CN111733483B - Gallium ferrite nanofiber, manufacturing method and application of gallium ferrite nanofiber - Google Patents

Gallium ferrite nanofiber, manufacturing method and application of gallium ferrite nanofiber Download PDF

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CN111733483B
CN111733483B CN201911220973.5A CN201911220973A CN111733483B CN 111733483 B CN111733483 B CN 111733483B CN 201911220973 A CN201911220973 A CN 201911220973A CN 111733483 B CN111733483 B CN 111733483B
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gallium ferrite
gallium
fiber
nanofiber
ferrite
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CN111733483A (en
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訾孟飞
钟高阔
李江宇
安峰
任传来
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y25/00—Nanomagnetism, e.g. magnetoimpedance, anisotropic magnetoresistance, giant magnetoresistance or tunneling magnetoresistance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/02—Preparation of spinning solutions
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/10—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials non-metallic substances, e.g. ferrites, e.g. [(Ba,Sr)O(Fe2O3)6] ferrites with hexagonal structure
    • H01F1/11—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials non-metallic substances, e.g. ferrites, e.g. [(Ba,Sr)O(Fe2O3)6] ferrites with hexagonal structure in the form of particles

Abstract

The invention relates to a gallium ferrite nanofiber, a manufacturing method of the gallium ferrite nanofiber and application of the gallium ferrite nanofiber. The gallium ferrite nanofiber is ferroelectric and ferromagnetic gallium ferrite nanofiber filament with room-temperature single-phase multiferroic property, and the composition chemical formula of the gallium ferrite nanofiber is GaxFe2‑xO3The value range of x is 0.6-1.0, and the diameter of the gallium ferrite nanofiber filament is below 300 nm. The method comprises the following steps: preparing a gallium ferrite precursor solution by adopting a sol-gel method; performing electrostatic spinning on the fully aged gallium ferrite precursor solution to obtain a gallium ferrite precursor fiber with a first fiber structure diameter; and carrying out heat treatment on the gallium ferrite precursor fiber to obtain the gallium ferrite nano fiber, wherein the gallium ferrite nano fiber has ferroelectricity and ferromagnetism of single-phase multiferroic at room temperature and has a second fiber structure diameter which is less than 300 nm. The gallium ferrite nanofiber yarn has ferroelectric and ferromagnetic properties at room temperature, and can be used for electronic equipment.

Description

Gallium ferrite nanofiber, manufacturing method and application of gallium ferrite nanofiber
Technical Field
The invention relates to the technical field of gallium ferrite, in particular to gallium ferrite nano-fibers, a manufacturing method of the gallium ferrite nano-fibers and application of the gallium ferrite nano-fibers.
Background
As is well known, ferroelectricity realizes the storage of digital information by spontaneous polarization formed by displacement of atoms in a ferroelectric crystal; in contrast, ferromagnetism enables the storage of information through the ordered arrangement of electron spins in ferromagnetic materials. A Magnetoelectric coupling multiferroic material (magnetic coupling multiferroics) refers to a compound having both ferroelectricity (electrical order) and ferromagnetism (magnetic order). The multiferroic material has the following characteristics: (1) ferroelectricity and ferromagnetism coexist, and the charge order and the spin order have strong association coupling; (2) the magnetic polarization state is changed by regulating the electric field, and the magnetic polarization state is applied to a high-density information memory, so that the generated Joule heat can be reduced. The application of the magnetoelectric material is helpful for solving the problem of high energy consumption of the memory, and the functions of low energy consumption, quick storage, processing and the like are realized; (3) the multiferroic material has two degrees of freedom of charge and spin, and can be respectively controlled by an external electric field and a magnetic field, so that the multiferroic material can be used for designing and developing a ternary or quaternary memory device and realizing high-density storage of information. The above advantages of multiferroic materials make them have great potential applications in non-volatile memories, magnetic sensors, tunable microwave devices, and spintronic devices.
In the transition metal oxide, the electric polarization needs to satisfy that the electron of the d electron orbital is 0, and the long-range magnetic order needs to satisfy that the d electron orbital has partial electrons. Therefore, in principle, it is difficult for ferroelectric property and long-range magnetic order to coexist and mutually regulate in the same material system. Single-phase multiferroic materials are made very rare and often limited to antiferromagnetic ordering and low temperature conditions, making their use in practical devices challenging. The multiferroic material most studied at present is BiFeO3However, it also has the disadvantages of weak ferromagnetism and large leakage current, so that a new multiferroic material needs to be found.
GaxFe2-xO3Is a room temperature piezoelectricity, low temperature sub-magnetic material, because of Fe3+And Ga3+The radii are similar, so that two ions can be randomly distributed at four cation sites, when the Fe ions are excessive, the excessive Fe ions can replace Ga ions at the Ga2 position, and the adjacent Fe ions have quite strong anti-ferromagnetic super cross-linking between Fe1 and Ga2 positionsThe exchange interaction can enhance the ferrimagnetic spin ordering and the ferromagnetism, so that the magnetic transition temperature can be raised to be higher than the room temperature by adjusting the stoichiometric ratio of Fe to Ga, and the GaxFe2-xO3Is a potential room-temperature single-phase multiferroic material, and has attracted more and more attention in recent years. However, Ga is disclosed at presentxFe2-xO3The material can have ferromagnetism at room temperature, but the piezoelectric property does not meet the requirements of nonvolatile storage, magnetic sensors, tunable microwave devices, spintronic devices and the like.
