 vol% -50 vol% ethanol solution, performing ultrasonic dispersion for 20 min-30 min, and then adding urea and Na2SnO3·3H2Continuously carrying out ultrasonic dispersion on O (sodium stannate trihydrate) for 10-20 mim, adding PVP-K30 (polyvinylpyrrolidone-K30), stirring for 20-30 min, uniformly mixing, transferring the obtained mixture system to a hydrothermal reaction kettle, and carrying out hydrothermal reaction on the mixture systemCarrying out hydrothermal reaction at 130-110 ℃ for 15-20 h, cooling to room temperature, washing with deionized water and/or absolute ethyl alcohol for 2-3 times, transferring to a vacuum drying oven, and drying at 70-90 ℃ for 1-12 h to obtain alpha-Fe2O3@m-SnO2And (3) colloid.
S3, converting the alpha-Fe obtained in the step S2 into alpha-Fe2O3/SnO2And dispersing the nano composite particles in water to obtain a dispersion liquid, adding a solvent, and uniformly mixing to obtain the ink.
In one embodiment, step S3 further includes the step of adding a surfactant, alpha-Fe, to the dispersion2O3/SnO2The sum of the weight of the nano composite particles and the surfactant accounts for 5-30% of the total weight of the ink.
In one embodiment, the surfactant is at least one selected from the group consisting of high polymer surfactants such as polyvinylpyrrolidone, polyethylene glycol octylphenyl ether, and carboxymethylcellulose. Preferably, PVP is used.
Specifically, the α -Fe obtained in step S22O3/SnO2Ultrasonically dispersing the nano composite particles in deionized water to form uniform dispersion liquid; then adding high polymer surfactant, continuously stirring for 12-24 h, adding solvent and preparing into ink.
In one embodiment, α -Fe2O3/SnO2The weight ratio of the nano composite particles to PVP is (0.1-0.5): thus, by controlling the contents of the components in the ink, an ink having surface tension, viscosity and the like suitable for printing can be obtained.
In one embodiment, the solvent is selected from at least one of water, ethanol, isopropanol, and ethylene glycol.
In another embodiment of the present invention, a gas sensor film is obtained by performing inkjet printing and drying on the ink prepared by the ink or the ink preparation method of the present invention.
Specifically, the ink is deposited on a substrate in an ink-jet printing mode, the temperature of a printing equipment platform is set to be 45-55 ℃, and the ink is evaporated, dried in vacuum, further calcined in a muffle furnace at the temperature of more than 300 ℃ for 2 hours and then connected to gas-sensitive sensor equipment to obtain the sensor film which is uniform in film thickness and sensitive to various gases.
The following are specific examples
Example 1
Ellipsoid alpha-Fe2O3Preparation of nanoparticles
Firstly, Fe (ClO)4)3Adding into NaH2PO4、CO(NH2)2Mixing and stirring the mixed aqueous solution for 30min to uniformly mix all phases of the system. And then transferring the precursor yellow solution into a hydrothermal reaction kettle, preserving the heat for 24 hours in an oven at 100 ℃, and naturally cooling to room temperature to obtain a red mixture. Wherein, Fe (ClO)4)30.1mol/L of NaH2PO4With Fe (ClO)4)3Is 0.04:1, CO (NH)2)2With Fe (ClO)4)3Is 1.2: 1.
② centrifuging the obtained red substance, washing the red substance for 3 times in absolute ethyl alcohol, drying the obtained substance for 12h at 40 ℃ to obtain the ellipsoidal alpha-Fe with high purity and good dispersibility2O3And (3) nanoparticles.
(II) mesoporous alpha-Fe2O3@m-SnO2Preparation of colloidal particles
0.1g of alpha-Fe2O3Dispersing in 90mL ethanol solution (volume fraction of absolute ethanol: 30 vol%) for 30min by ultrasonic dispersion; 2g of urea, 0.3g of Na2SnO3·3H2Adding O into the dispersion liquid, continuing ultrasonic dispersion for 10min, adding 0.1g PVP (k30), stirring for 30min, transferring the system into a hydrothermal reaction kettle, reacting for 20h at 160 ℃, cooling to room temperature, washing with absolute ethyl alcohol for 2 times, and then transferring to a vacuum drying oven to dry for 12h at 10 ℃.
(III) preparation of ink
100mg of the obtained mesoporous alpha-Fe2O3@m-SnO2The colloid is dispersed in 300mL under the ultrasonic state to be removedForming uniform dispersion liquid by using the sub-water;
② subsequently 1g PVP is added to the above system and stirring is continued for 12 h.
Thirdly, isopropanol is added into the mixture to prepare ink which can be sprayed and printed, wherein, the mesoporous alpha-Fe is calculated by weight percentage2O3@m-SnO2The colloid and PVP account for 30 percent of the total weight, and the ethanol solvent accounts for 70 percent of the total weight.