Chinese invention patent CN101410331B discloses a magnetic material having a magnetic property corresponding to epsilon-Fe2O3The X-ray diffraction peak of the crystal structure of (1), comprising Ga3+ Ionic substitution of epsilon-Fe2O3Crystalline part of Fe3+epsilon-Ga derived from ionic sitesxFe2-xO3Wherein 0 < X < 1 and comprises a mean particle volume of 20000nm as determined by TEM photography3The following fine powder particles. epsilon-Ga obtained by the schemexFe2-xO3The piezoelectric properties of the powder particles of (a) do not meet the requirements of nonvolatile memories, magnetic sensors, tunable microwave devices, spintronic devices, and the like.
In the prior art, a gallium ferrite material is made into a thin film, but the thin film is constrained by a substrate, and the ferroelectric property of the material can also be obviously influenced.
Disclosure of Invention
The invention aims to provide the gallium ferrite nanofiber which has a larger length-diameter ratio, has good ferroelectric and ferromagnetic properties at room temperature, and meets the requirements of nonvolatile storage, magnetic sensors, adjustable microwave equipment or spinning electronic equipment.
The purpose of the invention is realized by the following technical scheme: a gallium ferrite nanofiber is a ferroelectric and ferromagnetic gallium ferrite nanofiber filament with room-temperature single-phase multiferroic property, and the composition chemical formula of the gallium ferrite nanofiber filament is GaxFe2-xO3X is in the range of 0.6-1.0, and the diameter of the gallium ferrite nanofiber filament is 300nmThe following.
By adopting the technical scheme, the prepared gallium ferrite nanofiber has a larger length-diameter ratio, can amplify displacement caused by a piezoelectric effect or a magnetostrictive effect, is not constrained by a substrate, has better physical and chemical properties, and has a more remarkable magnetoelectric coupling effect. The material has good ferroelectricity and ferromagnetism at room temperature, and meets the requirements of nonvolatile storage, magnetic sensors, adjustable microwave equipment or spinning electronic equipment. Tests show that when the number of x is in the range, the gallium ferrite nanofiber filament can be ensured to have good ferroelectric property and ferromagnetic property at room temperature.
The invention is further configured to: the diameter of the second fiber structure of the gallium ferrite nanofiber filament is 100-250 nm.
Tests show that the diameter is easier to control, and the structure is more stable.
The invention also aims to provide a method for manufacturing the gallium ferrite nanofiber, the prepared gallium ferrite nanofiber is not restricted by a substrate, can amplify the displacement caused by piezoelectric effect or magnetostrictive effect, and has ferromagnetism and ferroelectricity at room temperature; the requirements of nonvolatile storage, magnetic sensors, adjustable microwave equipment, spinning electronic equipment and the like are met.
The second purpose of the invention is realized by the following technical scheme: the method for manufacturing the gallium ferrite nanofiber comprises the following steps:
preparing a gallium ferrite precursor solution by adopting a sol-gel method;
performing electrostatic spinning on the fully aged gallium ferrite precursor solution to obtain a gallium ferrite precursor fiber with a first fiber structure diameter;
and carrying out heat treatment on the gallium ferrite precursor fiber filament to obtain a gallium ferrite nano fiber filament, wherein the gallium ferrite nano fiber filament has ferroelectricity and ferromagnetism of single-phase multiferroic at room temperature and has a second fiber structure diameter, the second fiber structure diameter is smaller than the first fiber structure diameter, and the second fiber structure diameter of the gallium ferrite nano fiber filament is less than 300 nm.
The gallium ferrite precursor fiber is fully aged to enable all components to fully react, and is subjected to heat treatment to obtain the gallium ferrite precursor fiber filament, the gallium ferrite precursor fiber filament is regular in shape and uniform in components, has a nanofiber structure with a larger length-diameter ratio relative to a gallium ferrite nanofiber film, is not restricted by a substrate, can amplify displacement caused by a piezoelectric effect or a magnetostrictive effect, and has ferromagnetism and ferroelectricity at room temperature; the magnetic coupling material has better physical and chemical properties, has more obvious magnetoelectric coupling effect, and meets the requirements of nonvolatile storage, magnetic sensors, adjustable microwave equipment, spinning electronic equipment and the like. The preparation method is simple, the used device is simple, the operation is convenient, and the repeatability is high.
The diameter of the second fiber structure of the gallium ferrite nanofiber filament obtained after heat treatment is smaller, the gallium ferrite nanofiber filament is not easy to break in the contraction process, and the gallium ferrite nanofiber filament with excellent performance can be obtained more easily.
The invention is further configured to: the shrinkage rate of the diameter of the second fiber structure relative to the diameter of the first fiber structure is 20-80%.
The shrinkage rate is further controlled by controlling the raw material ratio, and tests show that the fracture is less prone to occur when the shrinkage rate is 20-80%.
The invention is further configured to: the shrinkage rate of the diameter of the second fiber structure relative to the diameter of the first fiber structure is 30-60%.
The shrinkage rate is further controlled by controlling the raw material ratio, and tests show that the fracture is less prone to occur when the shrinkage rate is 30-60%. The fiber filaments are less prone to agglomeration in the electrostatic spinning process, and the obtained yield is higher.