(IV) ink-jet printing and drying to form film
The ink is deposited on a substrate in an ink-jet printing mode, the temperature of a printing equipment platform is set to be 50 ℃, the ink is evaporated, dried and vacuum-dried, and then the ink is further calcined in a muffle furnace at 350 ℃ for 2 hours to obtain a gas sensor film with uniform thickness, and the gas sensor film is connected to gas sensor equipment, so that the sensor film sensitive to various gases is obtained.
Example 2
Ellipsoid alpha-Fe2O3Preparation of nanoparticles
Firstly, Fe (ClO)4)3To KaH2PO4、CO(NH2)2And mixing and stirring the mixed aqueous solution for 45min to uniformly mix all phases of the system. And then transferring the precursor yellow solution into a hydrothermal reaction kettle, preserving the temperature for 4 hours in an oven at 160 ℃, and naturally cooling to room temperature to obtain a red mixture. Wherein, Fe (ClO)4)3Is 0.1mol/L, KaH2PO4With Fe (ClO)4)3In a molar ratio of 0.06:1, CO (NH)2)2With Fe (ClO)4)3In a molar ratio of 1.5:1
② the obtained red substance is centrifuged and washed 3 times with absolute ethyl alcohol. The resulting material was dried at 60 ℃ for 1 h.
(II) mesoporous alpha-Fe2O3@m-SnO2Preparation of colloidal particles
0.1g of alpha-Fe2O3Dispersing in 90mL ethanol solution (volume fraction of absolute ethanol: 50 vol%) for 30min by ultrasonic dispersion; 1.5g of urea, 0.25g of Na2SnO3·3H2Adding O into the dispersion liquid to continue ultrasonic dispersion for 10min,0.1g of PVP-k30 was added and stirred for 30min, and then the above system was transferred to a hydrothermal reaction kettle to react at 130 ℃ for 24h, then cooled to room temperature, washed 2 times with absolute ethanol, and then transferred to a vacuum drying oven to dry at 70 ℃ for 12 h.
(III) preparation of ink
300mg of the above-obtained alpha-Fe2O3Dispersing the nano particles in 300mL of deionized water under an ultrasonic state to form uniform dispersion liquid;
② subsequently 2g PEG was added to the above system and stirring was continued for 24 h.
And thirdly, adding glycol into the mixture to prepare ink capable of being sprayed and printed.
Wherein, according to weight percentage, the mesoporous alpha-Fe2O3@m-SnO2The colloid and PVP account for 20 percent of the total weight, and the ethanol solvent accounts for 10 percent of the total weight.
(IV) ink-jet printing and drying to form film
The ink is deposited on a substrate in an ink-jet printing mode, the temperature of a printing equipment platform is set to be 50 ℃, and the ink is evaporated, dried in vacuum, further calcined in a muffle furnace at 400 ℃ for 2 hours and connected into related gas-sensitive sensor equipment to obtain a sensor film sensitive to various gases.
Example 3
Ellipsoid alpha-Fe2O3Preparation of nanoparticles
Firstly, Fe (ClO)4)3Adding into NaH2PO4、CO(NH2)2Mixing and stirring the mixed aqueous solution for 60min to uniformly mix all phases of the system. And then transferring the precursor yellow solution into a hydrothermal reaction kettle, preserving the temperature in an oven at 140 ℃ for 20h, and naturally cooling to room temperature. Wherein, Fe (ClO)4)30.1mol/L of NaH2PO4With Fe (ClO)4)3In a molar ratio of 0.06:1, CO (NH)2)2With Fe (ClO)4)3In a molar ratio of 1.5:1
② centrifuging the obtained red substance, washing the red substance for 2 times in absolute ethyl alcohol, and drying the obtained substance for 10 hours at 50 ℃.
(II) mesoporous alpha-Fe2O3@m-SnO2Preparation of colloidal particles
0.1gα-Fe2O3Dispersing in 90mL ethanol solution (volume fraction of absolute ethanol: 40 vol%) for 30min by ultrasonic dispersion; 2.5g of urea, 0.35g of Na2SnO3·3H2Adding O into the dispersion liquid, continuing ultrasonic dispersion for 10min, adding 0.15g PVP-k30, stirring for 30min, transferring the system into a hydrothermal reaction kettle, reacting at 160 ℃ for 20h, cooling to room temperature, washing with deionized water for 3 times, and transferring to a vacuum drying oven for drying at 10 ℃ for 12 h.
(III) preparation of ink
500mg of the above-obtained alpha-Fe2O3Dispersing the nano particles in 300mL of deionized water under an ultrasonic state to form uniform dispersion liquid;
② subsequently 2g PVP was added to the above system and stirring was continued for 24 h.
And thirdly, adding glycol into the mixture to prepare ink capable of being sprayed and printed.
Wherein, according to weight percentage, the mesoporous alpha-Fe2O3@m-SnO2The colloid and PVP account for 5 percent together, and the ethanol solvent accounts for 95 percent.