The invention is further configured to: the concentration of the gallium ferrite precursor solution is 0.2-0.5 mol/L.
By the technical scheme, the yarn is not easy to break in the electrostatic spinning process, and an injector used in the electrostatic spinning process is not easy to block.
The invention is further configured to: the preparation of the gallium ferrite precursor solution comprises the following steps:
dissolving ferric nitrate and gallium nitrate in a mixed solvent of deionized water and absolute ethyl alcohol, and stirring to fully dissolve the components; adding organic acid for complex reaction, wherein the organic acid is one or two of citric acid and oxalic acid;
and adding a spinning aid into the mixed solvent, uniformly stirring, and standing for 1-3 days to obtain a uniform, stable and transparent gallium ferrite precursor solution.
The volatility of the deionized water and the absolute ethyl alcohol is proper, so that the gallium ferrite precursor solution can form a Taylor cone at the spray head more easily, the spray head is not easy to be blocked, and the cellosilk is not easy to be bonded together. Tests show that the obtained cellosilk is more regular and uniform in shape and less prone to breakage because the deionized water and the absolute ethyl alcohol are mixed and other components are dissolved; the deionized water and the absolute ethyl alcohol are environment-friendly, energy-saving and low in cost.
The invention is further configured to: the volume ratio of the deionized water to the absolute ethyl alcohol in the step of preparing the gallium ferrite precursor solution is 1: 1; the molar ratio of the gallium nitrate to the ferric nitrate to the citric acid is x (2-x) to 2.
Tests show that the shapes of the fibers are more regular and uniform when the volume ratio of the deionized water to the absolute ethyl alcohol is 1:1, and the fibers are less prone to fracture. When the total molar weight of the ferric nitrate and the gallium nitrate and the molar weight of the citric acid are 1:1, the formed components are uniform, the viscosity and the surface tension are more suitable, and the obtained fiber filaments are longer and are not easy to break.
The invention is further configured to: the spinning aid is polyvinylpyrrolidone with the molecular weight of 100-150 ten thousand; and the concentration of polyvinylpyrrolidone in the gallium ferrite precursor solution is 0.04-0.05 g/mL.
Polyvinylpyrrolidone (PVP) is a synthetic water-soluble high-molecular compound, and has the general properties of a water-soluble high-molecular compound, such as colloid protection, film-forming property, cohesiveness, hygroscopicity, solubilization or coacervation. The PVP is selected to be better soluble with the mixed solvent, the K value of the PVP with the molecular weight of 100-150 ten thousand is 81.0-97.2, the viscosity is proper, and then the concentration of the PVP is adjusted, so that the fiber yarn is not easy to break in the electrostatic spinning process, and the diameter distribution of the first fiber structure and the diameter distribution of the second fiber structure are more uniform.
The invention is further configured to: the electrostatic spinning of the gallium ferrite precursor solution comprises the following steps:
putting a proper amount of gallium ferrite precursor solution into an injector, fixing the gallium ferrite precursor solution on an injection pump, and setting the speed of the injection pump to be 0.2-0.5 mL/h;
placing a substrate for receiving the gallium ferrite precursor fiber filaments on the receiving plate;
adjusting the distance between the needle point and the substrate to be 8-15 cm;
and (3) opening a high-voltage power supply to carry out spinning to obtain the gallium ferrite precursor fiber, wherein the size of the high-voltage power supply is 10-15 kV.
In electrostatic spinning, when the voltage applied to the solution reaches a certain critical value, the charge repulsion force on the surface of the solution is larger than the surface tension thereof, and the solution is jetted out of a jet flow and is stretched into filaments. The proper voltage is beneficial to maintaining and stabilizing the ejected Taylor cone and the distribution of the diameter of the first fiber structure of the gallium ferrite precursor fiber; the distance between the needle point and the substrate directly influences the electric field intensity, and the proper distance selected by the invention can ensure that the solvent is fully volatilized in the air, the bonding of the fiber yarns is not easy to cause, and the fine and uniform fiber yarns can be obtained; through the common limitation of the speed of the injection pump, the distance between the needle point and the substrate and the size of the high-voltage power supply, the shape of the Taylor cone at the needle point is better, the filament is more stable, the shape structure of the surface of the fiber can be further kept, and the diameter of the first fiber structure of the gallium ferrite precursor fiber is smaller and more uniform.
The invention is further configured to: the substrate is aluminum foil, YSZ/ITO or SiO2/Si。
The substrate has no obvious interference on the growth of the fiber yarns, and the piezoelectric property of the fiber yarns is not easily influenced; the aluminum foil is low in cost and convenient to use on a large scale.
The invention is further configured to: the heat treatment of the gallium ferrite precursor fiber comprises the following steps:
drying, and removing deionized water and absolute ethyl alcohol contained in the gallium ferrite precursor fiber;
removing plastic, namely heating the dried gallium ferrite precursor fiber to 380-420 DEGoC, preserving the heat for 0.5-1 h, removing organic matters in the gallium ferrite precursor fiber to obtain a primary gallium ferrite fiber;
annealing treatment, namely heating the primary gallium ferrite fiber filament after plastic removal to 750-850 DEG CoAnd C, preserving the heat for 1.5-2.5 h to obtain the gallium ferrite nanofiber.
The method comprises the steps of firstly drying to remove deionized water and absolute ethyl alcohol, then performing plastic removal to remove organic matters, so that components in the gallium ferrite precursor fiber are slowly removed, the structural morphology of the gallium ferrite precursor fiber can be better maintained, and the gallium ferrite precursor fiber is not easy to break. And the growth of gallium ferrite grains is promoted through annealing treatment, so that a gallium ferrite fiber filament structure is better obtained, the diameter of the second fiber structure of the gallium ferrite fiber filament is smaller, and the gallium ferrite fiber filament has a larger length-diameter ratio and better physical and chemical properties.
The invention is further configured to: and in the steps of plastic removal and annealing treatment, the heating rate is 5-10 ℃/min.
By controlling the temperature rise rate, the growth of gallium ferrite grains can be better promoted, the structural morphology of the gallium ferrite fiber filament is kept, and the gallium ferrite fiber filament is not easy to break.
The invention also aims to provide application of the gallium ferrite nanofiber in nonvolatile storage, magnetic sensors, adjustable microwave devices or spintronic devices.
The third purpose of the invention is realized by the following technical scheme: the gallium ferrite nanofiber is applied to nonvolatile storage, magnetic sensors, adjustable microwave devices or spinning electronic devices.
In summary, at least one beneficial technical effect of the present invention is:
1. the gallium ferrite precursor fiber is gelatinized and then is subjected to heat treatment to obtain the gallium ferrite precursor fiber filament which has a nanofiber structure with regular shape, uniform components and larger length-diameter ratio, is not restricted by a substrate, can amplify displacement caused by piezoelectric effect or magnetostrictive effect, and has ferromagnetism and ferroelectricity at room temperature; the magnetic coupling material has better physical and chemical properties, has more obvious magnetoelectric coupling effect, and meets the requirements of nonvolatile storage, magnetic sensors, adjustable microwave equipment, spinning electronic equipment and the like.
2. The diameter of the second fiber structure of the gallium ferrite nanofiber filament obtained after heat treatment is smaller, the gallium ferrite nanofiber filament is not easy to break in the contraction process, and the gallium ferrite nanofiber filament with excellent performance can be obtained more easily.
3. The preparation method is simple, the used device is simple, the operation is convenient, and the repeatability is high.
4. The volatility of the deionized water and the absolute ethyl alcohol is proper, so that the gallium ferrite precursor solution can form a Taylor cone at the spray head more easily, the spray head is not easy to be blocked, and the cellosilk is not easy to be bonded together. Tests show that the obtained cellosilk is more regular and uniform in shape and less prone to breakage because the deionized water and the absolute ethyl alcohol are mixed and other components are dissolved; the deionized water and the absolute ethyl alcohol are environment-friendly, energy-saving and low in cost.
5. The PVP is selected to be better soluble with the mixed solvent, the K value of the PVP with the molecular weight of 100-150 ten thousand is 81.0-97.2, the viscosity is proper, and then the concentration of the PVP is adjusted, so that the fiber yarn is not easy to break in the electrostatic spinning process, and the diameter distribution of the first fiber structure and the diameter distribution of the second fiber structure are more uniform.
6. Through the common limitation of the speed of the injection pump, the distance between the needle point and the substrate and the size of the high-voltage power supply, the shape of the Taylor cone at the needle point is better, the filament is more stable, the shape structure of the surface of the fiber can be further kept, and the diameter of the first fiber structure of the gallium ferrite precursor fiber is smaller and more uniform.
7. The method comprises the steps of firstly drying to remove deionized water and absolute ethyl alcohol, then performing plastic removal to remove organic matters, so that components in the gallium ferrite precursor fiber are slowly removed, the structural morphology of the gallium ferrite precursor fiber can be better maintained, and the gallium ferrite precursor fiber is not easy to break. And the growth of gallium ferrite grains is promoted through annealing treatment, so that a gallium ferrite fiber filament structure is better obtained, the diameter of the second fiber structure of the gallium ferrite fiber filament is smaller, and the gallium ferrite fiber filament has a larger length-diameter ratio and better physical and chemical properties.
8. When Ga isxFe2-xO3When the numerical range of the x is 0.6-1.0, the gallium ferrite nanofiber filament can be ensured to have good ferroelectric property and ferromagnetic property at room temperature.
Drawings
FIG. 1 is a schematic flow chart of the preparation of gallium ferrite nanofibers according to experimental examples 1, 2 and 3 of the present invention;
FIG. 2 is an X-ray powder diffraction (XRD) pattern of gallium ferrite nanofibers according to experimental examples 1, 2 and 3 of the present invention;
FIG. 3 is a Scanning Electron Microscope (SEM) image of gallium ferrite nanofibers in experimental examples 1, 2, and 3 of the present invention;
FIG. 4 is a Transmission Electron Microscope (TEM) image of gallium ferrite nanofibers according to experimental example 3 of the present invention.
FIG. 5 is a graph of magnetic susceptibility-temperature (M-T) curve and magnetic hysteresis curve (M-H) of gallium ferrite nanofibers in test examples 1, 2, and 3;
FIG. 6 is a second harmonic imaging (SHG) chart of the gallium ferrite nanofibers of experimental examples 1, 2, and 3.
Detailed Description
Noun interpretation
YSZ refers to a single crystal substrate ZrO of a high temperature superconducting thin film2；
The ITO conductive glass is manufactured by plating a layer of indium tin oxide (commonly called ITO) film on the basis of sodium-calcium-based or silicon-boron-based substrate glass by a magnetron sputtering method;
the K value represents the corresponding PVP average molecular weight range and is a characteristic value related to the relative viscosity of the PVP aqueous solution.