(IV) ink-jet printing and drying to form film
The ink is deposited on a substrate in an ink-jet printing mode, the temperature of a printing equipment platform is set to be 50 ℃, and the ink is evaporated, dried in vacuum, further calcined in a muffle furnace at the temperature of more than 300 ℃ for 2 hours and connected into related gas-sensitive sensor equipment to obtain a sensor film sensitive to various gases.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. An ink is characterized by mainly comprising alpha-Fe2O3/SnO2The nano composite particles and the solvent, the raw materials for preparing the ink also comprise the surfactant, and the alpha-Fe2O3/SnO2The sum of the weight of the nano composite particles and the surfactant accounts for 5-30% of the total weight of the ink, the surfactant is a high polymer surfactant, and the alpha-Fe2O3/SnO2The nano-composite particles have a core-shell structure in which alpha-Fe2O3As a nucleus, SnO2Is coated with alpha-Fe2O3Shell on core, SnO2The shell layer has a mesoporous structure, and the alpha-Fe2O3Is alpha-Fe with anisotropy2O3；
The alpha-Fe2O3/SnO2The nano composite particles are prepared by the following steps:
providing alpha-Fe with anisotropy2O3A nanoparticle;
subjecting the alpha-Fe to a reaction2O3Dispersing the nano particles in an ethanol water solution, adding urea, stannate and PVP-K30, uniformly mixing, washing and drying after finishing hydrothermal reaction at 130-180 ℃ to obtain alpha-Fe with a core-shell structure2O3/SnO2A nanocomposite particle.
2. The ink of claim 1, wherein the surfactant is selected from at least one of polyvinylpyrrolidone, polyethylene glycol octylphenyl ether, and carboxymethyl cellulose.
3. A method for preparing ink is characterized by comprising the following steps:
providing alpha-Fe with anisotropy2O3A nanoparticle;
in the alpha-Fe2O3SnO with mesoporous structure is formed on the surface of the nano particles2Shell layer to obtain alpha-Fe with core-shell structure2O3/SnO2Nanocomposite particles;
subjecting the alpha-Fe to a reaction2O3/SnO2Dispersing the nano composite particles in water to obtain a dispersion liquid, adding a surfactant and a solvent, and uniformly mixing to obtain the ink; the alpha-Fe2O3/SnO2The sum of the weight of the nano composite particles and the weight of the surfactant accounts for 5-30% of the total weight of the ink, and the surfactant is a high polymer surfactant;
wherein, in the alpha-Fe2O3SnO with mesoporous structure is formed on the surface of the nano particles2The shell layer comprises the following steps:
subjecting the alpha-Fe to a reaction2O3Dispersing the nano particles in an ethanol water solution, adding urea, stannate and PVP-K30, uniformly mixing, washing and drying after finishing hydrothermal reaction at 130-180 ℃ to obtain alpha-Fe with a core-shell structure2O3/SnO2Nanocomposite particles of, among others, alpha-Fe2O3As a nucleus, SnO2Is coated with alpha-Fe2O3Shell on core, SnO2The shell layer has a mesoporous structure.
4. The method of claim 3, wherein the α -Fe is2O3The weight ratio of the nano particles, the urea, the stannate and the PVP-K30 is 1 (1.5-2.5): (2.5-3.5): 1-2.
5. The production method according to claim 3, wherein the solvent is at least one selected from the group consisting of water, ethanol, isopropanol, and ethylene glycol.
6. The method according to claim 3, wherein the surfactant is at least one selected from the group consisting of polyvinylpyrrolidone, polyethylene glycol octylphenyl ether, and carboxymethylcellulose.
7. The method according to claim 3, further comprising the anisotropic α -Fe2O3The preparation steps of the nano particles are as follows:
mixing Fe (ClO)4)3The solution is added to the dihydrogen phosphate and CO (NH)2)2The mixed aqueous solution is uniformly mixed, after the hydrothermal reaction at the temperature of 100-160 ℃, solid is separated and taken, and the anisotropic alpha-Fe is obtained after washing and drying treatment2O3And (3) nanoparticles.
8. The method according to claim 7, wherein the α -Fe having anisotropy is in the range of α -Fe having anisotropy2O3In the preparation of nanoparticles, the dihydrogen phosphate is reacted with Fe (ClO)4)3The molar ratio of (0.02-0.06) to (1); CO (NH)2)2With Fe (ClO)4)3The molar ratio of (1-1.5) to (1).
9. The method according to any one of claims 3 to 8, wherein the concentration of the ethanol aqueous solution is 30 vol% to 50 vol%.
10. A gas sensor film, characterized in that the ink used for preparing the gas sensor film is the ink as claimed in any one of claims 1 to 2 or the ink prepared by the preparation method as claimed in any one of claims 3 to 9.
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| CN1400107A (en) * | 2001-08-03 | 2003-03-05 | 中国科学院金属研究所 | Ink jet printing method for preparing metal oxide functional film |
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| CN1400107A (en) * | 2001-08-03 | 2003-03-05 | 中国科学院金属研究所 | Ink jet printing method for preparing metal oxide functional film |
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