In the FC mode in the magnetic susceptibility-temperature curve, the temperature is firstly raised to be higher than the Curie temperature (Tc) without adding a magnetic field, and then the temperature is reduced by adding the magnetic field for measurement; in the ZFC mode, the temperature is raised without adding a magnetic field, then the temperature is lowered without adding the magnetic field, and then the temperature is raised by adding a small magnetic field for measurement.
Second Harmonic Generation (SHG for short)
In order to facilitate understanding of the technical solution of the present invention, the method for manufacturing the gallium ferrite nanofiber of the present invention is described in further detail below, but the present invention is not limited to the scope of the present invention.
The invention discloses a gallium ferrite nanofiber, which is a gallium ferrite nanofiber filament with room-temperature single-phase multiferroic ferroelectricity and ferromagnetism, and the composition chemical formula of the gallium ferrite nanofiber filament is GaxFe2- xO3The value range of x is 0.6-1.0, and the diameter of the gallium ferrite nanofiber filament is below 300 nm. Preferably, the diameter of the gallium ferrite nanofiber filament is 100-250 nm.
The embodiment of the invention discloses a method for manufacturing gallium ferrite nano-fibers, which comprises the following steps:
step one, preparing a gallium ferrite precursor solution by adopting a sol-gel method;
step two, performing electrostatic spinning on the fully aged gallium ferrite precursor solution to obtain a gallium ferrite precursor fiber with a first fiber structure diameter;
and thirdly, carrying out heat treatment on the gallium ferrite precursor fiber to obtain a gallium ferrite nanofiber, wherein the gallium ferrite nanofiber has ferroelectricity and ferromagnetism of single-phase multiferroic at room temperature and has a second fiber structure diameter, the second fiber structure diameter is smaller than the first fiber structure diameter, and the second fiber structure diameter of the gallium ferrite nanofiber is less than 300 nm.
Preferably, the shrinkage rate of the diameter of the second fiber structure relative to the diameter of the first fiber structure is 20-80%. Preferably, the shrinkage rate of the diameter of the second fiber structure relative to the diameter of the first fiber structure is 30-60%. Preferably, the shrinkage rate of the diameter of the second fiber structure relative to the diameter of the first fiber structure is 37.5-50%.
Regarding the preparation of the gallium ferrite precursor solution in the first step, in a preferred example, the method comprises the following steps:
dissolving ferric nitrate and gallium nitrate in a mixed solvent of deionized water and absolute ethyl alcohol, and stirring to fully dissolve the components; adding organic acid for complex reaction, wherein the organic acid is one or two of citric acid and oxalic acid;
adding a spinning aid into the mixed solvent, uniformly stirring, standing for 1-3 days, and fully aging to fully react the components to obtain a uniform, stable and transparent gallium ferrite precursor solution.
Wherein the volume ratio of the deionized water to the absolute ethyl alcohol is 1: 1; the molar ratio of the gallium nitrate to the ferric nitrate to the citric acid is x (2-x) to 2. The concentration of the gallium ferrite precursor solution is 0.2-0.5 mol/L.
Regarding the possible kinds of spinning aid in the step one, in a preferred example, the spinning aid is polyvinylpyrrolidone with molecular weight of 100-; preferably, the concentration of polyvinylpyrrolidone in the gallium ferrite precursor solution is 0.04-0.05 g/mL.
Regarding the electrostatic spinning in the second step, in a preferred example, the method comprises the following steps:
putting a proper amount of gallium ferrite precursor solution into an injector, fixing the gallium ferrite precursor solution on an injection pump, and setting the speed of the injection pump to be 0.2-0.5 mL/h;
placing a substrate for receiving the gallium ferrite precursor fiber filaments on the receiving plate;
adjusting the distance between the needle point and the substrate to be 8-15 cm;
and (3) opening a high-voltage power supply to carry out spinning to obtain the gallium ferrite precursor fiber, wherein the size of the high-voltage power supply is 10-15 kV.
Wherein the substrate is aluminum foil, YSZ/ITO or SiO2/Si。
Regarding the heat treatment in step three, in a preferred example, the method comprises the following steps:
drying, and removing deionized water and absolute ethyl alcohol contained in the gallium ferrite precursor fiber;
removing plastic, namely heating the dried gallium ferrite precursor fiber to 380-420 DEGoC, preserving the heat for 0.5-1 h, removing organic matters in the gallium ferrite precursor fiber to obtain a primary gallium ferrite fiber;
annealing treatment, namely heating the primary gallium ferrite fiber filament after plastic removal to 750-850 DEG CoAnd C, preserving the heat for 1.5-2.5 h to obtain the gallium ferrite nanofiber.
Wherein the heating rate in the steps of plastic removal and annealing treatment is 5-10 ℃/min.
The third embodiment of the invention discloses the application of the gallium ferrite nanofiber in the scheme in nonvolatile storage, magnetic sensors, adjustable microwave equipment or spintronic equipment.
The following three experimental examples are described in detail with reference to the accompanying drawings
Test example 1
As shown in fig. 1, a gallium ferrite nanofiber and a preparation method thereof, wherein the target product is prepared by a method combining a sol-gel method and electrospinning, and the method comprises the following steps:
(1) preparing a precursor solution by a sol-gel method: first, 4.2986g of iron nitrate (Fe (NO)3)3·9H2O), 1.3708g gallium nitrate (Ga (NO)3)3·xH2O), 3.3622g of citric acid (C)6H8O7·H2O) is sequentially dissolved in 20mL of mixed solvent of deionized water and absolute ethyl alcohol with the volume ratio of 1:1, wherein the molar ratio of each substance is Fe (NO)3)3·9H2O:Ga(NO3)3·xH2O:C6H8O7·H2O =1.33:0.67: 2; then stirring for 6 hours by using a magnetic stirrer to fully dissolve the mixture; and then, adding 0.8g of polyvinylpyrrolidone (PVP) with the molecular weight of 130 ten thousand into the solution, continuously stirring the solution for 7 hours by using a magnetic stirrer, and finally standing for 2 days to fully age the solution so as to fully react the components, thereby obtaining a uniform, stable and transparent gallium ferrite precursor solution with the concentration of 0.4 mol/L.
(2) Preparing gallium ferrite precursor fiber yarns by electrostatic spinning: firstly, taking a proper amount of the fully aged gallium ferrite precursor solution obtained in the step (1), placing the solution into a syringe, fixing the solution on a syringe pump, and setting the speed of the syringe pump to be 0.3 mL/h; then, placing an aluminum foil on a receiving plate as a substrate to receive the gallium ferrite precursor fiber yarns obtained by spinning, wherein the distance between the needle tip and the substrate is 12 cm; and finally, opening a high-voltage power supply to carry out spinning to obtain the gallium ferrite precursor fiber, wherein the size of the high-voltage power supply is 12 kV.
(3) Heat treatment of the gallium ferrite precursor fiber: firstly, putting the precursor fiber filament of gallium ferrite into 60oC, drying in a constant-temperature drying box for 12 hours to remove deionized water and absolute ethyl alcohol contained in the gallium ferrite precursor fiber; then, the resultant was put into a muffle furnace to be annealed at a temperature rise rate of 6oUnder the condition of C/min, firstly heating from room temperature to 400 DEG CoC, preserving the heat for 1h, and removing organic matters in the gallium ferrite precursor fiber; finally, the temperature is raised to 800oAnd C, preserving the heat for 2 hours to obtain the gallium ferrite nano-fiber filament with the diameter of 100-250 nm.
Test example 2
As shown in figure 1, the invention discloses a gallium ferrite nanofiber and a preparation method thereof, wherein a target product is prepared by a method combining a sol-gel method and electrostatic spinning, and the preparation method comprises the following steps:
(1) preparing a precursor solution by a sol-gel method: first, 3.8784g of iron nitrate (Fe (NO)3)3·9H2O), 1.6367g gallium nitrate (Ga (NO)3)3·xH2O), 3.3622g of citric acid (C)6H8O7·H2O) is sequentially dissolved in 20mL of mixed solvent of deionized water and absolute ethyl alcohol with the volume ratio of 1:1, wherein the molar ratio of each substance is Fe (NO)3)3·9H2O:Ga(NO3)3·xH2O:C6H8O7·H2O =1.2:0.8: 2; then stirring for 6 hours by using a magnetic stirrer to fully dissolve the mixture; and then, adding 0.8g of polyvinylpyrrolidone (PVP) with the molecular weight of 130 ten thousand into the solution, continuously stirring the solution for 7 hours by using a magnetic stirrer, and finally standing for 2 days to fully age the solution to obtain a uniform, stable and transparent gallium ferrite precursor solution with the concentration of 0.4 mol/L.
(2) Preparing gallium ferrite precursor fiber yarns by electrostatic spinning: firstly, taking a proper amount of fully aged gallium ferrite precursor solution obtained in the step (1), placing the solution into a syringe, fixing the solution on a syringe pump, and setting the speed of the syringe pump to be 0.3 mL/h; then, placing an aluminum foil on a receiving plate as a substrate to receive the gallium ferrite precursor fiber yarns obtained by spinning, wherein the distance between the needle tip and the substrate is 12 cm; and finally, opening a high-voltage power supply to carry out spinning to obtain the gallium ferrite precursor fiber, wherein the size of the high-voltage power supply is 12 kV.
(3) Heat treatment of precursor nanofibers: firstly, a fiber of a gallium ferrite precursor is put into 60oC, drying in a constant-temperature drying box for 12 hours to remove deionized water and absolute ethyl alcohol contained in the gallium ferrite precursor fiber; then, the resultant was put into a muffle furnace to be annealed at a temperature rise rate of 6oUnder the condition of C/min, firstly heating from room temperature to 400 DEG CoC, preserving the heat for 1h, and removing organic matters in the gallium ferrite precursor fiber; finally, the temperature is raised to 800oAnd C, preserving the heat for 2 hours to obtain the gallium ferrite nanofiber filaments with the diameters of 100-250 nm.
Test example 3
(1) Preparing a precursor solution by a sol-gel method: first, 3.2320g of iron nitrate (Fe (NO)3)3·9H2O), 2.0459g gallium nitrate (Ga (NO)3)3·xH2O), 3.3622g of citric acid (C)6H8O7·H2O) is sequentially dissolved in 20mL of mixed solvent of deionized water and absolute ethyl alcohol with the volume ratio of 1:1, wherein the molar ratio of each substance is Fe (NO)3)3·9H2O:Ga(NO3)3·xH2O:C6H8O7·H2O =1:1: 2; then stirring for 6 hours by using a magnetic stirrer to fully dissolve the mixture; and then, adding 0.8g of polyvinylpyrrolidone (PVP) with the molecular weight of 130 ten thousand into the solution, continuously stirring the solution for 7 hours by using a magnetic stirrer, and finally standing for 2 days to ensure that the solution is fully aged and all the components are fully reacted to obtain a uniform, stable and transparent gallium ferrite precursor solution with the concentration of 0.4 mol/L.
(2) Preparing gallium ferrite precursor fiber yarns by electrostatic spinning: firstly, taking a proper amount of fully aged gallium ferrite precursor solution obtained in the step (1), placing the solution into a syringe, fixing the solution on a syringe pump, and setting the speed of the syringe pump to be 0.3 mL/h; then, placing an aluminum foil on a receiving plate as a substrate to receive the gallium ferrite precursor fiber yarns obtained by spinning, wherein the distance between the needle tip and the substrate is 12 cm; and finally, opening a high-voltage power supply to carry out spinning to obtain the gallium ferrite precursor fiber, wherein the size of the high-voltage power supply is 12 kV.
(3) Heat treatment of the gallium ferrite precursor fiber: firstly, putting the precursor fiber filament of gallium ferrite into 60oC, drying in a constant-temperature drying box for 12 hours to remove deionized water and absolute ethyl alcohol contained in the gallium ferrite precursor fiber; then, the resultant was put into a muffle furnace to be annealed at a temperature rise rate of 6oUnder the condition of C/min, firstly heating from room temperature to 400 DEG CoC, preserving the heat for 1h, and removing organic matters in the gallium ferrite precursor fiber; finally, the temperature is raised to 800oAnd C, preserving the heat for 2 hours to obtain the gallium ferrite nano fiber with the diameter of 100-250 nm.
Performance testing
As shown in FIG. 2, the X-ray powder diffraction pattern of the gallium ferrite nanofiber filaments of test examples 1-3 and the standard PDF card GaFeO were sequentially arranged from top to bottom3-standard spectrum of PDF #76-1005, the crystallinity of the gallium ferrite nano-fiber filament prepared in the experimental examples 1-3 is good, and is similar to that of standard PDF card GaFeO3The PDF #76-1005 comparison shows that most diffraction peaks are from an orthogonal structure of gallium ferrite, and gallium ferrite with different iron contents has little influence on crystallinity.
As shown in fig. 3, fig. 3 (a), 3 (b), and 3 (c) are respectively the corresponding morphology diagrams of the gallium ferrite precursor fiber filaments prepared in experimental examples 1, 2, and 3 when they are not sintered, and fig. 3 (d), 3 (e), and 3 (f) are respectively the morphology diagrams of the gallium ferrite nano fiber filaments obtained after the gallium ferrite precursor fiber filaments prepared in examples 1, 2, and 3 are sintered. It can be clearly seen from the figure that the unsintered gallium ferrite precursor fiber filament has a smooth surface and a uniform diameter, which is approximately between 200 and 400 nm; the gallium ferrite nanofiber filament obtained after sintering becomes relatively rough, the diameter is reduced to about 100-250 nm, and the length-diameter ratio is increased. The shapes of the nano-fiber yarns with different iron contents are not obviously changed, the shapes of the nano-fiber yarns are regular, the diameters of the nano-fiber yarns are relatively close, the nano-fiber yarns are integrally arranged in order, obvious bending does not occur, and a plurality of broken nano-fiber yarns do not exist.
As shown in FIG. 4, FIG. 4 (a) and FIG. 4 (b) are low-magnification TEM images and high-magnification TEM images of the gallium ferrite nanofiber filament obtained in test example 3, respectively, and it can be seen that the fine microstructure, the regular shape and the diameter of the fiber filament are relatively close, and the lattice fringes in FIG. 4 (c) show that the plane spacing is 0.336 nm and are matched with the orthogonal gallium ferrite (130) plane. Fig. 4 (d), 4 (e), and 4 (f) show that Fe, Ga, and O are uniformly distributed in the nanofiber filament, respectively, and it is clear that each component is uniform, which indicates that the stability of the prepared nanofiber filament is good.
As shown in fig. 5, it is clear from the magnetic susceptibility-temperature curve of fig. 5 (a) that the curie temperature of test example 1 is 305K, the curie temperature of test example 2 is 364K, and the curie temperature of test example 1 exceeds 400K and is 403K in both FC mode and ZFC mode, so that the curie temperatures of the gallium ferrite nanofiber filaments prepared in test examples 1-3 are both above room temperature, and the curie temperature thereof increases with the increase of Fe content, which fully proves that the gallium ferrite nanofiber filaments prepared in the present invention have good ferromagnetic properties at room temperature. It can be seen from the hysteresis curve of fig. 5 (b) that as the content of iron increases, the remanent magnetization and coercive field also increase, further proving that the gallium ferrite nanofiber filament prepared by the invention has good ferromagnetic property at room temperature.
As shown in fig. 6, fig. 6 (a), 6 (b), and 6 (c) are SHG intensity graphs of the gallium ferrite nanofiber filaments prepared in experimental examples 1, 2, and 3, respectively, in the p-out polarization direction, and as can be seen from fig. 6, the obtained SHG signal is a double symmetric structure, indicating that the gallium ferrite nanofiber filaments have spontaneous polarization. The higher the SHG signal, the higher the polarization of the sample, the maximum polarization of the fiber when x =0.67, and the less symmetrical the SHG signal obtained when x =1.0, the weaker the polarization. SHG diagram macroscopically illustrates GaxFe2xO3The ferroelectricity of the fiber.
The embodiments of the present invention are preferred embodiments of the present invention, not all embodiments of the present invention, and the scope of the present invention is not limited by these embodiments, so: all technical solutions obtained by equivalent substitutions or equivalent transformations of the present invention should be included in the scope of the present invention.

Claims (13)

1. The gallium ferrite nanofiber is characterized by being a room-temperature single-phase multiferroic ferroelectric and ferromagnetic gallium ferrite nanofiber filament, and the composition chemical formula of the gallium ferrite nanofiber filament is GaxFe2-xO3The numerical range of x is 0.6-1.0, and the diameter of the gallium ferrite nanofiber filament is below 300 nm; the gallium ferrite nanofiber silk is of an orthogonal structure.
2. The gallium ferrite nanofiber according to claim 1, wherein the diameter of the gallium ferrite nanofiber filament is 100-250 nm.
3. The method for manufacturing the gallium ferrite nanofiber is characterized by comprising the following steps of:
preparing a gallium ferrite precursor solution by adopting a sol-gel method;
performing electrostatic spinning on the fully aged gallium ferrite precursor solution to obtain a gallium ferrite precursor fiber with a first fiber structure diameter;
and carrying out heat treatment on the gallium ferrite precursor fiber filament to obtain a gallium ferrite nano fiber filament, wherein the gallium ferrite nano fiber filament has ferroelectricity and ferromagnetism of single-phase multiferroic at room temperature and has a second fiber structure diameter, the second fiber structure diameter is smaller than the first fiber structure diameter, and the second fiber structure diameter of the gallium ferrite nano fiber filament is less than 300 nm.
4. The method of claim 3, wherein the shrinkage of the diameter of the second fiber structure relative to the diameter of the first fiber structure is 30 to 60%.
5. The method for producing a gallium ferrite nanofiber according to claim 3, wherein the concentration of the gallium ferrite precursor solution is 0.2 to 0.5 mol/L.
6. The method for manufacturing the gallium ferrite nano-fiber according to claim 5, wherein the step of preparing the gallium ferrite precursor solution comprises the following steps:
dissolving ferric nitrate and gallium nitrate in a mixed solvent of deionized water and absolute ethyl alcohol, and stirring to fully dissolve the components; adding organic acid for complex reaction, wherein the organic acid is one or two of citric acid and oxalic acid;
and adding a spinning aid into the mixed solvent, uniformly stirring, and standing for 1-3 days to obtain a uniform, stable and transparent gallium ferrite precursor solution.
7. The method for manufacturing the gallium ferrite nano-fiber according to claim 6, wherein the volume ratio of the deionized water to the absolute ethyl alcohol in the step of preparing the gallium ferrite precursor solution is 1: 1; the molar ratio of the gallium nitrate to the ferric nitrate to the citric acid is x (2-x) to 2.
8. The method for preparing gallium ferrite nano-fiber according to claim 6, wherein the spinning aid is polyvinylpyrrolidone with molecular weight of 100-150 ten thousand; and the concentration of polyvinylpyrrolidone in the gallium ferrite precursor solution is 0.04-0.05 g/mL.
9. The method for manufacturing gallium ferrite nanofibers according to claim 3, wherein electrospinning the gallium ferrite precursor solution comprises the steps of:
putting a proper amount of gallium ferrite precursor solution into an injector, fixing the gallium ferrite precursor solution on an injection pump, and setting the speed of the injection pump to be 0.2-0.5 mL/h;
placing a substrate for receiving the gallium ferrite precursor fiber filaments on the receiving plate;
adjusting the distance between the needle point and the substrate to be 8-15 cm;
and (3) opening a high-voltage power supply to carry out spinning to obtain the gallium ferrite precursor fiber, wherein the size of the high-voltage power supply is 10-15 kV.
10. The method of claim 9, wherein the substrate is aluminum foil, YSZ/ITO, or SiO2/Si。
11. The method of manufacturing a gallium ferrite nanofiber according to any one of claims 6 to 10, wherein the heat treatment of the gallium ferrite precursor fiber filament comprises the steps of:
drying, and removing deionized water and absolute ethyl alcohol contained in the gallium ferrite precursor fiber;
removing plastic, namely heating the dried gallium ferrite precursor fiber to 380-420 DEGoC, preserving the heat for 0.5-1 h, removing organic matters in the gallium ferrite precursor fiber to obtain a primary gallium ferrite fiber;
annealing treatment, namely heating the primary gallium ferrite fiber filament after plastic removal to 750-850 DEG CoAnd C, preserving the heat for 1.5-2.5 h to obtain the gallium ferrite nanofiber.
12. The method for manufacturing the gallium ferrite nanofiber according to claim 11, wherein the temperature rise rate in the steps of plastic removal and annealing treatment is 5-10 ℃/min.
13. Use of a gallium ferrite nanofiber according to any of claims 1-2 in non-volatile storage, magnetic sensors, tunable microwave devices or spintronic devices.
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